Compound , composition, method for exhibiting sensitizing effect, and method for producing the compound

Abstract

below: (wherein RG is a group comprising at least one cyclic structure, I is an iodine atom, R 1may be identical or different and is a C 0-30monovalent functional group free from comprising a polymeric unsaturated bond, n is an integer of

Description

[Technical Field]

[0001] This invention relates to compounds, compositions, methods for exhibiting sensitizing effects, and manufacturing methods. [Previous Technology]

[0002] In recent years, due to advancements in lithography technology, the miniaturization of semiconductors (patterns) and pixels in the manufacturing of semiconductor devices and liquid crystal display devices has been rapidly advancing. Therefore, materials for addressing this miniaturization are desired. For example, Patent Document 1 discloses a resist composition having a structure composed of cross-linked complex aromatic rings and containing a compound having iodine atoms. This resist composition exhibits excellent etching resistance. Furthermore, Patent Document 2 discloses a compound having polymerizable groups and iodine atoms. Resistant compositions containing these compounds can form resist patterns with excellent CD uniformity. [Prior Art Documents] [Patent Documents]

[0003] Patent Document 1: International Publication No. 2020 / 040161; Patent Document 2: Japanese Patent Application Publication No. 2021-188040 [Summary of the Invention]

[0004] [The problem that the invention aims to solve]

[0005] It is desirable to develop compositions for microlithography that can handle miniaturization, and preferably to develop compounds for use as resists. In view of this, the object of the present invention is to provide a compound useful as a composition for microlithography, a composition containing the compound, a method for exhibiting a sensitizing effect using the compound, and a method for manufacturing the compound. [Means for solving the problem]

[0006] The inventors discovered that compounds with specific structures can solve the aforementioned problems.

[0007] That is, the present invention includes the following states. [1] A compound represented by the following formula (1). (In the formula, RG is a group containing at least one cyclic structure, I is an iodine atom, R1 may be the same or different of a monovalent functional group with 0 to 30 carbons that does not contain polymerizable unsaturated bonds, n is an integer from 1 to 5, and m is an integer from 1 to 5.) [2] The compound as described above, wherein the aforementioned RG is derived from a group of benzene, naphthalene, anthracene, pyrene, heteroaromatic ring or polycyclic alicyclic ring that may have substituents, and the aforementioned R1 is one selected from the group of Rf selected from hydroxyl groups and ether groups having protecting groups, and hydrocarbon groups with 0 to 30 carbons that may have substituents. [3] The compound as described above, wherein the aforementioned Rf is Rf' selected from the group of one or more ether groups selected from hydroxyl groups and having protecting groups that can be removed by acid, base or heat. [4] In the above-described compounds, RG is derived from a group of benzene, naphthalene, anthracene, phenanthrene, pyrene, fumaryl, or adamantane that may have substituents. [5] In the above-described compounds, RG is derived from a group of benzene, naphthalene, or adamantane that may have substituents. [6] In the above-described compounds, R1 is selected from -OR2, -COOR3, -CH2-OR4, or -CHO, where R2 is a hydrogen atom, an alkyl group of 1 to 30 carbon atoms that may have substituents, or an aryl group of 1 to 30 carbon atoms; R3 is a hydrogen atom, an alkyl group of 1 to 29 carbon atoms that may have substituents, or an aryl group of 1 to 29 carbon atoms; and R4 is a hydrogen atom, an alkyl group of 1 to 29 carbon atoms that may have substituents, or an aryl group of 1 to 29 carbon atoms. [7] In the above-described compounds, R1 has a protecting group. [8] In the above-described compounds, it is represented by any of the following formulas. (In the formula, Z is I, R1, or a linking group used to form a dimer. The definitions of I and R1 are the same as in formula (1). A is a group with a protecting group. R is a non-functional organic group. R1, A, and R are bonded to bondable positions. r1 to r4 are integers from 0 to 5, and the sum of r1 to r4 in one benzene is less than or equal to the valence of benzene.) (In the formula, the definitions of I, A, and R1 are the same as above. R” is an organic group other than a hydrogen atom or R1. s1 is 1 to 7, s2 to s3 are 0 to 7, and s4 is an integer from 1 to 7. However, the sum of s1 to s4 is less than or equal to the valence of naphthalene, and the selection is made such that at least one of s2 and s3 is 1 or more.) (In the formula, the definitions of I, R1, and R” are the same as above.) t1 is 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 14. However, the sum of t1 to t3 is less than the valence of adamantane.) [9] The above-mentioned compounds are represented by any of the following formulas. (In the formula, the definitions of I, Z, R, R1, and A are the same as those in formula (Bz).(In the formula, the definitions of I, R1, A, and R” are the same as those of formula (N), x and y are 0 or 1, but at least one of them is 1, and s4' represents the number of R” that can be bonded to the 1, 7, and 8 positions of naphthalene, and is an integer from 1 to 3. (In the formula, the definitions of I, R1, and R” are the same as those of formula (Ad), one of D is I, and the other of D is R1.)

[10] The above-mentioned compound is represented by any of the following formulas. (In the formula, the definitions of I, Z, R, R1, and A are the same as those of formula (Bz). (In the formula, the definitions of I, R1, R”, A, x, y, and s4' are the same as those of formula (n). (In the formula, the definitions of I, R1, and R” are the same as those of formula (Ad).)

[11] The above-mentioned compound, wherein the aforementioned R1 is hydroxyl, carboxyl, ester, or hydroxyalkyl, and the aforementioned A is A' represented by -OR aOR b (R a is a straight-chain or branched alkyl group having 1 to 3 carbon atoms. Rb is a monovalent straight-chain, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group, and forms a ring together with an adjacent oxygen atom. ), containing one or more of the A'.

[12] In the above-described compounds, RG is derived from a phenyl group that may have substituents.

[13] In the above-described compounds, RG is a phenyl group, and when there are multiple R1s, R1 does not contain a combination of an alkoxy group (except for those with a protecting group) and an aldehyde group, a combination of an alkoxy group and a hydroxyl group, or a combination of a hydroxyl group and an aldehyde group; RG is a naphthyl group, and when there are multiple R1s, R1 does not contain a combination of a hydroxyl group and a carboxyl group.

[14] The above-described compounds are represented by the following formula (Bz4). (In the formula, the definitions of I, R, A, and Z are the same as in formula (Bz), R 1' is a monovalent functional group with 0 to 30 carbon atoms, excluding hydroxyl groups, and may be the same or different from it. r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is less than or equal to the valence of benzene. )

[15] The above-mentioned compound is represented by the following formula (Bz4-1). (In the formula, I, R, Z, and R1' are defined as in formula (Bz4), r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is less than or equal to the valence of benzene.)

[16] The above-mentioned compound is represented by the following formula (Bz4-2). (In the formula, I is defined as in formula (Bz4), r4' is an integer from 0 to 4, and r5' is an integer from 0 to 4.)

[17] The above-mentioned compound is represented by any of the following formulas.

[18] The compounds described above are represented by any of the following formulas. (In the formula, I, R, Z, A, and R1 are defined in the same way as in formula (Bz), A' is a protecting group and is represented by -OR aOR b, -O-CO-OR b, or -OR a-CO-OR b. Ra is a straight-chain or branched alkyl group having 1 to 3 carbon atoms.)Rb is a monovalent straight-chain, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group, and forms a ring together with an adjacent oxygen atom. )

[19] The above-described compounds are represented by any of the following formulas. (In the formula, I, R1, and A are defined as in formula (Bz), A' is a protecting group and is represented by -OR aOR b, -O-CO-OR b, or -OR a-CO-OR b. Ra is a monovalent straight-chain or branched alkyl group having 1 to 3 carbon atoms. Rb is a monovalent straight-chain, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group, and forms a ring together with an adjacent oxygen atom. Z' is I, R1, or a hydrogen atom. )

[20] The above-described compounds are represented by RG, which is derived from a naphthalene group that may have substituents.

[21] The above-described compounds are represented by any of the following formulas. (In the formula, I, R1, R”, A, x, y, s4’ are defined as in formula (n).)

[22] The above-mentioned compounds are represented by any of the following formulas. (In the formula, I, R1, R” are defined as in formula (n), A’ is a group with a protecting group and is represented by -OR aOR b, -O-CO-OR b or -OR a-CO-OR b. Ra is a straight-chain or branched alkyl group with 1 to 3 carbon atoms. Rb is a straight-chain, branched, or cyclic alkyl group with 1 to 3 carbon atoms in a monovalent form, or a divalent cyclic alkyl group, and forms a ring together with the adjacent oxygen atom.)

[23] The above-mentioned compounds are represented by R1, which is a hydroxyl, carboxyl, ester, or hydroxyalkyl group.

[24] The above-mentioned compounds are represented by any of the following formulas. (In the formula, the definitions of I, R1, A, A', x, and y are the same as those in formula (n).)

[25] In the above compounds, RG is derived from adamantane that may have substituents.

[26] In the above compounds, they are represented by any of the following formulas. (In the formula, the definitions of I, R1, and R” are the same as those in formula (Ad).)

[27] The compound described above, wherein R1 is a hydroxyl, carboxyl, ester, or hydroxyalkyl group.

[28] The compound described above is represented by any of the following formulas. (In the formula, the definitions of I and R1 are the same as those in formula (Ad).)

[29] A composition comprising the compound described above.

[30] The composition described above is used in lithography.

[31] The composition described above comprises two or more compounds represented by the aforementioned formula (1).

[32] The composition described above further comprises compounds represented by the following formula (DM0-1), or the following formula (BP0-1), or a combination thereof.(In the formula, RG, I, and R1 are defined in the same way as in formula (1), Q is a base or single bond derived from the bond between molecules, n' is 0 to 5 and is an integer less than n, m' is 1 to 5 and is an integer less than m, and b is an integer from 1 to 4.)

[33] As in the above composition, the compound represented by the aforementioned formula (DM0-1) is the compound represented by the following formula (DM1a), (Dn1) or (Da1), and the compound represented by the aforementioned formula (BP0-1) is the compound represented by the following formula (BP1a), (Bn1) or (Ba1). (In the formula, Z is I, R1, or a linking group used to form a dimer. The definitions of I and R1 are the same as in formula (1). A is a group with a protecting group. R is a non-functional organic group. R1, A, and R are bonded to bondable positions. r1 to r4 are integers from 0 to 5, and the total of r1 to r4 in one benzene is less than or equal to the valence of benzene.) (In the formula, the definitions of I, R1, and A are the same as in formula (DM1a). R” is a hydrogen atom or an organic group other than R1. I, R1, A, and R” are bonded to bondable positions. The definition of Q is the same as in formula (DM0-1). s1 is 1 to 7, s2 to s3 are 0 to 7, and s4 is an integer from 1 to 7. However, the total of s1 to s4 is less than or equal to the valence of naphthalene, and is selected in such a way that either s2 or s3 is 1 or more. nd is an integer from 1 to 4.) (In the formula, I, R1, R2, R3, R4 ... The definition of 1 is the same as in formula (Dn1), R” is a hydrogen atom or an organic group other than R1, Rd is a single bond or -O- (ether bond), t1 is 1~10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 13. However, regarding t1~t3, the sum of t1~t3 is below the valence of adamantane. (In the formula, the definitions of I, Z, R, R1, and A are the same as in formula (DM1a), r1, r2, and r3 are integers from 0 to 5, a1 and r4a are integers from 0 to 4, and a1 and r4a satisfy a1+r4a≦r4. Here, the definition of r4 is the same as in formula (DM1a). (In the formula, the definitions of I, R1, R”, and A are the same as in formulas (Dn1) and (Da1), and the definitions of s2~s4 are the same as in formula (Dn1). s1b is an integer from 0 to 6, and is an integer that satisfies s1b≦(s1-1). Here, the definition of s1 is the same as that of formula (Dn1). (In the formula, the definitions of I, R1, and R” are the same as those of formula (Dn1) and (Da1), the definitions of t2 and t3 are the same as those of formula (Da1), and t1b is an integer from 0 to 9, and is an integer that satisfies t1b≦(t1-1). Here, the definition of t1 is the same as that of formula (Da1).)

[34] The composition described above contains the compound represented by the aforementioned formula (DM0-1).

[35] The composition described above, wherein the compound represented by formula (1) and formula (DM0-1) satisfies the following relationship.0.1 ≧ [Amount of compound (DM0-1) (mol)] ÷ [Amount of compound (1) (mol)] ≧ 0.000001

[36] The composition described above includes the compound represented by formula (BP0-1).

[37] The composition described above, wherein the compound represented by formula (BP0-1) is a compound represented by formula (BP1a) and Z is not I, or a compound represented by formula (Bn1) or formula (Ba1).

[38] The composition described above, wherein the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relationship. 0.1 ≧ ([total amount of compounds of formula (DM0-1) and compounds of formula (BP0-1) (mol)]) ÷ [amount of compounds of formula (1) (mol)] ≧ 0.000001

[39] As described above, wherein the compounds represented by the aforementioned formula (DM0-1) are compounds represented by the following formulas (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x) or (Ba1-eb), and the compounds represented by the aforementioned formula (BP0-1) are compounds represented by the following formulas (BP1a-Dt), (Bn1-Dt) or (Ba1-Dt). (In the formula, the definitions of Z, R, R1, A, r1, r2, r3, r4a are the same as in formula (BP1a).) (In the formula, the definitions of Z, I, R1, A, R, r1~r4a are the same as in formula (DM1a).) (In the formula, the definitions of Z, R1, A, R, r1~r4a are the same as in formula (DM1a).) (In the formula, the definitions of R1, R”, A, s2~s4a are the same as in formula (Bn1).) (In the formula, the definitions of I, R1, A, R”, Q, s1~s4a are the same as in formula (Dn1).) (In the formula, the definitions of R1, A, R”, Q, s2~s4a are the same as in formula (Dn1).) (In the formula, the definitions of R1, R”, t2, t3a are the same as in formula (Ba1).) (In the formula, the definitions of I, R1, R”, R… The definitions of d, t1~t3 are the same as those in formula (Da1). (In the formula, the definitions of R1, R”, Rd, t2~t3 are the same as those in formula (Da1). (In the formula, the definitions of I, R1, R”, Rd, t1~t3 are the same as those in formula (Da1). (In the formula, the definitions of I, R1, R”, Rd, t1~t3 are the same as those in formula (Da1). (In the formula, the definitions of I, R1, R”, Rd, t1~t3 are the same as those in formula (Da1).)

[40] In the above composition, RG of the above formula (1) is derived from a phenyl group that may have substituents.

[41] In the above composition, RG of the above formula (1) is derived from a naphthalene group that may have substituents.

[42] In the above composition, RG of the above formula (1) is derived from an adamantane group that may have substituents.

[43] The composition described above exhibits a sensitizing effect under radiation irradiation.

[44] The composition described above contains a metal impurity content of less than 1 ppm.

[45] A method for exhibiting a sensitizing effect under radiation irradiation of a lithography composition, wherein the compound described above is used.

[46] The method described in

[45] uses two or more of the aforementioned compounds.

[47] A method for manufacturing the compound described above, comprising the step of introducing an iodine atom or an R1 group into a compound containing the aforementioned RG group.

[48] ​​A method for manufacturing a compound as described above, wherein the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, the definitions of I, Z, R1, A, R, r1~r4 are the same as those of formula (DM1a).) The aforementioned manufacturing method comprises: 1) a step of preparing a compound represented by formula (MB), (wherein, the definitions of I, R1, R, r1, r2 are the same as those of formula (Bz), and R1, R, OH are bonded at any bondable position.) 2) an iodination step of iodizing the compound, 3) a protecting group introduction step of introducing a protecting group into the compound, and 4) a reduction step of reducing the compound.

[49] The method for manufacturing a compound as described in

[48] , wherein the aforementioned protecting group introduction step comprises a step of introducing a protecting group using an inorganic base with the hydroxyl group of formula (MB).

[50] A method for manufacturing a compound as described above, which is a method for manufacturing a compound represented by the aforementioned formula (1), the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, the definitions of I, Z, R1, A, R, r1~r4 are the same as those of formula (DM1a).) The aforementioned manufacturing method includes: 1) a step of preparing a compound represented by formula (Bz4), (wherein, the definitions of I, R, A, Z are the same as those of formula (Bz), R1' may be the same or different and may be a 1-valent functional group excluding hydroxyl groups with 0 to 30 carbon atoms that do not contain polymerizable unsaturated bonds, r1', r2', r4' are integers from 0 to 5, and the total of r1', r2', r4' is less than or equal to the valence of benzene.) 2) a step of performing an iodination step of iodizing the compound once or twice or more.

[51] A method for manufacturing a compound as described above, which is a method for manufacturing a compound represented by the aforementioned formula (1), wherein the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, the definitions of I, Z, R1, A, R, r1~r4 are the same as those of formula (DM1a).) The aforementioned manufacturing method comprises: 1) a step of preparing a compound represented by formula (Bz5), (wherein, the definitions of I, Z, R1, A, R, r1~r4 are the same as those of formula (DM1a).) 2) a step of esterifying the carboxylic acid of the compound represented by formula (Bz5), 3) a step of reducing the obtained ester group to convert it into a hydroxymethyl group.

[52] A method for manufacturing the compound as described above, which is a method for manufacturing the compound represented by the aforementioned formula (1), the compound represented by the aforementioned formula (1) is represented by formula (N), (wherein, the definitions of I, R1, A, R” are the same as those of formulas (Dn1) and (Bn1), but I, R1, R” and A are bonded at any bondable position, s1 is 1~7, s2~s3 are 0~7, and s4 is an integer from 1 to 7. However, the sum of s1~s4 is less than the valence of naphthalene, and is selected such that either s2 or s3 is 1 or more.) The aforementioned manufacturing method includes: 1) a step of preparing the compound represented by formula (MN), (wherein, the definitions of R1, R”, s3, and s4 are the same as those of formula (N).) 2) an iodination step of iodizing the compound, 3) a protecting group introduction step of introducing a protecting group into the compound, and 4) a reduction step of reducing the compound.

[53] A method for manufacturing a compound as described above, which is a method for manufacturing a compound represented by the aforementioned formula (1), the compound represented by the aforementioned formula (1) is represented by formula (Ad), (where I, R1, R” are defined as in formula (Da1), I, R1, R” are bonded at any bondable position, t1 is 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 14. However, regarding t1 to t3, the sum of t1 to t3 is less than or equal to the valence of adamantane.) The aforementioned manufacturing method includes: 1) a step of preparing a compound represented by formula (MA), (where R1, R, t2, t3 are defined as in formula (Ad)). 2) an iodination step of iodizing the compound.

[54] A method for manufacturing a compound as described in any of

[48] to

[53] , wherein the aforementioned iodination step comprises a step of iodizing in a system composed of a multiphase, wherein the multiphase comprises an organic phase comprising an organic solvent as a solvent and an aqueous phase comprising water as a solvent.

[55] A method for manufacturing a compound as described in any of

[48] to

[53] , wherein the aforementioned iodination step comprises a step of distilling off water and concentrating the reaction solution during the reaction.

[56] A method for manufacturing a compound as described in any of

[48] to

[53] , wherein the aforementioned iodination step comprises a step of allowing the mixture to stand for 1 hour to 48 hours after feeding in the matrix and the iodizing agent.

[57] A method for manufacturing a compound as described above, comprising a step selected from any one or more of the following 1) to 3): 1) a step of preparing a compound represented by formula (Ad-A-3-0), 2) a step of preparing a compound represented by formula (Ad-A-3-1), and 3) a step of preparing a compound represented by formula (Ad-A-3-2).

[58] A method for manufacturing the compound of

[57] includes: 1) preparing the compound represented by formula (Ad-A-3-0), 2) oxidizing the compound represented by formula (Ad-A-3-0), 3) esterifying the carboxylic acid of the compound obtained by esterification, 4) hydrolyzing the ester group of the compound obtained by hydrolysis to convert it into a carboxylic acid, and 5) iodizing the compound by iodination.

[59] A method for manufacturing the compound of any one of

[47] to

[58] further includes a step of treating it with an adsorbent.

[60] The compound described above is represented by the following formula (Ad-A-3).

[61] The compound described above is represented by the following formula (Ad-A-4). [Effects of the Invention].

[0008] A compound useful as a component for lithography, a composition containing the compound, a method for exhibiting an enhancing effect using the compound, and a method for manufacturing the compound are provided. Furthermore, an enhancing effect can be obtained by using the compound and composition of the present invention in a lithography process.

Implementation Method

[0009] The present invention will be described in detail below. In the present invention, the "~" in "X~Y" etc. includes X and Y as its end values.

[0010] 1. The compound of this embodiment is represented by the following formula (1).

[0011]

[0012] [RG] Wherein, RG is a group containing at least one cyclic structure. The valence of RG may be appropriately adjusted according to the number of substituents other than I, R1, and R1 described below. The group containing the cyclic structure may contain aromatic rings, alicyclic rings, or heterocyclic rings, but preferably a group with 6 to 60 carbon atoms, and more preferably a group derived from aromatic rings such as benzene, naphthalene, biphenyl, anthracene, phenanthrene, pyrene, and fumonisin, heteroaromatic rings, cyclohexane, cyclododecane, dicyclopentane, tricyclodecane, or adamantane, which may have substituents. Furthermore, RG may not contain a ring assembly formed by a single bond connecting a single ring (e.g., biphenyl, naphthyl, bicyclopropyl, etc.). In this case, RG is specifically preferably a group having at least one cyclic structure selected from monocyclic aromatic ring structures, condensed ring aromatic structures, and polycyclic alicyclic structures.

