Compound, polymer, composition, film-forming composition, pattern formation method, method for forming insulating film, method for producing compound, iodine-containing vinyl polymer, and method for producing acetylated derivative thereof

Abstract

To provide a compound capable of giving a resist excellent in exposure sensitivity, and a method for producing the compound.SOLUTION: The compound is represented by the following formula and has one or more halogens and an unsaturated double bond. (In the formula, each X independently represents I, F, Cl, Br or a C1-30 organic group having one to five substituents selected from the group consisting of I, F, Cl and Br; each L1 independently represents a single bond, an ether group, an ester group or the like; each Y independently represents a hydroxyl group, an alkoxy group, an ester group or the like; Ra, Rb and Rc each independently represent H, I, F, Cl, Br or an optionally substituted C1-60 organic group; A represents an organic group; and each Z independently represents an alkoxy group, an ester group or the like.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound, a polymer, a composition, a film-forming composition, a pattern forming method, a method for forming an insulating film, and a method for producing a compound. The present invention also relates to a method for producing an iodine-containing vinyl polymer and an acetylated derivative thereof. [Background technology]

[0002] In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, semiconductors (patterns) and pixels have been rapidly miniaturized due to advances in lithography technology. In order to miniaturize pixels, the wavelength of the exposure light source is generally shortened. Specifically, ultraviolet rays such as g-line and i-line were used in the past, but nowadays, exposure methods using far ultraviolet rays such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm) have become the mainstream in mass production, and extreme ultraviolet (EUV) lithography (13.5 nm) is also being introduced. Electron beams (EB) are also used to form fine patterns.

[0003] Conventional resist materials are polymeric resist materials capable of forming amorphous films. For example, polymeric resist compositions such as polymethyl methacrylate, polyhydroxystyrene having an acid-dissociable group, or polyalkyl methacrylate can be mentioned (see, for example, Non-Patent Document 1). Conventionally, a line pattern of about 10 to 100 nm is formed by irradiating a thin resist film prepared by applying a solution of such a resist composition onto a substrate with ultraviolet light, far ultraviolet light, an electron beam, extreme ultraviolet light, or the like.

[0004] In addition, the reaction mechanism of electron beam or extreme ultraviolet lithography is different from that of normal photolithography (Non-Patent Document 2, Non-Patent Document 3). Furthermore, in electron beam or extreme ultraviolet lithography, the goal is to form a fine pattern of several nm to several tens of nm. As the dimensions of the resist pattern become smaller, a resist composition with higher sensitivity to the exposure light source is required. In particular, in extreme ultraviolet lithography, there is a demand for higher sensitivity in terms of throughput. As a resist material that overcomes the above-mentioned problems, a resist composition that contains a complex of a metal such as titanium, tin, hafnium, or zirconium has been proposed (see, for example, Patent Document 1).

[0005] Furthermore, as the dimensions of resist patterns become smaller, resist compositions with even higher sensitivity to the exposure light source are required, and iodine-containing 4-hydroxystyrene has been proposed as a raw material monomer for such compositions (see, for example, Patent Documents 2 and 3). However, no method for synthesizing iodine-containing hydroxystyrene or its acetylated derivatives has been disclosed.

[0006] On the other hand, many methods are known for synthesizing hydroxystyrene and its acetylated derivatives that do not contain iodine (e.g., Patent Documents 4 to 6). However, these methods generally require expensive reagents and severe conditions, and the yield is low. Furthermore, when these synthesis methods are applied to iodine-containing hydroxystyrene and its acetylated derivatives, the yield is generally even lower. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2015-108781 A [Patent Document 2] US2019 / 0187342 publication [Patent Document 3] WO2019 / 187881 publication [Patent Document 4] US4,316,995 publication [Patent Document 5] Publication US5,274,060 [Patent Document 6] WO2005 / 097719 publication [Non-patent literature]

[0008] [Non-Patent Document 1] Shinji Okazaki and 8 others, "Lithography Technology: 40 Years," S&T Publishing, December 9, 2016 [Non-Patent Document 2] H. Yamamoto, et al., Jpn.J.Appl.Phys.46,L142(2007) [Non-Patent Document 3] H. Yamamoto, et al., J.Vac.Sci.Technol.b 23,2728(2005) Summary of the Invention [Problem to be solved by the invention]

[0009] However, conventionally developed film-forming compositions have a problem in that their sensitivity to an exposure light source is not sufficiently high for forming finer patterns.

[0010] In order to solve these problems, an object of the present invention is to provide a compound, a polymer, a composition, a resist composition, a pattern forming method, a method for forming an insulating film, and a method for producing a compound, which are capable of obtaining a resist having excellent exposure sensitivity.

[0011] As described above, there are no known methods for producing iodine-containing hydroxystyrene and its acetylated derivatives, and these methods generally require expensive reagents and severe conditions, and have low yields.

[0012] In order to solve these problems, an object of the present invention is to provide a method for producing an iodine-containing vinyl polymer (iodine-containing hydroxystyrene) and its acetylated derivative in high yield without the need for expensive reagents or severe conditions. [Means for solving the problem]

[0013] Means for Solving the Problems The present inventors conducted intensive research to solve the above-mentioned problems and as a result discovered that a compound having a specific structure, or a polymer containing said compound as a structural unit, can increase the exposure sensitivity of a resist composition, thereby completing the present invention. That is, the present invention is as follows.

[0014] [1] A compound having one or more halogens and an unsaturated double bond. [2] The compound according to [1] above, having one or more hydrophilic groups or one degradable group. [3] The compound according to the above [1] or [2], which is represented by the following formula (1): [ka] (In formula (1), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1 are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R a , R b , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z's each independently represent an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group of Z may have a substituent; p is an integer of 1 or greater, m is an integer of 1 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater. [4] The compound according to the above [3], which is represented by the following formula (1a): [ka] (In formula (1a), X, L 1 , Y, A, Z, p, m, n, and r are the same as those in formula (1). [5] The compound according to the above [3], which is represented by the following formula (1b): [ka] (In formula (1b), X, L 1 , Y, A, Z, p, m, n, and r are the same as defined in formula (1); R a1 , Rb1 , and R c1 each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, R a1 , R b1 , and R c1 At least one of the above is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent.) [6] The compound according to any one of the above [3] to [5], wherein n+r is an integer of 1 or more. [7] The compound according to any one of the above [3] to [6], wherein Y is each independently a group represented by the following formula (Y-1): [ka] (In formula (Y-1), L 2 is a group which is cleaved by the action of an acid or a base, R 2 is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 1 to 30 carbon atoms, a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms containing a heteroatom, or an aromatic group having 1 to 30 carbon atoms containing a heteroatom, 2 The aliphatic group, aromatic group, aliphatic group containing a hetero atom, and aromatic group containing a hetero atom may further have a substituent. [8] The compound according to any one of the above [3] to [7], wherein A is an aromatic ring. [9] The compound according to any one of the above [3] to [7], wherein A is an alicyclic structure.

[10] The compound according to any one of the above [3] to [9], wherein A is a heterocyclic structure.

[11] The compound according to any one of the above [3] to

[10] , wherein n is 2 or more.

[12] The compound according to any one of the above [1] to

[11] , which contains a functional group that is improved in solubility in an alkaline developer by the action of an acid or a base.

[13] X is I and L 1 is a single bond.

[14] The compound according to any one of the above [3] to

[12] , wherein X is an aromatic group having one or more of F, Cl, Br or I introduced therein.

[15] The compound according to any one of the above [3] to

[12] , wherein X is an alicyclic group having one or more of F, Cl, Br or I introduced therein.

[16] A composition comprising a compound represented by formula (1C) in an amount of 1 ppm by mass or more and 10% by mass or less based on the total amount of the compounds according to any one of the above items [1] to

[15] . [ka] (In formula (1C), formula (1C1), and formula (1C2), X, L 1 , Y, A, Z, p, m, n, and r are the same as defined in formula (1); Rsub represents the formula (1C1) or the formula (1C2), R a1 , R b1 , and R c1 each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, R a1 , R b1 , and R c1 at least one of is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent; p-1 is an integer equal to or greater than 0, * indicates the bonding site with the adjacent structural unit.)

[17] A composition comprising the compound according to any one of the above [1] to

[15] and a compound represented by formula (1D) in an amount of 1 ppm by mass or more and 10% by mass or less relative to the compound. [ka] (In formula (1D), formula (1D1), or formula (1D2), X, L 1 , Y, A, Z, p, m, n, and r are the same as defined in formula (1); Rsub2 represents formula (1D1) or formula (1D2), R a1 , R b1 , and R c1 each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, R a1 , R b1 , and R c1 at least one of is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent; n2 represents an integer between 0 and 4, p-1 is an integer equal to or greater than 0, * indicates the bonding site with the adjacent structural unit.)

[18] A composition comprising a compound represented by formula (1E) in an amount of 1 ppm by mass or more and 10% by mass or less relative to the compound according to any one of the above items [3] to

[15] . [ka] (In formula (1E), X is each independently F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of F, Cl, and Br; L 1 are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and 1The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R a , R b , and R c each independently represents H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; However, X, L 1 , Y, R a , R b , R c , A and Z do not contain I; p is an integer of 1 or greater, m' is an integer of 0 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater.

[19] The compound includes the compound according to any one of the above items [1] to

[15] , A composition comprising the compound and an impurity containing K, the impurity being 1 ppm by mass or less in terms of elemental content.

[20] The composition according to

[19] , wherein the peroxide is present in an amount of 10 ppm by mass or less relative to the compound. [twenty one] The composition according to

[19] or

[20] above, wherein an impurity containing one or more elements selected from the group consisting of Mn, Al, Si, and Li is 1 ppm by mass or less relative to the compound, calculated as the element. [twenty two] The composition according to any one of the above

[19] to

[21] , wherein the phosphorus-containing compound is present in an amount of 10 ppm by mass or less relative to the compound. [twenty three] The composition according to any one of the above

[19] to

[22] , wherein the amount of maleic acid is 10 ppm by mass or less relative to the compound. [twenty four] A polymer comprising a structural unit derived from the compound according to any one of the above items [1] to

[15] . [twenty five] The polymer according to

[24] above, further comprising a constitutional unit represented by the following formula (C6): [ka] (In formula (C6), X C61 is a hydroxyl group or a halogen group, R C61 are each independently an alkyl group having 1 to 20 carbon atoms, * indicates the bonding site with the adjacent structural unit.)

[26] A film-forming composition comprising the compound according to any one of the above items [1] to

[15] or the polymer according to the above item

[24] or

[25] .

[27] The film forming composition according to

[26] above, further comprising an acid generator, a base generator or a basic compound.

[28] forming a resist film on a substrate using a film-forming composition containing the compound according to any one of the above items [1] to

[15] or the polymer according to the above item

[24] or

[25] ; exposing the resist film to a pattern; developing the resist film after the exposure; A method for forming a resist pattern comprising the steps of:

[29] A method for forming an insulating film, comprising the method according to

[28] above.

[30] a double bond introduction step of introducing an unsaturated double bond into a substituent Q of a compound represented by the following formula (S1); A method for producing a compound represented by the following formula (0): [ka] (In formula (S1), X 0 is an organic group having 1 to 30 carbon atoms, L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group, p is an integer of 1 or greater, m' is an integer of 0 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater. [ka] (In formula (0), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R a , R b , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; p is an integer of 1 or greater, m' is an integer of 0 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater.

[31] The compound represented by the formula (S1) is a compound represented by the following formula (SA1): A method for producing the compound according to the above

[30] , comprising the steps of A1 and A2 below: A1) A step of obtaining a compound represented by the following formula (SA2) using the compound represented by the formula (SA1) and a compound represented by the following formula (RM1) or malononitrile. A2) A step of converting the formula (SA2) into the formula (1) using a fluoride source. [ka] (In formulas (SA1), (RM1) and (SA2), X 0 , L 1, Y, A, Z, p, m', n, and r are defined as in formulas (S1) and (0), Q 1 is an aldehyde or ketone, LG is a group selected from a hydroxy group, an alkoxy group, a carbonate group, an acetal group, and a carboxy group, and the alkoxy group, the carbonate group, the acetal group, and the carboxy group each include an aliphatic group or an aromatic group which may have a substituent having 1 to 60 carbon atoms; R 3 represents a hydrogen group, or a carboxy group or ester group which may have a substituent having 1 to 60 carbon atoms, R 4 is a hydrogen radical, R 5 , R 6 each independently represents H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, XA is a group selected from a hydrogen group and a halogen group.

[32] The method for producing the compound according to

[31] above, wherein in the step A2, a decarboxylation reaction is carried out on the compound represented by formula (SA2) using the fluoride source at 100° C. or lower.

[33] The method for producing the compound according to

[31] or

[32] above, wherein in the step A1, a reducing agent is further used to obtain the compound represented by formula (SA2).

[34] The method for producing the compound according to any one of the above

[30] to

[33] , wherein in the above formula (S1), A is benzene, toluene, or a heteroaromatic ring.

[35] A method for producing a compound represented by the following formula (1), comprising: a step of forming a compound represented by the following formula (SB1) from at least one of compounds represented by the following formula (SB2A) and formula (SB3A) obtained through a step represented by the following formula B1A and at least one of the steps represented by the following formulas B2A and B3A; and a double bond introduction step of introducing an unsaturated double bond into a substituent Qb of the compound represented by formula (SB1). B1A) preparing a substrate SB1A containing one or more amino groups and a core B having an aldehyde group or a ketone group. B2A) A step of obtaining a compound represented by the following formula (SB2A) in which iodine is introduced into the mother nucleus B: B3A) A process for obtaining a compound represented by formula (SB3A) in which the amino group is replaced with a halogen group by the Sandmeyer reaction. [ka] (In formula (1), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1 are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R a , R b , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z's each independently represent an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group of Z may have a substituent; p is an integer of 1 or greater, m is an integer of 1 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater. In formulas (SB1A), (SB2A), (SB3A), and (SB1), Zb represents a hydrogen group or an amino group which may have a substituent selected from a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; rb represents an integer of 1 or more; Qb and L 1b , X b1 , B, pb, and mb' are the same as Q, L, X, A, p, and m in formula (1), respectively. X B2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br.

[36] The method for producing the compound according to the above item

[35] , wherein the step of introducing a double bond uses an organic phosphorus compound and a base.

[37] A method for producing the compound according to the above

[30] , comprising a halogen introduction step of reacting a compound represented by the above formula (S1) with a halogenating agent to introduce a halogen atom.

[38] The method for producing the compound according to any one of the items

[30] to

[34] , wherein the compound represented by formula (SA1) is at least one of the compounds represented by formula (SB2A) and formula (SB3A) below, obtained through a step represented by B1A below and at least one of the steps represented by B2A and B3A below. B1A) preparing a substrate SB1A containing one or more amino groups and a core B having an aldehyde group or a ketone group. B2A) A step of obtaining a compound represented by the following formula (SB2A) in which iodine is introduced into the mother nucleus B: B3A) A process for obtaining a compound represented by formula (SB3A) in which the amino group is replaced with a halogen group by the Sandmeyer reaction. [ka] (In formulas (SB1A), (SB2A), (SB3A), and (SA1A), Zb represents a hydrogen group or an amino group which may have a substituent selected from a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; rb represents an integer of 1 or more; Qb and L 1b , X b1 , B, pb, and mb' are the same as Q, L, X, A, p, and m in formula (1), respectively. X B2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br.

[39] The method for producing the compound according to

[36] above, wherein in the step B2A, iodine is introduced into the mother nucleus B using at least an iodine source and an oxidizing agent.

[40] The method for producing the compound according to the above

[30] , wherein the compound represented by formula (SA1) is produced by the process represented by the following B1B and at least one of the processes represented by the following B2B and B3B. B1B) preparing a substrate SB1B comprising a core B having one or more amino groups and an aldehyde group or a ketone group; B2B) A process for obtaining a compound represented by formula (SB2B) in which iodine is introduced into the mother nucleus B B3B) A step of obtaining a compound represented by formula (SB3B) in which the amino group is replaced with a halogen group. [ka] (In formulas (SB1B), (SB2B), (SB3B), and (SA1B), Zb represents a hydrogen group or an amino group which may have a substituent selected from a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; rb represents an integer of 1 or more; Qb and L 1b , X b1 , B, pb, and mb' are defined as Q, L, X, A, p, and m in formula (1), respectively. X B2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br.

[41] A method for producing the compound according to the above

[40] , further comprising the step shown in B4a below: B4a) Wittig process

[42] The method for producing the compound according to

[38] or

[41] , wherein in the step B2B, iodine is introduced into the mother nucleus B using at least an iodine source and an oxidizing agent.

[43] The method for producing the compound according to any one of the above

[40] to

[42] , wherein the mother nucleus B has an aromatic ring structure which may have a heteroatom.

[44] a halogen introduction step of reacting a compound represented by the following formula (S1) with a halogenating agent to introduce a halogen atom; a double bond introduction step of introducing an unsaturated double bond into the substituent Q; The method for producing a compound represented by the following formula (1) comprising the steps of: [ka] (In formula (S1), X 0 is an organic group having 1 to 30 carbon atoms, L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group, p is an integer of 1 or greater, m' is an integer of 0 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater. [ka] (In formula (1), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R a , Rb , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; p is an integer of 1 or greater, m is an integer of 1 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater.

[0015] Furthermore, as a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that, by going through specific steps, it is possible to provide a method for producing an iodine-containing vinyl polymer and an acetylated derivative thereof in high yield without the need for expensive reagents or severe conditions, and have thus completed the present invention. That is, the present invention is as follows.

[45] a) General structure represented by formula (1-1): [ka] (In formula (1-1), R 1 ~R 5 are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 6 ~R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 1 ~R 5 At least one of R is OH. 1 ~R 5 At least one of the groups is iodine, and R 6 ~R 10 (one of which is OH or OCH3) providing an iodine-containing alcoholic substrate having an iodine-containing alcoholic substrate; b) dehydrating the iodine-containing alcoholic substrate to obtain a compound having the general structure represented by formula (1): [ka] (In formula (1), R 1 ~R 5 are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 6 ~R 8 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 1 ~R 5 At least one of R is OH. 1 ~R 5 At least one of these is iodine. obtaining an iodine-containing vinyl monomer having the formula: The method for producing the iodine-containing vinyl monomer comprises:

[46] The step of preparing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1) includes: c) the general structure represented by formula (1-2); [ka] (In formula (1-2), R 1 ~R 5 are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 7 , R 8 and R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 1 ~R 5 At least one of R is OH. 1 ~R 5 At least one of these is iodine. providing an iodine-containing ketonic substrate having the formula: d) reducing the iodine-containing ketonic substrate to obtain an iodine-containing alcoholic substrate having the general structure represented by formula (1-1); The method for producing an iodine-containing vinyl monomer according to

[45] above, comprising:

[47] The step of preparing an iodine-containing alcoholic substrate having the general structure represented by formula (1-1) includes: e) General structure represented by formula (1-3); [ka] (In formula (1-3), R 11 ~R 15 are each independently H, OH, OCH3, or linear or branched alkyl; R 6 ~R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 11 ~R 15 At least one of R is OH. 6 ~R 10 (one of which is OH or OCH3) providing an alcoholic substrate having f) introducing iodine into the alcoholic substrate to obtain an iodine-containing alcoholic substrate having the general structure represented by formula (1-1); The method for producing an iodine-containing vinyl monomer according to

[45] above, comprising:

[48] The step of preparing an iodine-containing ketonic substrate having the general structure represented by formula (1-2) includes: g) General structure represented by formula (1-4); [ka] (In formula (1-4), R 11 ~R 15 are each independently H, OH, OCH3, or linear or branched alkyl; R 7 , R 8 and R 10are each independently H, OH, OCH3, a halogen or a cyano group; However, R 11 ~R 15 At least one of them is OH. providing a ketonic substrate having the formula: h) introducing iodine into the ketonic substrate to obtain an iodine-containing ketonic substrate having the general structure represented by formula (1-2); The method for producing an iodine-containing vinyl monomer according to

[46] above, comprising:

[49] The step of preparing an alcoholic substrate having a general structure represented by formula (1-3) includes: i) a general structure represented by formula (1-4); [ka] (In formula (1-4), R 11 ~R 15 are each independently H, OH, OCH3, or linear or branched alkyl; R 7 , R 8 and R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 11 ~R 15 At least one of them is OH. providing a ketonic substrate having the formula: j) reducing the ketonic substrate to provide an alcoholic substrate having the general structure represented by formula (1-3); The method for producing an iodine-containing vinyl monomer according to

[47] above, comprising:

[50] k) A general structure represented by formula (1): [ka] (In formula (1), R 1 ~R 5are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 6 ~R 8 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 1 ~R 5 At least one of R is OH. 1 ~R 5 At least one of these is iodine. providing an iodine-containing vinyl monomer having l) Acetylation of the iodine-containing vinyl monomer to form a vinyl monomer having the general structure represented by formula (2): [ka] (In formula (2), R 16 ~R 20 are each independently H, OH, OCH3, OAc, halogen, or linear or branched alkyl; R 6 ~R 8 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 16 ~R 20 At least one of the groups is OAc, and R 16 ~R 20 At least one of these is iodine. obtaining an iodine-containing acetylated vinyl monomer having the formula: The method for producing the iodine-containing acetylated vinyl monomer comprises:

[51] c) the general structure represented by formula (1-2); [ka] (In formula (1-2), R 1 ~R 5 are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 7, R 8 and R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 1 ~R 5 At least one of R is OH. 1 ~R 5 At least one of these is iodine. providing an iodine-containing ketonic substrate having the formula: d) reducing the iodine-containing ketonic substrate to obtain a compound having the general structure represented by formula (1-1): [ka] (In formula (1-1), R 1 ~R 5 are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 6 ~R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 1 ~R 5 At least one of R is OH. 1 ~R 5 At least one of the groups is iodine, and R 6 ~R 10 (one of which is OH or OCH3) obtaining an iodine-containing alcoholic substrate having the formula: A method for producing the iodine-containing alcoholic substrate, comprising:

[52] e) General structure represented by formula (1-3); [ka] (In formula (1-3), R 11 ~R 15 are each independently H, OH, OCH3, or linear or branched alkyl; R 6 ~R 10are each independently H, OH, OCH3, a halogen or a cyano group; However, R 11 ~R 15 At least one of R is OH. 6 ~R 10 (one of which is OH or OCH3) providing an alcoholic substrate having f) introducing iodine into the alcoholic substrate to form a compound having the general structure represented by formula (1-1): [ka] (In formula (1-1), R 1 ~R 5 are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 6 ~R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 1 ~R 5 At least one of R is OH. 1 ~R 5 At least one of the groups is iodine, and R 6 ~R 10 (one of which is OH or OCH3) obtaining an iodine-containing alcoholic substrate having the formula: A method for producing the iodine-containing alcoholic substrate, comprising:

[53] g) General structure represented by formula (1-4); [ka] (In formula (1-4), R 11 ~R 15 are each independently H, OH, OCH3, or linear or branched alkyl; R 7 , R 8 and R 10are each independently H, OH, OCH3, a halogen or a cyano group; However, R 11 ~R 15 At least one of them is OH. providing a ketonic substrate having the formula: h) introducing iodine into the ketone substrate to form a general structure represented by formula (1-2); [ka] (In formula (1-2), R 1 ~R 5 are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 7 , R 8 and R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 1 ~R 5 At least one of R is OH. 1 ~R 5 At least one of these is iodine. obtaining an iodine-containing ketonic substrate having the formula: The method for producing the iodine-containing ketonic substrate comprises:

[54] i) a general structure represented by formula (1-4); [ka] (In formula (1-4), R 11 ~R 15 are each independently H, OH, OCH3, or linear or branched alkyl; R 7 , R 8 and R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 11 ~R 15 At least one of them is OH. providing a ketonic substrate having the formula: j) reducing the ketonic substrate to form a compound represented by the general structure of formula (1-3); [ka] (In formula (1-3), R 11 ~R 15 are each independently H, OH, OCH3, or linear or branched alkyl; R 6 ~R 10 are each independently H, OH, OCH3, a halogen or a cyano group; However, R 11 ~R 15 At least one of R is OH. 6 ~R 10 (one of which is OH or OCH3) obtaining an alcoholic substrate having the formula: The method for producing the alcoholic substrate comprising: Effect of the Invention

[0016] According to the present invention, it is possible to provide a compound, a polymer, a composition, a resist composition, a pattern forming method, a method for forming an insulating film, and a method for producing a compound, which are capable of obtaining a resist having excellent exposure sensitivity.

[0017] Furthermore, the present invention can provide a method for producing an iodine-containing vinyl polymer and its acetylated derivative in high yield without the need for expensive reagents or severe conditions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] First Embodiment A first embodiment of the present invention will be described below (hereinafter, may be referred to as "the present embodiment"). Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment.

[0019] In this specification, the meanings of each term are as follows. "(Meth)acrylate" means at least one selected from acrylate, haloacrylate, and methacrylate. Haloacrylate means an acrylate in which a halogen is substituted at the methyl group position of a methacrylate. Other terms containing the expression (meth) are also interpreted in the same way as (meth)acrylate. The term "(co)polymer" refers to at least one selected from a homopolymer and a copolymer.

[0020] [Compound (A)] The compound according to this embodiment (hereinafter also referred to as "compound (A)") has one or more halogens and an unsaturated double bond. Compound (A) may further have one or more hydrophilic groups or one decomposable group. From the viewpoint of pattern roughness, it is preferable to have one or more hydrophilic groups or one decomposable group. That is, the compound according to this embodiment has one or more halogens, one or more hydrophilic groups or one decomposable group, and an unsaturated double bond. Compound (A) may further have one or more hydrophilic groups or one decomposable group. Examples of halogen include I, F, Cl, and Br. Among these, from the viewpoint of the sensitization effect by EUV and reduction of pattern roughness, I, F, or Br is preferred, I or F is more preferred, and I is even more preferred. The number of halogens is preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, and even more preferably 2 or 3.

[0021] The term "hydrophilic group" refers to a group that improves the affinity between the organic compound and water by bonding to the organic compound. Examples of hydrophilic groups include hydroxyl, nitro, amino, carboxyl, thiol, phosphine, phosphon, phosphoric acid, ether, thioether, urethane, urea, amide, and imide groups. Among these, hydroxyl and carboxyl groups are preferred, and hydroxyl groups are more preferred, from the viewpoint of the sensitization effect by EUV and reduction of pattern roughness. The number of hydrophilic groups is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, even more preferably 1 or 2, and particularly preferably 2.

[0022] The term "decomposable group" refers to a group that decomposes in the presence of an acid or a base, or by the action of radiation, an electron beam, extreme ultraviolet light (EUV), or irradiation from a light source such as ArF or KrF. The decomposable group is not particularly limited, and for example, an acid-dissociable functional group described in International Publication WO2013 / 024778 can be used. Among the decomposable groups, a hydrolyzable group is preferred. The term "hydrolyzable group" refers to a group that is hydrolyzed in the presence of an acid or a base. Examples of the hydrolyzable group include an alkoxy group, an ester group, an acetal group, and a carbonate ester group. The number of decomposable groups is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, even more preferably 1 or 2, and particularly preferably 2.

[0023] The unsaturated double bond is preferably a polymerizable unsaturated double bond. The group having an unsaturated double bond is not particularly limited, but examples thereof include a vinyl group, an isopropenyl group, a (meth)acryloyl group, and a haloacryloyl group. Examples of the haloacryloyl group include an α-fluoroacryloyl group, an α-chloroacryloyl group, an α-bromoacryloyl group, an α-iodoacryloyl group, an α,β-dichloroacryloyl group, and an α,β-diiodoacryloyl group. Among these unsaturated double bonds, an isopropenyl group and a vinyl group are preferred. The number of unsaturated double bonds is preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and even more preferably 1.

[0024] The compound (A) according to this embodiment is preferably represented by the following formula (1). The compound (A) preferably contains a functional group that improves the solubility in an alkaline developer by the action of an acid or a base. It is preferable that any of the following Z, Y, and X contains a functional group that improves the solubility in an alkaline developer by the action of an acid or a base. [ka]

[0025] In formula (1), Each X is independently I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br. Among these, each X is preferably independently I, F, Cl, or Br, more preferably independently I, F, or Br, more preferably independently I or F, and further preferably independently I.

[0026] In this embodiment, unless otherwise defined, "substitution" means that one or more hydrogen atoms in a functional group are substituted with a substituent. The "substituent" is not particularly limited, but examples thereof include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and an amino group having 0 to 30 carbon atoms. The alkyl group may be any of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.

[0027] Examples of the alkyl group having 1 to 30 carbon atoms include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, and a valerate group. Examples of the aryl group having 6 to 30 carbon atoms include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, and a perylene group. Examples of the alkenyl group having 2 to 30 carbon atoms include, but are not limited to, an ethynyl group, a propenyl group, a butynyl group, and a pentynyl group. Examples of the alkynyl group having 2 to 30 carbon atoms include, but are not limited to, an acetylene group, an ethynyl group, and the like. Examples of the alkoxy group having 1 to 30 carbon atoms include, but are not limited to, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.