[0013] In view of ease of acquisition, etc., RG is preferably derived from a group of benzene, naphthalene, anthracene, phenanthrene, pyrene, fumaryl or polycyclic alicyclic group that may have substituents, more preferably from a group of benzene, naphthalene, anthracene, pyrene, heteroaromatic or polycyclic alicyclic group that may have substituents, even more preferably from a group of benzene, naphthalene, anthracene, phenanthrene, pyrene, fumaryl or adamantane that may have substituents, further preferably from a group of benzene, naphthalene or adamantane that may have substituents, and especially preferably from a group of benzene, naphthalene or adamantane.

[0014] [I] Wherein, I is an iodine atom. n represents the number of I, and is an integer from 1 to 5. From the viewpoint of sensitizing effect, solubility in solvents, and chemical stability, n is preferably an integer from 1 to 3, and more preferably 1 or 2. By setting n greater than 1, a sensitizing effect can be obtained, and by setting n to 5 or less, the solubility of the compound in solvents widely used in the semiconductor field and the stability of the compound itself can be ensured.

[0015] [R 1] In the formula, R 1 can be the same or different, a monovalent functional group with 0 to 30 carbon atoms that does not contain polymerizable unsaturated bonds. By converting R 1 into other groups or bonding with other groups, derivatives of the compound of formula (1) can be produced. Polymerizable unsaturated bonds refer to vinyl double or triple bonds. If R 1 is set to one of the aforementioned, the stability and solubility are excellent.

[0016] R1 is a functional group, not an alkyl group. R1 can be, for example, an alkoxy group with 1 to 30 carbon atoms, a carboxyl group with 1 to 30 carbon atoms, a carboxylic acid ester group with 2 to 10 carbon atoms, an alkoxyalkyl group with 2 to 30 carbon atoms, a hydroxyalkyl group with 1 to 30 carbon atoms, an aldehyde group, a halogen atom other than an iodine atom, a nitro group, an amino group, a thiol group, a cyano group, or a hydroxyl group. From the viewpoint of enhancing sensitization, R1 is preferably a hydroxyl group, a carboxyl group, an ester group, a hydroxyalkyl group, a halogen atom other than an iodine atom, a nitro group, an amino group, or a cyano group. Among these groups, there may be substituents or substituted groups. Unless otherwise defined, "substitution" means that one or more hydrogen atoms in the functional group are replaced by substituents. The term "substituent" is not particularly limited, and examples include halogen atoms, hydroxyl groups, cyano groups, nitro groups, thiols, heterocyclic groups, straight-chain aliphatic hydrocarbon groups with 1 to 20 carbon atoms, branched aliphatic hydrocarbon groups with 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon groups with 3 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, amino groups with 0 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, alkynyl groups with 2 to 20 carbon atoms, acetylsyl groups with 1 to 30 carbon atoms (preferably alkoxy groups with 1 to 20 carbon atoms, aryloxy groups with 7 to 30 carbon atoms), alkoxycarbonyl groups with 2 to 20 carbon atoms, or alkylsilyl groups with 1 to 20 carbon atoms. These groups can form ring structures with substituents or groups containing substituents, or with other R1 groups. Preferred examples of groups that can form ring structures include glycidyl groups, cyclic acetal groups, and groups with two adjacent hydroxyl groups as acetal protecting groups.

[0017] Wherein, R1 is preferably a hydroxyl, carboxyl, ester, or hydroxyalkyl group, more preferably a group selected from those represented by -OR2, alkoxy groups with 1 to 30 carbon atoms, hydroxyl groups, carboxyl groups with 1 to 30 carbon atoms, carboxyl groups with 2 to 10 carbon atoms, alkoxyalkyl groups with 2 to 30 carbon atoms, alkoxyalkyl groups with 2 to 30 carbon atoms, hydroxyalkyl groups with 1 to 10 carbon atoms, or aldehyde groups. For example, R1 may be selected from -OR2, -COOR3, -CH2-OR4, or -CHO. Here, R2 is a hydrogen atom, an alkyl group with 1 to 30 carbon atoms, an aryl group with 1 to 30 carbon atoms, or a cyclic alkyl ether group with 1 to 5 carbon atoms. The aforementioned carboxyl or carboxyl ester group is more preferably represented by -COOR3. Here, R3 is a hydrogen atom, an alkyl group with 1 to 29 carbon atoms, or an aryl group with 1 to 29 carbon atoms. The aforementioned alkoxyalkyl or hydroxyalkyl group is preferably represented as -CH2-OR4. Here, R4 is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms. The aforementioned alkyl or aryl group may have substituents. Examples of such substituents include alkoxy groups. Therefore, in the aforementioned -OR2, R2 in one state sample may be -CH2-OC2H5.

[0018] The alkyl group in R2 to R4 is preferably methyl, ethyl, or propyl (including isomers. The same applies below). The aryl group is preferably phenyl or naphthyl.

[0019] R1 may have a protecting group. A protecting group is a group that dissociates under specific conditions, also called a dissociable group. Preferably, the protecting group is an acid-dissociable group that dissociates in the presence of an acid. Preferred examples of such a group include 1-substituted ethyl, 1-substituted n-propyl, 1-branched alkyl, silicone, acetyl, 1-substituted alkoxymethyl, cyclic ether, alkoxycarbonyl, or alkoxycarbonylalkyl. In one state, R1 may be a hydroxyl or carboxyl group protected by a protecting group. For example, R1 is -O-CH2-O-R'. R' is, for example, an alkyl group having 1 to 5 carbon atoms. This state corresponds to R1 being -OR2 (but R2 being CH3) and R2 having an alkoxy group (-O-R') as a substituent. When R1 is a group with a protecting group, as described later, R1 is sometimes designated as A or A'.

[0020] In the formula, m represents the number of R1, and is an integer from 1 to 5. From the viewpoint of solvent solubility, m is preferably 4, 3, 2 or 1. When m is 2 or 3, the complex R1s can be different or the same. m is more preferably 2 or 3, and even more preferably 2. The sum of m and n can be adjusted appropriately according to the valence of RG.

[0021] The aforementioned compound may, as needed, have an organogroup other than R1 as a substituent. Examples of such organogroups include alkyl groups having 1 to 30 carbon atoms. Multiple such groups may also be present. However, the aforementioned compound preferably does not contain any organogroup other than R1 and the iodine atom.

[0022] When RG is a phenyl group and a plurality of R1s are present, R1 preferably does not contain a combination of alkoxy and aldehyde groups, alkoxy and hydroxyl groups, or aldehyde and hydroxyl groups. The alkoxy group here excludes those with a protecting group. The alkoxy group is, for example, methoxy or ethoxy. When RG is a naphthalene group and a plurality of R1s are present, R1 preferably does not contain a combination of hydroxyl and carboxyl groups.

[0023] When RG is derived from a group consisting of benzene, naphthalene, anthracene, pyrene, heteroaromatic rings, or polycyclic alicyclic rings, R1 is preferably selected from one or more Rf groups and one or more Rg groups. Furthermore, R1 is selected from one or more Rf' groups and one or more Rg groups. Rf is selected from the group consisting of hydroxyl groups and ether groups having a protecting group. Rf' is selected from the group consisting of hydroxyl groups and ether groups having a protecting group that can be removed by acid, base, or heat. Rg is a hydrocarbon group with 0 to 30 carbon atoms that may have substituents. Especially when RG has a benzene or naphthalene structure, it is preferable that R1 is selected from one or more Rf groups selected from the group consisting of hydroxyl groups and ether groups having a protecting group, and one or more hydrocarbon groups with 0 to 30 carbon atoms that may have substituents, and it is even more preferable that Rf is selected from the group consisting of one or more hydroxyl groups and ether groups having a protecting group that can be removed by acid, base, or heat. If the compound of formula (1) has such groups as R1, then the reaction of linking the compound with other compounds can proceed smoothly.

[0024] As mentioned above, the compound of formula (1) can be linked with other compounds. For example, the compound of formula (1) can be made into dimers to pentamers. Polymers are described later.

[0025] 1-2. Preferred State Sample (1) First State Sample In the first state sample, RG is benzene. The compound represented by formula (1) in this state sample (hereinafter referred to as "the compound of formula (1)", etc.) is preferably represented by formula (Bz) from the viewpoint of sensitizing effect and ease of acquisition.

[0026]

[0027] In the formula, A is a group with a protecting group. A becomes a functional group by removing the protecting group, and is therefore one of R1. As mentioned above, the protecting group is preferably an acid-dissociable group. Therefore, the group with a protecting group is preferably a group formed by protecting a hydroxyl or carboxyl group with an acid-dissociable group. A can be A' represented by -OR aOR b, in which case the compound of formula (Bz) preferably contains more than one of the A'. Ra and Rb are described later.

[0028] In the formula, R is a non-functional organic group. Examples of such organic groups include alkyl groups with 1 to 30 carbon atoms.

[0029] In the formula, Z is I, R1, or a linking group used to form a dimer. When Z is used to form a linking group for a dimer, two molecules are bonded together by a single bond to form a dimer. The dimer is included in the compound represented by the formula (DM1a) described below. Z may not contain a linking group used to form a dimer. When Z does not contain a linking group used to form a dimer, Z is specifically designated as Z'.

[0030] In the formula, the definitions of I and R1 are the same as those described above. From the viewpoint of enhancing sensitization, R1 is preferably a hydroxyl, carboxyl, ester, hydroxyalkyl, halogen atom other than an iodine atom, nitro, amino, or cyano group.

[0031] R1, R, and A are bonded at any bondable position. r1 to r4 are integers from 0 to 5, and the sum of r1 to r4 is less than or equal to the valence of benzene. Furthermore, r1 to r4 are preferably integers from 1 to 4, more preferably integers from 1 to 3, and particularly preferably integers from 1 or 2. However, at least one of r2 and r3 is preferably 1 or more. Hereinafter, a preferred form of the compound will be described from the viewpoints of sensitizing effect and ease of acquisition.

[0032] [Bz1 system] Compounds of formula (Bz) are preferably represented by formula (Bz1). Compounds of formula (Bz1) have one R1 that is not derived from Z. In this invention, unless otherwise specified, each substituent of the compound is defined in the same way as the group of compounds to which the compound belongs.

[0033]

[0034] (Bz1-1 system) The compound of formula (Bz1) is preferably represented by formula (Bz1-1). The compound of formula (Bz1-1) has an R1 not derived from Z at the I-position.

[0035]

[0036] The compound of formula (Bz1-1) is preferably represented by formula (1b), and more preferably by formula (1b-3). Z' can be I, R1 or hydrogen atom, and A and Z or A and Z' can form a cyclic structure together with the protecting group.

[0037]

[0038] Furthermore, the compound of formula (Bz1-1) is preferably represented by formula (1b-1), and more preferably by formula (1b-4).

[0039]

[0040] (Bz1-2 system) The compound of formula (Bz1) is preferably represented by formula (Bz1-2). The compound of formula (Bz1-2) has an R1 not derived from Z at the para position of I. A and Z can form a cyclic structure together with the protecting group. Also, Z and R1 can form a cyclic structure together with the protecting group.

[0041]

[0042] The compound of formula (Bz1-2) is preferably represented by formula (Bz1-2-1), and more preferably by formula (Bz1-2-2). A and Z or A and Z' may form a cyclic structure together with the protecting group.

[0043]

[0044] (Bz1-3 system) Further, the compound of formula (Bz1) is preferably represented by formula (Bz1-3). This compound has an R1 not derived from Z at the ortho position of I. A and Z can form a cyclic structure together with the protecting group.

[0045]

[0046] The compound of formula (Bz1-3) is preferably represented by formula (Bz1-3-1), and more preferably by formula (Bz1-3-2).

[0047]

[0048] A' is a protecting group, represented by -OR aOR b, -O-CO-OR b, -OR a-CO-OR b, or -OR aO-CO-R b. Ra is a straight-chain or branched alkyl group having 1 to 3 carbon atoms. R b is a monovalent straight-chain, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group, and forms a ring together with the adjacent oxygen atom. A cyclic structure containing Ra and R b can be formed. However, there may be more than one A'.

[0049] [Bz2 system] The compound of formula (Bz) is preferably represented by formula (Bz2). The compound has two R1s that are not derived from Z, and the two R1s are located in non-adjacent positions.

[0050]

[0051] The compound (Bz2) is preferably represented by formula (Bz2-1).

[0052]

[0053] [Bz3 system] Furthermore, compounds of formula (Bz) are preferably represented by formula (Bz3). This compound has two R1s that are not derived from Z, and the two R1s are located in adjacent positions. The definition of A' is the same as above, and there is more than one.

[0054]

[0055] [Preferred Sample] From the viewpoint of enhancing sensitization effect, the compound of formula (Bz1) is particularly preferred. This compound has R1, two iodine atoms and one or more A' atoms. Hereinafter, the compound of formula (1b-1) will be described.

[0056] R1 is preferably a hydroxyalkyl or aldehyde group, and more preferably a hydroxyalkyl group. The method of introducing the hydroxyalkyl group into benzene is not limited, but examples include methods in which a carboxyl group is introduced as R1 followed by reduction. The reduction method can be carried out using conventional methods.

[0057] In formula (1b-1), A' is a protecting group, represented by -OR aOR b, -O-CO-OR b, -OR a-CO-OR b, or -OR aO-CO-R b. Ra is a straight-chain or branched alkyl group having 1 to 3 carbon atoms. R b is a monovalent straight-chain, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group, and forms a ring together with the adjacent oxygen atom. A cyclic structure containing Ra and R b can be formed. However, there may be more than one A'.

[0058] Rb in other states is a straight-chain, branched, or cyclic aliphatic group with 1 to 30 carbon atoms, an aromatic group with 6 to 30 carbon atoms, a straight-chain, branched, or cyclic aliphatic group containing heteroatoms with 1 to 30 carbon atoms, or a straight-chain, branched, or cyclic aromatic group containing heteroatoms with 1 to 30 carbon atoms. This aliphatic group, aromatic group, aliphatic group containing heteroatoms, or aromatic group containing heteroatoms may further have substituents. As substituents here, the foregoing can be listed, but it is preferred to be a straight-chain, branched, or cyclic aliphatic group with 1 to 20 carbon atoms, or an aromatic group with 6 to 20 carbon atoms. Of these, Rb is preferably an aliphatic group. The aliphatic group in Rb is preferably a branched or cyclic aliphatic group. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 3 to 10, and even more preferably 4 to 8. As an aliphatic group, it is not particularly limited, and examples include methyl, isopropyl, sec-butyl, tert-butyl, isobutyl, cyclohexyl, methylcyclohexyl, adamantyl, etc. Among these, tert-butyl, cyclohexyl, or adamantyl are preferred.

[0059] As other R b, a base having the following structure can be used.

[0060]

[0061] A' is represented as -CO-ORb or -C-CyE in other states. CyE is a cyclic ester group that may have substituents. A' is preferably represented, for example, by the following formula.

[0062]

[0063] When a compound of formula (Bz) contains a complex number of R1, R1 does not contain a combination of alkoxy (except for those with protecting groups) and aldehyde, a combination of alkoxy (except for those with protecting groups) and hydroxyl, or a combination of aldehyde and hydroxyl.

[0064] In the aforementioned formula (1b-1), R1 is preferably a hydroxyl, carboxyl, ester, aldehyde, or hydroxyalkyl group. A' is preferably represented by -OR aOR b.

[0065] Examples of specific compounds represented by the following formulas (1b-1) or (1b-4) are not limited to these.

[0066]

[0067] Examples of specific compounds represented by the following formulas (1b) or (1b-3), but not limited to such compounds.

[0068]

[0069] The following formula (Bz1-3-2) represents specific examples of compounds, but is not limited to them.

[0070]

[0071] The following are specific compounds belonging to formula (Bz).

[0072]

[0073] [Bz4 system] The compound of formula (Bz) is preferably represented by formula (Bz4) from the viewpoint of suppressing defects in the resist pattern.

[0074]

[0075] In the formula, the definitions of I, R, A and Z are the same as those mentioned above.

[0076] R 1' may be the same or different from a monovalent functional group (excluding hydroxyl groups) with 0 to 30 carbon atoms that does not contain polymerizable unsaturated bonds, and is preferably not an alkyl group. R 1' may be, for example, an alkoxy group with 1 to 30 carbon atoms, a carboxyl group with 1 to 30 carbon atoms, a carboxylic acid ester group with 2 to 10 carbon atoms, an alkoxyalkyl group with 2 to 30 carbon atoms, a hydroxyalkyl group with 2 to 30 carbon atoms, an aldehyde group, a halogen atom other than an iodine atom, a nitro group, an amino group, a cyano group, or a thiol group. Among these groups, R 1' is preferably a carboxyl group, an ester group, or a hydroxyalkyl group from the viewpoint of enhancing sensitization. Among these groups, substituents may be present, and substituents other than hydroxyl groups may be present. r1', r2', and r4' are preferably integers of 0 to 5, more preferably integers of 0 to 3, and particularly preferably integers of 0 to 2. r4' is preferably an integer from 0 to 5, more preferably an integer from 0 to 4, and especially preferably an integer from 0 to 3. The sum of r1', r2', and r4' is less than or equal to the valence of benzene.

[0077] [Preferred State] From the viewpoint of further suppressing defects in the resist pattern, the compound represented by formula (Bz4) is more preferably a compound represented by formula (Bz4-1). Furthermore, from the viewpoint of suppressing defects in the resist pattern, in formula (Bz4-1), the two ortho- and iodine atoms relative to one -CH2OH group are not bonded.

[0078]

[0079] In the formula, I, R, Z, and R1' are defined the same as in formula (Bz4). r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is less than or equal to the valence of benzene. The compound of formula (Bz4-1) is preferably represented by formula (Bz4-2). This compound has a hydroxymethyl group and an iodine atom.

[0080]

[0081] In the formula, I is defined the same as in formula (Bz4), r4' is an integer from 0 to 4, and r5' is an integer from 0 to 4. From the viewpoint of improving the sensitivity of the inhibitor, r4' is preferably an integer from 1 to 4, and more preferably an integer from 1 to 3. r5' is preferably an integer from 0 to 3, and more preferably an integer from 0 to 2.

[0082] The following are specific compounds belonging to formula (Bz4), formula (Bz4-1) and formula (Bz4-2).

[0083] (2) Second State Sample In the second state sample, RG is naphthalene. In the second state sample, the compound is preferably represented by formula (N) from the viewpoint of sensitizing effect and ease of acquisition.

[0084]

[0085] In the formula, R1 is a monovalent functional group with 0 to 30 carbon atoms that does not contain polymerizable unsaturated bonds, which may be the same or different. The definition of R1 is the same as in the first state sample, but from the viewpoint of sensitizing effect, R1 is preferably a hydroxyl, carboxyl, ester or hydroxyalkyl group. As explained in the first state sample, A is a group with a protecting group. A can be A' represented by -OR aOR b, but in this case, the compound of formula (N) preferably contains more than one of the A'. R” is a hydrogen atom or an organic group other than R1. I, R1, R” and A are bonded at any bondable position. s1 is preferably an integer from 1 to 7, more preferably an integer from 1 to 5, and particularly preferably an integer from 1 to 3. s2 to s3 are preferably integers from 0 to 7, more preferably integers from 0 to 5, and particularly preferably 1 to 3. s4 is preferably an integer from 1 to 7, more preferably an integer from 1 to 6. However, s4 must satisfy the condition s4 ≤ 8 - s1 - s2 - s3. Furthermore, the sum of s1 to s4 must be less than or equal to the valence of naphthalene. However, at least one of s2 and s3 must be 1 or more. Below, from the perspectives of sensitizing effect and ease of acquisition, a preferred compound will be explained.

[0086] In other states, the RG compound of naphthalene may have a linking group Z for forming a dimer. The compound is represented by formula (N'). In the formula, the definitions of each substituent are the same as described above, and their bonding positions are arbitrary. s1 is preferably an integer from 1 to 7, more preferably an integer from 1 to 5, and particularly preferably an integer from 1 to 3. s2 to s3 are preferably integers from 0 to 7, more preferably integers from 0 to 5, and particularly preferably 1 to 3. s4 is preferably an integer from 1 to 7, more preferably an integer from 1 to 6. s5 is preferably an integer from 1 to 2. However, the sum of s1 to s5 is less than or equal to the valence of naphthalene, and at least one of s2 and s3 is 1 or more.

[0087]

[0088] Compounds of formula (N) are preferably represented by formula (n), formula (2n), or formula (3n). The definitions of I, R1, A, and R” are the same as those of formula (N). x and y are 0 or 1, but at least one of them is 1. s4' represents the number of R” that can be bonded to positions 1, 7, and 8 of naphthalene (but the carbon at the topmost position of the right ring is set to position 1, and the same applies below). It is an integer from 1 to 3.

[0089]

[0090] [(n) system] The compound of formula (n) is preferably represented by formula (1n), and more preferably by (1n-1). As mentioned above, when there is a complex number R1, R1 does not contain a combination of hydroxyl and carboxyl groups.

[0091]

[0092] Furthermore, the compound of formula (n) is preferably represented by formula (1n'), and more preferably by (1n'-1). As mentioned above, when there is a complex number R1, R1 does not contain a combination of hydroxyl and carboxyl groups.

[0093]

[0094] [(2n) system] The compound of formula (2n) is preferably represented by formula (2n-1), and more preferably by (2n-1-1). As mentioned above, when there is a complex number R1, R1 does not contain a combination of hydroxyl and carboxyl groups.

[0095]

[0096] [(3n) system] The compound of formula (3n) is preferably represented by formula (3n-1), and more preferably by (3n-1-1). As mentioned above, when there is a complex number R1, R1 does not contain a combination of hydroxyl and carboxyl groups.

[0097]

[0098] The compound of formula (3n) is preferably represented by formula (3n-2), and more preferably by formula (3n-2-1). As mentioned above, when there is a complex number R1, R1 does not contain a combination of hydroxyl and carboxyl groups.

[0099]

[0100] Specific examples of compounds represented by the following formula (N). In the following examples, Rc is a monovalent group with 0 to 29 carbon atoms that does not contain polymerizable unsaturated bonds.

[0101]

[0102]

[0103]

[0104]

[0105] The following discloses non-limiting specific examples of compounds belonging to formula (N).

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] In the above formula, A is a base with a protecting group. Although not limited, A may be, for example, the following.

[0114]

[0115] (3) Third State Sample In the third state sample, RG is an alicyclic ring with a polycyclic structure having 3 to 30 carbon atoms. Substituents such as I and R1 in this alicyclic ring can exist at any position. As specific examples of this alicyclic ring, the following structures can be listed. These alicyclic rings can further have alicyclic structures.

[0116]

[0117] From the viewpoint of enhancing sensitization effect and ease of acquisition, RG is preferably adamantane. Therefore, the compound of formula (1) in this sample is preferably represented by formula (Ad).

[0118]

[0119] In the formula, I, R1, and R” are defined as described above. However, I, R1, and R” are bonded to any position in adamantane. When R1 is a group with a protecting group, the protecting group is as described above, preferably an acid-dissociable group. Therefore, the group with a protecting group is preferably a group formed by protecting a hydroxyl or carboxyl group with an acid-dissociable group. Among them, from the viewpoint of sensitizing effect, R1 is preferably a hydroxyl, carboxyl, ester, or hydroxyalkyl group. In this case, other R1s may be A, or A' represented by -OR aOR b. The compound of formula (Ad) preferably contains one or more A's. t1 is preferably an integer from 1 to 10, more preferably an integer from 1 to 5, and particularly preferably an integer from 1 to 3. t2 is preferably an integer from 1 to 9, more preferably an integer from 1 to 5, and particularly preferably an integer from 1 to 3. t3 is preferably an integer from 1 to 14, more preferably an integer from 5 to 14, and especially preferably an integer from 8 to 14. However, t3 must satisfy t3 ≤ 16 - t1 - t2. Furthermore, the sum of t1 to t3 is less than or equal to the valence of adamantane. The preferred compound will now be explained from the viewpoints of sensitizing effect and ease of acquisition. Additionally, compounds containing adamantane may have a linker group Z at any position for forming a dimer.

[0120] Compounds of formula (Ad) are preferably represented by formula (Ad1). In one state, one of the D atoms is I, and the other of the D atoms is R1. In other states, both D atoms are R1.

[0121]

[0122] Compounds of formula (Ad) are preferably represented by formula (1a), (2a) or (3a).

[0123]

[0124] Compounds of formulas (1a), (2a) and (3a) are preferably represented by the following formulas.

[0125]

[0126] Also, the compound of formula (Ad1) is preferably represented by the following formula.

[0127]

[0128] In this formula, I and R1 are defined as described above. The organogroup is as described in the first or second state sample. The compound preferably has 1 to 2 iodine atoms.

[0129] In formulas (1a) to (3a), R1 is preferably a hydroxyl group, a carboxyl group, an ester group (which may have a substituent such as a halogen other than an iodine atom) or a hydroxyalkyl group.

[0130] Specific examples of compounds represented by the following formula (Ad1) that are not limited.

[0131]

[0132]

[0133] In addition, for example, by using the following compounds as raw materials, 4-substituted adamantane having the above-mentioned iodine and carboxylic acid groups can be synthesized.

[0134]

[0135]

[0136]

[0137] 1-3. Polymers As described above, the compound of formula (1) may be a polymer. In this case, RG preferably does not contain a ring assembly formed by a single bond linking a single ring (e.g., biphenyl, naphthyl, bicyclopropyl, etc.). Specifically, RG is preferably a group having at least one cyclic structure selected from monocyclic aromatic ring structures, condensed ring aromatic structures, and polycyclic alicyclic structures. Furthermore, at least a portion of R1 is preferably a group that links two or more molecules with the following groups: alcohol group; acetal group; carbonate group; glycidyl group; carboxyl group; carboxylic acid halide group; aldehyde group; or an alkyl group or an aryl group having 1 to 30 carbon atoms that may have a substituent, and the substituent is any one of an alcohol group, acetal group, carbonate group, glycidyl group, carboxyl group, or carboxylic acid halide group. The aforementioned carbonate group may be an alkoxycarbonyloxy group or an aryloxycarbonyloxy group that may have a substituent.

[0138] When the compound of formula (1) is a polymer, the compound is preferably represented by the following formula.

[0139]

[0140] In the formula, the definitions of RG, I, and R1 are the same as in formula (1). n' is 0 to 5 and is an integer less than n, preferably an integer of 1 to 3. m' is 1 to 5 and is an integer less than m, preferably an integer of 1 to 4. b is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably an integer of 1 or 2. Q is a base derived from the intermolecular bond or a single bond. A base derived from the intermolecular bond can be a base derived from the intermolecular bond of R1. When Q is derived from Z, Q is a single bond, that is, it means that the repeating unit is bonded by a single bond. When Q is derived from the intermolecular bond of R1, Q is, for example, an ester group, etc.

[0141] [Bz system] The compound of the aforementioned formula (DM0-1) is represented by formula (DM1a) in the preferred state sample.

[0142]

[0143] In the formula, the definitions of R, R1, A, Z, and r1~r4 are the same as those for compounds in the system of formula (Bz). In this compound, Z is preferably R1.

[0144] The compound of formula (DM1a) is preferably the compound represented by formula (DM1b).

[0145]

[0146] In the formula, the definitions of I, R, R1, A, and Z are the same as those in formula (DM1a).

[0147] The compound represented by formula (DM1b) is preferably the compound represented by formula (DM1c1).

[0148]

[0149] In the formula, the definitions of I, R, R1, A, and Z are the same as those in formula (DM1a).

[0150] The compound represented by formula (DM1c1) is preferably represented by formula (DM1d11).

[0151]

[0152] In the formula, the definitions of I, R, R1, A, and Z are the same as those in formula (DM1a).

[0153] The compound represented by formula (DM1c1) is preferably represented by formula (DM1d12).

[0154]

[0155] In the formula, I, R, R1, and Z are defined in the same way as in formula (DM1a). A' is a protecting group, represented by -OR aOR b, -O-CO-OR b, or -OR a-CO-OR b, or -OR aO-CO-R b. Ra is a straight-chain or branched alkyl group with 1 to 3 carbon atoms. Rb is a monovalent straight-chain, branched, or cyclic alkyl group with 1 to 3 carbon atoms, or a divalent cyclic alkyl group, and forms a ring together with the adjacent oxygen atom. A cyclic structure containing Ra and Rb can be formed. However, there may be more than one A'.

[0156] The compound represented by formula (DM1b) is preferably represented by formula (DM1c2).

[0157]

[0158] In the formula, the definitions of I, R, R1, A, and Z are the same as those in formula (DM1a).

[0159] The compound represented by formula (DM1c2) is preferably the compound represented by formula (DM1d21) below.

[0160]

[0161] In the formula, the definitions of I, R, R1, A, and Z are the same as those in formula (DM1a).

[0162] The compound represented by formula (DM1c1) is preferably represented by formula (DM1d22).

[0163]

[0164] In the formula, the definitions of I, R, R1, and Z are the same as in formula (DM1a). The definition of A' is the same as in formula (DM1d12).

[0165] The compound represented by formula (DM1b) is preferably represented by formula (DM1c3).

[0166]

[0167] In the formula, the definitions of I, R, R1, A, and Z are the same as those in formula (DM1a).

[0168] The compound represented by formula (DM1c3) is preferably represented by formula (DM1d31).

[0169]

[0170] In the formula, the definitions of I, R, R1, A, and Z are the same as those in formula (DM1a).

[0171] The compound represented by formula (DM1b) is preferably the compound represented by formula (DM1c4).

[0172]

[0173] In the formula, the definitions of I, R, R1, A, and Z are the same as those in formula (DM1a).

[0174] The compound represented by formula (DM1c4) is preferably represented by formula (DM1d41).

[0175]

[0176] In the formula, the definitions of I, R, R1, A, and Z are the same as in formula (DM1a). The definition of A' is the same as in formula (DM1d12).

[0177] The compound of formula (DM1a) is preferably a compound represented by formula (DM1e).

[0178]

[0179] In the formula, the definitions of I, R, A, and Z are the same as those in formula (DM1a), and the definitions of R1', r1', r2', and r4' are the same as those in formula (Bz4).

[0180] The compound of formula (DM1e) is preferably the compound represented by formula (DM1e1).

[0181]

[0182] The compound of formula (DM1e1) is preferably a compound represented by formula (DM1e2).

[0183]

[0184] The following represents an example of a dimer compound. In the formula, I, R, R1, and A are defined in the same way as in formula (Bz). This compound is a compound of formula (1b) and is equivalent to Z being a linking group used to form a dimer.

[0185]

[0186] Specific dimer compounds are shown below.

[0187]

[0188] [N system] The compound of the aforementioned formula (DM0-1) is represented by formula (Dn1) in other preferred samples.

[0189]

[0190] The definitions of each substituent are the same as in equation (N). nd is an integer from 1 to 4, preferably an integer from 1 to 2. Preferably, Q is a single bond, and nd is 1.

[0191] The compound represented by formula (Dn1) is preferably the compound represented by formula (Dn1a).

[0192]

[0193] In formula (Dn1a), the definitions of I, R1, R”, A, and nd are the same as in formula (Dn1). x and y are 0 or 1 respectively, and at least either x or y is 1. s4' represents the number of R” bonds at positions 1, 7, and 8 of naphthalene.

[0194] The compound represented by formula (Dn1a) is preferably the compound represented by formula (Dn1b1).

[0195]

[0196] In equation (Dn1b1), the definitions of I, R1, R”, A, and nd are the same as in equation (Dn1), x and y are 0 or 1 respectively, and at least one of x and y is 1. The definition of s4' is the same as in equation (Dn1a).

[0197] The compound represented by formula (Dn1b1) is preferably the compound represented by formula (Dn1c11).

[0198]

[0199] In equation (Dn1c11), the definitions of I, R1, R”, A, and nd are the same as in equation (Dn1), x and y are 0 or 1 respectively, and at least either x or y is 1. nd is preferably 2.

[0200] The compound represented by formula (Dn1b1) is preferably represented by formula (Dn1c12).

[0201]

[0202] In formula (Dn1c12), the definitions of I, R1, R”, and nd are the same as in formula (Dn1). A' is a base with a protecting group, represented by -OR aOR b, -O-CO-OR b, or -OR a-CO-OR b. nd is preferably 2.

[0203] The compound represented by formula (Dn1a) is preferably the compound represented by formula (Dn1b2).

[0204]

[0205] In equation (Dn1b2), the definitions of I, R1, R”, A, and nd are the same as in equation (Dn1), x is 0 or 1, and at least one of them has x as 1. The definition of s4' is the same as in equation (Dn1a).

[0206] The compound represented by formula (Dn1b2) is preferably the compound represented by formula (Dn1c21).

[0207]

[0208] In formula (Dn1c21), the definitions of I, R1, R”, A, and nd are the same as in formula (Dn1), and the definition of Z is the same as in formula (DM1a). A' is a group with a protecting group and is represented by -OR aOR b, -O-CO-OR b, or -OR a-CO-OR b. Here, Ra is a straight-chain or branched alkyl group with 1 to 3 carbon atoms. Rb is a monovalent straight-chain, branched, or cyclic alkyl group with 1 to 3 carbon atoms, or a divalent cyclic alkyl group, and forms a ring together with the adjacent oxygen atom. nd is preferably 2.

[0209] The compound represented by formula (Dn1a) is preferably the compound represented by formula (Dn1b3).

[0210]

[0211] In equation (Dn1b3), the definitions of I, R1, R”, A, and nd are the same as in equation (Dn1), y is 0 or 1 respectively, and at least either x or y is 1. nd is preferably 2.

[0212] The compound represented by formula (Dn1b3) is preferably the compound represented by formula (Dn1c31).

[0213]

[0214] In formula (Dn1c31), the definitions of I, R1, R”, and nd are the same as in formula (Dn1), and the definition of Z is the same as in formula (DM1a). A' is a group with a protecting group and is represented by -OR aOR b, -O-CO-OR b, or -OR a-CO-OR b. Here, Ra is a straight-chain or branched alkyl group with 1 to 3 carbon atoms. Rb is a monovalent straight-chain, branched, or cyclic alkyl group with 1 to 3 carbon atoms, or a divalent cyclic alkyl group, and forms a ring together with the adjacent oxygen atom. nd is preferably 2.

[0215] The compound represented by formula (Dn1b3) is preferably the compound represented by formula (Dn1c32).

[0216]

[0217] In formula (Dn1c32), the definitions of I, R1, R”, and nd are the same as in formula (Dn1), and the definition of Z is the same as in formula (DM1a). A' is a group with a protecting group and is represented by -OR aOR b, -O-CO-OR b, or -OR a-CO-OR b. Here, Ra is a straight-chain or branched alkyl group having 1 to 3 carbon atoms. Rb is a monovalent straight-chain, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group that forms a ring together with the adjacent oxygen atom. nd is preferably 2. The following shows specific examples of formula (Dn1) that are not limited.

[0218]

[0219] [Ad System] The compound of the aforementioned formula (DM0-1) is further represented by formula (Da1) in other preferred embodiments. The compound of formula (Da1) is more preferably represented by formula (Da2).

[0220]

[0221] The definitions of each substituent are the same as those in formula (Ad).

[0222] The compound represented by formula (Da1) is preferably the compound represented by formula (Da1a).

[0223]

[0224] In formula (Da1a), the definitions of I, R, R1, R”, and Rd are the same as in formula (Da1).

[0225] The compound represented by formula (Da1a) is preferably represented by formula (Da1b).

[0226]

[0227] In equation (Da1b), the definitions of I, R, R1, R”, and Rd are the same as in equation (Da1a).

[0228] The compound of the aforementioned formula (DM0-1) is further represented by formula (Da1c11) in other preferred forms.

[0229]

[0230] In formula (Da1c11), the definitions of I, R”, and R1 are the same as in formula (Da1a), and ba is an integer from 2 to 5.

[0231] The compound represented by formula (Da1b) is preferably represented by formula (Da1c12).

[0232]

[0233] In formula (Da1c12), the definitions of I, R, R”, and R 1 are the same as those in formula (Da1a).

[0234] 1-4. Manufacturing Method The aforementioned compound can be manufactured by any method without impairing its effects. However, a preferred manufacturing method is the step of introducing an iodine atom or an R1 group into the compound containing the aforementioned RG group. For example, the step of introducing an iodine atom into a compound having an aromatic ring can be carried out by reacting iodine I2 with the compound having an aromatic ring under acidic or alkaline conditions. This reaction can produce compounds and dimers with different numbers of iodine atoms. The ratio of these products can be adjusted according to the reaction conditions. In particular, if the reaction temperature is lowered or the reaction time is shortened, there is a tendency for more compounds with fewer iodine atoms and fewer dimers. If the reaction temperature is increased or the reaction time is extended, there is a tendency for fewer compounds with fewer iodine atoms and more dimers. Furthermore, the step of introducing an iodine atom into a compound having an alicyclic ring can be carried out by reacting HI (hydrogen iodide) with the compound having an alicyclic ring. A preferred method for manufacturing the aforementioned compound may include an iodination step, which involves introducing iodine atoms into a raw material as a substitution reaction. The raw material comprises RG, a functional group that can substitute the iodine atom via a substitution reaction, and, if desired, R1. Alternatively, another method for manufacturing the aforementioned compound may include an iodination step, in which iodine is introduced into a raw material comprising RG and, if desired, R1, in the form of a free radical, cation, or anion.

[0235] [Iodination Step] As the iodination step, appropriate methods may be selected, such as introducing halogen from the amino group via the Sandmeier reaction, reacting iodine chloride in an organic solvent (e.g., Japanese Patent Application Publication No. 2012-180326, Japanese Patent Application Publication No. 2000-256231, Japanese Patent Application Publication No. 2010-159233, J.Chem.Soc. 636,1943), or adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (Japanese Patent Application Publication No. 63-101342, Japanese Patent Application Publication No. 2003-64012).

[0236] The iodizing agent is not particularly limited, and examples include iodine chloride, iodine, N-iodosuccinimide, iodic acid, and hydrogen iodide (including hydroiodic acid and aqueous solutions of hydrogen iodide). In the iodination step, the ratio of the iodizing agent to the matrix is ​​preferably 1.2 moles or more, more preferably 1.5 moles or more, and even more preferably 2.0 moles or more.

[0237] The iodination introduction reaction can be carried out at least by reacting the iodizing agent with the matrix. The desired compound can be obtained by using the conventional iodination introduction reaction conditions described in non-patent documents such as Adv. Synth. Catal. 2007, 349, 1159-1172, Organic Letters; Vol. 6; (2004); pp. 2785-2788, "Organic Synthetic Reagents and Synthetic Methods for Bromine and Iodine Compounds" (supervised by Hitomi Suzuki, written by MANAC Co., Ltd. Research Institute, Maruzen Publishing), US 5300506, US 5434154, US 2009 / 281114, EP1439164, and WO2006 / 101318. Examples of iodizing agents that can be used include iodine compounds such as iodine monochloride, N-iodosuccinimide, benzyltrimethyldichloroiodate ammonium, tetraethylammonium iodide, tetra-n-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodide fluoride, tert-butyl hypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetylated hypoiodide, iodo-iodic acid, iodo-periodic acid, iodo-hydrogen peroxide, 1-iodoheptafluoropropane, triphenyl phosphate-methyl iodine, iodo-thallium(I) acetate, 1-chloro-2-iodoethane, iodo-copper(II) acetate, etc., but are not limited to these.

[0238] In the iodination reaction, one or more additives may be added to promote the reaction or to suppress byproducts. Examples of additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, ferric chloride (III), 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 bicarbonate, and potassium bicarbonate; oxidizing agents such as cerium (IV) ammonium nitrate and sodium persulfate; inorganic compounds such as sodium chloride, potassium chloride, mercuric oxide (II), and cerium oxide; organic compounds such as acetic anhydride; and porous materials such as zeolites. The ratio of additives to iodizing agents in the iodination step is preferably 1.0 mol, more preferably 1.2 mol or more, more preferably 1.5 mol or more, and more preferably 2.0 mol or more.

[0239] In the iodination step, it is preferable to use at least an iodine source and an oxidizing agent to introduce iodine into the parent nucleus. Using an iodine source and an oxidizing agent is preferable from the viewpoint of improving reaction efficiency and purity. Examples of iodine sources include the iodine agents mentioned above. Examples of oxidizing agents include iodic acid, periodic acid, hydrogen peroxide, and other additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, silver trifluoroacetate, cerium(IV)ammonium nitrate (CAN), etc.). Furthermore, for phenols containing carboxylic acid or nitro groups, the iodination reaction can be carried out using iodine sources such as combined iodine and silver salts or fuming sulfuric acid to form iodocations. Furthermore, for other less inert aromatic compounds, the iodination reaction can be carried out by using a combination of an iodine source and an inorganic salt to form hypoiodic acid and iodocations. Examples of inorganic salts include potassium persulfate. Alternatively, methods that replace the reaction to introduce iodine into aliphatic alcohol groups can be appropriately used. As iodizing agents, hydrogen halides, phosphorus halides, sulfonates (a combination of NaI and acetone), thiolated halides, trimethylsilane halides, Wilsmeier reagents, and Appel reactions (a combination of triphenylphosphine and an iodine source) can be used appropriately.

[0240] The iodination step can be carried out under solvent-free pure reactant (Neat) conditions. Examples of reaction solvents that can be used include halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; alkyl solvents such as hexane, cyclohexane, heptane, pentane, and octane; aromatic hydrocarbon solvents such as benzene and toluene; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; ether solvents such as diethyl ether, diisopropyl ether, and tetrahydrofuran; acetic acid, dimethylformamide, dimethyl sulfoxide, and water.

[0241] The reaction temperature of the iodination step is not particularly limited and can be any temperature from the freezing point to the boiling point of the solvent used in the reaction, preferably 0°C to 150°C, more preferably 20°C to 150°C, and even more preferably 50°C to 120°C. Furthermore, the reaction time of the iodination step is not particularly limited, but preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours. For the purpose of more efficient iodination, the reaction system can be refluxed. Furthermore, for the purpose of controlling the concentration of the iodizing agent in the reaction system, the concentration of the iodizing agent in the reaction solution can be controlled by using a reflux tube equipped with a Dean-Stark apparatus or similar device.