[0028] Examples of the "organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br" include, but are not limited to, a monoiodophenyl group, a diiodophenyl group, a triiodophenyl group, a tetraiodophenyl group, a pentaiodophenyl group, a monoiodohydroxyphenyl group, a diiodohydroxyphenyl group, a triiodohydroxyphenyl group, a monoiodoacetoxyphenyl group, a diiodoacetoxyphenyl group, a triiodoacetoxyphenyl group, a monoiodo-t-butoxycarbonylphenyl group, a diiodo-t -butoxycarbonylphenyl group, triiodo-t-butoxycarbonylphenyl group, monoiododihydroxyphenyl group, diiododihydroxyphenyl group, triiododihydroxyphenyl group, monoiododiacetoxyphenyl group, diiododiacetoxyphenyl group, triiododiacetoxyphenyl group, monoiodo-di-t-butoxycarbonylphenyl group, diiodo-di-t-butoxycarbonylphenyl group, triiodo-di-t-butoxycarbonylphenyl group, monoiodotrihydroxyphenyl group, diiodotrihydroxy phenyl group, monoiodotriacetoxyphenyl group, diiodotriacetoxyphenyl group, monoiodo-tri-t-butoxycarbonylphenyl group, diiodo-tri-t-butoxycarbonylphenyl group, monoiodonaphthyl group, diiodonaphthyl group, triiodonaphthyl group, tetraiodonaphthyl group, pentaiodonaphthyl group, monoiodohydroxynaphthyl group, diiodohydroxynaphthyl group, triiodohydroxynaphthyl group, monoiodoacetoxynaphthyl group, diiodoacetoxynaphthyl group, triiodoacetoxynaphthyl group, monoiodo-t-butoxycarbonylnaphthyl group, diiodo-t-butoxycarbonylnaphthyl group, triiodo-t-butoxycarbonylnaphthyl group, monoiododihydroxynaphthyl group, diiododihydroxynaphthyl group, triiododihydroxynaphthyl group, monoiododiacetoxynaphthyl group, diiododiacetoxynaphthyl group, triiododiacetoxynaphthyl group, monoiodo-di-t-butoxycarbonylnaphthyl group, diiodo-di-t-butoxycarbonylnaphthyl group, triiodo-di-t-butoxycarbonylnaphthyl group,

[0029] Monoiodotrihydroxynaphthyl group, diiodotrihydroxynaphthyl group, monoiodotriacetoxynaphthyl group, diiodotriacetoxynaphthyl group, monoiodo-tri-t-butoxycarbonylnaphthyl group, diiodo-tri-t-butoxycarbonylnaphthyl group, monoiodoadamantyl group, diiodoadamantyl group, triiodoadamantyl group, monoiodohydroxyadamantyl group, diiodohydroxynaphthyl group, monoiodoacetoxynaphthyl group, diiodoacetoxyadamantyl group, monoiodo-t-butoxycarbonyladamantyl group, diiodo-t-butoxycarbonyladamantyl group, triiodo-t-butoxycarbonyladamantyl group, monoiododihydroxy siadamantyl group, monoiododiacetoxyadamantyl group, monoiodo-di-t-butoxycarbonyladamantyl group, monoiodocyclohexyl group, diiodocyclohexyl group, triiodocyclohexyl group, monoiodohydroxycyclohexyl group, diiodohydroxynaphthyl group, monoiodoacetoxynaphthyl group, diiodoacetoxycyclohexyl group, monoiodo-t-butoxycarbonylcyclohexyl group, diiodo-t-butoxycarbonylcyclohexyl group, triiodo-t-butoxycarbonylcyclohexyl group, monoiododihydroxycyclohexyl group, monoiododiacetoxycyclohexyl group, monoiodo-di-t-butoxycarbonylcyclohexyl group,

[0030] a monobromophenyl group, a dibromophenyl group, a tribromophenyl group, a tetrabromophenyl group, a pentabromophenyl group, a monobromohydroxyphenyl group, a dibromohydroxyphenyl group, a tribromohydroxyphenyl group, a monobromoacetoxyphenyl group, a dibromoacetoxyphenyl group, a tribromoacetoxyphenyl group, a monobromo-t-butoxycarbonylphenyl group, a dibromo-t-butoxycarbonylphenyl group, a tribromo-t-butoxycarbonylphenyl group, a monobromodihydroxyphenyl group, a dibromodihydroxyphenyl group, a tribromodihydroxyphenyl group, a monobromodiacetoxyphenyl group, a dibromodiacetoxyphenyl group, a tribromodiacetoxyphenyl group, a monobromodi-t-butoxycarbonylphenyl group, a dibromodi-t-butoxycarbonylphenyl group, a tribromodi-t-butoxycarbonylphenyl group,

[0031] a monobromotrihydroxyphenyl group, a dibromotrihydroxyphenyl group, a monobromotriacetoxyphenyl group, a dibromotriacetoxyphenyl group, a monobromotri-t-butoxycarbonylphenyl group, a dibromotri-t-butoxycarbonylphenyl group, a monobromoadamantyl group, a dibromoadamantyl group, a tribromoadamantyl group, a monobromohydroxyadamantyl group, a dibromohydroxynaphthyl group, a monobromoacetoxynaphthyl group, a dibromoacetoxyadamantyl group, a monobromo-t-butoxycarbonyladamantyl group, a dibromo-t-butoxycarbonyladamantyl group, a tribromo-t-butoxycarbonyladamantyl group, a monobromodihydroxyadamantyl group, a monobromodiacetoxyadamantyl group, a monobromo-di-t-butoxycarbonyladamantyl group,

[0032] Monofluorophenyl group, difluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, pentafluorophenyl group, monofluorohydroxyphenyl group, difluorohydroxyphenyl group, trifluorohydroxyphenyl group, monofluoroacetoxyphenyl group, difluoroacetoxyphenyl group, trifluoroacetoxyphenyl group, monofluoro-t-butoxycarbonylphenyl group, difluoro-t-butoxycarbonylphenyl group, trifluoro-t-butoxycarbonylphenyl group, monofluorodihydroxyphenyl group, difluorodihydroxyphenyl group, trifluorodihydroxyphenyl group, monofluorodiacetoxyphenyl group, difluorodiacetoxyphenyl group, trifluorodiacetoxyphenyl group, monofluorodi-t-butoxycarbonylphenyl group, difluorodi-t-butoxycarbonylphenyl group, trifluorodi-t -butoxycarbonylphenyl group, monofluorotrihydroxyphenyl group, difluorotrihydroxyphenyl group, monofluorotriacetoxyphenyl group, difluorotriacetoxyphenyl group, monofluorotri-t-butoxycarbonylphenyl group, difluorotri-t-butoxycarbonylphenyl group, monofluoroadamantyl group, difluoroadamantyl group, trifluoroadamantyl group, monofluorohydroxyadamantyl group, difluorohydroxynaphthyl group, monofluoroacetoxynaphthyl group, difluoroacetoxyadamantyl group, monofluoro-t-butoxycarbonyladamantyl group, difluoro-t-butoxycarbonyladamantyl group, trifluoro-t-butoxycarbonyladamantyl group, monofluorodihydroxyadamantyl group, monofluorodiacetoxyadamantyl group, monofluoro-di-t-butoxycarbonyladamantyl group,

[0033] monochlorophenyl group, dichlorophenyl group, trichlorophenyl group, tetrachlorophenyl group, pentachlorophenyl group, monochlorohydroxyphenyl group, dichlorohydroxyphenyl group, trichlorohydroxyphenyl group, monochloroacetoxyphenyl group, dichloroacetoxyphenyl group, trichloroacetoxyphenyl group, monochloro-t-butoxycarbonylphenyl group, dichloro-t-butoxycarbonylphenyl group, trichloro-t-butoxycarbonylphenyl group, monochlorodihydroxyphenyl group, dichlorodihydroxyphenyl group, trichlorodihydroxyphenyl group, monochlorodiacetoxyphenyl group, dichlorodiacetoxyphenyl group, trichlorodiacetoxyphenyl group, monochlorodi-t-butoxycarbonylphenyl group, dichlorodi-t-butoxycarbonylphenyl group, trichlorodi-t-butoxycarbonylphenyl group,

[0034] Examples of such groups include a monochlorotrihydroxyphenyl group, a dichlorotrihydroxyphenyl group, a monochlorotriacetoxyphenyl group, a dichlorotriacetoxyphenyl group, a monochlorotri-t-butoxycarbonylphenyl group, a dichlorotri-t-butoxycarbonylphenyl group, a monochloroadamantyl group, a dichloroadamantyl group, a trichloroadamantyl group, a monochlorohydroxyadamantyl group, a dichlorohydroxynaphthyl group, a monochloroacetoxynaphthyl group, a dichloroacetoxyadamantyl group, a monochloro-t-butoxycarbonyladamantyl group, a dichloro-t-butoxycarbonyladamantyl group, a trichloro-t-butoxycarbonyladamantyl group, a monochlorodihydroxyadamantyl group, a monochlorodiacetoxyadamantyl group, and a monochlorodi-t-butoxycarbonyladamantyl group.

[0035] For example, X may be an aromatic group having one or more F, Cl, Br or I introduced therein. Examples of such aromatic groups include groups having a benzene ring, such as a phenyl group having 1 to 5 halogens, and groups having a heteroaromatic ring, such as furan, thiophene or pyridine, each having 1 to 5 halogens. Examples of such aromatic groups include a phenyl group having 1 to 5 I, a phenyl group having 1 to 5 F, a phenyl group having 1 to 5 Cl, a phenyl group having 1 to 5 Br, a naphthyl group having 1 to 5 F, a naphthyl group having 1 to 5 Cl, a phenyl group having 1 to 5 Br, and the like. a naphthyl group having 1 to 5 I's, a phenol group having 1 to 4 F's, a phenol group having 1 to 4 Cl's, a phenol group having 1 to 4 Br's, a phenol group having 1 to 4 I's, a furan group having 1 to 3 F's, a furan group having 1 to 3 Cl's, a furan group having 1 to 3 Br's, a furan group having 1 to 3 I's, a thiophene group having 1 to 3 F's, a thiophene group having 1 to 3 Cl's, a thiophene group having 1 to 3 Br's, a a thiophene group having 3 F, a pyridine group having 1 to 4 Cl, a pyridine group having 1 to 4 Br, a pyridine group having 1 to 4 I, a benzodiazole group having 1 to 5 F, a benzodiazole group having 1 to 5 Cl, a benzodiazole group having 1 to 5 Br, a benzodiazole group having 1 to 5 I, a benzimidazole group having 1 to 4 F, a benzimidazole group having 1 to 4 Cl, a benzimidazole groups having 1 to 4 I, benzimidazole groups having 1 to 4 F, benzoxazole groups having 1 to 4 Cl, benzoxazole groups having 1 to 4 Br, benzoxazole groups having 1 to 4 I, benzothiophene groups having 1 to 4 F, benzothiophene groups having 1 to 4 Cl, benzothiophene groups having 1 to 4 Br, and benzothiophene groups having 1 to 4 I. X may also be an alicyclic group having one or more F, Cl, Br, or I introduced into the alicyclic group.Examples of such alicyclic groups include an adamantyl group having 1 to 3 halogens, an adamantyl group having 1 to 3 F, an adamantyl group having 1 to 3 Cl, an adamantyl group having 1 to 3 Br, an adamantyl group having 1 to 3 I, a cyclopentyl group having 1 to 3 F, a cyclopentyl group having 1 to 3 Cl, a cyclopentyl group having 1 to 3 Br, a cyclopentyl group having 1 to 3 I, a bicycloundecyl group having 1 to 3 F, a bicycloundecyl group having 1 to 3 Cl, a bicycloundecyl group having 1 to 3 Br, a bicycloundecyl group having 1 to 3 I, a norbornyl group having 1 to 3 F, a norbornyl group having 1 to 3 Cl, a norbornyl group having 1 to 3 Br, and a norbornyl group having 1 to 3 I.

[0036] L 1 is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphonic group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group. 1 is preferably a single bond. 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphoric acid group may have a substituent. Examples of such a substituent are as described above.

[0037] m is an integer of 1 or more, preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, and further preferably 2 or 3.

[0038] Each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent. Y is, for example, an alkoxy group [* 3 -OR 2 ], ester group [* 3 -O-(C=O)-R 2 OR* 3 -(C=O)-OR 2 ], acetal group [* 3 -O-(C(R 21 )2)-OR 2 (R 21 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. )], a carboxyalkoxy group [* 3 -OR 22 -(C=O)-OR 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate group [* 3 -O-(C=O)-OR 2 From the viewpoint of increasing sensitivity, the ester group is preferably a tertiary ester group. 3 is the binding site for A. Among these, from the viewpoint of high sensitivity, Y is preferably a tertiary ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group, more preferably an acetal group, a carbonate ester group, or a carboxyalkoxy group, and even more preferably an acetal group or a carboxyalkoxy group. Furthermore, from the viewpoint of stable quality polymer production by radical polymerization, an ester group, a carboxyalkoxy group, or a carbonate ester group is preferred.

[0039] Preferably, each Y is independently a group represented by the following formula (Y-1). [ka]

[0040] In formula (Y-1), L 2 is a group that is cleaved by the action of an acid or a base. Examples of groups that are cleaved by the action of an acid or a base include ester groups [* 1 -O-(C=O)-* 2 OR* 1 -(C=O)-O-* 2 ], acetal group [* 1 -O-(C(R 21 )2)-O-* 2 (R 21 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. )], a carboxyalkoxy group [* 1 -OR 22 -(C=O)-O-* 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate group [* 1 -O-(C=O)-O-* 2 From the viewpoint of achieving high sensitivity, the ester group is preferably a tertiary ester group. 1 is the binding site for A, * 2 is R 2 Among these, L 2 From the viewpoint of high sensitivity, the tertiary ester group, acetal group, carbonate ester group, or carboxyalkoxy group is preferable, the acetal group, carbonate ester group, or carboxyalkoxy group is more preferable, and the acetal group or carboxyalkoxy group is even more preferable. Furthermore, from the viewpoint of stable quality polymer production by radical polymerization, the ester group, carboxyalkoxy group, and carbonate ester group are preferable. As another effect, when the compound (A) of the present embodiment is used as a polymerization unit of a copolymer, Y is preferably a group represented by formula (Y-1) for the purpose of controlling the polymerizability of the resin and setting the degree of polymerization within a desired range. Since the compound A has a X group, it has a large effect on active species during the polymer formation reaction, making it difficult to achieve the desired control, and therefore, by having the hydrophilic group in the compound A have a group represented by formula (Y-1) as a protecting group, it is possible to suppress the variation in copolymer formation and polymerization inhibition caused by the hydrophilic group.

[0041] R 2 is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms containing a heteroatom, or a linear, branched or cyclic aromatic group having 1 to 30 carbon atoms containing a heteroatom, 2 The aliphatic group, aromatic group, aliphatic group containing a hetero atom, and aromatic group containing a hetero atom may further have a substituent. The substituent here may be any of those mentioned above, but a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms is preferred. R 2 Among these, an aliphatic group is preferable. 2 In the above formula, the aliphatic group is preferably a branched or cyclic aliphatic group. The number of carbon atoms in the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and further preferably 4 or more and 8 or less. The aliphatic group is not particularly limited, and examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group, and an adamantyl group. Among these, a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferred.

[0042] L 2 but* 1 -(C=O)-O-* 2Alternatively, if the group is a carboxyalkoxy group, when it is cleaved by the action of an acid or a base, a carboxylic acid group is formed, which increases the difference in solubility and the difference in dissolution rate between the dissociated and non-dissociated parts in the development process, thereby improving the resolution and suppressing residues at the bottom of the pattern, particularly in fine line patterns.

[0043] Specific examples of Y include the following, each of which is independently a group represented by any one of the following formulas (Y-1-1) to (Y-1-7). [ka]

[0044] Examples of alkoxy groups that can be used as Y include alkoxy groups having one or more carbon atoms. From the viewpoint of the solubility of the resin after being combined with other monomers to form a resin, alkoxy groups having two or more carbon atoms are preferred, and alkoxy groups having three or more carbon atoms or having a cyclic structure are preferred. Specific examples of the alkoxy group that can be used as Y include, but are not limited to, the following: [ka]

[0045] As the amino group and amide group that can be used as Y, a primary amino group, a secondary amino group, a tertiary amino group, a group having a quaternary ammonium salt structure, an amide having a substituent, etc. can be appropriately used. Specific examples of the amino group or amide group that can be used include, but are not limited to, the following. [ka]

[0046] n is an integer of 0 or greater, preferably an integer of 1 or greater, more preferably an integer of 1 or greater and 5 or less, even more preferably an integer of 1 or greater and 3 or less, even more preferably 1 or 2, and particularly preferably 2.

[0047] R a , R b , and R c are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent. The substituent of the organic group having 1 to 60 carbon atoms is not particularly limited, but examples thereof include I, F, Cl, Br, or other substituents. The other substituents are not particularly limited, but examples thereof include a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphine group, a urethane group, a urea group, an amide group, an imide group, and a phosphate group. Among these, the alkoxy group, the ester group, the carbonate ester group, the amino group, the ether group, the thioether group, the phosphine group, the phosphine group, the urethane group, the urea group, the amide group, the imide group, and the phosphate group may further have a substituent. In addition, examples of the substituent here include a linear, branched, or cyclic aliphatic group having 1 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.

[0048] R a , R b , and R c The organic group which may have a substituent preferably has 1 to 30 carbon atoms.

[0049] The organic group having 1 to 60 carbon atoms which may have a substituent is not particularly limited, but examples thereof include linear or branched aliphatic hydrocarbon groups having 1 to 60 carbon atoms, alicyclic hydrocarbon groups having 4 to 60 carbon atoms, and aromatic groups having 6 to 60 carbon atoms which may contain a heteroatom. The linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, a valerate group, and a 2-ethylhexyl group.

[0050] The alicyclic hydrocarbon group is not particularly limited, but examples thereof include a cyclohexyl group, a cyclododecyl group, a dicyclopentyl group, a tricyclodecyl group, and an adamantyl group. Furthermore, aromatic groups that may contain a heteroatom, such as a benzodiazole group, a benzotriazole group, and a benzothiadiazole group, can also be appropriately selected. Furthermore, a combination of these organic groups can be selected.

[0051] The aromatic group having 6 to 60 carbon atoms which may contain a heteroatom is not particularly limited, but examples thereof include a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a benzodiazole group, a benzotriazole group, and a benzothiadiazole group.

[0052] Among these organic groups having 1 to 60 carbon atoms which may have a substituent, a methyl group is preferred from the viewpoint of producing a polymer with stable quality.

[0053] R a When is an organic group having 1 to 8 carbon atoms, or a group selected from F, Cl and I, it is preferable that n and r are 0 or greater.

[0054] A is an organic group having 1 to 30 carbon atoms. A may be a monocyclic organic group or a polycyclic organic group, and may have a substituent. A is preferably an aromatic ring which may have a substituent. The number of carbon atoms in A is preferably 6 to 14, and more preferably 6 to 10. A is preferably a group represented by any one of the following formulae (A-1) to (A-4), more preferably a group represented by the following formulae (A-1) to (A-2), and even more preferably a group represented by the following formula (A-1).

[0055] [ka]

[0056] A may be an alicyclic structure which may have a substituent. Here, the "alicyclic structure" is a saturated or unsaturated carbon ring having no aromaticity. The alicyclic structure may be, for example, a saturated or unsaturated carbon ring having 3 to 30 carbon atoms, and preferably a saturated or unsaturated carbon ring having 3 to 20 carbon atoms. The alicyclic structure may be, for example, a group having cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloicosyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclopentadienyl, cyclooctadienyl, adamantyl, bicycloundecyl, decahydronaphthyl, norbornyl, norbornadienyl, cubane, basketane, or hashane. A may also be a heterocyclic structure which may have a substituent. The heterocyclic structure is not particularly limited, and examples thereof include cyclic nitrogen-containing structures such as pyridine, piperidine, piperidone, benzodiazole, and benzotriazole, triazine, cyclic urethane structure, cyclic urea, cyclic amide, cyclic imide, cyclic ethers such as furan, pyran, and dioxolane, and alicyclic groups having a lactone structure such as caprolactone, butyrolactone, nonalactone, decalactone, undecalactone, bicycloundecalactone, and phthalide.

[0057] p is an integer of 1 or more, preferably an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, and further preferably 1.

[0058] Each Z is independently an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate group. These groups may have a substituent, and examples of the substituent include a hydrocarbon group having 1 to 60 carbon atoms which may further have a substituent. r is an integer of 0 or more, preferably an integer of 0 or more and 2 or less, more preferably an integer of 0 or more and 1 or less, and even more preferably 0.

[0059] Z is, for example, an alkoxy group [*3 -OR 2 ], ester group [* 3 -O-(C=O)-R 2 OR* 3 -(C=O)-OR 2 ], acetal group [* 3 -O-(C(R 21 )2)-OR 2 (R 21 are each independently H or a hydrocarbon group having 1 to 10 carbon atoms. )], a carboxyalkoxy group [* 3 -OR 22 -(C=O)-OR 2 (R 22 is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate group [* 3 -O-(C=O)-OR 2 From the viewpoint of increasing sensitivity, the ester group is preferably a tertiary ester group. 3 is the binding site for A. Among these, from the viewpoint of high sensitivity, Z is preferably a tertiary ester group, an acetal group, a carbonate ester group, or a carboxyalkoxy group, more preferably an acetal group, a carbonate ester group, or a carboxyalkoxy group, and even more preferably an acetal group or a carboxyalkoxy group. Furthermore, from the viewpoint of stable quality polymer production by radical polymerization, an ester group, a carboxyalkoxy group, or a carbonate ester group is preferred.

[0060] As described above, n is an integer of 0 or more, and r is an integer of 0 or more, but at least one of n and r may be an integer of 1 or more. That is, n+r may be an integer of 1 or more.

[0061] Among the above compounds (A), the compound represented by the following formula (1a) is preferred. [ka] (In formula (1a), X, L 1, Y, A, Z, p, m, n, and r are the same as those in formula (1).

[0062] Examples of the compound (A) according to this embodiment (particularly the compound represented by formula (1a)) include compounds having the structure shown below.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] Among the above compounds (A), the compound represented by the following formula (1b) is preferred from the viewpoint of further improving sensitivity. [ka] (In formula (1b), X, L 1 , Y, A, Z, p, m, n, and r are the same as defined in formula (1); R a1 , R b1 , and R c1 each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, R a1 , R b1 , and R c1 At least one of the above is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent.) R a1 , R b1 , and R c1 The organic group having 1 to 60 carbon atoms which may have a substituent in R a , R b , and Rc R is defined as the organic group having 1 to 60 carbon atoms which may have a substituent. a1 R is preferably an organic group having 1 to 60 carbon atoms which may have a substituent, and more preferably a methyl group. b1 , and R c1 is preferably H.

[0067] Examples of the compound (A) according to this embodiment (particularly the compound represented by formula (1b)) include compounds having the structures shown below.

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] The compound (A) may be, for example, a compound represented by the following formula (1C): Although not particularly limited, it is preferable to use the compound represented by the following formula (1C) in combination with a compound (A) other than the compound, as described later. [ka] (In formula (1C), formula (1C1), and formula (1C2), X, L 1 , Y, A, Z, p, m, n, and r are the same as defined in formula (1); Rsub represents the formula (1C1) or the formula (1C2), R a1 , Rb1 , and R c1 each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, R a1 , R b1 , and R c1 at least one of is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent; p-1 is an integer equal to or greater than 0, * indicates the bonding site for each formula.)

[0073] When a compound represented by formula (1C) is used in a composition containing compound (A) according to this embodiment, the composition can contain a compound represented by the following formula (1C) in combination with a compound (A) other than the compound. In this case, the composition is preferably prepared so that the compound represented by formula (1C) is in the range of 1 mass ppm to 10 mass % relative to the total compound (A), more preferably in the range of 1 mass ppm to 5 mass %, even more preferably in the range of 1 mass ppm to 3 mass %, and particularly preferably in the range of 1 mass ppm to 1 mass %. In the resin form after forming a resin from a starting material containing the composition prepared in this way, a site containing X and a site consisting of Y or Z are present in a high density in the adjacent region, which becomes the starting point for improving sensitivity. Furthermore, the solubility in the resin is locally increased, which leads to a reduction in residue defects after development in the lithography process.

[0074] Examples of the compound (A) according to this embodiment (particularly the compound represented by formula (1C)) include compounds having the structure shown below.

[0075] [ka]

[0076] Furthermore, the compound (A) of the present embodiment may be used in combination with a compound represented by the following formula (1D), for example. [ka] (In formula (1D), formula (1D1), or formula (1D2), X, L 1 , Y, A, Z, p, m, n, and r are the same as defined in formula (1); Rsub2 represents formula (1D1) or formula (1D2), R a1 , R b1 , and R c1 each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, R a1 , R b1 , and R c1 at least one of is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent; n2 represents an integer between 0 and 4, p-1 is an integer equal to or greater than 0, * indicates the bonding site with the adjacent structural unit.)

[0077] When a compound represented by formula (1D) is used in a composition containing compound (A) of this embodiment, the composition can contain a compound represented by the following formula (1D) in combination with a compound (A) other than the compound. In this case, the composition is preferably prepared so that the compound represented by formula (1D) is in the range of 1 mass ppm to 10 mass % relative to the total compound (A), more preferably in the range of 1 mass ppm to 5 mass %, even more preferably in the range of 1 mass ppm to 3 mass %, and particularly preferably in the range of 1 mass ppm to 1 mass %. In the resin form formed from a starting material containing the composition prepared in this way, a site containing X and a site consisting of Y or Z are densely coexisted in the adjacent region, which becomes the starting point for improving sensitivity. Furthermore, the solubility in the resin is locally increased, thereby reducing residue defects after development in the lithography process.

[0078] Examples of the compound (A) according to this embodiment (particularly the compound represented by formula (1D)) include compounds having the structures shown below. [ka]

[0079] A composition containing the compound (A) of this embodiment may contain a compound represented by the following formula (1E). When using such a compound, the composition containing the compound (A) of this embodiment preferably contains the compound represented by formula (1E) in the range of 1 ppm by mass to 10% by mass, more preferably 1 ppm by mass to 5% by mass, even more preferably 1 ppm by mass to 3% by mass, and particularly preferably 1 ppm by mass to 1% by mass. The composition prepared in this manner tends to be more stable. Although the reason for this is unclear, it is presumed that this is due to an equilibrium reaction of iodine atoms between the iodine-containing compound (A) and the iodine-free compound (1E), resulting in stabilization. In this case, it is preferable that the composition further contains, as compound (1E), a compound having a structure in which an iodine atom has been removed from the compound exemplified as compound (A) above. Furthermore, the composition prepared in this manner has increased stability, which not only enhances storage stability but also leads to the formation of a resin with stable properties, the provision of stable resist performance, and the reduction of residue defects after development in the lithography process. The method of using the compound represented by formula (1E) in a composition containing compound (A) in an amount of 1 ppm by mass or more and 10% by mass or less relative to compound (A) is not particularly limited, and examples thereof include a method of adding compound (1E) to compound (A) and a method of by-producing compound (1E) during the production of compound (A).

[0080] [ka] (In formula (1E), X's each independently represent F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of F, Cl, and Br; L 1 are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R a , R b , and R c each independently represents H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; However, X, L 1 , Y, R a , R b , R c , A and Z do not contain I; p is an integer of 1 or greater, m' is an integer of 0 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater. If the compound represented by formula (1E) is contained in an amount of more than 10% by mass relative to compound (A), the effect of improving sensitivity may be reduced when a polymer containing compound (A) is formed and used for lithography purposes. On the other hand, if the compound is contained in an amount less than 1 ppm, the effect of improving stability over time may not be fully exhibited. In the compound represented by formula (1E), m' is preferably 0 for the purpose of further enhancing the effect of stability over time.

[0081] Examples of the compound (1E) according to this embodiment include compounds having the structure shown below. [ka] [ka]

[0082] [ka]

[0083] [ka]

[0084] [Method for producing compound (A)] The compound represented by formula (1) can be produced by various known synthesis methods.

[0085] An example of the synthesis method is not particularly limited, but it can be synthesized by introducing a halogen group of I, F, Cl, or Br into a hydroxyl group-containing aromatic aldehyde derivative, and then converting the aldehyde group into a vinyl group. Another example of the synthesis method can be appropriately selected from a method of reacting iodine chloride in an organic solvent by performing an iodination reaction on a hydroxybenzaldehyde derivative (e.g., JP 2012-180326 A), a method of dropping iodine into an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (JP 63-101342 A, JP 2003-64012 A), and the like.

[0086] In this embodiment, it is preferable to use an iodination reaction via iodine chloride in an organic solvent, particularly when the purpose is to introduce multiple iodines. The compound (A) of this embodiment can be synthesized by converting the aldehyde moiety of the synthesized iodine-introduced hydroxybenzaldehyde derivative into a vinyl group. As a method for converting the aldehyde moiety into a vinyl group, the method described in the Wittig reaction (e.g., Synthetic Communications; Vol. 22; nb4; 1992 p513, Synthesis; Vol. 49; nb. 23; 2017; p5217), the method of reacting malonic acid under a base (e.g., Tetrahedron; Vol. 46; nb. 40; 2005; p6893, Tetrahedron; Vol. 63; nb. 4; 2007; p900, US2004 / 118673), etc. can be appropriately used. As a method for synthesizing compound (A) of this embodiment, for example, the method described in the above-mentioned reference material can be appropriately used, but is not limited thereto.