[0242] The iodine substitution reaction in the iodination step can be carried out by at least reacting the iodizing agent with the matrix, for example, by using the Sandmeier reaction or other conventional iodine substitution reaction conditions described in Chemistry-A European Journal, 24(55), 14622-14626; 2018, Synthesis (2007)(1), 81-84.

[0243] [Protecting Group Introduction Step] The protecting group, denoted by A' in the preferred method of manufacturing the aforementioned compound, can be introduced into RG by conventional methods. For example, the method described in Green's Protective Groups in Organic Synthesis (Peter GM Wuts, WILEY) pp. 17-553 can be appropriately selected.

[0244] In the protecting group introduction step, the ratio of the protecting group introducer to the matrix is ​​not particularly limited, but it is preferably 0.5 mol or more, more preferably 1.0 mol or more, and even more preferably 1.5 mol or more. The reaction temperature for the protecting group introduction step is not particularly limited; generally, a temperature of 0°C to 200°C is suitable. From the viewpoint of yield, a temperature of 10°C to 190°C is preferred, more preferably 25°C to 150°C, and even more preferably 50°C to 100°C. In the reaction of this sample, the preferred temperature range is 0°C to 100°C. Furthermore, the reaction time for the protecting group introduction step is not particularly limited, but it is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.

[0245] [Reduction Step] In the compound of the aforementioned formula (1), if R 1 is a hydroxyalkyl or aldehyde group, for example, a carboxyl group, ester group or aldehyde group can be introduced as R 1 and then reduced to obtain the compound.

[0246] As a reduction method, conventional methods can be used, but methods using, for example, metal hydride compounds such as sodium borohydride, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride (SBMEA), and diisobutylaluminum hydride (DIBAL) can be used; methods using metal hydrides such as aluminum hydride; methods using such reducing agents in combination with reducing aids such as aluminum chloride and ethanedithiol; and so on. A portion of the reducing agent's structure can be modified to an alkoxy or hydrocarbon group, and its reducing power can be adjusted by combining it with Lewis acids. Common solvents such as methanol, ethanol, 2-propanol, DMF, and DMSO can be used as solvents for the reduction reaction. The reaction temperature can be carried out at room temperature or under heating conditions, and cooling can also be performed to adjust the reactivity; there are no particular limitations, but -20°C to 150°C is preferred, more preferably 0°C to 150°C, and even more preferably 20°C to 120°C. In the reduction step, the ratio of reducing agent to matrix is ​​not particularly limited, but preferably 0.5 moles or more, more preferably 1.0 moles or more, and even more preferably 1.5 moles or more. Furthermore, the reaction time of the reduction step is not particularly limited, but preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.

[0247] In this embodiment, after the compound is obtained as a crude product through the aforementioned reaction, it is preferable to further purify it to remove residual metal impurities. That is, from the perspective of preventing resin deterioration over time and maintaining stability, and further from the perspective of the impact of process suitability and defects on manufacturing yield when the resin is applied to semiconductor manufacturing processes, it is preferable to avoid residual metal impurities. Metal impurities may originate from reaction aids in the compound manufacturing process, or from the reaction vessel used in the manufacturing process, or other manufacturing equipment.

[0248] The residual amount of the aforementioned metal impurities is preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, further preferably less than 10 ppb, and most preferably less than 1 ppb, relative to the compound. In particular, for metals classified as transition metals such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al, if the residual metal amount is 1 ppm or more, there is a concern that the interaction with other compounds may lead to material degradation and deterioration over time. Furthermore, for alkali metals and alkaline earth metals such as Na, K, Ca, and Mg, if they are contained in the resin and the residual metal amount is 1 ppm or more, when using the compound to make a resin suitable for semiconductor engineering, the residual metal amount cannot be sufficiently reduced, thus becoming a factor in the yield reduction caused by defects or performance degradation due to residual metals in the semiconductor manufacturing process, and there is a concern that the doping effect of metal elements on the substrate may lead to a reduction in characteristics.

[0249] The purification method is not particularly limited, and methods described in International Publication No. 2015 / 080240 and International Publication No. 2018 / 159707, etc., may be used. Specifically, the purification method includes the following steps: dissolving the aforementioned compound in an organic solvent that is immiscible with water to obtain an organic phase; contacting the organic phase with an acidic aqueous solution to perform extraction treatment, thereby transferring the metal components contained in the organic phase containing the aforementioned compound and the organic solvent to the aqueous phase; and then separating the organic phase and the aqueous phase. An organic solvent that is immiscible with water refers to an organic solvent that is generally classified as a water-insoluble solvent. The organic solvent is not particularly limited, but is preferably an organic solvent that can be safely used in semiconductor manufacturing processes. The amount of organic solvent used is typically about 10% by mass relative to the compound used.

[0250] Specific examples of the organic solvents used may be listed in International Publication 2015 / 080240. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, etc., are preferred, and cyclohexanone and propylene glycol monomethyl ether acetate are particularly preferred.

[0251] As the aforementioned acidic aqueous solution, it is generally appropriate to select from known aqueous solutions formed by dissolving organic or inorganic compounds in water. Examples include those described in International Publication 2015 / 080240. These acidic aqueous solutions can be used individually or in combination of two or more. Examples of acidic aqueous solutions include aqueous solutions of inorganic acids and aqueous solutions of organic acids. Examples of inorganic acid aqueous solutions include aqueous solutions containing one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of organic acid aqueous solutions include aqueous solutions containing one or more acids 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. The pH range of the acidic aqueous solution is approximately 0 to 5, more preferably approximately 0 to 3.

[0252] Other methods of production may include: using a filter as described later, using an adsorbent ion exchange resin to disperse and suspend the ion exchange resin in a container by passing the liquid through a column, and using distillation.

[0253] In the manufacturing method of the compound represented by formula (1), the order and number of the aforementioned iodination step, protecting group introduction step and reduction step are not particularly limited, and can be appropriately selected according to the structure of the target compound.

[0254] 1-5. Purification Method [Filter Purification Step (Liquid Passage Step)] In the filter liquid passage step, the filter used to remove the metal components from the solution containing the aforementioned compound and solvent is generally a commercially available filter for liquid filtration. The filtration precision 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 0.1 μm or less, further preferably less than 0.1 μm, and even more preferably 0.05 μm or less. Furthermore, the lower limit of the nominal pore size of the filter is not particularly limited, but is generally 0.005 μm. The nominal pore size referred to here is the nominal pore size indicating the separation performance of the filter, such as the pore size determined by the filter manufacturer through test methods such as bubble point test, mercury intrusion porosimetry test, and standard particle replenishment test. When using commercially available products, the value recorded in the manufacturer's catalog is used. By setting the nominal pore size to 0.2 μm or less, the content of metal components in the solution after passing through a filter once can be effectively reduced. In the second embodiment, to further reduce the content of each metal component in the solution, the filter can be passed through a filter more than once.

[0255] As a filter type, hollow fiber membrane filters, membrane filters, pleated membrane filters, and filters filled with filter media such as non-woven fabric, cellulose, and diatomaceous earth can be used. Preferably, the filter is selected from one or more types grouped together with hollow fiber membrane filters, membrane filters, and pleated membrane filters. Furthermore, hollow fiber membrane filters are particularly preferred due to their high filtration accuracy and larger filtration area compared to other types.

[0256] The materials used for the aforementioned filters may include polyolefins such as polyethylene and polypropylene, polyethylene resins endowed with functional groups that provide ion exchange capacity based on graft polymerization, polyamide, polyester, polyacrylonitrile, and other resins containing polar groups, and fluorinated resins such as PTFE. Preferably, the filter media is selected from one or more materials grouped with polyamide, polyolefin resins, and fluoropolymers. Furthermore, from the viewpoint of reducing heavy metals such as chromium, polyamide is particularly preferred. Additionally, from the viewpoint of preventing metal leaching from the filter media, filters made of materials other than sintered metals are preferred.

[0257] As polyamide filters (hereinafter, trademarks), the following are not limited to: Polyfix Nylon series manufactured by KITZ Micro Filter Corporation; Ultipleat P-Nylon 66 and Ultipor N66 manufactured by Nihon Pall Ltd.; and LifeASSURE PSN series and LifeASSURE EF series manufactured by 3M Corporation. As polyolefin filters, the following are not limited to: Ultipleat PE Kleen and IonKleen manufactured by Nihon Pall Ltd.; Protego series, Microgard Plus HC10, and Optimizer D manufactured by Entegris Japan Co., Ltd. As polyester filters, the following are not limited to: DURAFLOW DFE manufactured by Central Filter Mfg. Co., Ltd.; and PLEATS type PMC manufactured by Nihon Filter Co., Ltd. As for polyacrylonitrile-based filters, they are not limited to the following, but may include, for example, Advantec Toyo Kaisha, Ltd.'s Ultra filter AIP-0013D, ACP-0013D, ACP-0053D, etc. As for fluoropolymer-based filters, they are not limited to the following, but may include, for example, Nihon Pall Ltd.'s Emflon HTPFR, 3M Inc.'s LifeASSURE FA series, etc. These filters can be used individually or in combination of two or more.

[0258] Furthermore, the aforementioned filter may include ion exchangers such as cation exchange resins, and cationic charge modifiers that generate a boundary potential in the filtered organic solvent solution. Filters containing ion exchangers are not limited to the following, but may include, for example, the Protego series manufactured by Entegris Japan Co., Ltd., and the KURANGRAFT series manufactured by Kurashiki Fiber Processing Co., Ltd. Furthermore, filters containing substances with a positive boundary potential such as polyamide, polyamine, epichlorohydrin, and cationic resins are not limited to the following, but may include, for example, the Zeta Plus 40QSH (registered trademark), Zeta Plus 020GN (registered trademark), or LifeASSURE EF (registered trademark) series manufactured by 3M Co., Ltd.

[0259] [Treatment Step Using Ion Exchange Resin] As other purification methods, methods of treating solutions containing the aforementioned compounds with ion exchange resins can be listed. As the ion exchange resin, conventional ion exchange resins that function to target metal elements can be appropriately used. Purification using ion exchange resins involves either performing ion exchange on the purified substance containing the aforementioned compounds or using chelating groups for ion adsorption. The components removed by the treatment step using ion exchange resins are not limited to these; examples include, for instance, acidic components and metal ions contained in metal components.

[0260] The method for performing the ion exchange method is not particularly limited, and conventional methods can be used. Typically, a method in which a solution containing the aforementioned compound is passed through a filling section filled with ion exchange resin can be listed. Alternatively, a method in which ion exchange resin is added to a solution containing the aforementioned compound, and after dispersion and suspension treatment in a processing vessel, the compound is separated and removed by methods such as filtration of the ion exchange resin to obtain a purified solution can also be listed. Using the ion exchange resin treatment step, the purified substance can be treated multiple times with the same ion exchange resin, or different ion exchange resins can be used to treat the purified substance.

[0261] As ion exchange resins, cation exchange resins and anion exchange resins can be cited. From the viewpoint that adjusting the content of the metal component makes it easy to make the mass ratio of the acid component content relative to the metal component content within the aforementioned range, it is preferable to use at least a cation exchange resin. From the viewpoint that the acid component content can be adjusted, it is even more preferable to use both a cation exchange resin and anion exchange resin simultaneously. When using both a cation exchange resin and anion exchange resin, liquid can be passed through a filling section filled with a mixed resin containing both resins, or liquid can be passed through multiple filling sections filled with individual resins.

[0262] Conventional cation exchange resins can be used as cation exchange resins, with gel-type cation exchange resins being preferred. Specifically, sulfonic acid type cation exchange resins and carboxylic acid type cation exchange resins can be cited as cation exchange resins. Commercially available products can be used as cation exchange resins, such as Amberlite IR-124, Amberlite IR-120B, Amberlite IR-200CT, ORLITE DS-1, ORLITE DS-4 (and above, manufactured by Organo Corporation), Duolite C20J, Duolite C20LF, Duolite C255LFH, Duolite C-433LF (and above, manufactured by Sumika Chemtex), DIAION SK-110, DIAION SK1B and DIAION SK1BH (and above, manufactured by Mitsubishi Chemical Corporation), Purolite S957 and Purolite S985 (and above, manufactured by Purolite Corporation), etc.

[0263] Conventional anion exchange resins can be used as the anion exchange resin, with gel-type anion exchange resins being preferred. Here, the acidic components present as ions in the purified substance can be categorized as inorganic acids derived from the catalyst used in the manufacture of the purified substance, and organic acids (e.g., reactants, isomers, and byproducts) produced after the reaction during the manufacture of the purified substance. From the perspective of the hard and soft acid-base (HSAB) theory, these acidic components are classified as hard acids to acids of intermediate hardness. Therefore, for the purpose of improving the removal efficiency of these acidic components through interaction with the anion exchange resin, anion exchange resin containing a base of intermediate hardness is preferred. This type of anion exchange resin, containing bases of varying hardness from hard to intermediate, is preferably selected from at least one type selected from the group consisting of a strong-base type I anion exchange resin having a trimethylammonium group, a slightly weaker-base type II anion exchange resin having a dimethylethanolammonium group, and a weak-base type anion exchange resin such as dimethylamine and diethylenetriamine. In the acid component, for example, organic acids are hard acids, and inorganic acids, sulfate ions are acids of intermediate hardness. Therefore, if used in combination with the aforementioned strong-base or slightly weaker-base anion exchange resins, or weak-base anion exchange resins of intermediate hardness, the acid content can be easily reduced to a suitable range.

[0264] Commercially available products can be used as anion exchange resins, such as Amberlite IRA-400J, Amberlite IRA-410J, Amberlite IRA-900J, Amberlite IRA67, ORLITE DS-2, ORLITE DS-5, ORLITE DS-6 (manufactured by Organo Corporation), Duolite A113LF, Duolite A116, Duolite A-375LF (manufactured by Sumika Chemtex), and DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, DIAION WA10 (manufactured by Mitsubishi Chemical Corporation), etc. Examples of anion exchange resins containing bases of hardness ranging from hard to intermediate include ORLITE DS-6, ORLITE DS-4 (and above, manufactured by Organo Corporation), DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, DIAION WA10 (and above, manufactured by Mitsubishi Chemical Corporation), Purolite A400, Purolite A500, and Purolite A850 (and above, manufactured by Purolite Corporation).

[0265] Ion adsorption using chelating groups can be performed, for example, using chelating resins with chelating groups. Chelating resins do not release substitute ions when capturing ions, and do not use highly reactive functional groups such as strong acids or bases, thereby suppressing side reactions to the organic solvent being purified, such as hydrolysis and condensation reactions. Therefore, purification can be performed with higher efficiency. Examples of chelating resins include those with chelating groups or chelating capabilities, such as those with chelating groups or chelating abilities, such as those with a metalloxime group, thiourea group, thiouronium group, iminodiacetic acid, acetic acid, phosphonic acid, aminophosphate, aminocarboxylic acid, N-methylglucosamine, alkylamine group, pyridine ring, cyclic anthocyanin, phthalocyanine ring, and cyclic ether. Commercially available chelating resins can be used, such as Duolite ES371N, Duolite C467, Duolite C747UPS, SUMICHELATE MC760, SUMICHELATE MC230, SUMICHELATE MC300, SUMICHELATE MC850, SUMICHELATE MC640 and SUMICHELATE MC900 (and above, manufactured by Sumika Chemtex), Purolite S106, Purolite S910, Purolite S914, Purolite S920, Purolite S930, Purolite S950, Purolite S957 and Purolite S985 (and above, manufactured by Purolite Corporation), etc.

[0266] There are no particular limitations on the method for implementing ion adsorption, and conventional methods can be used. Typically, a method of passing the purified substance through a filling section filled with chelating resin can be cited. By using the ion exchange resin treatment step, the purified substance can be passed through the same chelating resin multiple times, or the purified substance can be passed through different chelating resins.

[0267] The filling section typically includes a container and the aforementioned ion exchange resin filled in the container. Examples of containers include columns, cylinders, and packed towers, as well as any other type of container that allows the purified substance to pass through after being filled with the aforementioned ion exchange resin.

[0268] [Distillation Step] As another purification method, distillation of the aforementioned compound itself can be listed. As for the distillation method, there is no particular limitation, and conventional methods such as atmospheric distillation, vacuum distillation, molecular distillation, and steam distillation can be used.

[0269] [Preferred Manufacturing Method] (RG is a compound of benzene) The manufacturing method of the compound of formula (Bz) will be specifically described. It is preferred to use the compound represented by formula (MB) as the starting material. The definitions of substituents and r1 and r2 in this compound are the same as those described above. R1, R and OH are bonded at any bondable position. However, r1 and r2 in formula (MB) are selected in such a way that the sum of r1 to r4 is less than or equal to the valence of benzene when formula (Bz) is formed. Examples of compounds of formula (MB) include hydroxybenzaldehyde.

[0270]

[0271] The compound of formula (Bz) can be manufactured by various methods, but from the viewpoint of availability of raw materials and yield, it is preferred to manufacture it by a method including the following steps: a preparation step of the compound of formula (MB), an iodination step of introducing iodine atoms into the aforementioned compound, a protecting group introduction step of introducing a protecting group into the aforementioned compound, and a reduction step of reducing the aforementioned compound.

[0272] From the viewpoint of suppressing byproducts, it is preferable to perform the preparation step, the iodination step, the protecting group introduction step, and the reduction step in sequence.

[0273] 1) As solvents that can be used in the iodination step, a variety of solvents, including polar aprotic solvents and protic polar solvents, can be used. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can also be used. It is preferred to use polar protic solvents or mixtures thereof. From the viewpoint of suppressing side reactions, a mixture of polar protic solvent and water is preferred. The solvent is effective but not necessary. Suitable polar aprotic solvents are not limited, but examples include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amine solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphamide, and hexamethylphosphite triamide; ketone solvents such as acetone and ethyl methyl ketone; chlorine solvents such as dichloromethane and chloroform; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents are not limited to any particular type, but may include alcohol solvents such as water, methanol, ethanol, propanol, and butanol, as well as 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 solvent used can be appropriately set according to the matrix, catalyst, and reaction conditions used, and is not particularly limited. Generally speaking, 0 to 10,000 parts by mass relative to 100 parts by mass of the reactants is suitable, and from the perspective of yield, 100 to 2,000 parts by mass is preferred.

[0274] The raw material compound, catalyst, and solvent are added to the reactor to form a reaction mixture. Any suitable reactor can be used. Furthermore, the reaction can be carried out using conventional methods such as batch, semi-batch, or continuous reactions. The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the product formed, the choice of catalyst, and the desired yield. Generally, a reaction temperature of 0°C to 200°C is suitable; from the viewpoint of yield, a reaction temperature of 0°C to 100°C is preferred, more preferably 0°C to 70°C, and even more preferably 0°C to 50°C. In the reaction of this sample, the preferred reaction temperature range is 0°C to 100°C. In the iodination step, the ratio of the iodizing agent to the matrix is ​​preferably 0.5 moles or more, more preferably 1.0 moles or more, and even more preferably 1.5 moles or more. The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the product formed, the choice of catalyst, and the desired yield. Inert gases such as nitrogen are used, and pressure can be adjusted using a suction pump. The reaction under high pressure is not limited; conventional pressure reactors, including shaking vessels, rocker vessels, and stirred autoclaves, can be used. In this particular reaction, the preferred reaction pressure is reduced pressure to atmospheric pressure, preferably reduced pressure. The reaction time is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the product formed, the choice of catalyst, and the desired yield. However, most reactions last less than 6 hours, and the reaction time is generally from 15 minutes to 600 minutes. In this particular reaction, the reaction time range is from 15 minutes to 600 minutes, preferably from 15 minutes to 600 minutes, and more preferably from 15 minutes to 360 minutes. Separation and purification can be carried out after the reaction using appropriate methods known in the art. For example, the reaction mixture is injected into ice water and extracted in a solvent such as ethyl acetate or diethyl ether. The product is then recovered by evaporation under reduced pressure to remove the solvent. The desired high-purity compound can be separated and purified using separation and purification methods known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or combinations of these methods.

[0275] When synthesizing compounds represented by formulas (1), (Bz4), (Bz4-1), or (Bz4-2), from the viewpoint of improving productivity, it is preferable to perform one or two or more iodination steps, preferably two. Furthermore, when performing one or more iodination steps, the iodizing agent is not particularly limited, and examples include iodine chloride, iodine, N-iodosuccinimide, iodic acid, and hydrogen iodide (including hydroiodic acid and aqueous solutions of hydrogen iodide). Iodine and iodic acid are preferred. In the iodination step, the ratio of the iodizing agent to the matrix is ​​preferably 1.2 moles or more, more preferably 1.5 moles or more, and even more preferably 2.0 moles or more. In the second iodination step, it is preferable to use a method such as introducing halogen from the amino group via the Sandmeier reaction. (In the formula, RG is a group containing at least one cyclic structure, I is an iodine atom, R1 can be a monovalent functional group with 0 to 30 carbon atoms that does not contain polymerizable unsaturated bonds, n is an integer from 1 to 5, and m is an integer from 1 to 5.) (In the formula, the definitions of I, R, A, and Z are the same as in formula (Bz). R1' is a monovalent functional group with 0 to 30 carbon atoms that does not contain polymerizable unsaturated bonds, excluding hydroxyl groups, r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is less than or equal to the valence of benzene.)