[0087] The method for producing the compound represented by formula (0) is described below. The compound represented by formula (0) includes both compounds that do not contain halogen and compounds that contain halogen, but it is also possible to introduce halogen into the compound represented by formula (0) that does not contain halogen, for example, a compound that has an amino group instead of halogen, by the Sandmeyer reaction or the like to produce the compound represented by formula (1). The method for producing the compound represented by formula (0) according to this embodiment is as follows: The method preferably includes a step of introducing an unsaturated double bond into the substituent Q of a compound represented by the following formula (S1) (hereinafter, sometimes referred to as a "double bond introduction step"). The method may also include a step of reacting a halogenating agent with a compound represented by the following formula (S1) to introduce a halogen atom (hereinafter, sometimes referred to as a "halogen introduction step"). In this production method, the order of the halogen introduction step and the double bond introduction step is not particularly limited, and either step may be carried out first. By producing the compound represented by formula (0) by this method, it is possible to produce an unsaturated double bond site (and a halogen group when a halogen is present), which is less stable during production and requires careful handling, relatively stably, with good yield and efficiently. In addition, when a halogen introduction step is included, even if the halogen group is an atom with a large atomic radius such as iodine, the compound to be produced can be produced relatively stably, with good yield and efficiently.

[0088] [ka] (In formula (0), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R a , R b , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; p is an integer of 1 or greater, m' is an integer of 0 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater. [ka] (In formula (S1), X 0 is an organic group having 1 to 30 carbon atoms, L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group, p is an integer of 1 or greater, m' is an integer of 0 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater.

[0089] In addition, Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group, and when an aldehyde group or a carboxyl group is present, the number of carbon atoms means the total number of carbon atoms including the number of carbon atoms of these functional groups. From the viewpoint of preventing side reactions, Q is preferably an organic group having 1 to 30 carbon atoms and having a hydroxyl group, and is preferably a hydroxymethyl group.

[0090] The process of introducing halogen atoms (halogen introduction process) can be the above-mentioned method of introducing halogen groups. The halogenating agent is not particularly limited, but can be, for example, iodinating agents such as iodine chloride, iodine, N-iodosuccinimide, etc., fluorinating agents such as potassium fluoride, tetramethylammonium fluoride, etc., chlorinating agents such as thionyl chloride, dichloromethyl methyl ether, etc., bromine molecules, carbon tetrabromide, N-bromosuccinimide, etc., brominating agents. Among these, iodinating agents are preferred, and iodine chloride is more preferred.

[0091] In the step of introducing halogen atoms, the ratio of the halogenating agent to the compound represented by formula (S1) is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and even more preferably 2.0 molar times or more.

[0092] The reaction temperature in the step of introducing halogen atoms is not particularly limited, but is preferably 40 to 80° C. The reaction time is not particularly limited, but is preferably 1 to 3 hours.

[0093] When Q is an organic group having 1 to 30 carbon atoms and a hydroxyl group, the production method according to the present embodiment may include a step of oxidizing an alcohol to introduce an aldehyde group after the step of introducing a halogen atom. The oxidizing agent used in the oxidation is not particularly limited as long as it can introduce an aldehyde, and examples of the oxidizing agent include manganese dioxide and chromium trioxide. The reaction temperature in the step of introducing an aldehyde group is not particularly limited, but is preferably 10 to 40° C. The reaction time is not particularly limited, but is preferably 1 to 6 hours.

[0094] In the step of introducing an unsaturated double bond into the substituent Q (double bond introduction step), as described above, the unsaturated double bond can be introduced by the Wittig reaction, the method of reacting malonic acid in the presence of a base, or the like.

[0095] As the solvent used in the reaction, a commonly available solvent can be used. For example, alcohols, ethers, hydrocarbons, halogenated solvents, etc. can be used appropriately as long as they do not inhibit the reaction. A mixture of multiple solvents can also be used as long as they do not inhibit the reaction. Since water inhibits the reaction, it is preferable to use a dehydrated solvent.

[0096] The reaction temperature and reaction time depend on the substrate concentration and the catalyst used, but generally the reaction temperature is -20°C to 100°C, the reaction time is 1 to 10 hours, and the pressure is normal pressure, reduced pressure, or increased pressure. The reaction can be carried out by appropriately selecting a known method such as a batch system, a semi-batch system, or a continuous system.

[0097] A polymerization inhibitor may be added to the series of reactions, and a commercially available product may be used. For example, nitroso compounds such as 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, and N,N'-dimethyl-p-nitrosoaniline; sulfur-containing compounds such as phenothiazine, methylene blue, and 2-mercaptobenzimidazole; N,N'-diphenyl-p-phenylenediamine; and N-phenyl Examples of the additive include amines such as -N'-isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, and aminophenol, quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, and hydroquinone monomethyl ether, phenols such as p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechol, 3-s-butylcatechol, and 2,2-methylenebis-(6-t-butyl-4-methylphenol), imides such as N-hydroxyphthalimide, oximes such as cyclohexaneoxime and p-quinonedioxime, and dialkylthiodipropionate. The amount of the additive is, for example, 0.001 to 10 parts by mass, and preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the (meth)acrylic acid compound represented by the general formula (b).

[0098] The compound represented by formula (0) obtained by the reaction can be isolated and purified as a desired high-purity monomer by a known purification method such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, or a combination of these methods.

[0099] [Method for producing compound (0)] As a preferred method for producing compound of formula (0), a production method can be selected in which the compound represented by formula (S1) above is a compound represented by formula (SA1) below, and which includes a step represented by A1 below and a step represented by A2 below. A1) A step of obtaining a compound represented by the following formula (SA2) using a compound represented by the above formula (SA1) and a compound represented by the following formula (RM1) or malononitrile. A2) A step of converting the formula (SA2) into the formula (0) using a fluoride source. [ka] (In formulas (SA1), (RM1) and (SA2), X 0 , L 1 , Y, A, Z, p, m', n, and r are defined as in formulas (S1) and (0), Q 1 is an aldehyde or ketone, LG is a group selected from a hydroxy group, an alkoxy group, a carbonate group, an acetal group, and a carboxy group, and the alkoxy group, the carbonate group, the acetal group, and the carboxy group each include an aliphatic group or an aromatic group having 1 to 60 carbon atoms which may have a substituent; R 3 represents a hydrogen group, or a carboxy group or ester group which may have a substituent having 1 to 60 carbon atoms, R 4 is a hydrogen radical, R 5 , R 6 each independently represents H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, XA is a group selected from a hydrogen group and a halogen group. 3 may be bonded to LG to form a cyclic structure.

[0100] As described above, step A1 is a step of obtaining a compound represented by formula (SA2) using a compound represented by formula (SA1) and a compound represented by formula (RM1) or malononitrile. Specific examples of the compound represented by formula (RM1) include maleic acid, maleic acid ester derivatives such as dimethyl maleate, diethyl maleate, dipropyl maleate, isopropyl maleate, maleic anhydride, etc., acetate derivatives such as ethyl acetate, propyl acetate, butyl acetate, α-chloroethyl acetate, α-chloropropyl acetate, α-chlorobutyl acetate, etc. RM1 is preferably a derivative selected from malonic acid, malonic acid ester derivatives, acetate derivatives, and acetate ester derivatives.

[0101] In step A1, a general method such as Knoevenagel reaction or Dobner reaction can be used, and for example, the conditions described in Journal of Molecular Catalysis B: Enzymatic, 82, 92-95; 2012, Tetrahedron Letters, 46(40), 6893-6896; 2005, etc. can be used. Specifically, the compound represented by formula (RM1) or malononitrile can be reacted with a base in a solvent to obtain the compound represented by formula (SA2). An acid can also be used in addition to the base.

[0102] As the base, various known compounds can be used. For example, nitrogen-containing compounds such as nitrogen-containing cyclic compounds containing structures such as pyridine, piperidine, pyrrolidine, azole, diazole, triazole, and morpholine, and tertiary amines such as tributylamine, trimethylamine, and trihydroxyethylamine can be appropriately used.

[0103] The acid that may be used in combination with the base is not particularly limited, but a weak acid such as acetic acid or propionic acid is preferably used in combination.

[0104] The balance of acidity and basicity in the reaction system is not particularly limited, but when the compound of this embodiment in which m is an integer of 1 or more is the target compound, it is preferable to carry out the reaction under acidic conditions.

[0105] In step A1, when LG is an alkoxy group, a carbonate group, an acetal group, or a carboxyl group, it is preferable to obtain a compound represented by formula (SA3) by further adding a reaction of converting LG to a hydroxy group by a treatment such as hydrolysis. The treatment such as hydrolysis is not particularly limited as long as it can convert the LG group to a hydroxy group, and as an example of reaction conditions, for example, an acid such as hydrochloric acid, sulfuric acid, or paratoluenesulfonic acid can be used as a catalyst to carry out the deprotection reaction under temperature conditions such as reflux. As another example of reaction conditions, the deprotection reaction can be carried out by refluxing under solvent conditions such as toluene or xylene using an inorganic base such as sodium hydroxide or potassium hydroxide or an organic base such as a tertiary amine as a base. [ka] (In formula (SA3), X 0 , L 1 , Y, A, Z, p, m', n, and r are defined as in formulas (S1) and (0), R 5 , R 6 are each independently H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent. .)

[0106] In step A1, a reducing agent may be further used to obtain a compound represented by formula (SA2). When a reducing agent is used to obtain a compound represented by formula (SA2), a more stable RM1 can be used, which is advantageous in terms of conversion rate and purity. Various reducing agents can be used.

[0107] As the reducing agent, a wide variety of reducing agents that function under the reaction conditions of this embodiment are used. Suitable reducing agents include, but are not limited to, metal hydrides, metal hydrogen complex compounds, and the like. Specific examples include borane dimethyl sulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-s-butylborohydride, potassium tri-s-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-t-butoxyaluminum hydride, sodium bis(methoxyethoxy)aluminum hydride, and the like. The amount of the reducing agent used can be appropriately set depending on the substrate, reducing agent, reaction conditions, etc. used, and is not particularly limited. Generally, however, 1 to 500 parts by mass is suitable for 100 parts by mass of the reaction raw materials, and from the viewpoint of yield, 10 to 200 parts by mass is preferable.

[0108] In the compound represented by the above formula (S1), A is preferably benzene, toluene, or a heteroaromatic ring from the viewpoints of the effect per mass on the stability of the X group in the resin, the effect of the X group on improving lithography performance such as improving sensitivity, and the effect of suppressing the solubility of the resin in a developer and partial crystallinity in a resin matrix when incorporated as a structural unit of a copolymer in a resin for lithography.

[0109] As the reaction solvent for the deprotection reaction, various solvents can be used, and there are no particular limitations as long as the solvent dissolves the compound of formula (SA2) above. Examples of the solvent that can be used include methanol, ethanol, propanol, butanol, alcohol-based solvents, ketone-based solvents such as cyclohexanone, cyclopentanone, MEK, and MIBK, chain or cyclic ester-based solvents such as ethyl acetate, butyl acetate, ethyl propionate, isobutyl propionate, ethyl lactate, and gamma butyrolactone, ether-based solvents such as diethyl ether, glycol-based solvents such as diethylene glycol, PGMEA, and PGME, aromatic solvents such as toluene and benzene, amide-based solvents such as DMF, and water.

[0110] As described above, in step A2, a fluoride source is used to convert a carboxyl group of a compound represented by (SA2) or R 5 This is a process for decarboxylating the carboxyl groups and ester groups introduced into the As the fluoride source, various compounds that generate fluoride can be used, and examples of the fluoride source that can be used include salts of quaternary amines and fluorides, such as tetrabutylamine fluoride, tetramethylamine fluoride, and tetrahydroxyethylamine fluoride; salts of metal cations and fluorides, such as tetramethylaluminum; salts of phosphonium and fluorides, such as tetraoctadecylphosphonium; and fluoride salts of alkali metals, such as KF and NaF.

[0111] In step A2, a compound represented by formula (SA2) or (SA3) is subjected to a decarboxylation reaction using a fluoride source at a low reaction temperature of 100° C. or less to obtain a compound represented by formula (1). 1 Depending on the selection of the X group and the X group, the compound represented by formula (1) can be obtained at a lower reaction temperature of 80° C. or lower, or 60° C. or lower, more preferably 50° C. or lower, compared with formula (SA2) having a structure that is likely to denature or decompose at high temperatures.

[0112] A polymerization inhibitor may be added to the reaction in the series of step A2, and a commercially available product may be used. For example, nitroso compounds such as 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitrosonaphthol, p-nitrosophenol, and N,N'-dimethyl-p-nitrosoaniline, sulfur-containing compounds such as phenothiazine, methylene blue, and 2-mercaptobenzimidazole, N,N'-diphenyl-p-phenylenediamine, and N-phenyl Examples of the additive include amines such as -N'-isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, and aminophenol, quinones such as hydroxyquinoline, hydroquinone, methylhydroquinone, p-benzoquinone, and hydroquinone monomethyl ether, phenols such as p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, catechol, 3-s-butylcatechol, and 2,2-methylenebis-(6-t-butyl-4-methylphenol), imides such as N-hydroxyphthalimide, oximes such as cyclohexaneoxime and p-quinonedioxime, and dialkylthiodipropionate. The amount of the additive is, for example, 0.001 to 10 parts by mass, and preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the (meth)acrylic acid compound represented by the general formula (b).

[0113] The method for producing a compound represented by the following formula (1) includes a step of forming a compound represented by the following formula (SB1) from at least one of compounds represented by the following formula (SB2A) and formula (SB3A) obtained through a step represented by the following B1A and at least one of the steps represented by the following B2A and B3A, and a double bond introduction step of introducing an unsaturated double bond into a substituent Qb of the compound represented by formula (SB1). B1A) preparing a substrate SB1A containing one or more amino groups and a core B having an aldehyde group or a ketone group. B2A) A step of obtaining a compound represented by the following formula (SB2A) in which iodine is introduced into the mother nucleus B: B3A) A process for obtaining a compound represented by formula (SB3A) in which the amino group is replaced with a halogen group by the Sandmeyer reaction. [ka] (In formula (1), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1 are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and 1 The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R a , R b , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z's each independently represent an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group of Z may have a substituent; p is an integer of 1 or greater, m is an integer of 1 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater. In formulas (SB1A), (SB2A), (SB3A), and (SB1), Zb represents a hydrogen group or an amino group which may have a substituent selected from a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; rb represents an integer of 1 or more; Qb and L 1b , X b1 , B, pb, and mb' are the same as Q, L, X, A, p, and m in formula (1), respectively. X B2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br.

[0114] The step of introducing a double bond may use an organic phosphorus compound and a base. Examples of the organic phosphorus compound that can be used include phosphorus oxoacids, alkylated phosphorus oxoacids, and phosphates. Examples of phosphorus oxoacids include phosphoric acid and pyrophosphoric acid, examples of alkylated phosphorus oxoacids include dimethylphosphinic acid and triethyl phosphate, and examples of phosphates include diammonium hydrogen phosphate, but are not limited thereto. In addition, the organic phosphorus compound may be used in combination of not only one type but also two or more types. Examples of the base include alkali metal hydrides such as potassium hydride and sodium hydride, alkali metal carbonates such as potassium carbonate and cesium carbonate, quaternary ammonium salts (tetramethylammonium hydroxide), alkoxides (sodium ethoxide, potassium t-butoxide (t-BuOK)), metal amides (lithium diisopropylamide (LDA), potassium hexamethyldisilazide (KHMDS), lithium 2,2,6,6-tetramethylpiperidide (LiTMP)), metal alkyls (alkyl lithium, alkyl aluminum), pyridines (pyridine, DMAP), non-pyridine heterocyclic amines (DBU, DBN, imidazole), and other organic bases.

[0115] Another preferred method for obtaining the compound represented by formula (SA1) above includes a step (B1A) of preparing a starting compound (SB1A) having an aromatic mother nucleus B as A, having at least one amino group on the mother nucleus B, and having an alcohol group or a carbonyl group selected from at least one of an aldehyde group, a ketone group, and a carboxyl group, a step (B2A) of obtaining a compound represented by formula (SB2A) by introducing iodine into the mother nucleus B, and a step (B3A) of obtaining a compound represented by formula (SB3A) by substituting a halogen group for the amino group by a Sandmeyer reaction. The step (B1A) and at least one of steps (B2A) and (B3A) can be selected as a method for obtaining the compound represented by formula (SA1). [ka] (In formulas (SB1A), (SB2A), (SB3A), and (SA1A), Zb represents a hydrogen group or an amino group which may have a substituent selected from a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; rb represents an integer equal to or greater than 1, Qb, L 1b , X b1 , B, pb, and mb' are the same as Q, L, X, A, p, and m in formula (1), respectively. X B2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br.

[0116] That is, in the method for producing the compound represented by the above formula (SA1), it is preferable that the compound represented by the above formula (SA1) is at least one of the compounds represented by formula (SB2A) and formula (SB3A) obtained via a step represented by B1A and at least one of the steps represented by B2A and B3A, and the compound represented by the above formula (SA1) is produced. B1A) preparing a substrate SB1A containing one or more amino groups and a core B having an alcohol group, an aldehyde group or a ketone group; B2A) A step of obtaining a compound represented by formula (SB2A) by introducing iodine into the mother nucleus B B3A) A process for obtaining a compound represented by formula (SB3A) in which the amino group is replaced with a halogen group by the Sandmeyer reaction.

[0117] In this production method, the double bond introduction step (Step B1A) and the halogen introduction step (Step B2A or B3A) are carried out in this order. In the method described in step (B2A), the iodine introduction reaction into the compound represented by formula (SB1A) (substrate SB1A) can be carried out by reacting at least an iodinating agent with the compound represented by formula (SB1A). For example, the target compound can be obtained under known iodine introduction reaction conditions using the methods described in non-patent documents such as Adv. Synth. Catal. 2007, 349, 1159-1172 and Organic Letters; Vol. 6; (2004); p.2785-2788, and in patent documents such as US5300506, US5434154, US2009 / 281114, EP1439164, and WO2006 / 101318. Examples of iodinating agents that can be used include, but are not limited to, iodine compounds, monochloride iodide, N-iodosuccinimide, benzyltrimethylammonium dichloroiodate, tetraethylammonium iodide, tetra-normal-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodine fluoride, tert-butyl hypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetyl hypoiodide, iodine-iodic acid, iodine-periodic acid, iodine-hydrogen peroxide, 1-iodoheptafluoropropane, triphenylphosphate-methyl iodide, iodine-thallium (I) acetate, 1-chloro-2-iodoethane, iodine-copper (II) acetate, and the like.

[0118] In the iodination reaction, one or more additives can be added to promote the reaction or suppress by-products. Examples of additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, copper chloride, antimony pentachloride, silver sulfate, silver nitrate, and silver trifluoroacetate, bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate, oxidizing agents such as cerium (IV) ammonium nitrate and sodium peroxodisulfate, inorganic compounds such as sodium chloride, potassium chloride, mercury (II) oxide, and cerium oxide, organic compounds such as acetic anhydride, and porous substances such as zeolites.

[0119] In step (B2A), iodine is preferably introduced into the mother nucleus B using at least an iodine source and an oxidizing agent. The use of an iodine source and an oxidizing agent is preferred from the viewpoint of reaction efficiency and purity improvement. Examples of the iodizing source include the above-mentioned iodizing agents. Examples of the oxidizing agent include divalent iodic acid, hydrogen peroxide, and a specific additive (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, etc.).

[0120] From the viewpoint of solubility in a developer, the mother nucleus B in the substrate SB1A preferably has an aromatic ring structure which may have a heteroatom. In addition, the aromatic ring structure of the mother nucleus B preferably contains at least one of furan, thiophene, pyrrole, and indole from the viewpoint of the balance between solubility in a developer and the effect of improving sensitivity.

[0121] The reaction in step (B2A) can be carried out neat without a solvent, but examples of reaction solvents that can be used include halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; alkyl-based solvents such as hexane, cyclohexane, heptane, pentane, and octane; aromatic hydrocarbon-based solvents such as benzene and toluene; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; ether-based solvents such as diethyl ether, diisopropyl ether, and tetrahydrofuran; acetic acid, dimethylformamide, dimethyl sulfoxide, and water.

[0122] The reaction temperature in step (B2A) is not particularly limited and may be any temperature from the freezing point to the boiling point of the solvent used in the reaction, but is preferably 0°C to 150°C.

[0123] The iodine substitution reaction of the compound represented by formula (SB1A) in step (B2A) can be carried out by reacting at least an iodinating agent with the compound represented by formula (SB1A). For example, the target compound can be obtained under known iodine substitution reaction conditions such as a Sandmeyer reaction using the method described in Chemistry - A European Journal, 24(55), 14622-14626; 2018, Synthesis (2007)(1), 81-84, etc.

[0124] (Method for producing the compound represented by formula (1C)) As an example of a method for producing a compound represented by formula (1C), a compound represented by formula (1C) can be obtained by dimerizing the compound represented by formula (1) obtained by the above-mentioned production method, when Ra is a hydrogen group. The easiest method for dimerizing a compound represented by formula (1) is to subject the obtained compound (1) to high temperature or basic conditions, and dimerization can proceed from an active methylene site formed by the removal of the Ra group.

[0125] The compound represented by the above formula (SA1) may be produced by a production method including the step shown in the following B1B and at least one of the steps shown in the following B2B and B3B. B1B) preparing a substrate SB1B comprising a core B having one or more amino groups and an aldehyde group or a ketone group; B2B) A process for obtaining a compound represented by formula (SB2B) in which iodine is introduced into the mother nucleus B B3B) A step of obtaining a compound represented by formula (SB3B) in which the amino group is replaced with a halogen group. [ka] (In formulas (SB1B), (SB2B), (SB3B), and (SA1B), Zb represents a hydrogen group or an amino group which may have a substituent selected from a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; rb represents an integer of 1 or more; Qb and L 1b , X b1 , B, pb, and mb' are the same as Q, L, X, A, p, and m in formula (1), respectively. B2 represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br.

[0126] The method for producing the compound represented by the above formula (SA1) may further include the step represented by the following B4a. Inclusion of the step represented by the following B4a is preferable in terms of the reaction purity of the formed compound. B4a) Wittig process The Wittig process is a process for forming an alkene by a Witting reaction, and is a process for forming an alkene from a carbonyl moiety having an aldehyde or ketone using a phosphorus ylide, although it is not limited thereto. As the phosphorus ylide, a triphenylalkylphosphine bromide such as triphenylmethylphosphine bromide, which can form a stable phosphorus ylide, can be used. In addition, as the phosphorus ylide, a phosphonium salt can be reacted with a base to form a phosphorus ylide in the reaction system, and the phosphorus ylide can be used in the above reaction. As the base, a conventionally known base can be used, and for example, an alkali metal salt of an alkoxide can be appropriately used.

[0127] In the step B2B, iodine may be introduced into the mother nucleus B by using at least an iodine source and an oxidizing agent. The use of an iodine source and an oxidizing agent is preferable from the viewpoints of reaction efficiency and purity.

[0128] It is preferable that the mother nucleus B has an aromatic ring structure which may have a heteroatom, from the viewpoint of the balance between solubility in the developer and the effect of improving the sensitivity.

[0129] The method for producing a compound represented by the following formula (1) includes a halogen introduction step of reacting a compound represented by the following formula (S1) with a halogenating agent to introduce a halogen atom, and a double bond introduction step of introducing an unsaturated double bond into a substituent Q, and the double bond introduction step may use an organic phosphorus compound and a base. [ka] (In formula (S1), X 0 is an organic group having 1 to 30 carbon atoms, L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group, p is an integer of 1 or greater, m' is an integer of 0 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater. [ka] (In formula (1), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L 1 each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R a , Rb , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; p is an integer of 1 or greater, m is an integer of 1 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater.

[0130] The compound in this embodiment is preferably obtained as a crude product by the above-mentioned reaction, and then purified to remove remaining metal impurities. That is, from the viewpoint of preventing deterioration of the resin over time and storage stability, and further from the viewpoint of process suitability and manufacturing yield due to defects when resinified and applied to a semiconductor manufacturing process, it is preferable to avoid the remaining metal impurities resulting from the contamination of metal components used as reaction aids in the compound manufacturing process or contaminated from a reaction kettle or other manufacturing equipment.

[0131] The residual amount of the metal impurities is preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb. In particular, for metal species such as Fe, Ni, Sb, W, and Al classified as transition metals, if the residual amount of metal is 1 ppm or more, there is a concern that the interaction with the compound in this embodiment may cause the material to degenerate or deteriorate over time. Furthermore, if the residual amount of metal is 1 ppm or more, the metal residue cannot be sufficiently reduced when the compound is used to prepare a resin for semiconductor processing, and there is a concern that this may cause defects due to residual metals and performance deterioration in the semiconductor manufacturing process, resulting in a decrease in yield.

[0132] The purification method is not particularly limited, but includes a step of dissolving the compound of the present embodiment in a solvent to obtain a solution (S), and a step (first extraction step) of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the compound of the present embodiment, wherein the solvent used in the step of obtaining the solution (S) includes an organic solvent that is arbitrarily immiscible with water. According to the above purification method, it is possible to reduce the contents of various metals that may be contained in the resin as impurities. More specifically, the compound in the present embodiment can be dissolved in an organic solvent that is not miscible with water to obtain a solution (S), and the solution (S) can be contacted with an acidic aqueous solution to perform an extraction treatment, whereby the metal content in the solution (S) is transferred to the aqueous phase, and the organic phase and the aqueous phase are separated to obtain a resin with a reduced metal content.

[0133] The water-immiscible solvent used in the purification method is not particularly limited, but is preferably an organic solvent that can be safely applied to the semiconductor manufacturing process, specifically, an organic solvent whose solubility in water at room temperature is less than 30%, more preferably less than 20%, and particularly preferably less than 10%. The amount of the organic solvent used is preferably 1 to 100 times by mass relative to the total amount of the resin used.

[0134] Specific examples of solvents that are not arbitrarily miscible with water include, but are not limited to, ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 2-pentanone; glycol ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; aromatic hydrocarbons such as toluene and xylene; and halogenated hydrocarbons such as methylene chloride and chloroform. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, etc. are preferred, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferred, and methyl isobutyl ketone and ethyl acetate are even more preferred. Methyl isobutyl ketone, ethyl acetate, etc. have a relatively high saturated solubility of the compound in this embodiment and a relatively low boiling point, so that it is possible to reduce the load in the process of industrially distilling off the solvent or removing it by drying. Each of these solvents can be used alone, or two or more of them can be mixed and used.

[0135] The acidic aqueous solution used in the purification method is appropriately selected from among aqueous solutions in which a commonly known organic or inorganic compound is dissolved in water. Examples of the aqueous solution include, but are not limited to, aqueous mineral acids in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid is dissolved in water, or aqueous organic acids in which an organic acid such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, or trifluoroacetic acid is dissolved in water. These aqueous acidic solutions can be used alone or in combination of two or more. Among these acidic aqueous solutions, it is preferable to use one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or one or more organic acid aqueous solutions selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid, and more preferably, sulfuric acid, nitric acid, and carboxylic acid aqueous solutions such as acetic acid, oxalic acid, tartaric acid and citric acid, more preferably, sulfuric acid, oxalic acid, tartaric acid and citric acid aqueous solutions, and even more preferably, oxalic acid aqueous solutions. It is considered that polycarboxylic acids such as oxalic acid, tartaric acid and citric acid tend to be coordinated to metal ions and have a chelating effect, so that metals can be removed more effectively. In addition, it is preferable to use water with a low metal content, such as ion-exchanged water, in accordance with the purpose of the purification method in this embodiment.

[0136] Although the pH of the acidic aqueous solution used in the purification method is not particularly limited, it is preferable to adjust the acidity of the aqueous solution in consideration of the effect on the resin. The pH range is usually about 0 to 5, and preferably about 0 to 3.

[0137] The amount of the acidic aqueous solution used in the purification method is not particularly limited, but it is preferable to adjust the amount used from the viewpoint of reducing the number of extractions for removing metals and from the viewpoint of ensuring operability in consideration of the total liquid amount. From the above viewpoints, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, more preferably 20 to 100% by mass, relative to 100% by mass of the solution (S).

[0138] In the purification method, the acidic aqueous solution is brought into contact with the solution (S), whereby metal components can be extracted from the resin in the solution (S).

[0139] In the above purification method, the solution (S) may further contain an organic solvent that is arbitrarily miscible with water. When the solution (S) contains an organic solvent that is arbitrarily miscible with water, the amount of the resin charged can be increased, and the liquid separation property is improved, and purification tends to be performed with high efficiency. The method of adding the organic solvent that is arbitrarily miscible with water is not particularly limited. For example, any of the following methods may be used: adding the organic solvent to a solution containing the organic solvent in advance, adding the organic solvent to water or an acidic aqueous solution in advance, and adding the organic solvent after contacting the solution containing the organic solvent with water or an acidic aqueous solution. Among these, the method of adding the organic solvent to a solution containing the organic solvent in advance is preferred in terms of ease of operation and ease of management of the amount charged.

[0140] The organic solvent that is miscible with water and used in the above purification method is not particularly limited, but is preferably an organic solvent that can be safely applied to a semiconductor manufacturing process. The amount of the organic solvent that is miscible with water and used is not particularly limited as long as the solution phase and the aqueous phase are separated, but is preferably 0.1 to 100 times by mass, more preferably 0.1 to 50 times by mass, and even more preferably 0.1 to 20 times by mass, relative to the total amount of the resin used.

[0141] Specific examples of the organic solvent that is arbitrarily miscible with water used in the above purification method include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and N-methylpyrrolidone; and aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether, and the like are preferred, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferred. Each of these solvents can be used alone, or two or more of them can be mixed and used.

[0142] The temperature during the extraction treatment is usually in the range of 20 to 90°C, and preferably in the range of 30 to 80°C. The extraction operation is carried out, for example, by thoroughly mixing the solution by stirring or the like, and then allowing it to stand. This causes the metal content contained in the solution (S) to migrate to the aqueous phase. This operation also reduces the acidity of the solution, making it possible to suppress deterioration of the resin.

[0143] The mixed solution is separated into a solution phase containing a resin and a solvent and an aqueous phase by standing, and the solution phase is recovered by decantation or the like. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation of the solution phase containing the solvent and the aqueous phase. Usually, the standing time is 1 minute or more, preferably 10 minutes or more, and more preferably 30 minutes or more. In addition, the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation several times.

[0144] In the above purification method, it is preferable to further include a step (second extraction step) of contacting the solution phase containing the resin with water after the first extraction step to extract impurities in the resin. Specifically, for example, after the above extraction treatment is performed using an acidic aqueous solution, the solution phase containing the resin and the solvent extracted and recovered from the aqueous solution is preferably further subjected to an extraction treatment with water. The above extraction treatment with water is not particularly limited, but can be performed, for example, by thoroughly mixing the above solution phase and water by stirring or the like, and then allowing the resulting mixed solution to stand. The mixed solution after standing is separated into a solution phase containing the above resin and the solvent and an aqueous phase, and the solution phase can be recovered by decantation or the like. In addition, the water used here is preferably water with a low metal content, such as ion-exchanged water, in line with the object of this embodiment. The extraction treatment may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation several times. In addition, the conditions such as the ratio of both used in the extraction treatment, temperature, and time are not particularly limited, but may be the same as those in the contact treatment with the acidic aqueous solution.

[0145] Water that may be mixed into the solution containing the resin and the solvent thus obtained can be easily removed by performing an operation such as vacuum distillation, etc. Furthermore, if necessary, a solvent can be added to the above solution to adjust the resin concentration to an arbitrary concentration.

[0146] In the method for purifying the compound according to the present embodiment, the compound can also be purified by passing a solution in which the resin is dissolved in a solvent through a filter. According to the method for purifying a substance according to the present embodiment, the content of various metals in the resin can be effectively and significantly reduced. The amount of these metal components can be measured by the method described in the Examples below. In this embodiment, "passing through" means that the solution moves from the outside of the filter through the inside of the filter and then back to the outside of the filter, and excludes, for example, a case in which the solution is simply brought into contact with the surface of the filter, or a case in which the solution is brought into contact with the surface of the filter while moving outside the ion exchange resin (i.e., a case in which the solution is simply brought into contact).

[0147] [Filter purification process (liquid passing process)] In the filter passing step in this embodiment, the filter used to remove metals from the solution containing the resin and the solvent can be a commercially available filter for liquid filtration. The filtration accuracy of the filter is not particularly limited, but the nominal pore size of the filter is preferably 0.2 μm or less, more preferably less than 0.2 μm, even more preferably less than 0.1 μm, even more preferably less than 0.1 μm, and even more preferably 0.05 μm or less. The lower limit of the nominal pore size of the filter is not particularly limited, but is usually 0.005 μm. The nominal pore size here is a nominal pore size that indicates the separation performance of the filter, and is determined by a test method determined by the filter manufacturer, such as a bubble point test, a mercury porosimetry test, or a standard particle capture test. When a commercially available product is used, it is the value described in the catalog data of the manufacturer. By making the nominal pore size 0.2 μm or less, the content of metals after passing the solution through the filter once can be effectively reduced. In this embodiment, in order to further reduce the content of each metal in the solution, the filter passing step may be carried out two or more times.

[0148] As the form of the filter, a hollow fiber membrane filter, a membrane filter, a pleated membrane filter, and a filter filled with a filter material such as nonwoven fabric, cellulose, and diatomaceous earth can be used. Among the above, the filter is preferably one or more selected from the group consisting of a hollow fiber membrane filter, a membrane filter, and a pleated membrane filter. In addition, it is particularly preferable to use a hollow fiber membrane filter, because of its high-precision filtration accuracy and high filtration area compared to other forms.

[0149] The material of the filter may be polyolefin such as polyethylene or polypropylene, polyethylene-based resins provided with functional groups having ion exchange capacity by graft polymerization, polar group-containing resins such as polyamide, polyester, or polyacrylonitrile, or fluorine-containing resins such as fluorinated polyethylene (PTFE). Among the above, the filter medium is preferably one or more selected from the group consisting of polyamide, polyolefin resin, and fluororesin. In addition, polyamide is particularly preferred from the viewpoint of reducing heavy metals such as chromium. In addition, it is preferable to use a filter other than a sintered metal material from the viewpoint of preventing metal elution from the filter medium.

[0150] Examples of polyamide-based filters (hereinafter, trademarks) include, but are not limited to, the Polyfix Nylon series manufactured by Kitz Microfilter Co., Ltd., Ultipleats P-Nylon 66 and Ultipore N66 manufactured by Nippon Pole Co., Ltd., and the LifeAsure PSN series and LifeAsure EF series manufactured by 3M Limited. Examples of polyolefin filters include, but are not limited to, Ultipleats PE Clean and Ion Clean, both manufactured by Nippon Pole Co., Ltd., and Protego Series, Microguard Plus HC10, and Optimizer D, both manufactured by Nippon Entegris Co., Ltd. Examples of polyester-based filters include, but are not limited to, Gelaflow DFE manufactured by Central Filter Kogyo Co., Ltd., and Breeze Type PMC manufactured by Nippon Filter Co., Ltd. Examples of polyacrylonitrile filters include, but are not limited to, Ultrafilters AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantech Toyo Co., Ltd. Examples of fluororesin filters include, but are not limited to, Enflon HTPFR manufactured by Nippon Pall Co., Ltd., and Lifesure FA series manufactured by 3M Limited. These filters may be used alone or in combination of two or more kinds.

[0151] The filter may also contain an ion exchanger such as a cation exchange resin, or a cationic charge regulator that generates a zeta potential in the organic solvent solution to be filtered. Examples of filters containing an ion exchanger include, but are not limited to, the Protego series manufactured by Nippon Entegris Co., Ltd. and Clangraft manufactured by Kurashiki Sen-i Kako Co., Ltd. Furthermore, examples of filters containing substances having a positive zeta potential, such as polyamidepolyamine epichlorohydrin cationic resin (hereinafter, referred to as trademarks), include, but are not limited to, Zeta Plus 40QSH and Zeta Plus 020GN manufactured by 3M Limited, and the Life Asure EF series.

[0152] [Use of compound (A)] The compound (A) according to the present embodiment can be added to a film-forming composition as it is or as a polymer described later, thereby increasing the sensitivity to an exposure light source. The compound (A) or its polymer is preferably used in a photoresist.

[0153] [Composition] The composition of the present embodiment contains a compound (A). The content of the compound (A) in the present embodiment is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more.

[0154] As another preferred embodiment of the composition of the present embodiment, it is preferable to contain at least a compound represented by formula (1) other than formula (1C) and a compound represented by formula (1C) as compound (A). The proportion of the monomer represented by formula (1C) is preferably a small amount of 1 ppm by mass or more and 10% by mass or less, more preferably 20 ppm by mass or more and 2% by mass or less, and more preferably 50 ppm by mass or more and 1% by mass or less, relative to the monomer represented by formula (1).

[0155] By setting the content of the compound represented by formula (1C) within the above-described range, it is possible to reduce interactions between resins during resinification, and by suppressing crystallinity resulting from interactions between resins after a film is formed using the resin, it is possible to reduce the locality of solubility in a developer during development at a molecular level of several nanometers to several tens of nanometers, and to suppress deterioration of pattern quality such as line edge roughness and residual defects in a pattern formed in a pattern formation process in a series of lithography processes including exposure, post-exposure baking, and development, thereby making it possible to further improve resolution.

[0156] These effects on lithography performance are greater in the compound represented by formula (1) having a mother nucleus A into which a halogen element, particularly iodine or fluorine, has been introduced, and in the compound represented by formula (1C), the hydrophilicity is shifted to hydrophobicity, and polarization at the polar sites is increased, compared to a compound having a hydroxystyrene skeleton without iodine or the like introduced therein.

[0157] In the composition of the present embodiment, the amount of impurities including K (potassium) is, in elemental terms, preferably 1 ppm by mass or less, more preferably 0.5 ppm by mass or less, even more preferably 0.1 ppm by mass or less, and still more preferably 0.005 ppm by mass or less, relative to compound (A).

[0158] In the composition of the present embodiment, the content of one or more elemental impurities selected from the group consisting of Mn (manganese), Al (aluminum), Si (silicon), and Li (lithium) (preferably, one or more elemental impurities selected from the group consisting of Mn and Al) is preferably 1 ppm or less, more preferably 0.5 ppm or less, and even more preferably 0.1 ppm or less, in terms of element, relative to compound (A). The amounts of K, Mn, Al, etc. are measured by inorganic elemental analysis (IPC-AES / IPC-MS). An example of an inorganic elemental analyzer is the "AG8900" manufactured by Agilent Technologies.

[0159] In the composition of the present embodiment, the content of the phosphorus-containing compound is preferably 10 ppm or less, more preferably 8 ppm or less, and further preferably 5 ppm or less, relative to the compound (A).

[0160] In the composition of the present embodiment, the content of maleic acid relative to compound (A) is preferably 10 ppm or less, more preferably 8 ppm or less, and even more preferably 5 ppm or less. The amounts of phosphorus-containing compounds and maleic acid are calculated by gas chromatography-mass spectrometry (GC-MS) from the area fractions in the GC chart and the peak intensity ratios between the target peak and the reference peak.

[0161] In the composition of the present embodiment, the peroxide is preferably 10 ppm by mass or less, more preferably 1 ppm or less, and even more preferably 0.1 ppm or less, relative to the compound (A). The amount of peroxide is quantified by the ammonium ferrothiocyanate acid method (hereinafter referred to as the AFTA method) by adding trichloroacetic acid to the sample, then adding ammonium iron sulfate (II) and potassium thiocyanate, obtaining a calibration curve for a known peroxide as a standard substance, and measuring the absorbance at a wavelength of 480 μm.

[0162] In the composition of the present embodiment, the water content is preferably 100,000 ppm or less, more preferably 20,000 ppm or less, even more preferably 1,000 ppm or less, still more preferably 500 ppm or less, and even more preferably 100 ppm or less, based on the compound (A). The water content is measured by the Karl Fischer method (Karl Fischer water content meter).

[0163] [Polymer (A)] The polymer (A) of this embodiment contains a structural unit derived from the above-mentioned compound (A). The polymer (A) contains a structural unit derived from the compound (A), and thus can increase the sensitivity to the exposure light source when incorporated into a resist composition. In particular, even when extreme ultraviolet light is used as the exposure light source, the polymer (A) exhibits sufficient sensitivity and can satisfactorily form a fine line pattern with a narrow line width.

[0164] In addition, conventional resist compositions may lose their sensitivity to an exposure light source over time due to storage, etc., which makes it difficult to apply them to actual semiconductor manufacturing. However, according to the polymer (A) of the present embodiment, the stability of the resist composition is improved, and loss of sensitivity to an exposure light source is suppressed even when the resist composition is stored for a long period of time.

[0165] The polymer (A) of this embodiment contains a structural unit derived from the compound (A).

[0166] The constitutional unit derived from the compound (A) is a constitutional unit represented by the following formula (4). [ka]

[0167] In formula (4), X, L 1 , Y, R a , R b , R c , A, Z, p, m, n and r are the same as defined in formula (1). The polymer (A) can be obtained by polymerizing the compound (A) of the present embodiment or by copolymerizing the compound (A) with another monomer. The polymer (A) can be used, for example, as a film-forming material for lithography.

[0168] The constituent unit derived from the compound (A) is preferably a constituent unit represented by the following formula (5). [ka]

[0169] In formula (5), X, L 1 , Y, A, p, m and n are the same as defined in formula (1).

[0170] The constituent unit derived from compound (A) is more preferably a constituent unit represented by the following formula (6). [ka]

[0171] In formula (6), X, L 1 , Y, R a1 , R b1 , R c1 , A, Z, p, m, n and r are the same as defined in formula (1b).

[0172] The amount of the constitutional unit derived from the compound (A) is preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more, based on the total amount of the monomer components of the polymer (A). The amount of the constitutional unit derived from the compound (A) is 100 mol% or less, preferably 80 mol% or less, more preferably 50 mol% or less, and even more preferably 30 mol% or less, based on the total amount of the monomer components of the polymer (A).

[0173] As a preferred embodiment of the polymer of the present invention, the polymer (A) preferably contains at least a compound represented by formula (1) other than formula (1C) and a compound represented by formula (1C) as a monomer represented by compound (A) as a constituent unit of the polymer (A). The proportion of the monomer represented by formula (1C) is preferably 10 ppm or more and 10 mass % or less, more preferably 20 ppm or more and 2 mass % or less, and more preferably 50 ppm or more and 1 mass % or less, relative to the monomer represented by formula (1). By setting the content of the compound represented by formula (1C) within the above-described range, it is possible to reduce interactions between resins during resinification, and by suppressing crystallinity resulting from interactions between resins after a film is formed using the resin, it is possible to reduce the locality of solubility in a developer during development at a molecular level of several nanometers to several tens of nanometers, and to suppress deterioration of pattern quality such as line edge roughness and residual defects in a pattern formed in a pattern formation process in a series of lithography processes including exposure, post-exposure baking, and development, thereby making it possible to further improve resolution. These effects on lithography performance are greater in the monomer represented by formula (1C) because the compounds represented by formula (1) and formula (1C) having a mother nucleus A into which a halogen element, particularly iodine or fluorine, has been introduced have a shift in hydrophilicity to hydrophobicity and an increase in polarization at the polar sites compared to compounds having a hydroxystyrene skeleton without iodine or the like introduced therein.

[0174] The other monomer to be copolymerized with compound (A) preferably contains, as a polymerization unit, an aromatic compound having an unsaturated double bond as a substituent, and a polymerization unit having a functional group that improves the solubility in an alkaline developer by the action of an acid or a base.

[0175] Examples of the other monomers include, but are not limited to, those described in International Publication WO2016 / 125782, International Publication WO2015 / 115613, JP2015 / 117305, International Publication WO2014 / 175275, and JP2012 / 162498, or compounds represented by the following formula (C1) or formula (C2). Among these, compounds represented by the following formula (C1) or formula (C2) are preferred.

[0176] From the viewpoint of the quality of the pattern shape after exposure and development in the lithography process, particularly in terms of suppressing roughness and pattern collapse, the dissolution rate R of the resin in the alkaline developer that becomes the pattern convex part during alkaline development in the unexposed part during exposure is min and the dissolution rate R of the resin in the alkaline developer that becomes a recess in the pattern during alkaline development in the exposed area. maxIt is preferable that the difference between the dissolution rates is greater than or equal to three orders of magnitude, that the difference in dissolution rate between the presence and absence of a protecting group is greater, and that the rate of elimination of the protecting group during post-exposure baking (PEB) and development is greater. From these viewpoints, it is preferable that the other monomer to be copolymerized with compound (A) in polymer (A) has a constitutional unit represented by the following formula (C1). [ka]

[0177] In formula (C1), R C11 is H or a methyl group, R C12 is H or an alkyl group having 1 to 4 carbon atoms, R C13 is R C13 is, together with the carbon atom to which it is bonded, a cycloalkyl group or heterocycloalkyl group having 4 to 20 carbon atoms, * indicates the bonding site with the adjacent building block.

[0178] R C12 is preferably H or an alkyl group having 1 to 3 carbon atoms, and R C13 is preferably R C13 R is, together with the carbon atom to which it is bonded, a cycloalkyl group or heterocycloalkyl group having 4 to 10 carbon atoms. C13 The cycloalkyl group or heterocycloalkyl group may have a substituent (for example, an oxo group).

[0179] The amount of the constitutional unit represented by formula (C1) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, based on the total amount of the monomer components of the polymer (A). The amount of the constitutional unit represented by formula (C1) is preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, based on the total amount of the monomer components of the polymer (A).

[0180] The other monomer to be copolymerized with the compound (A) in the polymer (A) is preferably a structural unit represented by the following formula (C2) from the viewpoints of the quality of the pattern shape after exposure and development in the lithography process, in particular, suppression of roughness and pattern collapse.

[0181] [ka]

[0182] In formula (C2), R C21 is H or a methyl group, R C22 and R C23 are each independently an alkyl group having 1 to 4 carbon atoms, R C24 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, R C22 , R C23 , and R C24 two or three of these may form, together with the carbon atom to which they are bonded, an alicyclic structure having 3 to 20 carbon atoms, * indicates the bonding site with the adjacent building block.

[0183] R C22 is preferably an alkyl group having 1 to 3 carbon atoms, and R C24 is a cycloalkyl group having 5 to 10 carbon atoms. C22 , R C23 , and R C24 The alicyclic structure formed by may contain a plurality of rings such as an adamantyl group, etc. The alicyclic structure may have a substituent (for example, a hydroxyl group, an alkyl group).

[0184] The amount of the constitutional unit represented by formula (C2) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, based on the total amount of the monomer components of polymer (A). The amount of the constitutional unit represented by formula (C2) is preferably 80 mol% or less, more preferably 60 mol% or less, and even more preferably 40 mol% or less, based on the total amount of the monomer components of polymer (A).

[0185] Examples of monomer raw materials for the constitutional unit represented by formula (C2) include, but are not limited to, 2-methyl-2-(meth)acryloyloxyadamantane, 2-ethyl-2-(meth)acryloyloxyadamantane, 2-isopropyl-2-(meth)acryloyloxyadamantane, 2-n-propyl-2-(meth)acryloyloxyadamantane, 2-n-butyl-2-(meth)acryloyloxyadamantane, 1-methyl-1-(meth)acryloyloxycyclopentane, 1-ethyl-1-(meth)acryloyloxycyclopentane, 1-methyl -1-(meth)acryloyloxycyclohexane, 1-ethyl-1-(meth)acryloyloxycyclohexane, 1-methyl-1-(meth)acryloyloxycycloheptane, 1-ethyl-1-(meth)acryloyloxycycloheptane, 1-methyl-1-(meth)acryloyloxycyclooctane, 1-ethyl-1-(meth)acryloyloxycyclooctane, 2-ethyl-2-(meth)acryloyloxydecahydro-1,4:5,8-dimethanonaphthalene, 2-ethyl-2-(meth)acryloyloxynorbornane. Commercially available products can be used as these monomers.

[0186] In the polymer (A), the other monomer to be copolymerized with the compound (A) preferably has a structural unit represented by the following formula (C3).

[0187] [ka]

[0188] In formula (C3), R C31 is H or a methyl group, and m, A, and * are as defined in formula (4) above.

[0189] In the polymer (A), the other monomer to be copolymerized with the compound (A) preferably has a constitutional unit represented by the following formula (C4).

[0190] [ka]

[0191] In formula (C4), B represents an organic group having 5 to 30 carbon atoms and containing an aromatic ring; R C31 , m, and * are as defined in formula (C3) above.

[0192] In the polymer (A), the other monomer to be copolymerized with the compound (A) preferably has a constitutional unit represented by the following formula (C5).

[0193] [ka]

[0194] In formula (C5), B' represents an organic group having 5 to 30 carbon atoms and containing an aromatic ring; R C31 , m, and * are as defined in formula (C3) above.

[0195] The other monomer to be copolymerized with the compound (A) in the polymer (A) is preferably a constitutional unit represented by the following formula (C6), from the viewpoints of exposure in a lithography process, exposure sensitivity in pattern formation after development, and quality of the pattern shape, in particular, suppression of roughness and pattern collapse.

[0196] [ka]

[0197] In formula (C6), X C61is a hydroxyl group or a halogen group, R C61 are each independently an alkyl group having 1 to 20 carbon atoms, * indicates the bonding site with the adjacent building block.

[0198] X C61 is preferably F, Cl, Br, or I, more preferably Cl or I, and even more preferably I. C61 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0199] The amount of the structural unit represented by formula (C6) is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total amount of the monomer components of polymer (A). The amount of the structural unit represented by formula (C6) is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, based on the total amount of the monomer components of polymer (A).

[0200] The monomer raw material of the constitutional unit represented by formula (C6) is not limited, but for example, 2-chloroacrylic acid methyl ester, 2-chloroacrylic acid ethyl ester, 2-chloroacrylic acid butyl ester, 2-bromoacrylic acid methyl ester, 2-bromoacrylic acid ethyl ester, 2-bromoacrylic acid butyl ester, 2-iodoacrylic acid methyl ester, 2-iodoacrylic acid ethyl ester, and 2-iodoacrylic acid butyl ester can be mentioned. Commercially available products can be used as these monomers.

[0201] Next, a method for producing the polymer (A) will be described. The polymerization reaction is carried out by dissolving the monomers that will be the constituent units in a solvent, adding a polymerization initiator, and heating or cooling the mixture. The reaction conditions can be set arbitrarily depending on the type of polymerization initiator, the initiation method such as heat or light, the temperature, pressure, concentration, solvent, additives, etc. Examples of the polymerization initiator include radical polymerization initiators such as azoisobutyronitrile and peroxides, and anionic polymerization initiators such as alkyl lithium and Grignard reagents.

[0202] As the solvent used in the polymerization reaction, a commercially available product that is generally available can be used. For example, various solvents such as alcohols, ethers, hydrocarbons, halogenated solvents, etc. can be appropriately used within the range that does not inhibit the reaction. A mixture of multiple solvents can also be used within the range that does not inhibit the above reaction.

[0203] The polymer (A) obtained by the polymerization reaction can be purified by a known method, specifically, by a combination of ultrafiltration, crystallization, microfiltration, acid washing, washing with water having an electrical conductivity of 10 mS / m or less, and extraction.

[0204] [Film forming composition] The film-forming composition of this embodiment contains a compound (A) or a polymer (A), and is particularly suitable for lithography techniques. Although not particularly limited, the composition can be used for forming a film for lithography, for example, for forming a resist film (i.e., a "resist composition"). Furthermore, the composition can be used for forming an upper layer film (i.e., a "composition for forming an upper layer film"), for forming an intermediate layer (i.e., a "composition for forming an intermediate layer"), for forming an underlayer film (i.e., a "composition for forming an underlayer film"), etc. According to the composition of this embodiment, it is possible to form a film having high sensitivity and to impart a good resist pattern shape.

[0205] The film-forming composition of the present embodiment can also be used as an optical component-forming composition to which lithography technology is applied. In addition to being used in the form of a film or sheet, the optical components are useful as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast-enhancing lenses, etc.), retardation films, films for electromagnetic wave shielding, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition can be suitably used as an embedding film and planarizing film on a photodiode, planarizing films before and after a color filter, microlenses, planarizing films on microlenses, and conformal films, which are components of solid-state imaging elements that require a particularly high refractive index.

[0206] The film-forming composition of the present embodiment contains a compound (A) or a polymer (A), and may contain other components such as a base material (B), a solvent (S), an acid generator (C), and an acid diffusion controller (E) as necessary. Each component will be described below.

[0207] [Base material (B)] In this embodiment, the term "substrate (B)" refers to a compound (including resin) other than the compound (A) or the polymer (A) and is applied as a resist for g-line, i-line, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm) or electron beam (EB) (e.g., a substrate for lithography or a substrate for resist). Any of these substrates can be used as the substrate (B) in this embodiment without any particular limitation. Examples of the substrate (B) include phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof. Among these, from the viewpoint of the shape of the resulting resist pattern, preferred are phenol novolac resins, cresol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof.

[0208] The derivative is not particularly limited, but examples thereof include those into which a dissociable group has been introduced, those into which a crosslinkable group has been introduced, etc. The derivative into which a dissociable group or a crosslinkable group has been introduced can cause a dissociation reaction or a crosslinking reaction by the action of light, acid, etc.

[0209] The term "dissociable group" refers to a characteristic group that is cleaved to generate a functional group such as an alkali-soluble group that changes the solubility. The alkali-soluble group is not particularly limited, but examples thereof include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group, with the phenolic hydroxyl group and the carboxyl group being preferred, and the phenolic hydroxyl group being particularly preferred.

[0210] The term "crosslinkable group" refers to a group that crosslinks in the presence or absence of a catalyst. The crosslinkable group is not particularly limited, but examples thereof include an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, a group having a (meth)acryloyl group, a group having an epoxy (meth)acryloyl group, a group having a hydroxyl group, a group having a urethane (meth)acryloyl group, a group having a glycidyl group, and a group having a vinyl-containing phenylmethyl group.

[0211] [Solvent (S)] In the present embodiment, the solvent may be any known solvent that dissolves at least the above-mentioned compound (A) or polymer (A). The solvent is not particularly limited, but may be, for example, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, and n-amino lactate. lactic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, and other aliphatic carboxylic acid esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-3-methylpropionate, Examples of suitable esters include butyl butyrate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), and cyclohexanone (CHN); amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-lactone.The solvent used in the present embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, and ethyl lactate, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate.

[0212] The solid component concentration in the film-forming composition of the present embodiment is not particularly limited, but is preferably 1 to 80 mass %, more preferably 1 to 50 mass %, even more preferably 2 to 40 mass %, and even more preferably 2 to 10 mass %, relative to the total mass of the film-forming composition.

[0213] [Acid Generator (C)] The film-forming composition of the present embodiment preferably contains one or more acid generators (C) that generate an acid directly or indirectly upon irradiation with radiation. The radiation is at least one selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-rays, and ion beams. The acid generator (C) is not particularly limited, but for example, those described in International Publication WO2013 / 024778 can be used. The acid generators (C) can be used alone or in combination of two or more.

[0214] The amount of the acid generator (C) is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and even more preferably 10 to 25% by mass, based on the total mass of the solid components. By using the acid generator (C) within the above range, a pattern profile with high sensitivity and low edge roughness tends to be obtained. In this embodiment, the method of generating the acid is not particularly limited as long as an acid is generated in the system. If an excimer laser is used instead of ultraviolet rays such as g-rays and i-rays, finer processing is possible, and further finer processing is possible if an electron beam, extreme ultraviolet rays, X-rays, or ion beam is used as a high-energy beam.

[0215] [Acid diffusion controller (E)] The film-forming composition of this embodiment may contain an acid diffusion controller (E). The acid diffusion controller (E) controls the diffusion of the acid generated from the acid generator by radiation exposure in the resist film, thereby preventing undesirable chemical reactions from occurring in unexposed areas. The use of the acid diffusion controller (E) tends to improve the storage stability of the composition of this embodiment. In addition, the use of the acid diffusion controller (E) can improve the resolution of the film formed using the composition of this embodiment, and can suppress changes in the line width of the resist pattern caused by fluctuations between the delay time before radiation exposure and the delay time after radiation exposure, tending to provide excellent process stability. The acid diffusion controller (E) is not particularly limited, and examples thereof include radiation-decomposable basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.

[0216] The acid diffusion controller (E) is not particularly limited, but for example, those described in International Publication WO2013 / 024778 can be used. The acid diffusion controller (E) can be used alone or in combination of two or more kinds.

[0217] The amount of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3% by mass, based on the total mass of the solid components. When the amount of the acid diffusion controller (E) is within the above range, it tends to be possible to prevent a decrease in resolution, deterioration of the pattern shape, dimensional fidelity, and the like. Furthermore, even if the waiting time from electron beam irradiation to heating after radiation irradiation is long, it is possible to suppress deterioration of the shape of the upper layer part of the pattern. Furthermore, when the amount of the acid diffusion controller (E) is 10% by mass or less, it tends to be possible to prevent a decrease in sensitivity, developability of the unexposed part, and the like. Furthermore, by using such an acid diffusion controller, the storage stability of the resist composition is improved, and the resolution is improved, and the line width change of the resist pattern due to the variation of the waiting time before radiation irradiation and the waiting time after radiation irradiation can be suppressed, and the process stability tends to be excellent.

[0218] [Other components (F)] To the film-forming composition of this embodiment, one or more of various additives such as a crosslinking agent, a dissolution promoter, a dissolution control agent, a sensitizer, a surfactant, and an organic carboxylic acid or a phosphorus oxoacid or a derivative thereof may be added as other component (F) as necessary.