[0276] In formula (Bz4), the definitions of I, R, A, and Z are the same as described above. R1' may be the same or different from other functional groups with 0 to 30 carbon atoms, excluding hydroxyl groups, and is a monovalent functional group that does not contain polymerizable unsaturated bonds. Preferably, it is not an alkyl group. R1' is preferably, for example, an alkoxy group with 1 to 30 carbon atoms, a carboxyl group with 1 to 30 carbon atoms, a carboxylic acid ester group with 2 to 10 carbon atoms, an alkoxyalkyl group with 2 to 30 carbon atoms, a hydroxyalkyl group with 2 to 30 carbon atoms, an aldehyde group, a halogen atom other than an iodine atom, a nitro group, an amino group, a cyano group, or a thiol group. Among these groups, R1' is preferably a carboxyl group, an ester group, or a hydroxyalkyl group. Among these groups, there may be substituents, and there may be substituents other than hydroxyl groups. r1', r2', and r4' are preferably integers of 0 to 5, more preferably integers of 0 to 3, and particularly preferably integers of 0 to 2. r4' is preferably an integer from 0 to 5, more preferably an integer from 0 to 4, and especially preferably an integer from 0 to 3. However, the sum of r1', r2', and r4' is less than or equal to the valence of benzene. (In the formula, the definitions of I, R, Z, and R1' are the same as in formula (Bz4). r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is less than or equal to the valence of benzene. (In the formula, the definition of I is the same as in formula (Bz4), r4' is an integer from 0 to 4, and r5' is an integer from 0 to 4.)

[0277] 2) Protective group introduction step: Various solvents, including polar aprotic solvents and protic polar solvents, can be used as solvents in this step. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can also be used, preferably polar aprotic solvents or mixtures thereof. The solvent is an effective but not essential component. Suitable polar aprotic solvents are not limited, but examples include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amine solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphamide, and hexamethylphosphite triamide; ketone solvents such as acetone and ethyl methyl ketone; chlorine solvents such as dichloromethane and chloroform; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents are not limited to any particular type, but may include alcohol solvents such as water, methanol, ethanol, propanol, and butanol, as well as 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 solvent used can be appropriately set according to the matrix, catalyst, and reaction conditions used, and is not particularly limited. Generally, 0 to 10,000 parts by mass relative to 100 parts by mass of the reactants is appropriate, and from the perspective of yield, 100 to 2,000 parts by mass is preferred. Various protective agents that function under the reaction conditions of this embodiment can be used as protective agents. Examples of suitable protective agents are not limited to any particular type, but may include, for example, acetic halides, acid anhydrides, dicarbonates, and other active carboxylic acid derivatives, alkyl halides, vinyl alkyl ethers, dihydropyrans, and alkyl esters of halocarboxylic acids. In the protecting group introduction step, the ratio of the protecting group introducer to the matrix is ​​not particularly limited, but is preferably 0.5 moles or more, more preferably 1.0 moles or more, and even more preferably 1.5 moles or more. Various types of protecting catalysts that function under the reaction conditions of this embodiment can be used as the catalyst for the protecting step. An acid catalyst or a base catalyst is preferred. Examples of suitable acid catalysts are not limited to, and can include 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, ferric chloride, and boron trifluoride; and solid acids such as silicottitic acid, phosphotungstic acid, silicomolybdic acid, or phosphomolybdic acid.These acid catalysts can be used alone or in combination of two or more. From a manufacturing point of view, organic acids and solid acids are preferred, and hydrochloric acid or sulfuric acid are preferred from the perspective of ease of acquisition and processing. Examples of suitable base catalysts are not limited; examples of amine catalysts include pyridine, diisopropylethylamine, and ethylenediamine; examples of non-amine base catalysts are inorganic bases, such as metal salts, and particularly preferably potassium salts or acetates. Potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide are also suitable catalysts. The non-amine base catalysts of this embodiment are available from companies such as EMScience (Gibbstown) or Aldrich (Milwaukee). The amount of catalyst used can be appropriately set according to the matrix, catalyst and reaction conditions used, and is not particularly limited. Generally speaking, 1 to 5000 parts by mass relative to 100 parts by mass of the reactants is appropriate. From the point of view of yield, 50 to 3000 parts by mass is preferred.

[0278] In the protecting group introduction step, when introducing a protecting group into the hydroxyl group of a compound having a hydroxyl group, from the viewpoint of increasing yield and scaling up production, it is preferable to use an inorganic base to introduce the protecting group into the hydroxyl group, and more preferably, a combination of an amide-based solvent and an inorganic base. The inorganic base is not limited, and examples include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, potassium metasilicate, etc., among which sodium carbonate and potassium carbonate are preferred. The amide-based solvent is not limited, and examples include N-methyl-2-pyrrolidone (NMP), N,N-dimethylmethamide (DMF), N,N-dimethylacetamide (DMAc), etc., among which DMF is preferred. These can be used alone or in combination of two or more. Although not particularly limited, the inventors speculate that the HCl generated as a byproduct in the protecting group introduction step contributes to the decomposition reaction of the product, but by using an inorganic base, the inorganic base reacts with HCl, thereby inhibiting the decomposition of the product. Furthermore, it is deduced that by combining an inorganic base with an amide-based solvent, the component generated from the reaction of the inorganic base with HCl becomes insoluble in the amide-based solvent and is excluded from the reaction system, thereby inhibiting the decomposition of the product. Examples of compounds containing the aforementioned hydroxyl group with a protecting group include compounds in formulas (Bz) and (Bz4) where R1 is a hydroxyl group. Also, when R1 is a hydroxyl group in formula (MB), a protecting group can be introduced into R1.

[0279] The compound to be protected, the catalyst, and the solvent are added to the reactor to form a reaction mixture. Any suitable reactor can be used. Furthermore, the reaction can be carried out using conventional methods such as batch, semi-batch, or continuous reactions. The reaction temperature is not particularly limited. A preferred range varies depending on the concentration of the matrix, the stability of the product formed, the choice of catalyst, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable; from a yield perspective, a temperature of 10°C to 190°C is preferred, more preferably 25°C to 150°C, and even more preferably 50°C to 100°C. In this particular sample, the preferred temperature range is 0°C to 100°C. The reaction pressure is not particularly limited. A preferred range varies depending on the concentration of the matrix, 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 a suction pump. The reaction under high pressure is not limited, and conventional pressure reactors including shaking vessels, rocker vessels, and stirred autoclaves can be used. In this particular reaction, the preferred reaction pressure is reduced pressure to atmospheric pressure, preferably reduced pressure. The reaction time is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the product formed, the choice of catalyst, and the desired yield. However, most reactions last less than 6 hours, with reaction times generally ranging from 15 minutes to 600 minutes. In this particular reaction, the preferred reaction time range is 15 minutes to 600 minutes. Separation and purification can be carried out after the reaction using appropriate methods known in the art. For example, the reaction mixture can be injected into ice water and extracted in a solvent such as ethyl acetate or diethyl ether. The product is then recovered by evaporation under reduced pressure to remove the solvent. The desired high-purity monomer can be separated and purified using separation and purification methods known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or combinations of these methods.

[0280] 3) Reduction Step: Various solvents, including polar aprotic solvents and protic polar solvents, can be used as solvents for the reduction step. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, mixtures of polar aprotic solvents, mixtures of protic polar solvents, mixtures of polar aprotic solvents and protic polar solvents, and mixtures of aprotic or protic solvents and nonpolar solvents can also be used. Polar aprotic solvents or mixtures thereof are preferred. From the viewpoint of suppressing side reactions, mixtures of polar aprotic solvents and polar protic solvents are preferred. As for polar protic solvents, alcoholic solvents such as water, methanol, ethanol, propanol, and butanol are even more preferred. The solvent is an effective but not essential component. Suitable polar aprotic solvents are not limited to any particular type, but may include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amine solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphamide, and hexamethylphosphite triamide; ketone solvents such as acetone and ethyl methyl ketone; chlorine solvents such as dichloromethane and chloroform; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents are not limited to any particular type, but may include alcohol solvents such as water, methanol, ethanol, propanol, and butanol, as well as 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 solvent used can be appropriately set according to the matrix, reducing agent, and reaction conditions used, and is not particularly limited. Generally speaking, 0 to 10,000 parts by mass relative to 100 parts by mass of the reactants is appropriate, and from the perspective of yield, 100 to 2,000 parts by mass is preferred.

[0281] As a reducing agent, various reducing agents that function under the reaction conditions of this embodiment can be used. Suitable reducing agents are not limited to any particular type; examples include metal hydrides, metal hydride compounds, etc., such as borane dimethyl sulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, tris-butyl boron lithium, tris-butyl boron potassium, triethyl boron lithium, lithium aluminum hydride, tri-t-butoxy lithium aluminum hydride, sodium bis(methoxyethoxy) aluminum hydride, etc.

[0282] The amount of reducing agent used can be appropriately set according to the matrix, reducing agent and reaction conditions used, and is not particularly limited. Generally speaking, 1 to 500 parts by mass relative to 100 parts by mass of the reactant is appropriate. From the point of view of yield, 10 to 200 parts by mass is preferred.

[0283] As a quencher, various quenchers that function under the reaction conditions of this embodiment can be used. The quencher has the function of deactivating the reducing agent. The quencher is an effective but not essential component. Suitable quenchers are not limited, and examples include ethanol, ammonium chloride solution, water, hydrochloric acid, sulfuric acid, etc. The amount of quencher used can be appropriately set according to the amount of reducing agent used, and is not particularly limited. Generally speaking, 1 to 500 parts by mass relative to 100 parts by mass of reducing agent is appropriate, and from the point of view of yield, 50 to 200 parts by mass is preferred.

[0284] The compound to be reduced, the reducing agent, and the solvent are added to the reactor to form a reaction mixture. Any suitable reactor can be used. Furthermore, the reaction can be carried out using conventional methods such as batch, semi-batch, or continuous reactions. The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the product formed, the choice of the reducing agent, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable; from the viewpoint of yield, a temperature of 0°C to 100°C is preferred, more preferably 0°C to 70°C, and even more preferably 0°C to 50°C. The preferred temperature range is 0°C to 100°C. The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the product formed, the choice of the reducing agent, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen and a suction pump. The reaction under high pressure is not limited, and conventional pressure reactors including shaking vessels, rocker vessels, and stirred autoclaves can be used. In this particular reaction, the preferred reaction pressure is reduced pressure to atmospheric pressure, preferably reduced pressure. The reaction time is not particularly limited. The preferred range varies depending on the concentration of the matrix, the stability of the product formed, the choice of reducing agent, and the desired yield. However, most reactions last less than 6 hours, with reaction times generally ranging from 15 minutes to 600 minutes. In this particular reaction, the preferred reaction time range is 15 minutes to 600 minutes, more preferably 15 minutes to 360 minutes. Separation and purification can be carried out after the reaction using appropriate methods known in the art. For example, the reaction mixture can be injected into ice water and extracted in a solvent such as ethyl acetate or diethyl ether. The product is then recovered by evaporation under reduced pressure to remove the solvent. It is capable of separating and purifying the desired high-purity compound using separation and purification methods known in the field of technology, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or by combining such methods.

[0285] When R1 in formula (Bz) is a carboxylic acid, from the viewpoint of improving productivity, the aforementioned reduction step preferably includes the step of esterifying the aforementioned carboxylic acid and the step of converting the ester group obtained by reduction into a hydroxymethyl group. For example, in the step of esterifying the aforementioned carboxylic acid, if an alkyl ester group is obtained, the aforementioned ester group refers to a structure composed of a carbonyl group derived from a carboxylic acid and an alkoxy group derived from an alcohol. From the viewpoint of productivity, it is preferable to use an esterifying agent in the esterification step. Carboxylic acid halides and carboxylic anhydrides can also be used. Furthermore, as a compound in the aforementioned formula (Bz) where R1 is a carboxylic acid, it is preferably a compound represented by the following formula (Bz5). Also, it is preferable to attach an electrophilic group to a carboxylic acid, for example, an aromatic carboxylic acid having an iodine atom as a substituent, represented by the following formula (Bz5). (In the formula, the definitions of I, Z, R1, A, R, r1~r4 are the same as in formula (DM1a).)

[0286] Specific examples of compounds represented by the following formula (Bz5) are as follows.

[0287] The esterifying agent used in the esterification step is not particularly limited, but examples include acid catalysts, base catalysts, carbodiimide-based condensing agents, and phosgene derivative-based condensing agents. Acid catalysts, base catalysts, and carbodiimide-based condensing agents are preferred. Acid catalysts and base catalysts are not particularly limited, and the same as those described above can be used. The solvent is not particularly limited, and examples include THF, DMSO, chloroform, and toluene. THF is preferred.

[0288] The reducing agent used in the step of reducing the ester group to the hydroxyl group is not particularly limited, but boron-based reducing agents, lithium-based reducing agents, etc., can be listed. Boron-based reducing agents such as sodium borohydride and borane are preferred, and it is even more preferable to use the reducing agent in combination with calcium chloride or lithium chloride. The solvent is not particularly limited, but THF, DMSO, chloroform, toluene, etc., can be listed. Toluene is preferred, and it is even more preferable to use methanol in combination. Furthermore, after the step of esterifying the carboxylic acid, the step of reducing the ester group to the hydroxyl group can be performed without purification.

[0289] (RG is a compound of naphthalene) The method for manufacturing the compound of formula (N) will be specifically described. It is preferable to use the compound represented by formula (MN) as the starting material. The definitions of substituents, s3, s4, etc. in this formula are the same as those described above. However, s3 and s4 in formula (MN) are selected such that the sum of s1 to s4 is less than or equal to the valence of naphthalene when it becomes formula (N). R1 ​​is not limited and can include hydroxyl, amino, nitro, halogen atoms other than iodine atoms, aldehyde groups, etc. Specific examples of compounds of formula (MN) are not limited and can include, for example, (di)hydroxynaphthalaldehyde, aminonaphthalaldehyde, nitronaphthalaldehyde, chloronaphthalaldehyde, etc.

[0290]

[0291] Compounds of formula (N) can be manufactured by various methods, but from the viewpoint of availability of raw materials and yield, it is preferred to manufacture them by a method including the following steps: a preparation step of preparing a compound of formula (MN), an iodination step of introducing iodine atoms into the aforementioned compound, a protecting group introduction step of introducing a protecting group into the aforementioned compound, and a reduction step of reducing the aforementioned compound.

[0292] From the viewpoint of suppressing byproducts, it is preferable to perform the preparation step, the iodination step, the protecting group introduction step, and the reduction step in the following order, or to perform the preparation step, the protecting group introduction step, the iodination step, and the reduction step in the following order. The solvents and reaction conditions that can be used in each step can also be set as described in the method for manufacturing RG as a benzene compound.

[0293] (RG is a compound of adamantane) The method for manufacturing the compound of formula (Ad) will be specifically described. In this method, it is preferable to use the compound represented by formula (MA) as a raw material. In formula (MA), the definitions of R1, R”, t2, and t3 are the same as in formula (Ad). However, t2 and t3 in formula (MA) are selected such that the sum of t1 to t3 when it becomes formula (Ad) is less than or equal to the valence of adamantane. The compound is not limited, and examples include adamantanetriol, etc.

[0294]

[0295] The compound of formula (Ad) can be manufactured by various methods, but from the viewpoint of the availability of raw materials and yield, it is preferable to manufacture it by a method including the following steps: preparation steps of the compound of formula (MA), and iodination steps of introducing iodine atoms.

[0296] Furthermore, as another example of the method for manufacturing the compound represented by formula (1), in order to improve productivity, it is preferred to include a step selected from any one of the following: 1) the compound represented by preparative formula (Ad-A-3-0), 2) the compound represented by preparative formula (Ad-A-3-1), and 3) the compound represented by preparative formula (Ad-A-3-2).

[0297] Furthermore, when the step includes the compound represented by the preparative formula (Ad-A-3-0), it is preferable to include: 1) the step of the compound represented by the preparative formula (Ad-A-3-0), 2) the oxidation step of the compound represented by the oxidative formula (Ad-A-3-0), 3) the step of the carboxylic acid of the compound obtained by esterification, 4) the iodination step of iodination, and 5) the step of converting the ester group of the compound obtained by hydrolysis into the carboxyl group.

[0298] The oxidation step of a compound represented by the oxidation formula (Ad-A-3-O) is not particularly limited, but examples include methods using an oxidizing agent, methods of hydrolyzing bromides, and methods of oxidation using aceimine compounds. The oxidizing agent is not particularly limited, but examples include air, oxygen, ozone, nitric acid, halogens (chlorine, bromine, iodine), potassium nitrate, hypochlorous acid, permanganate, cerium ammonium nitrate, chromic acid, peroxides, Toron reagent, ruthenium compounds, etc., with ruthenium compounds being preferred. The ruthenium compound is not particularly limited, and examples include ruthenium metal, ruthenium dioxide, ruthenium tetroxide, ruthenium hydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium sulfate, or hydrates thereof. These can be used alone or in mixtures. Among ruthenium compounds, ruthenium chloride, ruthenium dioxide, or their hydrates are particularly preferred from the viewpoint that they readily react with periodates and hypochlorites, which are used as co-oxidants, to generate ruthenium in a highly oxidized state with high catalytic activity. Potassium periodate, sodium periodate, and calcium periodate are preferred as periodates, with sodium periodate being more preferred. One or more oxidants or co-oxidants can be used.

[0299] The steps for obtaining the carboxylic acid of the compound by the aforementioned esterification can be the same as the esterification steps in formula (Bz).

[0300] The step of converting the ester group of the compound obtained by the aforementioned hydrolysis into a carboxyl group is not particularly limited, but it is preferable to use an acid catalyst or a base catalyst for hydrolysis to convert into a carboxyl group. From the viewpoint of selectivity of hydrolysis, a base catalyst is preferred. As an acid catalyst, there are no particular limitations, but examples include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, ferric chloride, and boron trifluoride; or solid acids such as silicottitic acid, phosphotungstic acid, silicomolybdic acid, or phosphomolybdic acid. From the viewpoint of ease of acquisition and ease of processing, hydrochloric acid or sulfuric acid is preferred. The choice of alkaline catalyst is not particularly limited, but examples include organic alkaline catalysts such as pyridine, quinoline, isoquinoline, α-methylpyridine, β-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N,N-dimethylaniline, and N,N-diethylaniline, as well as inorganic alkaline catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate. Inorganic alkaline catalysts are preferred, and potassium hydroxide and sodium hydroxide are even more preferred. Furthermore, one or more acid or alkaline catalysts may be used. The iodination step in the compound represented by formula (Ad-A-3-0) can be the same as the aforementioned iodination step.

[0302] As another example of the method for manufacturing the compound represented by formula (1), in order to improve productivity, it is preferable to further include: 4) the step of preparing the compound represented by formula (Ad-A-3).

[0303]

[0304] Furthermore, when the step includes the compound represented by the preparative formula (Ad-A-3), it is preferable to include: 1) the step of the compound represented by the preparative formula (Ad-A-3), and 2) the reduction step of the compound represented by the reducing formula (Ad-A-3).

[0305] The reduction steps for reducing the aforementioned compound can be the same as the aforementioned reduction steps.

[0306] As a solvent that can be used in the iodination step, it can be one listed in the method for manufacturing a compound in which RG is benzene. In this step, the raw material compound, catalyst, and solvent are added to the reactor to form a reaction mixture. The reaction conditions, etc., can also be set as described in the method for manufacturing a compound in which RG is benzene.

[0307] Furthermore, in the iodination step, the reaction of obtaining alkyl iodide from an aqueous solution of hydrogen iodide and adamantanol as raw materials preferably includes a step of distilling off water and concentrating the reaction solution. The concentration of hydrogen iodide in the reaction solution is preferably 10% or more, more preferably 25% or more, even more preferably 40% or more, particularly preferably 45% or more, and most preferably 50% or more. Additionally, when the reaction solution is separated into two or more phases, the concentration of hydrogen iodide in the aqueous phase containing hydrogen iodide is preferably the above-mentioned concentration.

[0308] Adamantanol may have only one hydroxyl group in the molecule, or it may have two or more. Furthermore, the hydroxyl group undergoing iodination may be primary, secondary, or tertiary, preferably secondary or tertiary, and more preferably tertiary.

[0309] Adamantane alcohol is preferably represented by the following formula (MA-1). In the formula, R1 and R' are defined in the same way as in formula (Ad). However, R1 is preferably -OH, -NO2, or a monovalent group with 1 to 12 carbon atoms that may contain at least one functional group. The aforementioned functional group is selected from one or more groups in the group consisting of hydroxyl, ether, ester, carboxyl, halogen atom, -NO2, and NLL'. Then, the aforementioned L and L' are each independently a hydrogen atom, a hydroxyl group, or a monovalent group with 1 to 12 carbon atoms that may contain at least one functional group.

[0310]

[0311] The amount of hydrogen iodide relative to the hydroxyl group to which iodination is performed is preferably 1.01 or more, more preferably 1.1 or more, more preferably 1.3 or more, and especially preferably 1.5 or more, by mass ratio.