[0219] (Crosslinking agent) The film-forming composition of the present embodiment may contain a crosslinking agent. The crosslinking agent can crosslink at least one of the compound (A), the polymer (A) and the base material (B). The crosslinking agent is preferably an acid crosslinking agent capable of intramolecularly or intermolecularly crosslinking the base material (B) in the presence of an acid generated from the acid generator (C). Examples of such acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") capable of crosslinking the base material (B).

[0220] Examples of the crosslinkable group include (i) hydroxyalkyl groups, such as hydroxyalkyl groups (alkyl groups having 1 to 6 carbon atoms), alkoxy groups having 1 to 6 carbon atoms (alkyl groups having 1 to 6 carbon atoms), and acetoxy groups (alkyl groups having 1 to 6 carbon atoms), or groups derived therefrom; (ii) carbonyl groups, such as formyl groups and carboxy groups (alkyl groups having 1 to 6 carbon atoms), or groups derived therefrom; (iii) dimethylaminomethyl groups, diethylaminomethyl groups, dimethylolaminomethyl groups, diethylaminomethyl groups, (iv) glycidyl group-containing groups such as glycidyl ether group, glycidyl ester group, glycidylamino group, (v) groups derived from aromatic groups such as allyloxy (alkyl group having 1 to 6 carbon atoms) having 1 to 6 carbon atoms, aralkyloxy (alkyl group having 1 to 6 carbon atoms) having 1 to 6 carbon atoms, such as benzyloxymethyl group, benzoyloxymethyl group, (vi) polymerizable multiple bond-containing groups such as vinyl group, isopropenyl group, etc. As the crosslinkable group of the crosslinking agent in this embodiment, hydroxyalkyl group, alkoxyalkyl group, etc. are preferable, and alkoxymethyl group is particularly preferable.

[0221] The crosslinking agent having a crosslinkable group is not particularly limited, and for example, the acid crosslinking agents described in International Publication WO2013 / 024778 can be used. The crosslinking agents can be used alone or in combination.

[0222] In this embodiment, the amount of the crosslinking agent is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total mass of the solid components.

[0223] (solubility enhancer) The dissolution promoter is a component that has the effect of increasing the solubility of the solid component in the developer when the solubility is too low, and appropriately increasing the dissolution rate of the compound during development. The dissolution promoter is preferably a low molecular weight one, and examples thereof include low molecular weight phenolic compounds. Examples of low molecular weight phenolic compounds include bisphenols, tris(hydroxyphenyl)methane, etc. These dissolution promoters can be used alone or in combination of two or more kinds.

[0224] The amount of the dissolution promoter is appropriately adjusted depending on the type of the solid component used, but is preferably 0 to 49 mass% of the total mass of the solid components, more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0225] (Dissolution control agent) The dissolution controller is a component that has the effect of controlling the solubility of a solid component in a developer when the solubility of the solid component is too high in the developer, thereby appropriately reducing the dissolution rate during development. As such a dissolution controller, it is preferable that the dissolution controller does not undergo chemical changes during steps such as baking, irradiation, and development of the resist film.

[0226] The dissolution controller is not particularly limited, but examples thereof include aromatic hydrocarbons such as phenanthrene, anthracene, acenaphthene, etc., ketones such as acetophenone, benzophenone, phenyl naphthyl ketone, etc., sulfones such as methyl phenyl sulfone, diphenyl sulfone, dinaphthyl sulfone, etc. These dissolution controllers may be used alone or in combination.

[0227] The amount of the dissolution controller is appropriately adjusted depending on the type of the compound used, but is preferably 0 to 49 mass% of the total mass of the solid components, more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0228] (sensitizer) The sensitizer is a component that absorbs the energy of the irradiated radiation, transfers the energy to the acid generator (C), and thereby increases the amount of acid generated, thereby improving the apparent sensitivity of the resist. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, fluorenes, etc. These sensitizers can be used alone or in combination.

[0229] The amount of the sensitizer to be added is appropriately adjusted depending on the type of the compound used, but is preferably 0 to 49 mass % of the total mass of the solid components, more preferably 0 to 5 mass %, even more preferably 0 to 1 mass %, and particularly preferably 0 mass %.

[0230] (Surfactant) The surfactant is a component that has the effect of improving the coatability and striation of the composition of this embodiment, the developability of the resist, and the like. The surfactant may be any of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. A preferred surfactant is a nonionic surfactant. The nonionic surfactant has good affinity with the solvent used in the production of the composition of this embodiment, and can further enhance the effect of the composition of this embodiment. Examples of nonionic surfactants include, but are not limited to, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol. Commercially available products of these surfactants include, under the trade names below, F-TOP (manufactured by JEMCO), Megafac (manufactured by Dainippon Ink and Chemicals), Fluorad (manufactured by Sumitomo ThreeM), Asahi Guard, Surflon (all manufactured by Asahi Glass Co., Ltd.), Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and Polyflo (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.).

[0231] The amount of the surfactant to be added is appropriately adjusted depending on the type of the solid components used, but is preferably 0 to 49 mass% of the total mass of the solid components, more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0232] (Organic carboxylic acid or phosphorus oxoacid or its derivative) For the purpose of preventing deterioration in sensitivity or improving resist pattern shape, post-deposition stability, etc., an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof may be further contained as an optional component. The organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof may be used in combination with an acid diffusion control agent or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are suitable. As the oxo acid of phosphorus or a derivative thereof, there may be mentioned derivatives of phosphoric acid or esters thereof such as phosphoric acid, di-n-butyl phosphoric acid ester, diphenyl phosphoric acid ester, etc., phosphonic acid or esters thereof such as phosphonic acid, dimethyl phosphonic acid ester, di-n-butyl phosphonic acid ester, phenylphosphonic acid, diphenyl phosphonic acid ester, dibenzyl phosphonic acid ester, etc., phosphinic acid, phenylphosphinic acid, etc., and esters thereof. Among these, phosphonic acid is particularly preferable.

[0233] The organic carboxylic acid or phosphorus oxo acid or its derivative may be used alone or in combination of two or more. The amount of the organic carboxylic acid or phosphorus oxo acid or its derivative is appropriately adjusted depending on the type of the compound used, but is preferably 0 to 49 mass % of the total mass of the solid components, more preferably 0 to 5 mass %, even more preferably 0 to 1 mass %, and particularly preferably 0 mass %.

[0234] [Other additives] Furthermore, the composition of the present embodiment may contain one or more additives other than the above-mentioned components, if necessary. Examples of such additives include dyes, pigments, and adhesion aids. For example, the incorporation of a dye or pigment is preferable because it can visualize the latent image of the exposed area and reduce the effect of halation during exposure. In addition, the incorporation of an adhesion aid is preferable because it can improve adhesion to the substrate. Furthermore, examples of other additives include antihalation agents, storage stabilizers, defoamers, shape improvers, and the like, specifically 4-hydroxy-4'-methylchalcone.

[0235] In the composition of the present embodiment, the total amount of optional component (F) can be 0 to 99 mass% of the total mass of the solid components, preferably 0 to 49 mass%, more preferably 0 to 10 mass%, even more preferably 0 to 5 mass%, even more preferably 0 to 1 mass%, and particularly preferably 0 mass%.

[0236] [Method of forming resist pattern] The method for forming a resist pattern according to the present embodiment includes the steps of: forming a resist film on a substrate using a film-forming composition containing the compound (A) or the polymer (A); exposing the resist film to a pattern; developing the resist film after the exposure; Includes.

[0237] The coating method in the process of forming the resist film is not particularly limited, but examples thereof include a spin coater, a dip coater, and a roller coater. The substrate is not particularly limited, but examples thereof include a silicon wafer, a metal, a plastic, a glass, and a ceramic. After forming the resist film, a heat treatment may be performed at a temperature of about 50°C to 200°C. The thickness of the resist film is not particularly limited, but is, for example, 50 nm to 1 μm.

[0238] In the exposure step, exposure may be performed through a predetermined mask pattern, or shot exposure may be performed without a mask. The thickness of the coating film is, for example, about 0.1 to 20 μm, preferably about 0.3 to 2 μm. For exposure, light rays of various wavelengths, such as ultraviolet rays and X-rays, can be used. For example, as a light source, far ultraviolet rays such as F2 excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm), extreme ultraviolet rays (wavelength 13n), X-rays, electron beams, etc. are appropriately selected and used. Among these, extreme ultraviolet rays are preferred. In addition, exposure conditions such as the exposure dose are appropriately selected depending on the blending composition of the above-mentioned resin and / or compound, the type of each additive, etc.

[0239] In this embodiment, in order to stably form a highly accurate fine pattern, it is preferable to perform a heat treatment at a temperature of 50 to 200° C. for 30 seconds or more after exposure. In this case, if the temperature is less than 50° C., there is a risk of widening the variation in sensitivity depending on the type of substrate. Thereafter, a predetermined resist pattern is formed by developing with an alkaline developer, usually at 10 to 50° C. for 10 to 200 seconds, preferably at 20 to 25° C. for 15 to 90 seconds.

[0240] As the alkaline developer, for example, an alkaline aqueous solution in which an alkaline compound such as an alkali metal hydroxide, ammonia water, an alkylamine, an alkanolamine, a heterocyclic amine, a tetraalkylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene is dissolved to a concentration of usually 1 to 10% by mass, preferably 1 to 3% by mass, is used. In addition, a water-soluble organic solvent or a surfactant can be appropriately added to the developer made of the alkaline aqueous solution.

[0241] The composition of the present embodiment can also be used as an optical component forming composition to which lithography technology is applied. In addition to being used in the form of a film or sheet, the optical components are useful as plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, films for electromagnetic wave shielding, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). The composition can be suitably used as an embedding film and planarizing film on a photodiode, planarizing films before and after a color filter, microlenses, planarizing films on microlenses, and conformal films, which are components of solid-state imaging elements that require a high refractive index.

[0242] The composition of the present embodiment can also be used as a patterning material for lithography. The lithography process can be used for various applications, such as semiconductors, liquid crystal display panels, display panels using OLEDs, power devices, CCDs and other sensors, etc. In particular, for integrated circuits of semiconductors and devices, in the process of forming device elements on a silicon wafer, a pattern is formed on the insulating film on the substrate side by etching based on a pattern formed on the upper surface side of an insulating layer such as a silicon oxide film or other oxide film using the composition of the present embodiment, and further, a metal film or semiconductor material is laminated based on the formed insulating film pattern to form a circuit pattern, thereby constructing semiconductor elements and other devices, and the composition of the present embodiment can be suitably used.

[0243] Second Embodiment The second embodiment of the present invention will be described below. The second embodiment relates to a method for producing an iodine-containing vinyl monomer, preferably an iodine-containing hydroxystyrene, having the formula (1) described below. The production method of the second embodiment can be used as a method for producing the compound of the first embodiment.

[0244] [Method for producing iodine-containing vinyl monomer represented by formula (1)] A second embodiment is a method for producing an iodine-containing vinyl monomer, preferably an iodine-containing hydroxystyrene, having the following formula (1):

[0245] [ka]

[0246] (In formula (1), R 1 ~R 5 are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 6 ~R 8 are each independently H, OH, OCH3, a halogen, or a cyano group, provided that R 1 ~R 5At least one of the is OH and at least one is iodine.

[0247] Examples of hydroxystyrenes produced by the method of the present embodiment include, but are not limited to, iodine-containing 2-hydroxystyrene, iodine-containing 3-hydroxystyrene, iodine-containing 4-hydroxystyrene, iodine-containing 3-methoxy-4-hydroxystyrene, iodine-containing 3,5-dimethoxy-4-hydroxystyrene, iodine-containing 2,3-dihydroxystyrene, iodine-containing 2,4-dihydroxystyrene, iodine-containing 2,5-dihydroxystyrene, iodine-containing 2,6-dihydroxystyrene, iodine-containing 3,4-dihydroxystyrene, iodine-containing 3,5-dihydroxystyrene, iodine-containing 2,3,4-trihydroxystyrene, iodine-containing 2,4,6-trihydroxystyrene, iodine-containing 3,4,5-trihydroxystyrene, and iodine-containing α-cyano-4-hydroxystyrene. At least one iodine is introduced, and it is preferable that two or more iodines are introduced. At least one OH group is introduced, and preferably two or more OH groups are introduced.

[0248] Specific examples of hydroxystyrene produced by the method of the present embodiment are shown below, but are not limited thereto.

[0249] [ka]

[0250] (Iodine-containing alcoholic substrate) The iodine-containing alcoholic substrate used in the present invention is represented by the formula (1-1):

[0251] [ka]

[0252] (In formula (1-1), R 1 ~R 5are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 6 ~R 10 are each independently H, OH, OCH3, a halogen, or a cyano group, provided that R 1 ~R 5 At least one of R is OH and at least one of R is iodine. 6 ~R 10 is an iodine-containing alcoholic substrate having an iodine atom, one of which is OH or OCH3.

[0253] Examples of suitable iodine-containing alcoholic substrates include, but are not limited to, 2-(1-hydroxyethyl)phenol containing iodine, 3-(1-hydroxyethyl)phenol containing iodine, 4-(1-hydroxyethyl)phenol containing iodine, 4-(1-hydroxyethyl)-1-methoxyphenol containing iodine, 4-(1-hydroxyethyl)-2,6-dimethoxyphenol containing iodine, 3-(1-hydroxyethyl)benzene-1,2-diol containing iodine, 4-(1-hydroxyethyl)benzene-1,3-diol containing iodine, 2-(1-hydroxyethyl)benzene-1,4-diol containing iodine, 6-(1-hydroxyethyl)benzene-1,5-diol containing iodine, 4-(1-hydroxyethyl)benzene-1,2-diol containing iodine, 5-(1-hydroxyethyl)benzene-1,3-diol containing iodine, 4-(1-hydroxyethyl)benzene-1,2,3-triol containing iodine, 2-(1-hydroxyethyl)benzene-1,3,5-triol containing iodine, 5-(1-hydroxyethyl)benzene-1,2,3-triol containing iodine, 2-(1-cyano-1-hydroxyethyl)phenol with iodine, 2-(2-hydroxyphenyl)ethanol with iodine, 2-(3-hydroxyphenyl)ethanol with iodine, 2-(4-hydroxyphenyl)ethanol with iodine, 2-(3-methoxy-4-hydroxyphenyl)ethanol with iodine, 2-(3,5-dimethoxy-4-hydroxyphenyl)ethanol with iodine, 2-(2,3-dihydroxyphenyl)ethanol with iodine, 2-(2,4-dihydroxyphenyl)ethanol with iodine, 2-( 2-(2,5-dihydroxyphenyl)ethanol containing iodine, 2-(2,6-dihydroxyphenyl)ethanol containing iodine, 2-(3,4-dihydroxyphenyl)ethanol containing iodine, 2-(3,5-dihydroxyphenyl)ethanol containing iodine, 2-(2,3,4-trihydroxyphenyl)ethanol containing iodine, 2-(2,4,6-trihydroxyphenyl)ethanol containing iodine, 2-(3,4,5-trihydroxyphenyl)ethanol containing iodine, and 1-cyano-2-(4-hydroxyphenyl)ethanol containing iodine.At least one iodine is introduced, and preferably two or more iodines are introduced. At least one OH is introduced, and preferably two or more OHs are introduced. OH may be substituted with OMe.

[0254] Specific examples of iodine-containing alcoholic substrates that can be used in the present invention include, but are not limited to, those shown below.

[0255] [ka] [ka] [ka] [ka]

[0256] These iodine-containing alcoholic substrates can be obtained by many methods, but it is preferable to obtain them by the method described below from the viewpoints of availability of raw materials and yield.

[0257] The method for producing the iodine-containing vinyl monomer represented by formula (1) is as follows: a) providing an iodine-containing alcoholic substrate having the formula (1-1); and b) dehydrating the iodine-containing alcoholic substrate; The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0258] A wide variety of solvents can be used in the dehydration step, including polar aprotic solvents and protic polar solvents. A single protic polar solvent or a single polar aprotic solvent can be used. In addition, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. The solvent is an effective but not essential component. Suitable polar aprotic solvents include, but are not limited to, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, triglyme, ester solvents such as ethyl acetate, γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphite triamide, dimethylsulfoxide, etc. Dimethylsulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, water, alcohol solvents such as methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of the solvent used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0259] As the catalyst that can be used in the dehydration step, a wide variety of catalysts that function under the reaction conditions of this embodiment are used. An acid catalyst is preferred. Examples of suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid, organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride, and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid. These acid catalysts are used alone or in combination of two or more. Among these, from the viewpoint of production, organic acids and solid acids are preferred, and from the viewpoint of production, such as ease of availability and ease of handling, it is preferred to use hydrochloric acid or sulfuric acid. The amount of the catalyst used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0260] As the polymerization inhibitor that can be used in the dehydration step, a wide variety of polymerization inhibitors that function under the reaction conditions of this embodiment are used. The polymerization inhibitor is effective but not essential. Examples of suitable polymerization inhibitors include, but are not limited to, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors, such as Prostab® 5415 (bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, CAS#2516-92-9, available from Ciba Specialty Chemicals, Tarrytown, NY), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, available from TCI, and ... 1-yloxy, CAS#2226-96-2) and Uvinul® 4040P (1,6-hexamethylene-bis(N-formyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amine), commercially available from BASF Corp., Worcester, Mass. The amount of the polymerization inhibitor used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0261] As the polymerization inhibitor that can be used in the dehydration step, a wide variety of polymerization inhibitors that function under the reaction conditions of this embodiment are used. The polymerization inhibitor is effective but not essential. It is also effective to use a polymerization retarder in combination with a polymerization inhibitor. Polymerization retarders are well known in the art and are compounds that slow down the polymerization reaction but cannot prevent all polymerization. Common retarders are aromatic nitro compounds such as dinitro-ortho-cresol (DNOC) and dinitrobutylphenol (DNBP). Methods for making polymerization retarders are common and well known in the art (see, for example, U.S. Pat. No. 6,339,177; Park et al., Polymer (Korea) (1988), 12(8), 710-19), and their use in controlling styrene polymerization is well documented (see, for example, Bushby et al., Polymer (1998), 39(22), 5567-5571). The amount of the polymerization inhibitor used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0262] (Reaction conditions) The iodine-containing alcoholic substrate having the formula (1-1), the catalyst and the solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by appropriately selecting a known method such as a batch method, a semi-batch method, or a continuous method.

[0263] The reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the choice of the catalyst, and the desired yield. In general, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 10°C to 190°C is preferred, a temperature of 25°C to 150°C is more preferred, and a temperature of 50°C to 100°C is even more preferred. For reactions using 1-(4-hydroxy-3,5-diiodophenyl)ethanol as substrate, the preferred temperature range is from 0°C to 100°C.

[0264] The reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the choice of catalyst and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, and using an air suction pump, etc. For reactions at high pressure, conventional pressure reactors are used, including, but not limited to, shaker vessels, rocker vessels and stirred autoclaves. For reactions using 1-(4-hydroxy-3,5-diiodophenyl)ethanol as a substrate, the preferred reaction pressure is reduced pressure to normal pressure, with reduced pressure being preferred.

[0265] From the viewpoint of reaction rate, it is preferable to carry out the reaction while removing low boiling point products such as water and methanol produced from the reaction system. The low boiling point products can be removed by using a conventionally known appropriate method. For example, they can be removed by evaporation, and it is preferable to remove them by evaporation under reduced pressure.

[0266] The reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 minutes to 600 minutes are common. For reactions using 1-(4-hydroxy-3,5-diiodophenyl)ethanol as the substrate, the preferred reaction time range is from 15 minutes to 600 minutes.

[0267] Isolation and purification can be carried out using a suitable method known in the art after the completion of the reaction. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified by separation and purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are well known in the art, or a combination thereof.

[0268] [Method for producing an iodine-containing alcoholic substrate represented by formula (1-1) (I)] The iodine-containing ketonic substrate used in the preparation of formula (1-1) is represented by the formula (1-2):

[0269] [ka]

[0270] (In formula (1-2), R 1 ~R 5 are each independently H, OH, OCH3, halogen, or linear or branched alkyl; R 7 , R 8 and R 10 are each independently H, OH, OCH3, a halogen, or a cyano group, provided that R 1 ~R 5 wherein at least one is OH and at least one is iodine.

[0271] Examples of suitable iodine-containing ketonic substrates include, but are not limited to, iodine-containing 2-hydroxyphenyl methyl ketone, iodine-containing 3-hydroxyphenyl methyl ketone, iodine-containing 4-hydroxyphenyl methyl ketone, iodine-containing 3-methoxy-4-hydroxyphenyl methyl ketone, iodine-containing 3,5-dimethoxy-4-hydroxyphenyl methyl ketone, iodine-containing 2,3-dihydroxyphenyl methyl ketone, iodine-containing 2,4-dihydroxyphenyl methyl ketone, iodine-containing 2,4-dihydroxyphenyl methyl ketone, iodine-containing 2,5-dihydroxyphenyl methyl ketone, iodine-containing 2,6-dihydroxyphenyl methyl ketone, iodine-containing 2,7-dihydroxyphenyl methyl ketone, iodine-containing 2,8-dihydroxyphenyl methyl ketone, iodine-containing 2,9-dihydroxyphenyl methyl ketone, iodine-containing 2,10-dihydroxyphenyl methyl ketone, iodine-containing 2,11-dihydroxyphenyl methyl ketone, iodine-containing 2,12-dihydroxyphenyl methyl ketone, iodine-containing 2,2-dihydroxyphenyl methyl ketone, iodine-containing 2,3-dihydroxyphenyl methyl ketone, iodine-containing 2,4-dihydroxyphenyl methyl ketone, iodine-containing 2,5-dihydroxyphenyl methyl ketone, iodine-containing 2,6-dihydroxyphenyl methyl ketone, iodine-containing 2,7-dihydroxyphenyl methyl ketone, iodine-containing 2,8-dihydroxyphenyl methyl ketone, iodine-containing 2,9-dihydroxyphenyl methyl ketone, iodine-containing 2, Examples of the iodine-containing 2,5-dihydroxyphenyl methyl ketone include iodine-containing 2,6-dihydroxyphenyl methyl ketone, iodine-containing 3,4-dihydroxyphenyl methyl ketone, iodine-containing 3,5-dihydroxyphenyl methyl ketone, iodine-containing 2,3,4-trihydroxyphenyl methyl ketone, iodine-containing 2,4,6-trihydroxyphenyl methyl ketone, iodine-containing 3,4,5-trihydroxyphenyl methyl ketone, and iodine-containing 4-hydroxyphenyl α-cyanomethyl ketone. At least one iodine atom is introduced, and preferably two or more iodines are introduced. At least one OH atom is introduced, and preferably two or more OH atoms are introduced.

[0272] Specific examples of iodine-containing ketonic substrates that can be used in the present invention include, but are not limited to, the following:

[0273] [ka]

[0274] These iodine-containing ketone substrates can be obtained by many methods, but it is preferable to obtain them by the method described below from the viewpoints of availability of raw materials and yield.

[0275] The method for producing the iodine-containing alcoholic substrate represented by formula (1-1) includes the steps of: c) providing an iodine-containing ketonic substrate having the formula (1-2); and d) reducing the iodine-containing ketonic substrate; The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0276] A wide variety of solvents, including polar aprotic solvents and protic polar solvents, are used as solvents that can be used in the reduction step. A single protic polar solvent or a single polar aprotic solvent can be used. In addition, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred, and a mixture of polar aprotic solvents and polar protic solvents being preferred from the viewpoint of suppressing side reactions, and as polar protic solvents, water, and alcohol-based solvents such as methanol, ethanol, propanol, and butanol are more preferred. The solvent is effective but not essential. Suitable polar aprotic solvents include, but are not limited to, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, triglyme, ester solvents such as ethyl acetate, γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphite triamide, dimethylsulfoxide, etc. Dimethylsulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, water, alcohol solvents such as methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of the solvent used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0277] A wide variety of reducing agents that function under the reaction conditions of the present embodiment can be used as reducing agents in the reduction step. Suitable reducing agents include, but are not limited to, metal hydrides, metal hydrogen complex compounds, and the like, such as borane dimethylsulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-s-butylborohydride, potassium tri-s-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-t-butoxyaluminum hydride, sodium bis(methoxyethoxy)aluminum hydride, and the like. The amount of the reducing agent used can be appropriately set depending on the substrate, reducing agent, reaction conditions, etc. used, and is not particularly limited. Generally, however, 1 to 500 parts by mass is suitable for 100 parts by mass of the reaction raw materials, and from the viewpoint of yield, 10 to 200 parts by mass is preferable.

[0278] As the quenching agent, a wide variety of quenching agents that function under the reaction conditions of this embodiment can be used. The quenching agent has the function of deactivating the reducing agent. The quenching agent is effective but not essential. Suitable quenching agents include, but are not limited to, ethanol, aqueous ammonium chloride, water, hydrochloric acid, sulfuric acid, and the like. The amount of the quenching agent used can be appropriately set depending on the amount of the reducing agent used and is not particularly limited. Generally, however, 1 to 500 parts by mass is suitable for 100 parts by mass of the reducing agent, and from the viewpoint of yield, 50 to 200 parts by mass is preferable.

[0279] (Reaction conditions) The iodine-containing ketonic substrate having the formula (1-2), the reducing agent, and the solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by appropriately selecting a known method such as a batch method, a semi-batch method, or a continuous method.

[0280] The reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the selection of the reducing agent and the desired yield. In general, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred, a temperature of 0°C to 70°C is more preferred, and a temperature of 0°C to 50°C is even more preferred. For reactions using 4'-hydroxy-3',5'-diiodoacetophenone as substrate, the preferred temperature range is 0°C to 100°C.

[0281] The reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the selection of the reducing agent, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, and using an air intake pump, etc. For reactions at high pressure, conventional pressure reactors are used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4'-hydroxy-3',5'-diiodoacetophenone as a substrate, the reaction pressure is preferably reduced pressure to normal pressure, with reduced pressure being preferred.

[0282] The reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the selection of the reducing agent and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 minutes to 600 minutes are common. For reactions using 4'-hydroxy-3',5'-diiodoacetophenone as the substrate, the preferred reaction time range is from 15 minutes to 600 minutes.

[0283] Isolation and purification can be carried out using a suitable method known in the art after the reaction is completed. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity compound can be isolated and purified by separation and purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are well known in the art, or a combination thereof.

[0284] [Method for producing an iodine-containing alcoholic substrate represented by formula (1-1) (II)] The alcoholic substrate used in the production of formula (1-1) is represented by the formula (1-3):

[0285] [ka]

[0286] (In formula (1-3), R 11 ~R 15 are each independently H, OH, OCH3, or linear or branched alkyl; R 6 ~R 10 are each independently H, OH, OCH3, a halogen, or a cyano group, provided that R 11 ~R 15 At least one of R is OH. 6 ~R 10 is an alcoholic substrate, with one of the groups being OH or OCH3.

[0287] Examples of suitable alcoholic substrates include, but are not limited to, 2-(1-hydroxyethyl)phenol, 3-(1-hydroxyethyl)phenol, 4-(1-hydroxyethyl)phenol, 4-(1-hydroxyethyl)-1-methoxyphenol, 4-(1-hydroxyethyl)-2,6-dimethoxyphenol, 3-(1-hydroxyethyl)benzene-1,2-diol, 4-(1-hydroxyethyl)benzene-1,3-diol, 2-(1-hydroxyethyl)benzene-1,4-diol, 6-(1-hydroxyethyl)benzene-1,5-diol, 4-(1-hydroxyethyl)benzene-1,2-diol, 5-(1-hydroxyethyl)benzene-1,3-diol, 4-(1-hydroxyethyl)benzene-1,2,3-triol, 2-(1-hydroxyethyl)benzene-1,3,5-triol, 5 ... Examples of the hydroxyphenyl group include -(1-cyano-1-hydroxyethyl)phenol, 2-(2-hydroxyphenyl)ethanol, 2-(3-hydroxyphenyl)ethanol, 2-(4-hydroxyphenyl)ethanol, 2-(3-methoxy-4-hydroxyphenyl)ethanol, 2-(3,5-dimethoxy-4-hydroxyphenyl)ethanol, 2-(2,3-dihydroxyphenyl)ethanol, 2-(2,4-dihydroxyphenyl)ethanol, 2-(2,5-dihydroxyphenyl)ethanol, 2-(2,6-dihydroxyphenyl)ethanol, 2-(3,4-dihydroxyphenyl)ethanol, 2-(3,5-dihydroxyphenyl)ethanol, 2-(2,3,4-trihydroxyphenyl)ethanol, 2-(2,4,6-trihydroxyphenyl)ethanol, 2-(3,4,5-trihydroxyphenyl)ethanol, and 1-cyano-2-(4-hydroxyphenyl)ethanol. At least one OH is introduced, and preferably two or more are introduced. OH may be substituted with OMe.

[0288] Specific examples of alcoholic substrates that can be used in this embodiment include, but are not limited to, those shown below.

[0289] [ka] [ka]

[0290] These alcoholic substrates can be obtained by many methods, but it is preferable to obtain them by the methods described below from the viewpoints of availability of raw materials and yield.

[0291] The method for producing the iodine-containing alcoholic substrate represented by formula (1-1) includes the steps of: e) providing an alcoholic substrate having the formula (1-3); f) introducing iodine into the alcoholic substrate; The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0292] As the solvent that can be used in the iodine introduction step, a wide variety of solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. In addition, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar protic solvents or mixtures thereof being preferred, and a mixture of polar protic solvents and water being preferred from the viewpoint of suppressing side reactions. The solvent is an effective but not essential component. Suitable polar aprotic solvents include, but are not limited to, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, triglyme, ester solvents such as ethyl acetate, γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphite triamide, dimethylsulfoxide, etc. Dimethylsulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, water, alcohol solvents such as methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of the solvent used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0293] (Reaction conditions) The alcoholic substrate having the formula (1-3), the catalyst and the solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by appropriately selecting a known method such as a batch method, a semi-batch method, or a continuous method.

[0294] The reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the choice of the catalyst and the desired yield. In general, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred, a temperature of 0°C to 70°C is more preferred, and a temperature of 0°C to 50°C is even more preferred. For reactions using 1-(4-hydroxyphenyl)ethanol as substrate, the preferred temperature range is from 0°C to 100°C.

[0295] The reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, and using an air intake pump, etc. For reactions at high pressure, conventional pressure reactors are used, including, but not limited to, shaker vessels, rocker vessels and stirred autoclaves. In the reaction using 1-(4-hydroxyphenyl)ethanol as a substrate, the reaction pressure is preferably reduced pressure to normal pressure, with reduced pressure being preferred.

[0296] The reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the choice of catalyst and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 minutes to 600 minutes are common. For reactions using 1-(4-hydroxyphenyl)ethanol as the substrate, the preferred reaction time range is from 15 minutes to 600 minutes.

[0297] Isolation and purification can be carried out using a suitable method known in the art after the reaction is completed. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity compound can be isolated and purified by separation and purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are well known in the art, or a combination thereof.

[0298] [Method for producing an iodine-containing ketonic substrate represented by formula (1-2)] The ketone substrate used in the preparation of formula (1-2) is represented by the formula (1-4):

[0299] [ka]

[0300] (In formula (1-4), R 11 ~R 15 are each independently H, OH, OCH3, or linear or branched alkyl; R 7 ~R 8 and R 10 are each independently H, OH, OCH3, a halogen, or a cyano group, provided that R 11 ~R 15 where at least one of the groups is OH.

[0301] Examples of suitable ketonic substrates include, but are not limited to, 2-hydroxyphenyl methyl ketone, 3-hydroxyphenyl methyl ketone, 4-hydroxyphenyl methyl ketone, 3-methoxy-4-hydroxyphenyl methyl ketone, 3,5-dimethoxy-4-hydroxyphenyl methyl ketone, 2,3-dihydroxyphenyl methyl ketone, 2,4-dihydroxyphenyl methyl ketone, 2,5-dihydroxyphenyl methyl ketone, 2,6-dihydroxyphenyl methyl ketone, 3,4-dihydroxyphenyl methyl ketone, 3,5-dihydroxyphenyl methyl ketone, 2,3,4-trihydroxyphenyl methyl ketone, 2,4,6-trihydroxyphenyl methyl ketone, 3,4,5-trihydroxyphenyl methyl ketone, 4-hydroxyphenyl α-cyanomethyl ketone.

[0302] Specific examples of ketone substrates for use in this embodiment are shown below, but are not limited thereto.

[0303] [ka]

[0304] These ketonic substrates can be obtained in a number of ways.

[0305] The method for producing the iodine-containing ketonic substrate represented by formula (1-2) includes the steps of: g) providing a ketonic substrate having the formula (1-4); and h) introducing iodine into the ketonic substrate The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0306] As the solvent that can be used in the iodine introduction step, a wide variety of solvents including polar aprotic solvents and protic polar solvents are used. A single protic polar solvent or a single polar aprotic solvent can be used. In addition, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar protic solvents or mixtures thereof being preferred, and a mixture of polar protic solvents and water being preferred from the viewpoint of suppressing side reactions. The solvent is an effective but not essential component. Suitable polar aprotic solvents include, but are not limited to, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, triglyme, ester solvents such as ethyl acetate, γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphite triamide, dimethylsulfoxide, etc. Dimethylsulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, water, alcohol solvents such as methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of the solvent used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0307] (Reaction conditions) The ketonic substrate having formula (1-4), the catalyst and the solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by appropriately selecting a known method such as a batch method, a semi-batch method, or a continuous method.

[0308] The reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the choice of the catalyst and the desired yield. In general, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred, a temperature of 0°C to 70°C is more preferred, and a temperature of 0°C to 50°C is even more preferred. For reactions using 4'-hydroxyacetophenone as substrate, the preferred temperature range is from 0°C to 100°C.

[0309] The reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, and using an air intake pump, etc. For reactions at high pressure, conventional pressure reactors are used, including, but not limited to, shaker vessels, rocker vessels and stirred autoclaves. In the reaction using 4'-hydroxyacetophenone as the substrate, the reaction pressure is preferably reduced pressure to normal pressure, with reduced pressure being preferred.

[0310] The reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 minutes to 600 minutes are common. For reactions using 4'-hydroxyacetophenone as the substrate, the preferred reaction time range is from 15 minutes to 600 minutes.

[0311] Isolation and purification can be carried out using a suitable method known in the art after the reaction is completed. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity compound can be isolated and purified by separation and purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are well known in the art, or a combination thereof.

[0312] [Method for producing an alcoholic substrate represented by formula (1-3)] The ketone substrate used in the production of the compound of formula (1-3) is a ketone substrate having the above-mentioned formula (1-4).

[0313] The method for producing an alcoholic substrate represented by formula (1-3) includes the following steps: i) providing a ketonic substrate having the formula (1-4); and j) reducing the ketonic substrate; The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0314] A wide variety of solvents, including polar aprotic solvents and protic polar solvents, are used as solvents that can be used in the reduction step. A single protic polar solvent or a single polar aprotic solvent can be used. In addition, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred, and a mixture of polar aprotic solvents and polar protic solvents being preferred from the viewpoint of suppressing side reactions, and as polar protic solvents, water, and alcohol-based solvents such as methanol, ethanol, propanol, and butanol are more preferred. The solvent is effective but not essential. Suitable polar aprotic solvents include, but are not limited to, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, triglyme, ester solvents such as ethyl acetate, γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphite triamide, dimethylsulfoxide, etc. Dimethylsulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, water, alcohol solvents such as methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of the solvent used can be appropriately set depending on the substrate, reducing agent, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0315] A wide variety of reducing agents that function under the reaction conditions of this embodiment can be used as the reducing agent. Suitable reducing agents include, but are not limited to, metal hydrides, metal hydrogen complex compounds, and the like, such as borane dimethylsulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-s-butylborohydride, potassium tri-s-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-t-butoxyaluminum hydride, sodium bis(methoxyethoxy)aluminum hydride, and the like. The amount of the reducing agent used can be appropriately set depending on the substrate, reducing agent, reaction conditions, etc. used, and is not particularly limited. Generally, however, 1 to 500 parts by mass is suitable for 100 parts by mass of the reaction raw materials, and from the viewpoint of yield, 10 to 200 parts by mass is preferable.

[0316] As the quenching agent, a wide variety of quenching agents that function under the reaction conditions of this embodiment can be used. The quenching agent has the function of deactivating the reducing agent. The quenching agent is effective but not essential. Suitable quenching agents include, but are not limited to, ethanol, aqueous ammonium chloride, water, hydrochloric acid, sulfuric acid, and the like. The amount of the quenching agent used can be appropriately set depending on the amount of the reducing agent used and is not particularly limited. Generally, however, 1 to 500 parts by mass is suitable for 100 parts by mass of the reducing agent, and from the viewpoint of yield, 50 to 200 parts by mass is preferable.

[0317] (Reaction conditions) A ketonic substrate having formula (1-4), a reducing agent, and a solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by appropriately selecting a known method such as a batch method, a semi-batch method, or a continuous method.

[0318] The reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the selection of the reducing agent and the desired yield. In general, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 0°C to 100°C is preferred, a temperature of 0°C to 70°C is more preferred, and a temperature of 0°C to 50°C is even more preferred. For reactions using 4'-hydroxyacetophenone as substrate, the preferred temperature range is from 0°C to 100°C.

[0319] The reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the selection of the reducing agent, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, and using an air intake pump, etc. For reactions at high pressure, conventional pressure reactors are used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction using 4'-hydroxyacetophenone as the substrate, the reaction pressure is preferably reduced pressure to normal pressure, with reduced pressure being preferred.

[0320] The reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the selection of the reducing agent and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 minutes to 600 minutes are common. For reactions using 4'-hydroxyacetophenone as the substrate, the preferred reaction time range is from 15 minutes to 600 minutes.

[0321] Isolation and purification can be carried out using a suitable method known in the art after the reaction is completed. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity compound can be isolated and purified by separation and purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are well known in the art, or a combination thereof.

[0322] [Method for producing iodine-containing acetylated vinyl monomer represented by formula (2)] In this embodiment, the formula (2)

[0323] [ka] (In formula (2), R 16 ~R 20 are each independently H, OH, OCH3, OAc, halogen, or linear or branched alkyl; R 6 ~R 8 are each independently H, OH, OCH3, a halogen, or a cyano group, provided that R 16 ~R 20 wherein at least one of the groups is OAc and at least one of the groups is iodine.

[0324] Examples of iodine-containing acetylated vinyl monomers produced by the method of the present embodiment include, but are not limited to, 2-acetoxystyrene containing iodine, 3-acetoxystyrene containing iodine, 4-acetoxystyrene containing iodine, 3-methoxy-4-acetoxystyrene containing iodine, 3,5-dimethoxy-4-acetoxystyrene containing iodine, 2,3-acetoxystyrene containing iodine, 2,4-acetoxystyrene containing iodine, 2,5-acetoxystyrene containing iodine, 2,6-acetoxystyrene containing iodine, 3,4-acetoxystyrene containing iodine, 3,5-acetoxystyrene containing iodine, 2,3,4-triacetoxystyrene containing iodine, 2,4,6-triacetoxystyrene containing iodine, 3,4,5-triacetoxystyrene containing iodine, and α-cyano-4-acetoxystyrene containing iodine. At least one iodine atom, and preferably two or more iodines, are introduced, and at least one OAc atom, and preferably two or more OAc atoms are introduced.

[0325] Specific examples of the iodine-containing acetylated vinyl monomer produced by the method of the present embodiment are shown below, but are not limited thereto.

[0326] [ka] (In the formula, Ac represents an acetyl group.)

[0327] The method for producing an iodine-containing acetylated vinyl monomer (iodine-containing acetoxystyrene) represented by formula (2) is as follows: k) providing an iodine-containing vinyl monomer (iodine-containing hydroxystyrene) having the formula (1); and l) acetylating the iodine-containing hydroxystyrene; The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0328] A wide variety of solvents can be used in the acetylation step, including polar aprotic solvents and protic polar solvents. A single protic polar solvent or a single polar aprotic solvent can be used. In addition, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. The solvent is an effective but not essential component. Suitable polar aprotic solvents include, but are not limited to, ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, triglyme, ester solvents such as ethyl acetate, γ-butyrolactone, nitrile solvents such as acetonitrile, hydrocarbon solvents such as toluene, hexane, amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphite triamide, dimethylsulfoxide, etc. Dimethylsulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, water, alcohol solvents such as methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of the solvent used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.

[0329] As the acetylating agent, a wide variety of acetylating agents that function under the reaction conditions of this embodiment can be used. Examples of suitable acetylating agents include, but are not limited to, for example, acetic anhydride, acetyl halides, and acetic acid, with acetic anhydride being preferred.

[0330] As a catalyst that can be used in the acetylation step, a wide variety of acetylation catalysts that function under the reaction conditions of this embodiment can be used. Acid catalysts or base catalysts are preferred. Examples of suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid, organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride, and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid. These acid catalysts may be used alone or in combination of two or more. Among these, from the viewpoint of production, organic acids and solid acids are preferred, and from the viewpoint of production, such as ease of availability and ease of handling, it is preferred to use hydrochloric acid or sulfuric acid. Examples of suitable base catalysts include, but are not limited to, amine-containing catalysts such as pyridine and ethylenediamine, non-amine base catalysts such as metal salts and particularly potassium or acetate salts, suitable catalysts include, but are not limited to, potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide and magnesium oxide. All of the non-amine base catalysts of this embodiment are commercially available, for example, from EM Science (Gibbstown) or Aldrich (Milwaukee). The amount of the catalyst used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 1 to 5,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 50 to 3,000 parts by mass is preferable.

[0331] As the polymerization inhibitor that can be used in the acetylation step, a wide variety of polymerization inhibitors that function under the reaction conditions of this embodiment are used. The polymerization inhibitor is effective but not essential. Examples of suitable polymerization inhibitors include, but are not limited to, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, phenothiazine, N-oxyl (nitroxide) inhibitors, such as Prostab® 5415 (bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, CAS#2516-92-9, available from Ciba Specialty Chemicals, Tarrytown, NY), 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, available from TCI, and ... 1-yloxy, CAS#2226-96-2) and Uvinul® 4040P (1,6-hexamethylene-bis(N-formyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)amine), commercially available from BASF Corp., Worcester, Mass. The amount of the polymerization inhibitor used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0332] As the polymerization inhibitor that can be used in the acetylation process, a wide variety of polymerization inhibitors that function under the reaction conditions of the present embodiment are used. The polymerization inhibitor is effective but not essential. It is also effective to use a polymerization retarder in combination with the polymerization inhibitor. Polymerization retarders are well known in the art and are compounds that slow down the polymerization reaction but cannot prevent all polymerization. Common retarders are aromatic nitro compounds such as dinitro-ortho-cresol (DNOC) and dinitrobutylphenol (DNBP). Methods for making polymerization retarders are common and well known in the art (see, for example, U.S. Pat. No. 6,339,177; Park et al., Polymer (Korea) (1988), 12(8), 710-19), and their use in controlling styrene polymerization is well documented (see, for example, Bushby et al., Polymer (1998), 39(22), 5567-5571). The amount of the polymerization inhibitor used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited. Generally, however, an amount of 0.0001 to 100 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 0.001 to 10 parts by mass is preferable.

[0333] (Reaction conditions) The iodine-containing hydroxystyrene having formula (1), the catalyst, and the solvent are added to a reactor to form a reaction mixture. Any suitable reactor may be used. The reaction can be carried out by appropriately selecting a known method such as a batch method, a semi-batch method, or a continuous method.

[0334] The reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the choice of the catalyst and the desired yield. In general, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 10°C to 190°C is preferred, a temperature of 25°C to 150°C is more preferred, and a temperature of 50°C to 100°C is even more preferred. For reactions using 4-hydroxy-3,5-diiodostyrene as substrate, the preferred temperature range is from 0°C to 100°C.

[0335] The reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, and using an air intake pump, etc. For reactions at high pressure, conventional pressure reactors are used, including, but not limited to, shaker vessels, rocker vessels and stirred autoclaves. In the reaction using 4-hydroxy-3,5-diiodostyrene as a substrate, the reaction pressure is preferably reduced pressure to normal pressure, with reduced pressure being preferred.

[0336] The reaction time is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. However, most reactions are carried out in less than 6 hours, and reaction times of 15 minutes to 600 minutes are common. For reactions using 4-hydroxy-3,5-diiodostyrene as the substrate, the preferred reaction time range is from 15 minutes to 600 minutes.

[0337] Isolation and purification can be carried out using a suitable method known in the art after the completion of the reaction. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified by separation and purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are well known in the art, or a combination thereof.

[0338] According to the production method of the present embodiment, iodine-containing hydroxystyrene and its acetylated derivatives can be produced in high yield using inexpensive raw materials under mild conditions. The resulting iodine-containing hydroxystyrenes and their acetylated derivatives are suitable for use as raw material monomers for resist compositions for extreme ultraviolet lithography, and are useful in a wide variety of industrial applications, including various semiconductor and electronic materials. EXAMPLES

[0339] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0340] [Measurement method] [Nuclear magnetic resonance (NMR)] The structure of the compound was confirmed by NMR measurement using a nuclear magnetic resonance apparatus "Advance 600II spectrometer" (product name, manufactured by Bruker) under the following conditions. [ 1 H-NMR measurement] Frequency: 400MHz Solvent: CDCl3 or d6-DMSO Internal standard: TMS Measurement temperature: 23℃ [ 13 C-NMR measurement] Frequency: 500MHz Solvent: CDCl3 or d6-DMSO Internal standard: TMS Measurement temperature: 23℃

[0341] [Inorganic element content] The metal contents contained in the compounds prepared in the examples and comparative examples were measured using an inorganic elemental analysis (ICP-AES / ICP-MS) device "AG8900" (product name, manufactured by Agilent Technologies, Inc.).

[0342] [Organic impurity content] The organic impurity contents contained in the compounds prepared in the Examples and Comparative Examples were calculated from the area fractions in the GC charts and the peak intensity ratios between the target peak and the reference peak by gas chromatography mass spectrometry (GC-MS).

[0343] Example A1: Synthesis of Compound A1 represented by Formula (M1) A 200mL glass flask was used as a reaction vessel, and 4.96g (40mmol) of 4-hydroxybenzyl alcohol was dissolved in butanol as a solvent. Then, 20% by mass aqueous iodine chloride solution (81.2g, 100mmol) was added dropwise at 50°C over 60 minutes, and the mixture was stirred at 50°C for 2 hours to react 4-hydroxybenzyl alcohol with iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution and the mixture was stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate that separated out by cooling was filtered, washed, and dried to obtain 12.1g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and 4-hydroxy-3,5-diiodobenzyl alcohol was confirmed.

[0344] MnO2 (3.4 g, 40 mmol) was added to the methylene chloride solvent and stirred, and then a 50% by mass solution of the synthesized 4-hydroxy-3,5-diiodobenzyl alcohol dissolved in methylene chloride was added dropwise while stirring for 1 hour, and then the mixture was stirred at room temperature for 4 hours. After that, the reaction solution was filtered and the solvent was distilled off to obtain 4-hydroxy-3,5-diiodobenzaldehyde.

[0345] A solution was prepared by dissolving dimethyl malonate (5.3 g, 40 mmol) and the total amount of 4-hydroxy-3,5-diiodobenzaldehyde synthesized above in DMF solvent, and then a solution of ethylenediamine (0.3 g) dissolved in DMF was added dropwise while stirring for 1 hour, and then the liquid temperature was controlled to 150 ° C. with an oil bath while stirring for 6 hours to react. After that, ethyl acetate and water were added, and then a 2 mol / L HCl aqueous solution was added to control the pH to 4 or less, and the organic phase was separated by a separation operation. The obtained organic phase was further washed with a 2 mol / L sodium carbonate aqueous solution, water, and saline in that order by a separation operation, and then filtered and purified, and the solvent was distilled off from the organic phase to obtain 8.1 g of compound A1 (4-hydroxy-3,5-diiodostyrene (compound represented by the following formula (M1))). The inorganic element content and organic impurity content were measured by the above-mentioned method, and the results are shown in Table 1.

[0346] [ka]

[0347] Example A2: Synthesis of Compound A2 represented by Formula (M2) In a 2L flask, 400mL of dichloromethane, 41g of the obtained compound A1, 16.2g of triethylamine, and 0.7g of N-(4-pyridyl)dimethylamine (DMAP) were dissolved in nitrogen flow. 33.6g of di-tert-butyl dicarbonate was dissolved in 100mL of dichloromethane, and then added dropwise to the 2L flask while stirring, and then stirred at room temperature for 3 hours. Then, washing with water was performed three times by a separation operation using 100mL of water, and the solvent was distilled off from the obtained organic phase, and the origin component was removed with dichloromethane / hexane by silica gel chromatography, and the solvent was further distilled off to obtain 4.5g of the BOC group-substituted compound of compound A1 (a compound represented by the following formula (M2), hereinafter also referred to as "compound A2"), which is the target component. The inorganic element content and organic impurity content were measured by the above-mentioned method, and the results are shown in Table 1.

[0348] [ka]

[0349] Example A3: Synthesis of Compound A3 represented by Formula (M3) In a 2L flask, 400mL of dichloromethane, 41g of the obtained compound A1, 16.2g of triethylamine, and 0.7g of N-(4-pyridyl)dimethylamine (DMAP) were dissolved in a nitrogen flow. 20.7g of dimethyl dicarbonate was dissolved in 100mL of dichloromethane, and then added dropwise to the 2L flask while stirring, and then stirred at room temperature for 3 hours. Then, washing with water was performed three times by a separation operation using 100mL of water, and the solvent was distilled off from the obtained organic phase, and the origin component was removed with dichloromethane / hexane by silica gel chromatography, and the solvent was further distilled off to obtain 4.5g of the BOC group-substituted compound of compound A1 (a compound represented by the following formula (M3), hereinafter also referred to as "compound A3"), which is the target component. The inorganic element content and organic impurity content were measured by the above-mentioned method, and the results are shown in Table 1.

[0350] [ka]

[0351] Example A4: Synthesis of Compound A4 represented by formula (M4) In a 2L flask, 400mL of dichloromethane, 41g of the obtained compound A1, 16.2g of triethylamine, and 0.7g of N-(4-pyridyl)dimethylamine (DMAP) were dissolved in nitrogen flow. 20.7g of dibenzyl dicarbonate was dissolved in 100mL of dichloromethane, and then added dropwise to the 2L flask while stirring, and then stirred at room temperature for 3 hours. Then, washing with water was performed three times by a separation operation using 100mL of water, and the solvent was distilled off from the obtained organic phase, and the origin component was removed with dichloromethane / hexane by silica gel chromatography, and the solvent was further distilled off to obtain 4.5g of the BOC group-substituted compound of compound A1 (a compound represented by the following formula (M4), hereinafter also referred to as "compound A4"), which is the target component. The inorganic element content and organic impurity content were measured by the above-mentioned method, and the results are shown in Table 1.

[0352] [ka]

[0353] Example A5: Synthesis of Compound A5 represented by Formula (M5) A 200mL glass flask was used as a reaction vessel, and 5.6g (40mmol) of 3,4-dihydroxybenzyl alcohol was dissolved in butanol as a solvent. Then, 20% by mass aqueous iodine chloride solution (81.2g, 100mmol) was added dropwise at 50°C over 60 minutes, and the mixture was stirred at 50°C for 2 hours to react 3,4-dihydroxybenzyl alcohol with iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution and the mixture was stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate that separated out by cooling was filtered, washed, and dried to obtain 11.3g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and 3,4-dihydroxy-2,5-diiodobenzyl alcohol was confirmed.

[0354] MnO2 (3.4 g, 40 mmol) was added to the methylene chloride solvent and stirred, and then a 50% by mass solution of the synthesized 3,4-dihydroxy-2,5-diiodobenzyl alcohol dissolved in methylene chloride was added dropwise while stirring for 1 hour, and then the mixture was stirred at room temperature for 4 hours. After that, the reaction solution was filtered and the solvent was distilled off to obtain 3,4-dihydroxy-2,5-diiodobenzaldehyde.

[0355] A solution was prepared by dissolving dimethyl malonate (5.3 g, 40 mmol) and the total amount of 3,4-dihydroxy-2,5-diiodobenzaldehyde synthesized above in DMF solvent, and then a solution of ethylenediamine (0.3 g) dissolved in DMF was added dropwise while stirring for 1 hour, and then the liquid temperature was controlled to 150 ° C. with an oil bath while stirring for 6 hours to react. After that, ethyl acetate and water were added, and a 2 mol / L HCl aqueous solution was added to control the pH to 4 or less, and the organic phase was separated by a separation operation. The obtained organic phase was further washed with a 2 mol / L sodium carbonate aqueous solution, water, and saline in that order by a separation operation, and then filtered and purified, and the solvent was distilled off from the organic phase to obtain 7.8 g of compound A5 (3,4-dihydroxy-2,5-diiodostyrene (compound represented by the following formula (M5))). The inorganic element content and organic impurity content were measured by the above-mentioned method, and the results are shown in Table 1.

[0356] [ka]

[0357] Example A6: Synthesis of Compound A6 represented by formula (M6) A 200mL glass flask was used as a reaction vessel, and 5.6g (40mmol) of 3,5-dihydroxybenzyl alcohol was dissolved in butanol as a solvent. Then, 20% by mass aqueous iodine chloride solution (105.6g, 130mmol) was added dropwise at 50°C over 60 minutes, and the mixture was stirred at 50°C for 2 hours to react 3,5-dihydroxybenzyl alcohol with iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution and the mixture was stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate that precipitated upon cooling was filtered, washed, and dried to obtain 14.4g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and 3,5-dihydroxy-2,4,6-triiodobenzyl alcohol was confirmed.

[0358] MnO2 (3.4 g, 40 mmol) was added to the methylene chloride solvent and stirred, and then a 50 mass% solution of the synthesized 3,5-dihydroxy-2,4,6-triiodobenzyl alcohol dissolved in methylene chloride was added dropwise while stirring for 1 hour, and then the mixture was stirred at room temperature for 4 hours. After that, the reaction solution was filtered and the solvent was distilled off to obtain 3,5-dihydroxy-2,4,6-triiodobenzaldehyde.

[0359] A solution was prepared by dissolving dimethyl malonate (5.3 g, 40 mmol) and the total amount of 3,4-dihydroxy-2,5-diiodobenzaldehyde synthesized above in DMF solvent, and then a solution of ethylenediamine (0.3 g) dissolved in DMF was added dropwise while stirring for 1 hour, and then the liquid temperature was controlled to 150 ° C. with an oil bath while stirring for 6 hours to react. After that, ethyl acetate and water were added, and a 2 mol / L HCl aqueous solution was added to control the pH to 4 or less, and the organic phase was separated by a separation operation. The obtained organic phase was further washed with a 2 mol / L sodium carbonate aqueous solution, water, and saline in that order by a separation operation, and then filtered and purified, and the solvent was distilled off from the organic phase to obtain 9.8 g of compound A6 (3,5-dihydroxy-2,4,6-triiodostyrene (compound represented by the following formula (M6))). The inorganic element content and organic impurity content were measured by the above-mentioned method, and the results are shown in Table 1.

[0360] [ka]

[0361] Example A7: Synthesis of Compound A7 represented by formula (M7) In a 200mL container equipped with a stirrer, a cooling tube and a buret, 4.61g (12.4mmol) of the compound A1 obtained in Example A1 and 2.42g (12.4mmol) of tert-butyl bromoacetate were charged in 100mL of acetone, 1.71g (12.4mmol) of potassium carbonate and 0.4g of 18-crown-6 (IUPAC name: 1,4,7,10,13,16-hexaoxacyclooctadecane) were added, and the contents were stirred under reflux for 3 hours to carry out the reaction to obtain a reaction solution. Next, the reaction solution was concentrated, and 100g of pure water was added to the concentrated solution to precipitate the reaction product, which was then cooled to room temperature and filtered to separate the solid matter. The solid matter obtained was filtered and dried, and then separated and purified by column chromatography to obtain 3.2 g of compound A7 (a compound represented by the following formula (M7)). Furthermore, the inorganic element content and organic impurity content were measured by the above-mentioned method, and the results are shown in Table 1.

[0362] [ka]

[0363] Example A8: Synthesis of Compound A8 represented by formula (M8) 3,5-diiodo-4-hydroxybenzaldehyde was obtained by the same process as described in Example A1. Specifically, the following method was used.

[0364] (Step 1) Iodination reaction A 200mL glass flask was used as a reaction vessel, and 5.52g (40mmol) of 4-hydroxybenzalcohol was dissolved in butanol as a solvent. Then, 20% by mass aqueous iodine chloride solution (81.2g, 100mmol) was added dropwise at 50°C over 60 minutes, and the mixture was stirred at 50°C for 2 hours to react 4-hydroxybenzalcohol with iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution and the mixture was stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate that separated out by cooling was filtered, washed, and dried to obtain 15.3g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and 4-hydroxy-3,5-diiodobenzyl alcohol was confirmed.

[0365] (Step 2) Oxidation reaction MnO2 (3.4 g, 40 mmol) was added to the methylene chloride solvent and stirred, and then a 50% by mass solution of the synthesized 4-hydroxy-3,5-diiodobenzyl alcohol dissolved in methylene chloride was added dropwise while stirring for 1 hour, and then the mixture was stirred at room temperature for 4 hours. After that, the reaction liquid was filtered and the solvent was distilled off to obtain 14.5 g of 4-hydroxy-3,5-diiodobenzaldehyde.

[0366] (Step 3) Malonic acid addition reaction Using a 200mL eggplant flask connected to a Dean-Stark reflux condenser, 14.6g (38mmol) of 3,5-diiodo-4-hydroxybenzaldehyde was mixed with dimethyl malonate (10.6g, 80mmol), piperidine (3.4g, 40mmol), acetic acid (2.4g, 40mmol), and 40mL of benzene, and reacted under reflux conditions for 3 hours. The resulting reaction solution was washed with 20mL of 5% by mass HCl aqueous solution, and then washed with 5% NaHCO3 aqueous solution. The resulting organic phase was dried over magnesium sulfate and concentrated under reduced pressure to obtain 15.8g of the reaction product M8-CINMe.