[0312] When a compound of formula (MA-1) has two or more hydroxyl groups in its molecule, all hydroxyl groups can be iodinated, or one or more hydroxyl groups may remain. As a method for selectively retaining one or more hydroxyl groups, examples include: performing iodination in a system consisting of a multiphase system comprising an organic phase and an aqueous phase, wherein the organic phase comprises an organic solvent and the aqueous phase comprises water. Hydrophobic solvents can be used as organic solvents, meaning solvents that are not miscible with water in any proportion. When the aqueous phase originates from an aqueous hydrogen halide solution, iodination of hydroxyl groups is performed in the aqueous phase within a reaction system in which the aqueous hydrogen halide solution and the hydrophobic solvent are separated into two phases: an aqueous phase and a hydrophobic solvent phase. In an alcohol having two or more hydroxyl groups, an iodinated alkyl group with one or more remaining hydroxyl groups is extracted into the hydrophobic solvent phase, thereby potentially obtaining an iodinated alkyl group with one or more remaining hydroxyl groups. Furthermore, by extracting the generated alkyl iodides into a hydrophobic solvent, the yield reduction caused by side reactions can be suppressed. Therefore, using a hydrophobic solvent is also effective when iodinizing all hydroxyl groups.

[0313] The hydrophobic solvent may or may not azeotropically react with water, but it is preferred to use a hydrophobic solvent that azeotropically reacts with water. Examples of hydrophobic solvents that azeotropically react with water include dichloromethane, chloroform, carbon tetrachloride, nitromethane, 1,2-dichloroethane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, pentane, cyclohexane, hexane, benzene, toluene, o-xylene, m-xylene, p-xylene, cumene, nitrobenzene, phenol, S-butanol, cyclopentylmethyl ether, cyclohexanone, etc. Hexane, toluene, o-xylene, m-xylene, and p-xylene are preferred. Furthermore, the hydrophobic solvent can be used alone or in combination with two or more hydrophobic solvents.

[0314] The hydrophobic solvent, relative to the alcohol of the raw material, is preferably 50 or less by mass, more preferably 30 or less, and even more preferably 20 or less.

[0315] Acids may be used in combination during the reaction. Examples of acids include sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid, citric acid, oxalic acid, malic acid, lactic acid, glycolic acid, succinic acid, chromic acid, and boric acid.

[0316] Metal iodides may also be used in conjunction with the reaction. For example, LiI, NaI, KI, MgI 2, CaI 2, AlI 3, etc. are effective.

[0317] To prevent sudden boiling during the reaction, it is preferable to use a stirred reaction liquid. Various shapes of agitators are suitable, such as flat rotor blades, tilting rotor blades, turbine blades, disc turbine blades, propeller blades, three-bladed rearward blades, anchored blades, ribbon blades, screw blades, anchored blades, MAXBLEND, full-area agitator blades, TWISTER, etc.

[0318] The stirring speed can be set to any speed. When using a hydrophobic solvent, if the reaction solution separates into two phases, the stirring speed can be set to the degree of interfacial shaking, the stirring speed to the generation and dispersion of some oil or water droplets, or the stirring speed to the state of complete dispersion. Furthermore, the iodination reaction time can be shortened by feeding in the matrix and iodizing agent, allowing it to stand, and then stirring. The standing time is preferably 1 to 48 hours, more preferably 4 to 24 hours, and even more preferably 8 to 12 hours.

[0319] The reaction temperature is preferably set to 0~150℃, more preferably 20~150℃, and even more preferably 50~120℃. On the other hand, in order to obtain iodoalkyl groups in high yield, it is preferable to distill off water during the reaction and concentrate the reaction solution. In order to distill off water, it is necessary to set the reaction temperature to the boiling point of the reaction solution. When the boiling point changes due to the use of hydrophobic solvents, the reaction temperature can be controlled by setting the reaction under reduced pressure or increased pressure.

[0320] The reaction temperature can be controlled by changing the stirring speed. Generally speaking, when a hydrophobic solvent azeoses with water, its azeotropic point is lower than the boiling point of the solvent. When using a hydrophobic solvent that azeoses with water, and the reaction liquid separates into two liquid phases, as the stirring speed increases, the two phases approach a completely dispersed state. Along with this, the boiling point also approaches the azeotropic point. Therefore, the reaction temperature can be controlled by the stirring speed.

[0321] When concentrating the reaction liquid, the water distilled from the single distillation can be completely removed. A Dean-Stark apparatus or similar device can be used to remove the necessary amount, but it is preferable to use a Dean-Stark apparatus or similar device to remove the necessary amount.

[0322] The amount of water removed by distillation is preferably determined in a way that maintains the hydrogen iodide concentration at or above a specified concentration. This concentration is preferably at least 15% lower than the feed hydrogen iodide concentration, more preferably at least 10% lower than the feed hydrogen halide concentration, even more preferably at least 5% lower than the feed hydrogen iodide concentration, and most preferably at or above the feed hydrogen iodide concentration. Furthermore, water can be continuously removed by distillation at a fixed rate, or it can be removed by total distillation at specified intervals. After the reaction is complete, purification and separation of the alkyl iodide are performed.

[0323] In the reaction, iodine monomer is generated by oxidation of hydrogen iodide. If residual iodine monomer remains, it can cause discoloration, etc. Therefore, it is preferable to reduce it to hydrogen iodide by a reducing agent. The type of reducing agent is not particularly limited, and examples include sodium sulfite, sodium bisulfite, and phosphonic acid.

[0324] A preferred method for removing iodine from the monomer is to add an iodide salt to the reaction solution, thereby transferring the iodine from the monomer to the aqueous layer for removal. Potassium iodide, etc., can be used as the iodide salt.

[0325] The reducing agent can be added directly to the reaction solution or in the form of an aqueous solution. Furthermore, the reducing agent can be added when hydrogen iodide remains in the reaction solution, or after the hydrogen iodide has been neutralized with an alkali. The alkali used in the aforementioned neutralization operation is not particularly limited; examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate.

[0326] The iodination step is also preferably a method using a combination of trimethylsilyl chloride and sodium or potassium iodide, or adamantanol as a raw material. The solvent is preferably a polar aprotic solvent, but is not limited to any particular type; examples include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amine solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, hexamethylphosphamide, and hexamethylphosphite triamide; ketone solvents such as acetone and ethyl methyl ketone; chlorine solvents such as dichloromethane and chloroform; and dimethyl sulfoxide. Acetonitrile is preferred. The ratio of trimethylsilyl chloride to sodium iodide used is preferably 1.0 moles or more, more preferably 1.5 moles or more, and even more preferably 2.0 moles or more. When acetonitrile is used as the solvent, the reaction temperature is preferably under reflux conditions.

[0327] The concentration method, type of reducing agent, stirring speed, and form of filter used in the iodination reaction using a combination of trimethylsilyl chloride and sodium iodide or potassium iodide can be the same as those used in the iodination reaction using hydrogen iodide.

[0328] When adamantane polyol is used as a raw material, hydrogen iodide is preferred as an iodizing agent when introducing multiple iodine atoms, and a combination of trimethylsilyl chloride and sodium iodide or potassium iodide is preferred as an iodizing agent when introducing 1 iodine atom.

[0329] When using a hydrophobic solvent, purification can be achieved by washing the hydrophobic solvent phase with water. Suitable water washes include, for example, pure water, aqueous sodium chloride solution, aqueous nitric acid solution, aqueous oxalic acid solution, aqueous sulfuric acid solution, and aqueous hydrogen chloride solution. Alternatively, a hydrophobic solvent may be added for washing after the reaction is complete. The hydrophobic solvent added after the reaction may be the same as or different from the hydrophobic solvent used in the reaction.

[0330] Generally, water washing can be carried out at near room temperature, but if products precipitate during water washing at room temperature, water washing can be carried out while heating. The preferred temperature for water washing is below the azeotropic temperature of the hydrophobic solvent and water.

[0331] As mentioned above, the solution can be passed through ion exchange resin, chelating resin, metal removal filter, microparticle removal filter, etc., for purification. Ion exchange resin, chelating resin, metal removal filter, and microparticle removal filter can be used alone or in combination with operations such as water washing during purification.

[0332] The separation of the compound of formula (Ad) can be carried out by distillation or crystallization. When separating by distillation, the method of distillation is not particularly limited, and methods such as batch single distillation, equilibrium flash vaporization, batch rectification, and continuous rectification can be appropriately applied. Furthermore, the compound of formula (Ad) can be distilled off and recovered, or it can be recovered as a residue or bottom liquid.

[0333] When separating by crystallization, the hydrophobic solvent used in the reaction can be used directly as the solvent, or a new solvent can be added. Furthermore, the solvent can be a single solvent, or two or more solvents can be used together.

[0334] The solvent used during crystallization is preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less, and particularly preferably 3 or less, by mass ratio to the compound of formula (Ad). The ratio of solvent to compound of formula (Ad) can also be adjusted by distilling off the solvent.

[0335] Crystallization can be induced by adding seed crystals, or crystallization can be induced by cooling the solution without adding seed crystals. Furthermore, the slurry is cooled after crystallization to increase yield. The cooling rate is preferably 30°C / h or less, more preferably 20°C / h or less, even more preferably 10°C / h or less, and particularly preferably 5°C / h or less.

[0336] The temperature at which the slurry is separated from the solid-liquid mixture after cooling is preferably -50~40℃, more preferably -20~30℃, and even more preferably -20~10℃. Furthermore, the time from when the slurry temperature reaches the solid-liquid separation temperature to when solid-liquid separation occurs is not particularly limited, but is preferably within 24 hours, and more preferably within 10 hours.

[0337] The method of solid-liquid separation is not particularly limited, and methods such as Nutsche filtration, centrifugation, and pressure filtration can be appropriately applied.

[0338] Furthermore, when iodizing a compound (MA), a base or oxidizing agent can be used. When the base or oxidizing agent has high reactivity, a compound (Da2) can be synthesized. Examples of such bases include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, and potassium bicarbonate. Examples of such oxidizing agents are not particularly limited, but examples include periodic acid, hydrogen peroxide, and specified additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, etc.). Furthermore, by using strong acids or other condensation agents to recombine the hydroxyl groups of the compound (MA), a compound (Da2) can also be synthesized.

[0339] The method for manufacturing compound (B) described in this invention preferably further includes a step of treatment using an adsorbent. The method for manufacturing compound (B) can utilize an adsorbent to remove impurities, and various filters and adsorbents can be appropriately combined. Examples of adsorbents include conventional adsorbents such as inorganic adsorbents like alumina, activated alumina, silica gel, silica-alumina, zeolite (synthetic zeolite, others), mica, and activated carbon, molecular sieves, and ion exchange resins. When these adsorbents come into contact with a target organism on a clean solid surface, the target component is adsorbed on the surface through the interaction between the atoms on the solid surface and the target component. This adsorption allows for the adsorption and removal of specific components. Furthermore, based on the mode of interaction, adsorption phenomena can be classified into two types: physisorption and chemisorption. Physical adsorption refers to the phenomenon of atoms and molecules adsorbing onto a solid surface. Adsorption is primarily caused by the Van der Waals interactions between gas molecules and surface atoms. Its characteristics include low specificity due to the substance, rapid adsorption rate, low heat of adsorption (~20 kJ mol⁻¹), the ability to induce multilayer adsorption, reversible detachment, and non-dissociation. On the other hand, chemisorption refers to the phenomenon of atoms and molecules adsorbing onto a solid surface. Adsorption is caused by the interaction of chemical bonds and charge movement. Chemisorption primarily affects gas molecules and atoms in metals and metal oxides. Its characteristics include high specificity due to the substance, slow adsorption rate, high heat of adsorption (hundreds of kJ mol⁻¹), and the induction of only monolayer adsorption.

[0340] The removal of impurities using an adsorbent is not particularly limited, as long as the compound (B) coexisting with the impurities is brought into contact with the adsorbent. Examples include adding the adsorbent (also known as silica dispersion) to the reaction solution, passing the reaction solution through a column filled with adsorbent, dissolving the compound (B) coexisting with the impurities in an organic solvent and adding the adsorbent, and passing the compound (B) coexisting with the impurities through a column filled with adsorbent. From a production point of view, adding the adsorbent to the reaction solution is preferred. Furthermore, from the viewpoint of selectively removing impurities from the compound (B) and suppressing the introduction of impurities from the adsorbent, alumina, activated alumina, silica gel, and silica-alumina are preferred as adsorbents, with silica gel and silica-alumina being more preferred.

[0341] 2. Composition The aforementioned compound is useful as a composition. The aforementioned compound is particularly useful as a composition for photolithography, and therefore can be used as a composition for photolithography. Hereinafter, a composition containing this compound will be described using a photolithography composition as an example.

[0342] The aforementioned compounds exhibit a sensitizing effect on lithography components containing them under radiation irradiation. Therefore, one embodiment of this invention can be a method for exhibiting a sensitizing effect on lithography components under radiation irradiation using the aforementioned compounds, preferably using two or more of the aforementioned compounds. This reason is not limited, but it is believed that the aforementioned compounds can promote radiation absorption. This effect is particularly significant under extreme ultraviolet (EUV) irradiation. The sensitizing effect can have multiple forms. When a photosensitive layer made using lithography components is used as a lithography resist film, it can be confirmed, for example, by the following methods: 1) Using a patternless surface exposure method, after exposure, a PEB step (a step of performing heat treatment after exposure) and a development step (a step of removing the exposed or unexposed areas by dissolving them with developer) are performed as needed, and the film thickness of the obtained film is measured. 2) The exposure amount is changed, the film thickness of the obtained film is measured, and the exposure amount at which the film thickness changes drastically is defined as the sensitivity in the surface exposure method. 3) If sensitivity is confirmed at a low exposure level, an enhancing effect can be considered. Furthermore, in the method of pattern formation by exposure, 1) when a pattern is formed by changing the exposure level, the exposure level at which the linewidth becomes the specified value after exposure is defined as the sensitivity. 2) If sensitivity is confirmed at an even lower exposure level, an enhancing effect can be considered. Furthermore, lithography compositions containing the aforementioned compounds are used to suppress defects in resist patterns. Especially in extreme ultraviolet (EUV) pattern evaluation, defects such as pitting and bridging can be identified. These defects arise from exposure states similar to optical exposure fluctuations or substantial deficiencies due to low exposure. However, if the resist film has an enhancing effect, these fluctuations and deficiencies are avoided by promoting absorption, thus reducing the aforementioned defects. When the aforementioned compounds are used in lithography compositions, they can be used directly as constituent components of the composition. Alternatively, it can be processed into the form of a resin (substrate (A)) containing the aforementioned compound as part of its structure, additives (acid generator (C), crosslinking agent (G), acid diffusion inhibitor (E), other components (F), etc.), or a photolithography composition containing such resin and additives as constituent components can be used.

[0343] The lithography composition of this embodiment includes the compound represented by formula (1) (hereinafter also referred to as "compound (B)"). It may also include other components such as substrate (A), solvent (S), acid generator (C), crosslinking agent (G), and acid diffusion control agent (E) as needed. The components will be described below.

[0344] [Compound (B)] The composition in this embodiment includes one or more compounds (B). Although not limited, the composition preferably includes two or more compounds (B). If two or more compounds (B) are included, there is a tendency for the etching defects shown in the embodiments described later to be reduced. The reason for the reduction in etching defects is not yet clear, but it is believed that there is a possibility, for example, that the compatibility of compounds (B) in the composition is improved, and fine defects during film formation are reduced. The RG of compound B is preferably derived from a group of benzene, naphthalene, or adamantane that may have substituents. When two or more compounds B are included, the groups from which RG is derived may be the same or different.

[0345] The amount of compound (B) is not limited. When there is a compound (B) with a small amount of doping (let's call this compound (B')), from the viewpoint of improving the etching defect, the amount of compound (B') is preferably 1 ppm or more, and more preferably 10 ppm or more, in the total amount of compound (B). When there is a compound (B) with the largest amount of doping (let's call this compound (B')), from the viewpoint of improving sensitivity, the content of compound (B'') with a smaller iodine atom content in the molecule of compound (B') is preferably 40% or less by mass in the total amount of compound (B), more preferably 10% or less by mass, and most preferably 5% or less by mass.

[0346] In a single-state sample, in compound (B), if the monomeric compound with more iodine atoms is designated as H, the monomeric compound with fewer iodine atoms as L, and the dimer compound as D, the following combinations can be exemplified. H / L (mass ratio, the same below) = (97~99.999): (3~0.001) H / D = (97~99.999): (3~0.001) H / L / D = (95~99.999): (2.5~0.0005): (2.5~0.0005) Furthermore, the following combinations are more preferred. H / L = (98~99.99): (2~0.01) H / D = (98~99.99): (2~0.01) H / L / D = (97~99.99): (1.5~0.005): (1.5~0.005) Furthermore, the following combinations are even better: H / L = (99~99.9): (1~0.1) H / D = (99~99.9): (1~0.1) H / L / D = (98~99.9): (1~0.05): (1~0.05) Furthermore, the following combinations are particularly preferred. H / L=(99.5~99.9): (0.5~0.1) H / D=(99.5~99.9): (0.5~0.1) H / L / D=(99~99.9): (0.5~0.05): (0.5~0.05)

[0347] The method of mixing two or more compounds (B) is not limited. Two or more compounds (B) can be mixed. During the synthesis of compound (B), it is possible to synthesize them simultaneously in the form of a mixture.

[0348] The following are preferred embodiments of compound B. 1) A combination of the compound represented by the reference formula (1) and a compound represented by formula (1) but with fewer iodine atoms than the aforementioned reference compound (preferably the compound represented by formula (BP0-1) described later). 2) A combination of the compound represented by the reference formula (1) and a polymer of the compound represented by formula (1) (preferably the compound represented by formula (DM0-1) described above). 3) A combination of the compound represented by the reference formula (1), the aforementioned compound with fewer iodine atoms, and the aforementioned polymer. Furthermore, the compound with fewer iodine atoms may be a compound that does not contain iodine atoms.

[0349] The composition is represented by a compound with the inclusion formula (DM0-1), and is expected to be particularly effective in ensuring the long-term stability of inorganic substances and components, and is related to the improvement of long-term stability due to the high capture effect of the element components. Furthermore, as another preferred embodiment, the composition is represented by a compound with the inclusion formula (BP0-1), and is expected to be effective in ensuring long-term stability due to the redox potential difference with the compound represented by formula (1), and is related to the improvement of long-term stability due to natural oxidation and the long-term deterioration of coexisting substances.

[0350] The compounds represented by formula (DM0-1) are as described above. The compounds represented by formula (DM0-1) are preferably those represented by the aforementioned formula (DM1a), (Dn1), or (Da1), or those represented by the following formulas (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb). (In the formula, the definitions of Z, I, R1, A, R, r1~r4 are the same as in formula (DM1a).) (In the formula, the definitions of Z, R1, A, R, r1~r4 are the same as in formula (DM1a).) (In the formula, the definitions of I, R1, A, R”, Q, s1~s4 are the same as in formula (Dn1).) (In the formula, the definitions of R1, A, R”, Q, s2~s4 are the same as in formula (Dn1).) (In the formula, the definitions of I, R1, R”, Rd, t1~t3 are the same as in formula (Da1).) (In the formula, the definitions of R1, R”, Rd, t2~t3 are the same as in formula (Da1).) (In the formula, the definitions of I, R1, R”, Rd, t1~t3 are the same as in formula (Da1).) (In the formula, the definitions of I, R1, R”, Rd, t1~t3 are the same as in formula (Da1).) (In the formula, the definitions of I, R1, R”, R… The definitions of d, t1~t3 are the same as in equation (Da1). (In the equation, the definitions of I, R1, R”, Rd, t1~t3 are the same as in equation (Da1).)

[0351] As for the aforementioned compounds with a small number of iodine atoms, examples include compounds represented by formula (BP0-1).

[0352]

[0353] RG, I, R1 are defined in the same way as in formula (1). n' is 0 to 5 and is an integer less than n, preferably an integer between 0 and 3. When the composition includes compounds represented by formula (DM0-1) and formula (BP0-1), n' in formula (BP0-1) is preferably an integer that is 1 less than the value of n' in formula (DM0-1). m' is 1 to 5 and is an integer less than m. When n' is 1 to 5, the compound of formula (BP0-1) is one of the compounds represented by formula (1).

[0354] The compound represented by formula (BP0-1) is preferably represented by the following formula. In the formula, R, R1, R”, A, r1~r4, s2~s3, t2~t3 are defined as above. a1 and r4a are integers from 0 to 4, and a1 and r4a are numbers that satisfy a1+r4a≦r4. The definition of r4 is the same as above, but is preferably synonymous with r4 in formula (Bz). s1b is an integer from 0 to 6, and is an integer that satisfies s1b≦(s1-1). The definition of s1 is the same as above, but is preferably synonymous with s1 in formula (N). t1b is an integer from 0 to 9, and is an integer that satisfies t1b≦(t1-1). The definition of t1 is the same as above, but is preferably synonymous with t1 in formula (Ad).

[0355]

[0356] Furthermore, the compound represented by formula (BP0-1) is preferably represented by the following formulas (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt). (In the formulas, the definitions of Z, R, R1, A, r1, r2, r3, and r4a are the same as those in formula (BP1a). (In the formulas, the definitions of R1, R”, A, and s2~s4 are the same as those in formula (Bn1). (In the formulas, the definitions of R1, R”, t2, and t3 are the same as those in formula (Ba1).)