[0367] [ka] (M8-CINMe)

[0368] (Step 4) Hydrolysis reaction Using a 1L eggplant flask connected to a reflux condenser, hydrochloric acid (6N, 131mL) and acetic acid (131mL) were added to the product M8-CINMe (38mmol) obtained above, and refluxed for 48 hours. After that, 500mL of 6M NaOH aq. was added, and the mixture was extracted with 250mL of ethyl acetate to recover an organic phase consisting of ethyl acetate. The obtained organic phase was dehydrated with magnesium sulfate, and the filtrate was filtered and concentrated under reduced pressure to obtain 15.2g of cinnamic acid derivative M8-CIN.

[0369] [ka]

[0370] (Step 5) Decarboxylation reaction Using a 1L eggplant flask, 40 mmol of the cinnamic acid derivative M8-CIN prepared above was dissolved in 40 mL of dimethyl sulfoxide, and a solution of 0.13 g (0.4 mmol) of tetrabutylammonium fluoride trihydrate dissolved in 20 mL of dimethyl sulfoxide was slowly added at 10°C and stirred, then the temperature was raised to 40°C and stirring was continued for 12 hours. The reaction solution obtained was washed three times with 20 mL of pure water, dried over magnesium sulfate, and the filtrate obtained after filtration was concentrated under reduced pressure to obtain 14.4 g of the compound (M8-OH) represented by the formula (M8-OH).

[0371] [ka]

[0372] (Step 6) Acetyl protecting group introduction reaction Using a 1L eggplant flask, 6.1g (60mmol) of acetic anhydride, 6.0g (60mmol), 0.8g (6mmol) of DMAP, and 350mL of solvent (dichloromethane) were added and stirred to prepare a reaction solution. In a state of ice-cooling at 4°C, 14.4g (37mmol) of the compound M8-OH prepared in the previous step was dissolved in 50mL of dichloromethane to prepare a solution of compound M8-OH, and added to the solution prepared in the 1L eggplant flask over 30 minutes. After stirring at 4°C for 2 hours to allow the reaction to proceed sufficiently, the mixture was thoroughly washed with 400mL of ice water and 400mL of saline, and the obtained organic phase was dried over magnesium sulfate, and the filtrate after filtration was concentrated under reduced pressure to obtain a reaction product. The mixture was further purified using a column, and the developing solvent was distilled off to obtain 14.8g of the target compound A8 represented by formula (M8). The yield was 90% by mass. Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, confirming that the compound had the above chemical structure. δ(ppm)(d6-DMSO): 2.3(3H, -CH3), 7.7(2H, Ph), 6.7(1H, -CH=), 5.3(1H, =CH2), 5.7(1H, =CH2)

[0373] [ka]

[0374] Example A9: Synthesis of Compound A9 represented by formula (M9) Compound A9 represented by formula (M9) was synthesized by the method described below. [ka]

[0375] (Process 1) A 200mL glass flask was used as a reaction vessel, and 5.52g (40mmol) of 3,4-dihydroxybenzaldehyde was dissolved using methanol as a solvent, and then 20% by mass aqueous iodine chloride solution (81.2g, 100mmol) was dropped over 60 minutes under ice-cooled conditions. Further, 4.90g (20mmol) of 71.9% by mass aqueous iodic acid solution was dropped over 30 minutes under ice-cooled conditions so that the liquid temperature was 8°C or less. Then, the mixture was stirred at 40°C for 3 hours to react 3,4-dihydroxybenzaldehyde and iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution after the reaction, and the mixture was stirred for 1 hour, and the liquid temperature was cooled to 10°C. The precipitate precipitated by cooling was filtered, washed, and dried to obtain 15.3g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the substance was identified as 2,5-diiodo-3,4-dihydroxybenzaldehyde.

[0376] (Process 2) Using a 200mL eggplant flask connected to a Dean-Stark reflux condenser, 15.3g (39mmol) of 2,5-diiodo-3,4-dihydroxybenzaldehyde was mixed with malononitrile (3.97g, 60mmol), piperidine (3.4g, 40mmol), acetic acid (2.4g, 40mmol), and 40mL of benzene, and reacted under reflux conditions for 3 hours. The resulting reaction solution was washed with 20mL of 5% by mass HCl aqueous solution, and then washed with 5% NaHCO3 aqueous solution. The resulting organic phase was dried over magnesium sulfate and concentrated under reduced pressure to obtain the reaction product represented by the following formula M9-CN. [ka]

[0377] (Step 3) Using a 1L eggplant flask connected to a reflux condenser, hydrochloric acid (6N, 131mL) and acetic acid (131mL) were added to the product M9-CN obtained above (39mmol), and refluxed for 48 hours. After that, 6M, 500mL NaOH aq. was added, and the mixture was extracted with 250mL of ethyl acetate to recover an organic phase consisting of ethyl acetate. The obtained organic phase was dehydrated with magnesium sulfate, and the filtrate was filtered and concentrated under reduced pressure to obtain 16.4g (38mmol) of the cinnamic acid derivative represented by the following (M9-CA). [ka]

[0378] (Step 4) Decarboxylation reaction Using a 1L eggplant flask, 38 mmol of the cinnamic acid derivative M9-CA prepared above was dissolved in 40 mL of dimethyl sulfoxide, and a solution of 0.13 g (0.4 mmol) of tetrabutylammonium fluoride trihydrate dissolved in 20 mL of dimethyl sulfoxide was slowly added at 10°C and stirred, then the temperature was raised to 40°C and stirring was continued for 12 hours. The reaction solution obtained was washed three times with 20 mL of pure water, dried over magnesium sulfate, and the filtrate obtained after filtration was concentrated under reduced pressure to obtain 14.4 g (37 mmol) of the compound (M9-OH) represented by the formula (M9-OH). [ka]

[0379] (Step 5) Acetyl protecting group introduction reaction Using a 1L eggplant flask, 6.1g (60mmol) of acetic anhydride, 6.0g (60mmol), 0.8g (6mmol) of DMAP, and 350mL of solvent (dichloromethane) were added and stirred to prepare a reaction solution. In a state of ice-cooling at 4°C, 14.4g (37mmol) of the compound M9-OH prepared in the previous step was dissolved in 50mL of dichloromethane to prepare a solution of compound M9-OH, and added to the solution prepared in the 1L eggplant flask over 30 minutes. After stirring at 4°C for 2 hours to allow the reaction to proceed sufficiently, the mixture was thoroughly washed with 400mL of ice water and 400mL of saline, and the obtained organic phase was dried over magnesium sulfate, and the filtrate after filtration was concentrated under reduced pressure to obtain a reaction product. The mixture was further purified using a column, and 16.5g of compound A9, which is the compound of the desired compound formula (M9), was separated by distilling off the developing solvent. The yield was 88% by mass. Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the following chemical structure. δ(ppm)(d6-DMSO): 2.3(6H, -CH3), 7.4(1H, Ph), 7.4(1H, -CH=), 5.6(1H, =CH2), 5.7(1H, =CH2) [ka]

[0380] Example A10: Synthesis of Compound A10 Represented by Formula (M10) Compound A10 represented by formula (M10) was synthesized by the method described below. [ka]

[0381] (Process 1) A 200mL glass flask was used as a reaction vessel, and 5.52g (40mmol) of 3,5-dihydroxybenzaldehyde was dissolved in methanol as a solvent, and then 20% by mass aqueous iodine chloride solution (121.8g, 150mmol) was added dropwise over 90 minutes under ice-cooled conditions. Further, 7.45g (30mmol) of 71.9% by mass aqueous iodic acid solution was added dropwise over 30 minutes under ice-cooled conditions so that the liquid temperature was 8°C or less. Then, the mixture was stirred at 40°C for 3 hours to react 3,5-dihydroxybenzaldehyde with iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution and stirred for 1 hour, and the liquid temperature was cooled to 10°C. The precipitate precipitated by cooling was filtered, washed, and dried to obtain 20.1g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the substance was identified as 2,4,6-triiodo-3,5-dihydroxybenzaldehyde.

[0382] (Process 2) Using a 200mL eggplant flask connected to a Dean-Stark reflux condenser, 20.1g (39mmol) of 2,4,6-triiodo-3,5-dihydroxybenzaldehyde was mixed with malonic acid (15.6g, 150mmol), piperidine (12.8g, 150mmol), acetic acid (90g, 150mmol), and benzene 40mL, and reacted under reflux conditions for 3 hours. The resulting reaction solution was washed with 20mL of 5% HCl aqueous solution, and then washed with 5% NaHCO3 aqueous solution. The resulting organic phase was dried over magnesium sulfate and concentrated under reduced pressure to obtain 20.6g of cinnamic acid derivative (M10-CA). [ka]

[0383] (Step 3) Decarboxylation reaction Using a 1L eggplant flask, 0.6g (37mmol) of the cinnamic acid derivative M10-CA prepared above was dissolved in 40mL of dimethyl sulfoxide, and a solution of 0.13g (0.4mmol) of tetrabutylammonium fluoride trihydrate dissolved in 20mL of dimethyl sulfoxide was slowly added at 10℃ and stirred, then the temperature was raised to 40℃ and stirring was continued for 12 hours. The reaction solution obtained was washed three times with 20mL of pure water, dried with magnesium sulfate, and the filtrate obtained after filtration was concentrated under reduced pressure to obtain 18.0g (35mmol) of the compound (M10-OH) represented by the formula (M10-OH).

[0384] (Step 4) Acetyl protecting group introduction reaction Using a 1L eggplant flask, 6.1g (60mmol) of acetic anhydride, 6.0g (60mmol), 0.8g (6mmol) of DMAP, and 350mL of solvent (dichloromethane) were added and stirred to prepare a reaction solution. In a state of being cooled to 4°C with ice water, 18.0g (35mmol) of the compound M10-OH prepared in the previous step was dissolved in 50mL of dichloromethane to prepare a solution of the compound M10-OH, and the solution was added to the solution prepared in the 1L eggplant flask over 30 minutes. After that, the reaction was sufficiently carried out by stirring at 4°C for 2 hours, and then washing was sufficiently carried out with 400mL of ice water and 400mL of saline, and the obtained organic phase was dried with magnesium sulfate, and the filtrate after filtration was concentrated under reduced pressure to obtain a reaction product. The reaction product was further purified by a column, and 20.3g of the target compound M10 was separated by distilling off the developing solvent. The yield was 85% by mass.

[0385] Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the following chemical structure. δ(ppm)(d6-DMSO): 2.3(6H, -CH3), 7.4(1H, -CH=), 5.6(1H, =CH2), 5.7(1H, =CH2) [ka]

[0386] Example A11 and Example A12: Synthesis of Compound A11 represented by Formula (M11) and Compound A12 represented by Formula (M12) Compound A11 represented by formula (M11) and compound A12 represented by formula (12) were synthesized by the method described below. [ka]

[0387] (Step 1) Iodination reaction A 200mL glass flask was used as a reaction vessel, and 5.45g (40mmol) of 4-hydroxybenzyl alcohol was dissolved in butanol as a solvent. Then, 20% by mass aqueous iodine chloride solution (40.6g, 50mmol) was added dropwise at 50°C over 60 minutes, and the mixture was stirred at 50°C for 2 hours to react 4-hydroxybenzaldehyde with iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution and the mixture was stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate that separated out by cooling was filtered, washed, and dried to obtain 10.3g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and 4-hydroxy-3-iodobenzyl alcohol was confirmed.

[0388] (Step 2) Oxidation reaction MnO2 (3.4 g, 40 mmol) was added to the methylene chloride solvent and stirred, and then a 50% by mass solution of the synthesized 4-hydroxy-3-iodobenzyl alcohol dissolved in methylene chloride was added dropwise while stirring for 1 hour, and then the mixture was stirred at room temperature for 4 hours. After that, the reaction liquid was filtered and the solvent was distilled off to obtain 14.5 g of 4-hydroxy-3-iodobenzaldehyde.

[0389] (Step 3) Malonic acid addition reaction Using a 200mL eggplant flask connected to a Dean-Stark reflux condenser, 14.6g (38mmol) of 4-iodo-3-hydroxybenzaldehyde was mixed with dimethyl malonate (10.6g, 80mmol), piperidine (3.4g, 40mmol), acetic acid (2.4g, 40mmol), and benzene 40mL, and reacted under reflux conditions for 3 hours. The resulting reaction solution was washed with 20mL of 5% by mass HCl aqueous solution, and then washed with 5% NaHCO3 aqueous solution. The resulting organic phase was dried over magnesium sulfate and concentrated under reduced pressure to obtain 13.4g of the reaction product M11-CINMe. [ka]

[0390] (Step 4) Hydrolysis reaction Using a 1L eggplant flask connected to a reflux condenser, hydrochloric acid (6N, 131mL) and acetic acid (131mL) were added to the product M11-CINMe13.4 (37mmol) obtained above, and refluxed for 48 hours. After that, 500mL of 6M NaOH aq. was added, and the mixture was extracted with 250mL of ethyl acetate to recover an organic phase consisting of ethyl acetate. The obtained organic phase was dehydrated with magnesium sulfate, and the filtrate was filtered and concentrated under reduced pressure to obtain 0.4g of cinnamic acid derivative MA11-CA1. [ka]

[0391] (Step 5) Decarboxylation reaction Using a 1L eggplant flask, the above-prepared cinnamic acid derivative MA11-CA10.4 (36 mmol) was dissolved in 40 mL of dimethyl sulfoxide, and a solution of 0.13 g (0.4 mmol) of tetrabutylammonium fluoride trihydrate dissolved in 20 mL of dimethyl sulfoxide was slowly added at 10° C. and stirred, then the temperature was raised to 40° C. and stirring was continued for 12 hours. The reaction solution obtained was washed three times with 20 mL of pure water, dried over magnesium sulfate, and the filtrate obtained after filtration was concentrated under reduced pressure to obtain 8.6 g of compound (A11) represented by formula (M11). Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the following chemical structure. δ(ppm)(d6-DMSO): 2.3(3H, -CH3), 7.7(2H, Ph), 6.7(1H, -CH=), 5.3(1H, =CH2), 5.7(1H, =CH2) [ka]

[0392] (Step 6) Acetyl protecting group introduction reaction Using a 1L eggplant flask, 6.1g (60mmol) of acetic anhydride, 6.0g (60mmol), 0.8g (6mmol) of DMAP, and 350mL of solvent (dichloromethane) were added and stirred to prepare a reaction solution. In a state of ice-cooling at 4°C, 8.6g (36mmol) of compound A11 prepared in the previous step was dissolved in 50mL of dichloromethane to prepare a solution of compound A11, and added to the solution prepared in the 1L eggplant flask over 30 minutes. After stirring at 4°C for 2 hours to sufficiently proceed with the reaction, the mixture was thoroughly washed with 400mL of ice water and 400mL of saline, and the obtained organic phase was dried with magnesium sulfate, and the filtrate after filtration was concentrated under reduced pressure to obtain a reaction product. The mixture was further purified using a column, and the developing solvent was distilled off to obtain 10.0g of the target compound A12 represented by formula (M12). The yield was 88% by mass. Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the following chemical structure. δ(ppm)(d6-DMSO): 2.3(3H, -CH3), 7.7(2H, Ph), 6.7(1H, -CH=), 5.3(1H, =CH2), 5.7(1H, =CH2) [ka]

[0393] Examples A13 and A14: Synthesis of Compounds A13 and A14 Represented by Formulae (M13) and (M14) Compound A13 represented by formula (M13) and compound A14 represented by formula (M14) were synthesized by the method described below. [ka]

[0394] (Process 1) A 200mL glass flask was used as a reaction vessel, and 5.52g (40mmol) of 3,4-dihydroxybenzaldehyde was dissolved in methanol as a solvent, and then 20% by mass aqueous iodine chloride solution (40.6g, 50mmol) was added dropwise over 60 minutes under ice-cooled conditions. Further, 2.45g (10mmol) of 71.9% by mass aqueous iodic acid solution was added dropwise over 30 minutes under ice-cooled conditions so that the liquid temperature was 8°C or less. Then, the mixture was stirred at 40°C for 3 hours to react 3,4-dihydroxybenzaldehyde with iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution and stirred for 1 hour, and the liquid temperature was cooled to 10°C. The precipitate precipitated by cooling was filtered, washed, and dried to obtain 10.2g of a white solid. Furthermore, a white solid sample was analyzed by liquid chromatography-mass spectrometry (LC-MS) using silica gel chromatography, and the result confirmed the presence of 2-iodo-3,4-dihydroxybenzaldehyde.

[0395] (Process 2) Using a 200mL eggplant flask connected to a Dean-Stark reflux condenser, 10.3g (39mmol) of 2-iodo-3,4-dihydroxybenzaldehyde was mixed with malononitrile (3.97g, 60mmol), piperidine (3.4g, 40mmol), acetic acid (2.4g, 40mmol), and 40mL of benzene, and reacted under reflux conditions for 3 hours. The resulting reaction solution was washed with 20mL of 5% by mass HCl aqueous solution, and then washed with 5% by mass NaHCO3 aqueous solution. The resulting organic phase was dried over magnesium sulfate and concentrated under reduced pressure to obtain 11.9g of the reaction product (M13-CINMe). [ka]

[0396] (Step 3) Using a 1L eggplant flask connected to a reflux condenser, hydrochloric acid (6N, 131mL) and acetic acid (131mL) were added to the product 11.9 (38mmol) obtained above, and refluxed for 48 hours. After that, 500mL of 6M NaOH aq. was added, and the mixture was extracted with 250mL of ethyl acetate to recover an organic phase consisting of ethyl acetate. The obtained organic phase was dehydrated with magnesium sulfate, and the filtrate was filtered and concentrated under reduced pressure to obtain 11.6g of cinnamic acid derivative (M13-CA). [ka]

[0397] (Step 4) Decarboxylation reaction Using a 1L eggplant flask, 11.6g (38mmol) of the cinnamic acid derivative prepared above was dissolved in 40mL of dimethyl sulfoxide, and a solution of 0.023g (0.4mmol) of potassium fluoride trihydrate dissolved in a mixed solution of 4mL of acetic acid and 16mL of dimethyl sulfoxide was slowly added at 10°C and stirred, then the temperature was raised to 40°C and stirring was continued for 12 hours. The reaction solution obtained was washed three times with 20mL of pure water, dried with magnesium sulfate, and the filtrate obtained after filtration was concentrated under reduced pressure to obtain 9.1g of compound A13 represented by formula (M13). Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the chemical structure of Compound A13. δ(ppm)(d6-DMSO): 9.5(1H, OH), 9.6(1H, OH), 7.0(2H, Ph), 6.7(1H, -CH=), 5.3(1H, =CH2), 5.7(1H, =CH2)

[0398] (Step 5) Acetyl protecting group introduction reaction Using a 1L eggplant flask, 6.1g (60mmol) of acetic anhydride, 6.0g (60mmol), 0.8g (6mmol) of DMAP, and 350mL of solvent (dichloromethane) were added and stirred to prepare a reaction solution. In a state of ice-cooling at 4°C, 9.1g (35mmol) of compound A13 prepared in the previous step was dissolved in 50mL of dichloromethane to prepare a solution of compound A13, and added to the solution prepared in the 1L eggplant flask over 30 minutes. After stirring at 4°C for 2 hours to allow the reaction to proceed sufficiently, the mixture was thoroughly washed with 400mL of ice water and 400mL of saline, and the obtained organic phase was dried over magnesium sulfate, and the filtrate after filtration was concentrated under reduced pressure to obtain a reaction product. The mixture was further purified using a column, and the developing solvent was distilled off to obtain 12.1g of the target compound A14 represented by formula (M14). Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the chemical structure of Compound A14. δ(ppm)(d6-DMSO): 2.3(6H, -CH3), 7.7(2H, Ph), 6.7(1H, -CH=), 5.3(1H, =CH2), 5.7(1H, =CH2)

[0399] Examples A15 and A16: Synthesis of Compounds A15 and A16 Represented by Formulae (M15) and (M16) Compound A15 represented by formula (M15) and compound A16 represented by formula (M16) were synthesized by the method described below.

[0400] (Step 1) Formation of 4-iodo-3,5-dihydroxybenzaldehyde A 200mL glass flask was used as a reaction vessel, and 5.52g (40mmol) of 3,5-dihydroxybenzaldehyde was dissolved in methanol as a solvent, and then 20% by mass aqueous iodine chloride solution (40.6g, 50mmol) was added dropwise over 60 minutes under ice-cooled conditions. Further, 2.45g (10mmol) of 71.9% by mass aqueous iodic acid solution was added dropwise over 30 minutes under ice-cooled conditions so that the liquid temperature was 8°C or less. Then, the mixture was stirred at 40°C for 3 hours to react 3,5-dihydroxybenzaldehyde and iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution after the reaction, and the mixture was stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate precipitated by cooling was filtered, washed, and dried to obtain 10.2g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS) and the substance was confirmed to be 4-iodo-3,5-dihydroxybenzaldehyde.

[0401] (Step 2) Formation of cinnamic acid derivative structure Using a 200mL eggplant flask connected to a Dean-Stark reflux condenser, 10.3g (39mmol) of 4-iodo-3,5-dihydroxybenzaldehyde was mixed with malonic acid (6.24g, 60mmol), piperidine (3.4g, 40mmol), acetic acid (2.4g, 40mmol), and benzene 40mL, and reacted under reflux conditions for 3 hours. The resulting reaction solution was washed with 20mL of 5% by mass HCl aqueous solution, and then washed with 5% NaHCO3 aqueous solution. The resulting organic phase was dried over magnesium sulfate and concentrated under reduced pressure to obtain 11.7g of a reaction product (M15-CA) consisting of cinnamic acid derivatives. [ka]

[0402] (Step 3) Decarboxylation reaction Using a 1L eggplant flask, 11.7g (38mmol) of the cinnamic acid derivative (M15-CA) prepared above was dissolved in 40mL of dimethyl sulfoxide, and a solution of 0.13g (0.4mmol) of tetrabutylammonium fluoride trihydrate dissolved in 20mL of dimethyl sulfoxide was slowly added at 10°C and stirred, then the temperature was raised to 40°C and stirring was continued for 12 hours. The reaction solution obtained was washed three times with 20mL of pure water, dried with magnesium sulfate, and the filtrate obtained after filtration was concentrated under reduced pressure to obtain 9.4g of compound (A15) represented by formula (M15). Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the following chemical structure. δ(ppm)(d6-DMSO): 11.6(2H, OH), 6,0(2H, Ph), 6.7(1H, -CH=), 5.3(1H, =CH2), 5.7(1H, =CH2) [ka]

[0403] (Step 4) Acetyl protecting group introduction reaction Using a 1L eggplant flask, 6.1g (60mmol) of acetic anhydride, 6.0g (60mmol), 0.8g (6mmol) of DMAP, and 350mL of solvent (dichloromethane) were added and stirred to prepare a reaction solution. In a state of ice-cooling at 4°C, 9.4g (36mmol) of compound A15 prepared in the previous step was dissolved in 50mL of dichloromethane to prepare a solution of compound A15, and added to the solution prepared in the 1L eggplant flask over 30 minutes. After stirring at 4°C for 2 hours to allow the reaction to proceed sufficiently, the mixture was thoroughly washed with 400mL of ice water and 400mL of saline, and the obtained organic phase was dried over magnesium sulfate, and the filtrate after filtration was concentrated under reduced pressure to obtain a reaction product. The mixture was further purified using a column, and the developing solvent was distilled off to obtain 12.3g of the desired compound A16. Also, under the above measurement conditions 1When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the chemical structure of Compound A16. δ(ppm)(d6-DMSO): 2.3(6H, -CH3), 6.7(2H, Ph), 6.7(1H, -CH=), 5.3(1H, =CH2), 5.7(1H, =CH2)

[0404] Synthesis Example ACL1: Synthesis of Compound MCL1 Represented by Formula (MCL1) A compound MCL1 represented by formula (MCL1) was synthesized by the method described below.

[0405] (Step 1) Diiodination of 4-hydroxyacetophenone A 200mL glass flask was used as a reaction vessel, and 6.1g (45mmol) of 4-hydroxyacetophenone was dissolved in butanol as a solvent. Then, 20% by mass aqueous iodine chloride solution (81.2g, 100mmol) was added dropwise at 50°C over 60 minutes, and the mixture was stirred at 50°C for 2 hours to react 4-hydroxyacetophenone with iodine chloride. After the reaction, an aqueous sodium thiosulfate solution was added to the reaction solution and the mixture was stirred for 1 hour, and then the liquid temperature was cooled to 10°C. The precipitate that precipitated upon cooling was filtered, washed, and dried to obtain 16.3g of a white solid. A sample of the white solid was analyzed by liquid chromatography-mass spectrometry (LC-MS), and 4-hydroxy-3,5-diiodoacetophenone was confirmed. [ka] (Raw material acetophenone derivative) Mw 387.94,

[0406] (Step 2) Introduction of chloro group at α position In a flask, 0.6g (6.1mmol) of CuCl, 1.3g (13mmol) of triethylamine, 5.2g (34mmol) of POCl3 (phosphorus (V) oxychloride), and 15mL of heptane were stirred at 25°C, and 16.3g (42mmol) of 4-hydroxy-3,5-diiodoacetophenone prepared in step 1 was added and dissolved. After heating the solution temperature to 100°C and reacting for 20 hours, it was cooled to 45°C and 25mL of pure water was added dropwise to terminate the reaction. After removing the aqueous layer, the mixture was washed with pure water (10mL) and saturated saline (10mL) by liquid separation, and then magnesium sulfate was added to perform dehydration. The filtrate after filtration was concentrated to obtain the compound represented by formula (MCL1). Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the following chemical structure. δ(ppm)(d6-DMSO): 9.6(1H, -OH), 7.5(2H, Ph), 5.4(1H, =CH2), 5.7(1H, =CH2) [ka] (Target) Mw406.39

[0407] Synthesis Example AD1: Synthesis of compound MD1 represented by formula (MD1) A compound MD1 represented by formula (MD1) was synthesized by the method described below. [ka]

[0408] 15.6g of 1-(4-hydroxy-3,5-diiodophenyl)ethanol, 0.12g of concentrated sulfuric acid, 0.04g of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 1.60mL of DMSO were charged into the reactor, and stirring was started. Next, the reduced pressure conditions were adjusted to reflux at 120°C using a Dean-Stark and condenser, and air was started to be blown into the reaction solution at a flow rate of 1mL / min. The water collected in the Dean-Stark was appropriately discharged outside the system. Next, the reactor was immersed in a water bath at 90°C, and stirring was continued for 30 hours. Next, the reactor was immersed in a water bath at 25°C, and the reaction solution was cooled. Next, the reaction solution was gradually added to 400g of a 0.1 mass percent aqueous sodium hydrogen sulfite solution while being strongly stirred and mixed. Next, the precipitate was filtered off with a suction filter, squeezed, and washed with 200mL of a 33.3 volume percent aqueous methanol solution. The obtained precipitate was subjected to column purification to isolate only the main component, and then the solvent was removed by evaporation to obtain a solid, which was then vacuum dried at 40° C. to obtain 9.7 g of a white solid. The yield was 66%. Analysis by liquid chromatography-mass spectrometry (LC-MS) confirmed that the compound had a molecular weight of 743.9, and was identified as compound MD1 represented by formula (MD1). Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the chemical structure of compound MD1. δ(ppm)(d6-DMSO): 9.6(2H, OH), 7.5(2H, Ph), 7.9(2H, Ph), 3.5(1H, -CH-), 1.3(3H, -CH3), 4.9(1H, =CH2), 5.3(1H, =CH2)

[0409] Synthesis Example AD2: Synthesis of compound MD2 represented by formula (MD2) Compound MD2 represented by formula (MD2) was synthesized by the method described below. [ka]

[0410] 15.6g of 1-(4-hydroxy-3,5-diiodophenyl)ethanol, 0.12g of concentrated sulfuric acid, 0.2g of 4-methoxyphenol, and 150mL of toluene were charged into the reactor, and stirring was started. Then, using a Dean-Stark and condenser, air was started to be blown into the reaction solution at a flow rate of 1mL / min under reflux conditions at 113°C. The water collected in the Dean-Stark was appropriately discharged outside the system. Then, the reactor was immersed in a water bath at 90°C, and stirring was continued for 30 hours. Then, the reactor was immersed in a water bath at 25°C, and the reaction solution was cooled. Then, the reaction solution was gradually added to 400g of a 0.1 mass percent aqueous sodium hydrogen sulfite solution while being strongly stirred, and mixed. Then, the precipitate was filtered off with a suction filter, squeezed, and washed with 200mL of a 33.3 volume percent aqueous methanol solution. The obtained precipitate was subjected to column purification to isolate only the main component, and then the solvent was removed by evaporation to obtain a solid, which was then vacuum dried at 40° C. to obtain 5.9 g of a white solid. The yield was 41%. Analysis by liquid chromatography-mass spectrometry (LC-MS) confirmed that the compound had a molecular weight of 743.89, and was identified as compound MD2 represented by formula (MD2).

[0411] Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the chemical structure of compound MD2. δ(ppm)(d6-DMSO): 9.6(2H, OH), 7.5(2H, Ph), 7.6(2H, Ph), 2.3(2H, -CH2-), 2.6(2H, -CH2-), 4.9(1H, =CH2), 5.3(1H, =CH2)

[0412] Synthesis Example AD3: Synthesis of compound MD3 represented by formula (MD3) A compound MD3 represented by formula (MD3) was synthesized by the method described below. [ka]

[0413] The following steps were carried out using the compound MD1 synthesized above. Using a 1L eggplant flask, 1.57g of acetic anhydride, 1.53g of triethylamine, 0.19g of DMAP, and 35mL of solvent (dichloromethane) were added and stirred to prepare a reaction solution while cooling the mixture to 4℃ with ice water. 7.43g (10mmol) of compound MD1 prepared in the previous step was dissolved in 10mL of dichloromethane while cooling the mixture to 4℃, and a solution of compound MD1 was prepared. The solution was added to the solution prepared in the 1L eggplant flask over 30 minutes. After stirring at 4℃ for 2 hours to allow the reaction to proceed sufficiently, the mixture was thoroughly washed with 40mL of ice water and 40mL of saline, and the obtained organic phase was dried with magnesium sulfate. The filtrate after filtration was concentrated under reduced pressure to obtain the reaction product. The mixture was further purified using a column, and the developing solvent was distilled off to obtain 6.7g of the desired compound MD3. Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the chemical structure of MD3. δ(ppm)(d6-DMSO): 2.3(6H, -CH3), 7.7(2H, Ph), 8.0(2H, Ph), 1.3(3H, -CH3), 3.4(1H, -CH-), 4.9(1H, =CH2), 5.3(1H, =CH2)

[0414] Synthesis Example AD4: Synthesis of compound MD4 represented by formula (MD4) A compound MD4 represented by formula (MD4) was synthesized by the method described below. [ka]

[0415] The following steps were carried out using the compound MD2 synthesized above. Using a 1L eggplant flask, 1.57g of acetic anhydride, 1.53g of triethylamine, 0.19g of DMAP, and 35mL of solvent (dichloromethane) were added and stirred to prepare a reaction solution while cooling the mixture to 4℃ with ice water. Compound MD2 (7.43g, 10mmol) prepared in the previous step was dissolved in 10mL of dichloromethane while cooling the mixture to 4℃, and a solution of compound MD2 was prepared. The solution was added to the solution prepared in the 1L eggplant flask over 30 minutes. After stirring at 4℃ for 2 hours to allow the reaction to proceed sufficiently, the mixture was thoroughly washed with 40mL of ice water and 40mL of saline, and the organic phase obtained was dried over magnesium sulfate. The filtrate after filtration was concentrated under reduced pressure to obtain the reaction product. The mixture was further purified using a column, and the developing solvent was distilled off to obtain 7.1g of the target compound MD4. Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the chemical structure of MD4. δ(ppm)(d6-DMSO): 2.3(6H, -CH3), 7.7(4H, Ph), 2.6(2H, -CH2-), 2.3(2H, -CH2), 5.0(1H, =CH2), 5.3(1H, =CH2)

[0416] Example AH1: Synthesis of a compound represented by formula (MH1) (Process 1) A 200mL glass flask was used as a reaction vessel, and 6.24g (44mmol) of BF3·OEt2 complex was added to 4.28g (40mmol) of 3-pyridinecarbaldehyde, followed by the addition of 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex (100mL, 44mmol, 1.2M / THF) at -40℃. After stirring for 30 minutes, a solution of I2 (20g, 80mmol) dissolved in 80mL of THF was slowly added dropwise, and the temperature was raised to 25℃ and the mixture was stirred. After that, the mixture was washed with 180mL of saturated aqueous NH4Cl solution, followed by washing with 20mL of aqueous ammonium solution and 40mL of aqueous Na2SO3 solution, and extracted with diethyl ether. After drying by adding sodium sulfate, the resulting diethyl ether solution was concentrated and purified by silica gel chromatography to obtain 5.7 g of the target product, 2-iodo-3-pyridinecarbaldehyde.

[0417] (Step 2) Wittig A 200mL glass flask was used as a reaction vessel, and 6.4g (16.8mmol) of triphenylphosphonium methyl bromide and 20mL of toluene were dissolved in it. 2.2g (19.6mmol) of potassium tert-butoxide was dissolved in 9mL of THF to prepare a KTB solution, and the KTB solution was added dropwise to the toluene solution in an ice bath while adjusting the temperature to 0℃ or less, and then stirred as it is for 30 minutes. Further, while adjusting the temperature to 0℃ or less, a solution of 4.66g (20.0mmol) of 2-iodo-3-pyridinecarbaldehyde dissolved in 15mL of toluene was added dropwise, and then stirred as it is for 4 hours. After that, the mixture was further washed with 10mL of water, 10mL of 10% sodium bisulfite solution, 10mL of 5% sodium bicarbonate solution, and 10mL of pure water in that order. 8.1g of the target product, 3-vinyl-2-iodopyridine represented by the formula (MH1), was isolated using a silica gel column. Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the chemical structure represented by formula (MH1). δ(ppm)(d6-DMSO): 8.0 (1H, Pyridine), 7.4 (1H, Pyridine), 7.2 (1H, Pyridine), 7.1 (1H, -CH=), 5.9 (1H, =CH2), 5.4 (1H, =CH2)

[0418] [ka] Example AH2: Synthesis of a compound represented by formula (MH2) (Process 1) A 200mL glass flask was used as a reaction vessel, and 4.56g (40mmol) of 5-oxooxolane-3-carbaldehyde was dissolved in 20mL of THF. Lithium diisopropylamide·THF solution (22mL, 44mmol, 2mol / L) was added at -40℃. After stirring for 30 minutes, a solution of I2 (20g, 80mmol) dissolved in 80mL of THF was slowly added dropwise, and the temperature was raised to 25℃ and stirring was continued. Then, 3mL of isopropanol was slowly added dropwise and the mixture was stirred for another 30 minutes. After that, the mixture was washed with 180mL of saturated aqueous NH4Cl solution, followed by washing with 20mL of aqueous ammonium solution and 40mL of aqueous Na2SO3 solution, and extracted with diethyl ether. After adding sodium sulfate and drying, the resulting diethyl ether solution was concentrated and purified by silica gel chromatography to obtain 6.7g of the target compound represented by the formula (MH2-AL). [ka]

[0419] (Step 2) Wittig A 200mL glass flask was used as a reaction vessel, and 6.4g (16.8mmol) of triphenylphosphonium methyl bromide and 20mL of toluene were dissolved in it. 2.2g (19.6mmol) of potassium tert-butoxide was dissolved in 9mL of THF to prepare a KTB solution, and the KTB solution was added dropwise to the toluene solution in an ice bath while adjusting the temperature to below 0℃, and then stirred as it is for 30 minutes. Further, while adjusting the temperature to below 0℃, a solution of 4.8g (20.0mmol) of 2-iodo-5-oxooxolane-3-carbaldehyde in 15mL of toluene was added dropwise, and then stirred as it is for 4 hours. After that, the mixture was further washed with 10mL of water, 10mL of 10% sodium bisulfite solution, 10mL of 5% sodium bicarbonate solution, and 10mL of pure water in that order. 8.1g of the target compound represented by the formula (MH2) was isolated using a silica gel column. Also, under the above measurement conditions 1 When H-NMR measurement was performed, the following peaks were found, and it was confirmed that the compound had the chemical structure represented by formula (MH2). δ(ppm)(d6-DMSO): 4.9(1H, -CH(I)-), 2.93(1H, -CH(C)), 4.4(2H, -CH2-O), 5.7(1H, -CH=), 5.0(1H, =CH2), 5.1(1H, =CH2)

[0420] [ka] Synthesis Example B1: Synthesis of 1,3-divinylbenzene

[0421] (Malonic acid addition reaction step) Using a 200mL eggplant flask connected to a Dean-Stark reflux condenser, 5.36g (40mmol) of 1,3-benzenedicarboxaldehyde was mixed with malonic acid (10.4g, 100mmol), piperidine (6.8g, 80mmol), acetic acid (4.8g, 80mmol), and 80mL of benzene, and reacted under reflux conditions for 3 hours. The resulting reaction solution was washed with 40mL of 5% by mass HCl aqueous solution, and then washed with 5% NaHCO3 aqueous solution. The resulting organic phase was dried over magnesium sulfate and concentrated under reduced pressure to obtain 8.3g of a reaction product consisting of cinnamic acid derivatives.

[0422] (Decarboxylation reaction process) Using a 1L eggplant flask, 8.3g (38mmol) of the cinnamic acid derivative prepared above was dissolved in 40mL of dimethyl sulfoxide, and a solution of 0.13g (0.4mmol) of tetrabutylammonium fluoride trihydrate dissolved in 20mL...

Claims

1. A compound having one or more halogens and an unsaturated double bond.

2. The compound of claim 1 having one or more hydrophilic groups or one degradable group.

3. The compound according to claim 1 or 2, which is represented by the following formula (1): 【Chemistry 1】 (In formula (1), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L １ are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and １ The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, Y's each independently represent a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent, R ａ , R ｂ , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z's each independently represent an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group of Z may have a substituent; p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, and r is an integer of 0 or more.

4. The compound according to claim 3, represented by the following formula (1a): 【Chemistry 2】 (In formula (1a), X, L １ , Y, A, Z, p, m, n, and r are the same as those in formula (1).

5. The compound according to claim 3, represented by the following formula (1b): 【Chemistry 3】 (In formula (1b), X, L １ , Y, A, Z, p, m, n, and r are the same as defined in formula (1); R ａ１ , R ｂ１ , and R ｃ１ each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, R ａ１ , R ｂ１ , and R ｃ１ At least one of is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent.

6. The compound according to any one of claims 3 to 5, wherein n+r is an integer of 1 or more.

7. The compound according to any one of claims 3 to 6, wherein Y is each independently a group represented by the following formula (Y-1): 【Chemistry 4】 (In formula (Y-1), L ２ is a group which is cleaved by the action of an acid or a base, R ２ is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 1 to 30 carbon atoms, a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms containing a heteroatom, or an aromatic group having 1 to 30 carbon atoms containing a heteroatom, ２ The aliphatic group, aromatic group, aliphatic group containing a hetero atom, and aromatic group containing a hetero atom may further have a substituent.)

8. The compound according to any one of claims 3 to 7, wherein A is an aromatic ring.

9. The compound according to any one of claims 3 to 7, wherein A is an alicyclic structure.

10. The compound according to any one of claims 3 to 9, wherein A is a heterocyclic structure.

11. The compound according to any one of claims 3 to 10, wherein n is 2 or more.

12. The compound according to any one of claims 1 to 11, which contains a functional group whose solubility in an alkaline developer is improved by the action of an acid or a base.

13. X is I, L １ The compound according to any one of claims 3 to 12, wherein is a single bond.

14. The compound according to any one of claims 3 to 12, wherein X is an aromatic group having one or more of F, Cl, Br or I introduced therein.

15. The compound according to any one of claims 3 to 12, wherein X is an alicyclic group having one or more of F, Cl, Br or I introduced therein.

16. A composition comprising a compound represented by formula (1C) in an amount of 1 ppm by mass or more and 10% by mass or less based on the total amount of the compound according to any one of claims 1 to 15. 【Chemistry 5】 (In formula (1C), formula (1C1), and formula (1C2), X, L １ , Y, A, Z, p, m, n, and r are the same as defined in formula (1); Rsub represents the formula (1C1) or the formula (1C2), R ａ１ , R ｂ１ , and R ｃ１ each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, R ａ１ , R ｂ１ , and R ｃ１ at least one of is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent; p-1 is an integer equal to or greater than 0; * indicates the bonding site with the adjacent structural unit.)

17. A composition comprising the compound according to any one of claims 1 to 15 and a compound represented by formula (1D) in an amount of 1 ppm by mass or more and 10% by mass or less relative to the compound. 【Chemistry 6】 (In formula (1D), formula (1D1), or formula (1D2), X, L １ , Y, A, Z, p, m, n, and r are the same as defined in formula (1); Rsub2 represents the formula (1D1) or the formula (1D2), R ａ１ , R ｂ１ , and R ｃ１ each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, R ａ１ , R ｂ１ , and R ｃ１ at least one of is I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent; n2 represents an integer of 0 to 4, p-1 is an integer equal to or greater than 0; * indicates the bonding site with the adjacent structural unit.)

18. A composition comprising a compound represented by formula (1E) in an amount of 1 ppm by mass or more and 10% by mass or less relative to the compound according to any one of claims 3 to 15. 【Chemistry 7】 (In formula (1E), X is each independently F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of F, Cl, and Br; L １ are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and １ The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R ａ , R ｂ , and R c each independently represents H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; However, X, L １ , Y, R ａ , R ｂ , R c , A and Z do not contain I; p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.

19. The compound according to any one of claims 1 to 15, The composition, wherein the amount of impurities containing K is 1 ppm by mass or less based on the compound in terms of element.

20. 20. The composition of claim 19, wherein the peroxide is less than or equal to 10 ppm by weight relative to the compound.

21. The composition according to claim 19 or 20, wherein the amount of impurities containing one or more elements selected from the group consisting of Mn, Al, Si, and Li is 1 ppm by mass or less based on the compound in terms of element.

22. The composition according to any one of claims 19 to 21, wherein the phosphorus-containing compound is present in an amount of 10 ppm by weight or less relative to the compound.

23. The composition according to any one of claims 19 to 22, wherein maleic acid is present in an amount of 10 ppm by mass or less relative to the compound.

24. A polymer comprising a structural unit derived from the compound according to any one of claims 1 to 15.

25. The polymer according to claim 24, further comprising a constitutional unit represented by the following formula (C6): 【Chemistry 8】 (In formula (C6), X Ｃ６１ is a hydroxyl group or a halogen group, R Ｃ６１ are each independently an alkyl group having 1 to 20 carbon atoms, * indicates the bonding site with the adjacent structural unit.)

26. A film-forming composition comprising the compound according to any one of claims 1 to 15, or the polymer according to claim 24 or 25.

27. The film-forming composition according to claim 26, further comprising an acid generator, a base generator, or a base compound.

28. forming a resist film on a substrate using a film-forming composition comprising the compound according to any one of claims 1 to 15 or the polymer according to claim 24 or 25; exposing the resist film to a pattern; developing the resist film after the exposure; A method for forming a resist pattern comprising the steps of:

29. A method for forming an insulating film, comprising the method of claim 28.

30. a double bond introduction step of introducing an unsaturated double bond into a substituent Q of a compound represented by the following formula (S1); A method for producing a compound represented by the following formula (0): 【Chemistry 9】 (In formula (S1), X 0 is an organic group having 1 to 30 carbon atoms, L １ each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group; p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more. 【Chemistry 10】 (In formula (0), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L １ each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R ａ , R ｂ , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more.

31. The compound represented by formula (S1) is a compound represented by formula (SA1): A method for producing the compound according to claim 30, comprising the steps of A1 and A2 below. A1) a step of obtaining a compound represented by the following formula (SA2) using the compound represented by the formula (SA1) and a compound represented by the following formula (RM1) or malononitrile: A2) A step of converting the compound represented by formula (SA2) into the compound represented by formula (0) using a fluoride source. 【Chemistry 11】 (In the formulae (SA1), (RM1) and (SA2), X 0 , L １ , Y, A, Z, p, m', n, and r are the same as defined in formulas (S1) and (0); Q １ is an aldehyde or ketone, LG is a group selected from a hydroxy group, an alkoxy group, a carbonate group, an acetal group, and a carboxy group, and the alkoxy group, the carbonate group, the acetal group, and the carboxy group each include an aliphatic group or an aromatic group having 1 to 60 carbon atoms which may have a substituent; R ３ represents a hydrogen group, or a carboxy group or ester group having 1 to 60 carbon atoms which may have a substituent, R ４ is a hydrogen radical, R ５ , R ６ each independently represents H, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, XA is a group selected from a hydrogen group and a halogen group.

32. The method for producing a compound according to claim 31, wherein in the step A2, a decarboxylation reaction is carried out on a compound represented by formula (SA2) using the fluoride source at 100°C or lower.

33. The method for producing the compound according to claim 31 or 32, further comprising using a reducing agent in the step A1 to obtain the compound represented by formula (SA2).

34. The method for producing a compound according to any one of claims 30 to 33, wherein in the formula (S1), A is benzene, toluene, or a heteroaromatic ring.

35. A method for producing a compound represented by formula (1) below, comprising: a step of forming a compound represented by formula (SB1) below from at least one of compounds represented by formula (SB2A) and formula (SB3A) below obtained through a step represented by formula B1A below and at least one of steps represented by formulas B2A and B3A below; and a double bond introduction step of introducing an unsaturated double bond into a substituent Qb of the compound represented by formula (SB1). B1A) A step of preparing a substrate SB1A comprising one or more amino groups and a core B having an aldehyde group or a ketone group. B2A) A step of obtaining a compound represented by the following formula (SB2A) in which iodine is introduced into the mother nucleus B B3A) A step of obtaining a compound represented by formula (SB3A) in which the amino group is substituted with a halogen group by a Sandmeyer reaction. 【Chemistry 12】 (In formula (1), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L １ are each independently a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and １ The ether group, ester group, thioether group, amino group, thioester group, acetal group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, or phosphate group may have a substituent, Y's each independently represent a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent, R ａ , R ｂ , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z's each independently represent an alkoxy group, an ester group, an acetal group, a carboxyalkoxy group, or a carbonate ester group, and the alkoxy group, ester group, acetal group, carboxyalkoxy group, or carbonate ester group of Z may have a substituent; p is an integer of 1 or greater, m is an integer of 1 or greater, n is an integer of 0 or greater, and r is an integer of 0 or greater. In formulae (SB1A), (SB2A), (SB3A), and (SB1), Zb represents a hydrogen group or an amino group which may have a substituent selected from a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; rb represents an integer of 1 or more; Qb and L １ｂ , X ｂ１ , B, pb, and mb' are defined as Q, L, X, A, p, and m in formula (1), respectively. Ｂ２ represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br.

36. The method according to claim 35, wherein the step of introducing a double bond uses an organophosphorus compound and a base.

37. A method for producing the compound according to claim 30, comprising a halogen introduction step of reacting the compound represented by formula (S1) with a halogenating agent to introduce a halogen atom.

38. The compound represented by formula (SA1) is at least one of compounds represented by formula (SB2A) and formula (SB3A) obtained through a step represented by B1A below and at least one of steps represented by B2A and B3A below. The method for producing the compound according to any one of claims 30 to 34. B1A) A step of preparing a substrate SB1A comprising one or more amino groups and a core B having an aldehyde group or a ketone group. B2A) A step of obtaining a compound represented by the following formula (SB2A) in which iodine is introduced into the mother nucleus B B3A) A step of obtaining a compound represented by formula (SB3A) in which the amino group is substituted with a halogen group by a Sandmeyer reaction. 【Chemistry 13】 (In formulas (SB1A), (SB2A), (SB3A), and (SA1A), Zb represents a hydrogen group or an amino group which may have a substituent selected from a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; rb represents an integer of 1 or more; Qb and L １ｂ , X ｂ１ , B, pb, and mb' are defined as Q, L, X, A, p, and m in formula (1), respectively. Ｂ２ represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br.

39. The method for producing the compound according to claim 36, wherein in the step B2A, iodine is introduced into the mother nucleus B using at least an iodine source and an oxidizing agent.

40. The method for producing the compound according to claim 30, wherein the compound represented by formula (SA1) is produced by the process shown in B1B below and at least one of the processes shown in B2B and B3B below. B1B) preparing a substrate SB1B comprising a core B having one or more amino groups and an aldehyde or ketone group; B2B) A step of obtaining a compound represented by formula (SB2B) by introducing iodine into the mother nucleus B B3B) A step of obtaining a compound represented by formula (SB3B) in which the amino group is substituted with a halogen group. 【Chemistry 14】 (In formulas (SB1B), (SB2B), (SB3B), and (SA1B), Zb represents a hydrogen group or an amino group which may have a substituent selected from a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; rb represents an integer of 1 or more; Qb and L １ｂ , X ｂ１ , B, pb, and mb are the same as Q, L, X, A, p, and m in formula (1), respectively. Ｂ２ represents I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br.

41. A method for producing the compound according to claim 40, further comprising the step shown in B4a below: B4a) Wittig process

42. The method for producing the compound according to claim 38 or 41, wherein in the step B2B, iodine is introduced into the mother nucleus B using at least an iodine source and an oxidizing agent.

43. The method for producing the compound according to any one of claims 40 to 42, wherein the mother nucleus B has an aromatic ring structure which may have a heteroatom.

44. a halogen introduction step of reacting a compound represented by the following formula (S1) with a halogenating agent to introduce a halogen atom; a double bond introduction step of introducing an unsaturated double bond into the substituent Q; The method for producing a compound represented by the following formula (1) comprising the formula (1), wherein the step of introducing a double bond uses an organic phosphorus compound and a base. 【Chemistry 15】 (In formula (S1), X 0 is an organic group having 1 to 30 carbon atoms, L １ each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; Q is an organic group having 1 to 30 carbon atoms and having a hydroxyl group, an aldehyde group, a carboxyl group, or a ketone group; p is an integer of 1 or more, m' is an integer of 0 or more, n is an integer of 0 or more, and r is an integer of 0 or more. 【Chemistry 16】 (In formula (1), X's each independently represent I, F, Cl, Br, or an organic group having 1 to 30 carbon atoms and having 1 to 5 substituents selected from the group consisting of I, F, Cl, and Br; L １ each independently represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group; each Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphone group, a urethane group, a urea group, an amide group, an imide group, or a phosphate group, and the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphone group, urethane group, urea group, amide group, imide group, and phosphate group of Y may have a substituent; R ａ , R ｂ , and R c each independently represents H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent, A is an organic group having 1 to 30 carbon atoms; Z is independently an alkoxy group, an ester group, an acetal group, or a carbonate group; p is an integer of 1 or more, m is an integer of 1 or more, n is an integer of 0 or more, and r is an integer of 0 or more.

45. a) A general structure represented by formula (1-1): 【Chemistry 17】 (In formula (1-1), R １ ~R ５ are each independently H, OH, or OCH ３ , halogen or linear or branched alkyl; R ６ ~R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １ ~R ５ At least one of R is OH; １ ~R ５ At least one of R is iodine; ６ ~R １０ One of them is OH or OCH ３ (It is) providing an iodine-containing alcoholic substrate having b) dehydrating the iodine-containing alcoholic substrate to obtain a compound having the general structure represented by formula (1): 【Chemistry 18】 (In formula (1), R １ ~R ５ are each independently H, OH, or OCH ３ , halogen or linear or branched alkyl; R ６ ~R ８ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １ ~R ５ At least one of R is OH; １ ~R ５ At least one of these is iodine. obtaining an iodine-containing vinyl monomer having the formula: The method for producing the iodine-containing vinyl monomer comprises:

46. The step of preparing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1) includes: c) a general structure represented by formula (1-2): 【Chemistry 19】 (In formula (1-2), R １ ~R ５ are each independently H, OH, or OCH ３ , halogen or linear or branched alkyl; R ７ , R ８ and R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １ ~R ５ At least one of R is OH; １ ~R ５ At least one of these is iodine. providing an iodine-containing ketonic substrate having d) reducing the iodine-containing ketonic substrate to obtain an iodine-containing alcoholic substrate having the general structure represented by formula (1-1); 46. ​​A method for producing the iodine-containing vinyl monomer of claim 45, comprising:

47. The step of preparing an iodine-containing alcoholic substrate having a general structure represented by the formula (1-1) includes: e) a general structure represented by formula (1-3): 【Chemistry 20】 (In formula (1-3), R １1 ~R １５ are each independently H, OH, or OCH ３ or linear or branched alkyl; R ６ ~R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １１ ~R １５ At least one of R is OH; ６ ~R １０ One of them is OH or OCH ３ (It is) providing an alcoholic substrate having f) introducing iodine into the alcoholic substrate to obtain an iodine-containing alcoholic substrate having the general structure represented by formula (1-1); 46. ​​A method for producing the iodine-containing vinyl monomer of claim 45, comprising:

48. The step of preparing an iodine-containing ketonic substrate having a general structure represented by formula (1-2) includes: g) A general structure represented by formula (1-4): 【Chemistry 21】 (In formula (1-4), R １１ ~R １５ are each independently H, OH, or OCH ３ or linear or branched alkyl; R ７ , R ８ and R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １１ ~R １５ At least one of the is OH. providing a ketonic substrate having h) introducing iodine into the ketonic substrate to obtain an iodine-containing ketonic substrate having the general structure represented by formula (1-2); 47. A method for producing the iodine-containing vinyl monomer of claim 46, comprising:

49. The step of preparing an alcoholic substrate having a general structure represented by formula (1-3) i) a general structure represented by formula (1-4): 【Chemical 22】 (In formula (1-4), R １１ ~R １５ are each independently H, OH, or OCH ３ or linear or branched alkyl; R ７ , R ８ and R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １１ ~R １５ At least one of the is OH. providing a ketonic substrate having j) reducing the ketonic substrate to obtain an alcoholic substrate having the general structure represented by formula (1-3); 48. A method for producing the iodine-containing vinyl monomer of claim 47, comprising:

50. k) A general structure represented by formula (1): 【Chemistry 23】 (In formula (1), R １ ~R ５ are each independently H, OH, or OCH ３ , halogen or linear or branched alkyl; R ６ ~R ８ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １ ~R ５ At least one of R is OH; １ ~R ５ At least one of these is iodine. providing an iodine-containing vinyl monomer having l) Acetylation of the iodine-containing vinyl monomer to obtain a vinyl monomer having the general structure represented by formula (2): 【Chemistry 24】 (In formula (2), R １６ ~R ２０ are each independently H, OH, or OCH ３ , OAc, halogen or linear or branched alkyl; R ６ ~R ８ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １６ ~R ２０ At least one of R is OAc; １６ ~R ２０ At least one of these is iodine. and obtaining an iodine-containing acetylated vinyl monomer having the formula: The method for producing the iodine-containing acetylated vinyl monomer comprises:

51. c) a general structure represented by formula (1-2): 【Chemistry 25】 (In formula (1-2), R １ ~R ５ are each independently H, OH, or OCH ３ , halogen or linear or branched alkyl; R ７ , R ８ and R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １ ~R ５ At least one of R is OH; １ ~R ５ At least one of these is iodine. providing an iodine-containing ketonic substrate having d) reducing the iodine-containing ketonic substrate to obtain a compound having the general structure represented by formula (1-1): 【Chemistry 26】 (In formula (1-1), R １ ~R ５ are each independently H, OH, or OCH ３ , halogen or linear or branched alkyl; R ６ ~R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １ ~R ５ At least one of R is OH; １ ~R ５ At least one of R is iodine; ６ ~R １０ One of them is OH or OCH ３ (It is) obtaining an iodine-containing alcoholic substrate having the formula: A method for producing the iodine-containing alcoholic substrate, comprising:

52. e) a general structure represented by formula (1-3): 【Chemistry 27】 (In formula (1-3), R １1 ~R １５ are each independently H, OH, or OCH ３ or linear or branched alkyl; R ６ ~R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １１ ~R １５ At least one of R is OH; ６ ~R １０ One of them is OH or OCH ３ (It is) providing an alcoholic substrate having f) introducing iodine into the alcoholic substrate to obtain a compound having a general structure represented by formula (1-1): 【Chemistry 28】 (In formula (1-1), R １ ~R ５ are each independently H, OH, or OCH ３ , halogen or linear or branched alkyl; R ６ ~R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １ ~R ５ At least one of R is OH; １ ~R ５ At least one of R is iodine; ６ ~R １０ One of them is OH or OCH ３ (It is) obtaining an iodine-containing alcoholic substrate having the formula: A method for producing the iodine-containing alcoholic substrate, comprising:

53. g) A general structure represented by formula (1-4): 【Chemical 29】 (In formula (1-4), R １１ ~R １５ are each independently H, OH, or OCH ３ or linear or branched alkyl; R ７ , R ８ and R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １１ ~R １５ At least one of the is OH. providing a ketonic substrate having h) introducing iodine into the ketone substrate to obtain a general structure represented by formula (1-2): 【Chemistry 30】 (In formula (1-2), R １ ~R ５ are each independently H, OH, or OCH ３ , halogen or linear or branched alkyl; R ７ , R ８ and R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １ ~R ５ At least one of R is OH; １ ~R ５ At least one of these is iodine. obtaining an iodine-containing ketonic substrate having the formula: The method for producing the iodine-containing ketonic substrate comprises:

54. i) a general structure represented by formula (1-4): 【Chemistry 31】 (In formula (1-4), R １１ ~R １５ are each independently H, OH, or OCH ３ or linear or branched alkyl; R ７ , R ８ and R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １１ ~R １５ At least one of the is OH. providing a ketonic substrate having j) reducing the ketonic substrate to give a general structure represented by formula (1-3); 【Chemistry 32】 (In formula (1-3), R １1 ~R １５ are each independently H, OH, or OCH ３ or linear or branched alkyl; R ６ ~R １０ are each independently H, OH, or OCH ３ , halogen or cyano group; However, R １１ ~R １５ At least one of R is OH; ６ ~R １０ One of them is OH or OCH ３ (It is) obtaining an alcoholic substrate having The method for producing the alcoholic substrate comprising:

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