[0357] The composition of compounds represented by formula (1) and compounds represented by formula (DM0-1) or formula (BP0-1) exhibits excellent storage stability. While the reason is not limited, it is presumed that this is because the compounds represented by formula (DM0-1) or formula (BP0-1) stereoscopically or electronically capture factors and components that degrade storage stability. From this perspective, the lower limit of the total amount of compounds represented by formula (DM0-1) and formula (BP0-1) relative to the total amount of the compound represented by formula (1) is preferably 1 ppm or more, more preferably 2 ppm or more, even more preferably 5 ppm or more, and particularly preferably 10 ppm or more. Furthermore, the upper limit of this total amount is preferably 10,000 ppm or less, more preferably 8,000 ppm or less, even more preferably 5,000 ppm or less, and particularly preferably 3,000 ppm or less.

[0358] When the composition further includes a compound represented by formula (DM0-1), the compounds represented by formula (1) and formula (DM0-1) preferably satisfy the following relationship: 0.1 ≧ [amount (mol) of compound (DM0-1)] ÷ [amount (mol) of compound (1)] ≧ 0.000001

[0359] When the composition further includes the compound represented by formula (DM0-1) and the compound represented by formula (BP0-1), the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) preferably satisfy the following relationship: 0.1 ≧ ([total amount of the compound of formula (DM0-1) and the compound of formula (BP0-1) (mol)]) ÷ [amount of the compound of formula (1) (mol)] ≧ 0.000001

[0360] In addition to the effects described above, from the viewpoint of improving the heat resistance of the compound, it is preferable to use a compound represented by formula (DM0-1), and more preferably a compound represented by formulas (DM1a), (Dn1), (Da1), (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb). Dimers are particularly preferred.

[0361] In addition to the effects described above, from the viewpoint of compatibility, when the composition contains a compound B that is different from the compound represented by the formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), (Ba1-eb), (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt), it is preferable to have the same parent core as compound B.

[0362] In addition to the effects described above, from the viewpoint of improving the solubility and stability of the compound, compounds represented by formula (BP0-1) are preferred, as are compounds represented by formulas (BP1a), (Bn1), or (Ba1) that have fewer iodine atoms. Compounds represented by formulas (BP1a), (Bn1), and (Ba1) can also achieve the desired effect even when they do not contain iodine atoms. In this particular sample, Z in formula (BP1a) may not contain I. Preferred compounds will be described below.

[0363] The compound represented by formula (BP1a) is preferably the compound represented by formula (BP1b).

[0364]

[0365] In equation (BP1b), the definitions of I, R, R1, A, and Z are the same as in equation (BP1a), and a11 and a12 are integers from 0 to 2 that satisfy a11+a12≦r4. The definition of r4 is the same as above, but it is preferred to be synonymous with r4 in equation (Bz) (hereinafter the same).

[0366] The compound represented by formula (BP1b) is preferably the compound represented by formula (BP1c1).

[0367]

[0368] In equation (BP1c1), the definitions of I, R, R1, A, and Z are the same as in equation (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.

[0369] The compound represented by formula (BP1c1) is preferably the compound represented by formula (BP1d11).

[0370]

[0371] In equation (BP1d11), the definitions of I, R, R1, A, and Z are the same as those in equation (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.

[0372] The compound represented by formula (BP1c1) is preferably represented by formula (BP1d12).

[0373]

[0374] In formula (BP1d12), the definitions of I, R, R1, and Z are the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4. A' is a protecting group, represented by -OR aOR b, -O-CO-OR b, -OR a-CO-OR b, or -OR aO-CO-R b. Ra is a straight-chain or branched alkyl group with 1 to 3 carbon atoms. Rb is a monovalent straight-chain, branched, or cyclic alkyl group with 1 to 3 carbon atoms, or a divalent cyclic alkyl group, and forms a ring together with the adjacent oxygen atom. A cyclic structure containing Ra and Ra can also be formed. However, there may be more than one A'.

[0375] The compound represented by formula (BP1b) is preferably represented by formula (BP1c2).

[0376]

[0377] In equation (BP1c2), the definitions of I, R, R1, A, and Z are the same as in equation (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.

[0378] The compound represented by formula (BP1c2) is preferably the compound represented by formula (BP1d21).

[0379]

[0380] In equation (BP1d21), the definitions of I, R, R1, A, and Z are the same as those in equation (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.

[0381] The compound represented by formula (BP1c1) is preferably represented by formula (BP1d22).

[0382]

[0383] In equation (BP1dd22), the definitions of I, R, and R1 are the same as in equation (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4. The definition of A' is the same as in equation (BP1d12).

[0384] The compound represented by formula (BP1b) is preferably the compound represented by formula (BP1c3).

[0385]

[0386] In equation (BP1c3), the definitions of I, R, R1, A, and Z are the same as in equation (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.

[0387] The compound represented by formula (BP1c3) is preferably the compound represented by formula (BP1d31).

[0388]

[0389] In equation (BP1d31), the definitions of I, R, R1, A, and Z are the same as in equation (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.

[0390] The compound represented by formula (BP1b) is preferably the compound represented by formula (BP1c4).

[0391]

[0392] In equation (BP1c4), the definitions of I, R, R1, A, and Z are the same as in equation (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.

[0393] The compound represented by formula (BP1c4) is preferably the compound represented by formula (BP1d41).

[0394]

[0395] In equation (BP1d41), the definitions of I, R, and R1 are the same as in equation (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4. The definition of A' is the same as in equation (BP1d12).

[0396] The compound represented by formula (Bn1) is preferably the compound represented by formula (Bn1a).

[0397]

[0398] In equation (Bn1a), the definitions of I, R1, R”, and A are the same as in equation (Bn1). x' and y' are 0 or 1 respectively, and relative to x and y in equation (1n), they satisfy (x'+y')≦(x+y-1).

[0399] The compound represented by formula (Bn1a) is preferably the compound represented by formula (Bn1b1).

[0400]

[0401] In equation (Bn1b1), the definitions of I, R1, R”, and A are the same as in equation (Bn1). x' and y' are 0 or 1 respectively, and relative to x and y in equation (1n), they satisfy (x'+y')≦(x+y-1). The definition of s4' is as described above.

[0402] The compound represented by formula (Bn1b1) is preferably represented by formula (Bn1c11).

[0403]

[0404] In equation (Bn1c11), the definitions of I, R1, R”, and A are the same as in equation (Bn1). x' and y' are 0 or 1 respectively, and relative to x and y in equation (1n), they satisfy (x'+y')≦(x+y-1).

[0405] The compound represented by formula (Bn1b1) is preferably represented by formula (Bn1c12).

[0406]

[0407] In formula (Bn1c12), the definitions of R1 and R” are the same as in formula (Bn1), and the definition of A' is the same as in formula (BP1d12).

[0408] The compound represented by formula (Bn1a) is preferably represented by formula (Bn1b2).

[0409]

[0410] In equation (Bn1b2), the definitions of I, R1, R”, and A are the same as in equation (Bn1). x” is 0 or 1. The definition of s4’ is as described above.

[0411] The compound represented by formula (Bn1b2) is preferably the compound represented by formula (Bn1c21).

[0412]

[0413] In formula (Bn1c21), the definitions of R1 and R” are the same as in formula (Bn1), and the definition of A’ is the same as in formula (BP1d12).

[0414] The compound represented by formula (Bn1a) is preferably the compound represented by formula (Bn1b3).

[0415]

[0416] In equation (Bn1b3), the definitions of I, R1, R”, and A are the same as in equation (Bn1). x' and y' are 0 or 1 respectively, and relative to x and y in equation (1n), they satisfy (x'+y')≦(x+y-1). The definition of s4' is as described above.

[0417] The compound represented by formula (Bn1b3) is preferably the compound represented by formula (Bn1c31).

[0418]

[0419] In equation (Bn1c31), the definitions of R1 and R” are the same as in equation (Bn1), and the definition of A’ is the same as in equation (BP1d12).

[0420] The compound represented by formula (Bn1b3) is preferably the compound represented by formula (Bn1c32).

[0421]

[0422] In formula (Bn1c32), the definitions of R1 and R” are the same as those in formula (Bn1), and the definition of A’ is the same as that in formula (BP1d12).

[0423] The compound represented by formula (Ba1) is preferably the compound represented by formula (Ba1a).

[0424]

[0425] In equation (Ba1a), the definitions of I, R1, and R” are the same as in equation (Ba1). 1c1, 1c2, and 1c3 are integers of 0 or 1 that satisfy (1c1+1c2+1c3)≦t1b. The definition of t1b is as described above, but it is preferred to be the same as t1b in equation (Ba1) (hereinafter, the same).

[0426] The compound represented by formula (Ba1a) is preferably represented by formula (Ba1b).

[0427]

[0428] In equation (Ba1b), the definitions of I, R”, and R1 are the same as in equation (Ba1a). 1c1, 1c2, and 1c3 are integers of 0 or 1 that satisfy (1c1+1c2+1c3)≦t1b.

[0429] The compound represented by formula (Ba1b) is preferably the compound represented by formula (Ba1c11) below.

[0430]

[0431] In equation (Ba1c11), the definitions of I, R”, and R1 are the same as in equation (Ba1a). 1d1 and 1d2 are integers of 0 or 1 that satisfy (1d1+1d2)≦t1b.

[0432] The compound represented by formula (Ba1b) is preferably the compound represented by formula (Ba1c12) below.

[0433]

[0434] (In formula (Ba1c12), the definitions of I, R”, and R1 are the same as those in formula (Ba1a), and 1e1, 1e2, and 1e3 are integers of 0 or 1 that satisfy (1e1+1e2+1e3)≦t1b.

[0435] Compound B is preferably composed of a compound with an added solvent. Examples of compounds with added solvents include those represented by the following formulas (Ba1-tl), (Ba1-x), or (Ba1-eb). (In these formulas, the definitions of I, R1, R”, Rd, and t1~t3 are the same as in formula (Da1).)

[0436] The following are examples of compounds represented by formula (DM0-1) and formula (BP0-1) that do not contain iodine atoms.

[0437] [Substrate (A)] In this embodiment, substrate (A) refers to a compound other than compound (B) and a material that can be used as a resist. Substrate (A) may be a resin. For example, substrate (A) may be a substrate used as a resist for g-line, i-line, KrF excimer laser (248nm), ArF excimer laser (193nm), extreme ultraviolet (EUV) lithography (13.5nm), and electron beam (EB) (e.g., lithography substrate, resist substrate). Examples of substrate (A) include phenolic varnish resin, cresol varnish resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene / (meth)acrylic copolymer, cyclic olefin-maleic anhydride copolymer, cyclic olefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials containing metallic elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof. From the viewpoint of the shape of the obtained resist pattern, phenolic resin, cresol resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene / (meth)acrylic copolymer, and inorganic resist materials containing metallic elements such as titanium, tin, hafnium, and zirconium, as well as their derivatives, are preferred.

[0438] The weight-average molecular weight of the substrate (A) is preferably 2000~49900, more preferably 2000~29900, and even more preferably 2000~14900, from the viewpoint of reducing defects in the film formed by using the composition and achieving a good pattern shape. The aforementioned weight-average molecular weight can be obtained by using GPC to determine the weight-average molecular weight of polystyrene.

[0439] [Solvent (S)] The solvent in this embodiment may be any solvent that dissolves compound (B), and conventional solvents may be used as appropriate. Specific examples of solvents include ethylene glycol monoalkyl ether acetates; ethylene glycol monoalkyl ethers; propylene glycol monoalkyl ether acetates (e.g., propylene glycol monomethyl ether acetate); propylene glycol monoalkyl ethers; lactates; aliphatic carboxylic acid esters; other esters; aromatic hydrocarbons; ketones; acetamides (3:9); lactones, etc. Specific examples of these include those disclosed in Patent Document 1.

[0440] The solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), CHN (cyclohexanone), CPN (cyclopentanone), 2-heptanone, anisole, butyl acetate and ethyl lactate, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN and ethyl lactate.

[0441] In this embodiment, the amount of solid components and the amount of solvent are not particularly limited. Relative to the total mass of the solid components and solvent, it is preferably 1-80% by mass of solid components and 20-99% by mass of solvent, more preferably 1-50% by mass of solid components and 50-99% by mass of solvent, even more preferably 2-40% by mass of solid components and 60-98% by mass of solvent, and particularly preferably 2-10% by mass of solid components and 90-98% by mass of solvent. Furthermore, the total mass of the solid components (including the solid components of any used components such as the substrate (A), compound (B), acid generating agent (C), crosslinking agent (G), acid diffusion control agent (E), and other components (F), hereinafter the same) is defined as the amount of solid components.

[0442] [Acid Generator (C)] The composition of this embodiment preferably includes one or more acid generators (C). The acid generator (C) refers to a material that directly or indirectly generates acid upon irradiation by any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-rays, and ion beam. As the acid generator (C), for example, that described in International Publication No. 2013 / 024778 may be used. Two or more acid generators (C) may also be used in combination.

[0443] The amount of acid generating agent (C) used is preferably 0.001 to 49% by mass of the total mass of the solid components, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and most preferably 10 to 25% by mass. By using acid generating agent (C) within the aforementioned range, there is a tendency to obtain pattern contours with high sensitivity and low edge roughness.

[0444] [Crosslinking Agent (G)] The composition of this embodiment preferably includes one or more crosslinking agents (G). The crosslinking agent (G) can crosslink at least either the substrate (A) or the compound (B). The aforementioned crosslinking agent (G) can cause the substrate (A) to undergo intramolecular or intermolecular crosslinking in the presence of an acid generated by an acid generator (C). Examples of such acid crosslinking agents include compounds having one or more crosslinkable substrate (A) groups (hereinafter referred to as "crosslinking groups"). As the crosslinking agent (G) having such crosslinking groups, for example, the one described in International Publication No. 2013 / 024778 can be used. Two or more crosslinking agents (G) can also be used together.

[0445] In this embodiment, the amount of crosslinking agent (G) used is preferably 0.5 to 50% by mass of the total solid content, more preferably 0.5 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass. If the aforementioned crosslinking agent (G) is set to 0.5% by mass or more, the effect of inhibiting the solubility of the resist film in the alkaline developer is improved, and there is a tendency to reduce the residual film rate, suppress the swelling of the pattern, and suppress the formation of serpentine. On the other hand, if it is set to 50% by mass or less, there is a tendency to suppress the decrease in the heat resistance of the resist.

[0446] [Acid Diffusion Control Agent (E)] The composition of this embodiment may include an acid diffusion control agent (E). The acid diffusion control agent (E) controls the diffusion of acid generated by an acid generator under radiation irradiation in the resist film and has the function of preventing undesirable chemical reactions in unexposed areas. By using an acid diffusion control agent (E), there is a tendency to improve the storage stability of the composition of this embodiment. Furthermore, by using an acid diffusion control agent (E), the resolution of the film formed using the composition of this embodiment can be improved. In addition, by using an acid diffusion control agent (E), the linewidth change of the resist pattern caused by the variation of the resting time before and after radiation irradiation can be suppressed, and there is a tendency to improve process stability. As an acid diffusion control agent (E), a radioactive decomposing alkaline compound as described in International Publication No. 2013 / 024778 can be listed. Two or more acid diffusion control agents (E) may also be used together.

[0447] The doping amount of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass of the total solid content, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass. If the doping amount of the acid diffusion control agent (E) is within the aforementioned range, there is a tendency to prevent degradation of resolution, pattern shape, and dimensional fidelity. Furthermore, even if the resting time from electron beam irradiation to post-radiation heating is prolonged, the shape degradation of the upper layer of the pattern can be suppressed. Also, if the doping amount is 10% by mass or less, there is a tendency to prevent degradation of sensitivity and developability of unexposed areas. Furthermore, by using such an acid diffusion control agent, the storage stability of the resist composition is improved, and the linewidth variation of the resist pattern caused by changes in resting time before and after radiation can be suppressed while improving resolution, thus tending to improve process stability.

[0448] [Other Components (F)] The composition of this embodiment may include one or more of the following additives as other components (F). (Solubility Promoter) The solubility promoter improves the solubility of the solid component in the developer when the solubility is too low, and appropriately increases the dissolution rate of the aforementioned compound during development. As the aforementioned solubility promoter, it is preferably a low molecular weight compound, such as a low molecular weight phenolic compound. Examples of low molecular weight phenolic compounds include bisphenols, s(hydroxyphenyl)methane, etc. Two or more solubility promoters may also be used together.

[0449] The amount of dissolution promoter can be appropriately adjusted according to the type of the aforementioned solid components used, but it is preferably 0 to 49% of the total mass of the solid components, more preferably 0 to 5% of the total mass, even more preferably 0 to 1% of the total mass, and most preferably 0% of the total mass.

[0450] (Solubility Control Agent) A solubility control agent controls the solubility of a solid component in the developer when the solubility of the solid component is too high, thereby appropriately reducing the dissolution rate during development. Preferably, such a solubility control agent does not undergo chemical changes during the firing, radiation irradiation, and development steps of the resist coating.

[0451] As a solubility control agent, there is no particular limitation, and examples include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and ternaries such as methylphenyl ternary, diphenyl ternary, and dinaphthyl ternary. Two or more solubility control agents may also be used together. The amount of solubility control agent may be appropriately adjusted according to the type of compound mentioned above used, but it is preferably 0 to 49% by mass of the total mass of the solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and most preferably 0% by mass.

[0452] (Sensitizer) The sensitizer absorbs the energy of the irradiated radiation and transfers that energy to the acid generator (C), thereby increasing the amount of acid generated and enhancing the apparent sensitivity of the inhibitor. Examples of such sensitizers include benzophenones, diacetyl groups, pyrene groups, phenothiazines, and fumonisins. Two or more sensitizers may also be used in combination. The amount of sensitizer can be appropriately adjusted according to the type of compound mentioned above used, but it is preferably 0 to 49% by mass of the total mass of the solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and most preferably 0% by mass.

[0453] (Surfactant) The surfactant improves the coatability, striation, and developability of the composition of this embodiment. The surfactant can be anionic, cationic, nonionic, or amphoteric. Nonionic surfactants are preferred. Nonionic surfactants have good affinity with the solvents used in the manufacture of the composition of this embodiment, thereby improving the effect of the composition. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and polyethylene glycol higher fatty acid diesters, but are not particularly limited. Commercially available surfactants described in Patent Document 1 can also be used. The amount of surfactant can be appropriately adjusted according to the type of solid component used, but it is preferably 0 to 49% of the total mass of the solid component, more preferably 0 to 5% of the total mass, even more preferably 0 to 1% of the total mass, and most preferably 0% of the total mass.

[0454] (Organic carboxylic acid, or phosphorus oxyacid, or derivative thereof) Organic carboxylic acid, or phosphorus oxyacid, or derivative thereof (hereinafter also referred to as "acid or derivative") has the function of preventing sensitivity degradation, improving the pattern shape of the resist, or improving storage stability. Examples of organic carboxylic acids include malonic acid as described in Patent Document 1. Examples of phosphorus oxyacids or their derivatives include phosphonic acids or their ester derivatives as described in Patent Document 1, among which phosphonic acids are particularly preferred.

[0455] The aforementioned acid or derivative may be used alone or in combination of two or more. The amount of the acid or derivative may be appropriately adjusted according to the type of the aforementioned compound used, but it is preferably 0 to 49% by mass of the total mass of the solid components, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and most preferably 0% by mass.

[0456] (Other Additives) Furthermore, the composition of this embodiment may include additives other than the above-mentioned components as needed. Examples of such additives include dyes, pigments, and adhesives. For example, if dyes or pigments are added, it is preferable because they make the latent image of the exposed section visible and can mitigate the effect of halo during exposure. Also, if adhesives are added, it is preferable because they can improve adhesion to the substrate. Furthermore, other additives include halo inhibitors, preservation stabilizers, defoamers, shape modifiers, etc., specifically 4-hydroxy-4'-methylchalcone, etc.

[0457] [Blending Ratio of Each Component in the Composition] In the composition of this embodiment, the amount of compound B is preferably 10 ppm to 10% by mass of the total solid components of the composition. In this invention, the total mass of the solid components refers to the sum of any solid components including substrate (A), compound (B), acid generator (C), crosslinking agent (G), acid diffusion control agent (E), and other components (F). The mass ratio of substrate (A) to compound (B) is preferably 3:97 to 99.5:0.5, more preferably 10:90 to 99:1. If this mass ratio is within this range, it results in high sensitivity and a tendency to suppress inconsistent exposure in the depth direction. The aforementioned mass ratio is more preferably 30:70 to 98:2, and even more preferably 50:50 to 97:3.

[0458] In the composition of this embodiment, the total amount of substrate (A) and compound (B) is preferably 50 to 99.4% of the total mass of the solid components, more preferably 55 to 95% of the total mass, even more preferably 60 to 95% of the total mass, and most preferably 70 to 95% of the total mass. When the total amount of substrate (A) and compound (B) is as described above, there is a tendency for the resolution to be further improved and the line edge roughness (LER) to be reduced.

[0459] In the composition of this embodiment, the mass ratio (mass%) of (A) / (B) / (C) / (G) / (E) / (F) relative to the total mass of the solid components of the composition of this embodiment is: preferably 1.5~99.0 / 0.2~96.4 / 0.001~49 / 0~49 / 0.001~49 / 0~49, more preferably 5~98.5 / 0.5~89 / 1~40 / 0~40 / 0.01~10 / 0~5, even more preferably 15~97.5 / 1~69 / 3~30 / 0~30 / 0.01~5 / 0~1, and particularly preferably 25~96.5 / 1.5~50 / 3~30 / 0~30 / 0.01~3 / 0.

[0460] The blending ratio of each component is selected from various ranges such that its total is 100% by mass. If the above formula is used, there is a tendency for excellent performance such as sensitivity, resolution, and developability. "Solid components" means the components after removing the solvent, and "total mass of solid components" means that the total of the components that constitute the composition after removing the solvent is set to 100% by mass.

[0461] The components of this embodiment are usually dissolved in a solvent to form a homogeneous solution during use. Then, as needed, the solution is filtered through a filter with a pore size of about 0.2 μm to prepare it.

[0462] [Physical properties of the composition, etc.] The composition of this embodiment can be formed into an amorphous film by spin coating. Furthermore, the composition of this embodiment is applicable to general semiconductor manufacturing processes. Also, the composition of this embodiment can be made into either a positive resist pattern or a negative resist pattern, depending on the type of developer used.

[0463] Lithography compositions containing compound (B) produce excellent sensitization effects during EUV exposure. Therefore, the present invention also provides a method for increasing the sensitivity of lithography compositions during EUV exposure. As mentioned above, it is preferable to use two or more compounds (B) in this sensitization method.

[0464] The residual amount of metallic impurities in the composition is preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, further preferably less than 10 ppb, and most preferably less than 1 ppb. In particular, regarding metals classified as transition metals such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al, if the residual amount of the aforementioned metals is 1 ppm or more, there is a concern that they may become a factor contributing to material degradation and deterioration over time due to interactions with other compounds. Furthermore, if the residual amount of alkali metals and alkaline earth metals such as Na, K, Ca, and Mg is 1 ppm or more, when using compounds to prepare resins suitable for semiconductor engineering, it is impossible to sufficiently reduce the residual metal amount, and there is a concern that it may become a factor contributing to reduced yield in semiconductor manufacturing processes due to defects or performance degradation caused by residual metals. [Example]

[0465] [Measurement Method] [Nuclear Magnetic Resonance (NMR)] The structure of the compound was confirmed by NMR determination using an "Avance 500III spectrometer" (manufactured by Bruker) under the following conditions. [1H-NMR Determination] Frequency: 500MHz Solvent: CDCl3 or d6-DMSO Internal Standard: TMS Measurement Temperature: 23℃ [13C-NMR Determination] Frequency: 125MHz Solvent: CDCl3 or d6-DMSO Internal Standard: Measured Temperature: 23℃

[0466] [Molecular weight] The molecular weight of the compound was determined by liquid chromatography-mass spectrometry (LC-MS) using an Acquity UPLC / MALDI-Synapt HDMS manufactured by Water.

[0467] [Example 1] A compound was prepared using benzene as the parent nucleus according to the following procedure. The reaction was carried out under a nitrogen flow.

[0468]

[0469] (Synthesis of Compounds 1-2) A flask equipped with a stirrer and cooling tube was immersed in an ice-water bath. 40 g (0.11 mol) of Compound 1-1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 120 mL of acetone were fed into the flask and stirred. The internal temperature was 4°C. Next, 15.6 g (1.1 equivalents relative to Compound 1-1) of diisopropylethylamine (DIPEA) was added dropwise to the flask. After the addition of diisopropylethylamine was completed, 12.3 g (1.2 equivalents relative to Compound 1-1) of chloromethyl ethyl ether was added dropwise, and the reaction was carried out under a nitrogen stream for 2 hours. After the reaction was completed, 120 mL of water was added to the flask to obtain the precipitate. The precipitate was then filtered and washed with water, followed by washing with methanol, and then filtered and dried to obtain Compound 1-2. The yield was 84%. The formation was confirmed by NMR and LC-MS. The molecular weight was 432.

[0470] (Synthesis 2 of Compounds 1-2) A flask equipped with a stirrer and a cooling tube was immersed in an ice-water bath. 40 g (0.11 mol) of Compound 1-1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 80 mL of dimethylformamide were fed into the flask and stirred. The internal temperature was 4°C. Next, 15.2 g (1.0 equivalent relative to Compound 1-1) of potassium carbonate was added to the flask. After the addition of potassium carbonate was completed, 12.3 g (1.2 equivalent relative to Compound 1-1) of chloromethyl ethyl ether was added dropwise, and the reaction was carried out under a nitrogen stream for 1 hour. After the reaction was completed, 180 mL of water was added to the flask to obtain the precipitate. The precipitate was then filtered and washed with water, then washed with methanol, filtered again, and dried to obtain Compound 1-2. The yield was 89%.

[0471] (Synthesis of Compounds 1-3) A flask equipped with a stirrer and cooling tube was immersed in an ice-water bath. 33 g of Compounds 1-2 and 100 mL of dehydrated ethanol were fed into the flask. The internal temperature was 3°C. Then, 2.88 g (less than 1.0 equivalent relative to Compounds 1-2) of NaBH4 was added in portions over 1 hour. The reaction was then carried out under a nitrogen stream for 45 minutes. Next, 78 g of 5% ammonium chloride (a reagent manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.) and 100 g of water were added, followed by filtration, washing with water, and drying to obtain Compounds 1-3. The yield was 85%. The formation was confirmed by NMR and LC-MS. The molecular weight was 434.

[0472] [Example 1a] Compound 2, with benzene as the parent nucleus, was added to 60 ml of acetone along with 16 g (65 mmol) of 5-iodovanillin and cooled on ice. 8.2 g (63 mmol) of diisopropylethylamine was added under nitrogen, followed by 6.4 ml (0.84 mol) of chloromethyl ethyl ether dropwise at below 12°C. The mixture was stirred at 3°C ​​for 15 minutes, and 100 ml of water was slowly added. The precipitate was separated by filtration and washed with water. The solid obtained was suspended and stirred in 70 ml of methanol and filtered. The solid was dried at room temperature for use in the next step. 2 g of the solid was added to 15 ml of ethanol and cooled on ice. 225 mg (5.9 mmol) of sodium borohydride was added in portions over 5 minutes. The reaction was carried out directly for 30 minutes, followed by the addition of 20 ml of water. 400 mg (7.5 mmol) of ammonium chloride was added, followed by the dropwise addition of 20 ml of water. After extraction with ethyl acetate, the mixture was dried over sodium sulfate, and the organic solvent was removed by distillation using an evaporator to obtain compound 2. The formation was confirmed by NMR and LC-MS. The molecular weight was 338.

[0473]

[0474] [Example 1b] Compound 3, with benzene as the parent nucleus, was obtained in the same manner as in Example 1, by replacing 12.3 g of chloromethyl ethyl ether with 9.38 g of ethyl vinyl ether. Alternatively, 22 g (60 mmol) of 4-hydroxy-3,5-diiodobenzaldehyde was added to 100 ml of dichloromethane and the mixture was ice-cooled. 43.2 g (600 mmol) of ethyl vinyl ether was added under nitrogen, followed by 1.5 g (6 mmol) of p-toluenesulfonium (P-P) ... The reaction was carried out directly for 30 minutes, followed by the addition of 20 ml of water. Then, 240 mg (4.5 mmol) of ammonium chloride was added, and 20 ml of water was added dropwise. After extraction with ethyl acetate, the mixture was dried over sodium sulfate, and the organic solvent was removed by distillation using an evaporator to obtain compound 3. The formation was confirmed by NMR and LC-MS. The molecular weight was 448.

[0475]

[0476] [Example 1c] Compound 4, with benzene as the parent nucleus, was obtained by replacing 43.2 g of ethyl vinyl ether with 50.5 g of 3,4-dihydro-2H-pyran in the same manner as in Example 1b. The formation was confirmed by NMR and LC-MS. The molecular weight was 460.

[0477]

[0478] [Example 1d] Compound 5, with benzene as the parent nucleus, was obtained by replacing 12.3 g of chloromethyl ethyl ether with 14.2 g of di-tert-butyl dicarbonate in the same manner as in Example 1. The formation was confirmed by NMR and LC-MS. The molecular weight was 474.

[0479]

[0480] [Example 1e] Compound 6, with benzene as the parent nucleus, was used to obtain 3,5-diiodo-4-hydroxybenzyl alcohol in the same manner as in Example 1. 3,5-diiodo-4-hydroxybenzyl alcohol and THF were added and stirred until dissolved. Phosgene (2 equivalents relative to the starting material, 20% toluene solution, Merck) was added dropwise under nitrogen and ice-cooling conditions, and the mixture was stirred for 2 hours under ice-cooling conditions. Then, the mixture was stirred at 25°C for 12 hours. Afterward, nitrogen bubbling was performed for 2 hours, and the carbonate (1e0) was obtained by vacuum concentration. The obtained carbonate (1e0) was added to chloroform and stirred until dissolved under ice-cooling conditions. Then, 1-methylcyclopentanol (1.2 equivalents relative to the aforementioned (1e0)) was added dropwise under ice-cooling conditions and stirred. Pyridine (1.2 equivalents relative to the aforementioned (1e0)) was added dropwise under ice-cooling conditions and stirred. After stirring for 1 hour, the mixture was stirred at 25°C for 12 hours. Subsequently, after adding ion-exchanged water, the organic phase was recovered. The obtained organic phase was washed with 5% sodium bicarbonate solution, followed by five washes with ion-exchanged water. Compound 6 was then concentrated under reduced pressure. Its formation was confirmed by NMR and LC-MS. The molecular weight was 502.

[0481]

[0482] [Example 1f] Compound 7, with benzene as the parent nucleus, was obtained by replacing 12.3 g of chloromethyl ethyl ether with 10.5 g of chloromethyl methyl ether in the same manner as in Example 1. The formation was confirmed by NMR and LC-MS. The molecular weight was 420.

[0483]

[0484] [Example 1g] Compound 8, with benzene as the parent nucleus, was prepared according to the following procedure. The reaction was carried out under a nitrogen flow.

[0485]

[0486] Using a 200L glass-lined reaction vessel connected to a reflux duct, 10 kg of 4-aminobenzyl alcohol and 100 L of methanol were added, and the mixture was stirred at 220 rpm for 1 hour under a nitrogen flow to dissolve it. 21 kg of iodine was added. 10 L of water was added, and the mixture was ice-cooled. 9.2 kg of 30 wt% hydrogen peroxide was added dropwise. The mixture was then stirred at 24°C and 70 rpm for 24 hours. Afterward, 10 L of 10 wt.% sodium sulfite aqueous solution was added while stirring at 120 rpm, followed by 3.5 L of pure water. The precipitate formed was filtered and recovered. 5 kg of compound 8 was obtained by drying. The formation was confirmed by NMR and LC-MS. The molecular weight was 249.

[0487] [Example 1h] Compound 9, with benzene as the parent nucleus, was prepared according to the following procedure. The reaction was carried out under a nitrogen flow.

[0488]

[0489] Using a 200L glass-lined reaction vessel connected to a reflux duct, 10 kg of compound (8) and 20 L of methanol were added, and the mixture was stirred at 220 rpm for 1 hour under a nitrogen flow to dissolve it. 1.2 aq. of concentrated hydrochloric acid was added, and the mixture was ice-cooled. 1.1 aq. of 40 wt% sodium nitrite aqueous solution was added dropwise. Then, the mixture was stirred at 24°C and 70 rpm for 24 hours. After that, potassium iodide aqueous solution was added at 120 rpm, and 7.0 L of pure water was added. The precipitate formed was filtered and recovered. 5 kg of compound 9 was obtained by drying. The formation was confirmed by NMR and LC-MS. The molecular weight was 360.

[0490] [Example 1i] Compound 10 (1) with benzene as the parent nucleus was prepared according to the following procedure. The reaction was carried out under a nitrogen flow.

[0491]

[0492] Using a 200 mL flask connected to a reflux tube, 760 mg of lithium aluminum hydride and 100 mL of superhydrated THF were added, and the mixture was stirred at 220 rpm for 1 hour under a nitrogen flow. Then, 10 g of 2,3,5-triiodobenzoic acid was gradually added in 10 portions over 40 minutes. The mixture was then stirred at 24°C and 70 rpm for 24 hours. 3500 mL of pure water was added, and the precipitate formed was filtered and recovered. The precipitate was dried to obtain 0.4 g (4% yield) of compound 10. The formation was confirmed by NMR and LC-MS. The molecular weight was 486.

[0493] [Example 1j] Compound 10 (2) with benzene as the parent nucleus was obtained in the same manner as in Example 1i except that sodium borohydride was used instead of lithium aluminum hydride.

[0494] [Example 1k] Compound 10(3) with benzene as the parent nucleus was prepared according to the following procedure. The reaction was carried out under a nitrogen flow.

[0495]

[0496] [Esterification Step] In a flask connected to a reflux duct, 5 g of 2,3,5-triiodobenzoic acid, 50 mL of toluene, and 0.01 mL of dimethylformamide were added and the mixture was ice-cooled. Then, 2.38 g (2.0 equivalents) of thionyl chloride was added dropwise, and the mixture was heated to room temperature and stirred for 2 hours. The temperature was then raised to 60°C and stirred for another 2 hours. Next, 3.2 g (10 equivalents) of methanol was added, and the reaction was allowed to proceed for 2 hours. The reaction mixture was concentrated under reduced pressure, and 25 mL of water and sodium carbonate were added to make it alkaline. Then, 50 mL of ethyl acetate was added, and the mixture was stirred at room temperature for 30 minutes. 25 mL of water was added, and the mixture was separated. After removing the aqueous layer and concentrating the organic layer, hexane was added, and the mixture was filtered and dried to obtain 4.6 g of methyl 2,3,5-triiodobenzoic acid (90% yield). The formation was confirmed by NMR and LC-MS. The molecular weight was 514. [Reduction Step] In a container connected to a reflux duct, add 0.90 g (1.05 equivalents) of calcium chloride and 30 mL of ethanol. Add 0.64 g (2.2 equivalents) of sodium borohydride under ice cooling. Then add 4 g of methyl 2,3,5-triiodobenzoate obtained in the aforementioned esterification step. Stir at room temperature for 1.5 hours, then at 40°C for 1.5 hours. After the reaction is complete, add 90 mL of water, and further add hydrochloric acid to adjust the pH to 3-4. Next, extract the organic layer with ethyl acetate. After dehydration and concentration, add hexane and filter. Wash with chloroform and dry. Purify the crude product of compound 10 by column chromatography to obtain 3.0 g (80% yield) of compound 10. Compared to Example 1i, the yield of compound 10 is significantly improved.

[0497] [Example 11] Compound 10 (4) with benzene as the parent nucleus was placed in a container connected to a reflux tube. 15 g of 2,3,5-triiodobenzoic acid, 150 mL of toluene, 20 g of methanol (20 equivalents), and 1.8 g of sulfuric acid (0.6 equivalents) were added. The esterification step of Example 1k was carried out under reflux conditions. After 8 hours, 1.8 g of sulfuric acid (0.6 equivalents) was added again, and the reaction was allowed to proceed for 16 hours. After cooling, the mixture was washed with 100 mL of water, and then washed again with 100 mL of 10% sodium carbonate aqueous solution. After concentration, hexane was added, and the mixture was filtered and dried. The yield was changed to 7.2 g (46.7% yield) of methyl 2,3,5-triiodobenzoic acid, yielding 3.2 g (85%) of compound 10.

[0498] [Example 1m] Compound 10 (5) with benzene as the parent nucleus was obtained by replacing calcium chloride with lithium chloride in the same manner as in Example 1k, yielding 2.1 g (55% yield) of compound 10.

[0499] [Example 1n] Compound 10 (6) with benzene as the parent nucleus was prepared in the same manner as in Example 1k, but without calcium chloride, by adding 2 mL of methanol to obtain 1.4 g of compound 10 (yield 40%).

[0500] [Example 1o] Compound 10 (7) with benzene as the parent nucleus was prepared in the same manner as in Example 1k, but without calcium chloride, and with lithium aluminum hydride instead of sodium borohydride, to obtain 0.6 g of compound 10 (yield 15%).

[0501] (Synthesis Example L1) [Iodination Step]

[0502]

[0503] Using a 100L glass-lined reaction vessel connected to a reflux pipe, 700g of 4-hydroxybenzaldehyde, 4900ml of methanol, and 1260mL of pure water were added and stirred at 220rpm for 1 hour under a nitrogen flow to dissolve the soluble compounds. Then, 1590g of sodium bicarbonate was gradually added in 10 portions over 10 minutes, followed by 3200g of iodine in 10 portions over 40 minutes. At this point, the liquid temperature rose to 47°C, and foaming was observed. The internal temperature was maintained at 46°C using a hot water bath, and the mixture was stirred for 8 hours. An additional 300g of iodine was added after 5 hours of stirring. The mixture was then stirred at 24°C and 70rpm for 24 hours. Finally, 21L of 6M hydrochloric acid aqueous solution was added dropwise over 1 hour at 120rpm, followed by stirring for 30 minutes. Next, while stirring, 2.3 L of a 20 wt.% sodium sulfite aqueous solution was added, followed by 3.5 L of pure water. The precipitate formed by filtration was then separated and recovered. After further washing with 2 L of methanol, the product was dried to obtain 1880 g of 4-hydroxy-3,5-diiodobenzaldehyde in a yield of 87%.

[0504] [Protective Base Import Steps]

[0505]

[0506] Using a 100L glass-lined reaction vessel connected to a reflux pipe, under a nitrogen flow and ice bath atmosphere, 1822g of 4-hydroxy-3,5-diiodobenzaldehyde and 3650mL of dehydrated dimethylformamide (DMF) were added and stirred with a stirrer blade until dissolved. Then, under ice bath conditions, 673g of potassium carbonate (1.0 equivalent relative to the matrix) was added while stirring for 60 minutes. 553g of chloromethyl ethyl ether (1.2 equivalent relative to the matrix) was added dropwise to the stirred reaction solution over 60 minutes using a dropping funnel, followed by stirring under ice bath conditions for 30 minutes. Afterwards, 7.2L of pure water was added under ice bath conditions, and after stirring for 60 minutes, the precipitate was filtered and recovered. The recovered solid was suspended in 5.8L of methanol under ice bath conditions and stirred for 30 minutes, then filtered to obtain a white solid (2450g) as the protectant of the target compound. The yield was 99%. The formation was confirmed by NMR and LC-MS. The molecular weight was 432.

[0507] [Restore Steps]

[0508]

[0509] Using a 20L separable flask, fill with 5L of ethanol under ice bath conditions, then slowly add 2450g of the protective medium obtained in the previous step and suspend it. Under nitrogen flow and stirring, add 50g of sodium borohydride in 5g increments over 60 minutes. Then, stir for 1 hour under ice bath conditions, add 842g of 5% ammonium chloride aqueous solution dropwise over 15 minutes. Under ice cooling, slowly add the obtained reaction solution to 21L of pure water and stir for 30 minutes. After filtering to separate the precipitate that gradually forms during stirring, wash with 5L of pure water. Dissolve the obtained precipitate in 10.5L of ethyl acetate and wash three times with 3.5L of 10% NaCl aqueous solution. After recovering the obtained ethyl acetate solution, add 200g of magnesium sulfate and suspend for 30 minutes. Concentrate the filtrate obtained by filtration to a concentration of approximately 50% ± 5% and then add to 9L of heptane for crystallization. The filtered crystals were then washed with cold heptane and dried to obtain 1680 g of compounds (1-3), with a yield of 77% and an LC purity of 99.8%. The formation was confirmed by NMR and LC-MS. The molecular weight was 434.

[0510] (Synthesis Example L1-1) The obtained precipitate was dissolved in 10.5 L of ethyl acetate, and then 50 g of silica gel was added for silica gel dispersion. An additional step of recovering the organic phase by filtration was performed. The other operations were the same as in Synthesis Example L1 to obtain 1660 g of compound (1-3) with high purity, yield 76%, and LC purity > 99.9%.

[0511] (Synthesis Example L2)

[0512] Except for replacing 4-hydroxybenzaldehyde with salicylaldehyde and setting the iodination step as iodination step L2 described below, the [iodination step], [protecting group introduction step], and [reduction step] were performed in the same manner as in synthesis example L1 to obtain compounds (1-4). The formation was confirmed by NMR and LC-MS. The molecular weight changed from 432 to 434 before and after the reduction step.

[0513]

[0514] [Iodization Step L2] Using a 100L glass-lined reaction vessel connected to a reflux pipe, 700g of salicylaldehyde, 5700ml of ethanol, and 1164g of iodine were fed into the vessel. Under a nitrogen flow, the mixture was heated in a water bath at an internal temperature of 40°C and stirred at 220rpm for 1 hour to dissolve the iodine. Then, 2490g of a 20% (w / w) iodic acid aqueous solution was slowly added dropwise over 60 minutes. After that, the internal temperature was raised to 50°C and stirred for 2 hours. Then, while stirring, 2.3L of a 20wt.% sodium sulfite aqueous solution was added, followed by 7.6L of pure water. The precipitate formed by filtration was separated and recovered. After rinsing with 5L of pure water, the mixture was dried to obtain 2-hydroxy-3,5-diiodobenzaldehyde (2046g) with a yield of 95.5%.

[0515]

[0516] (Synthesis Example L3) Except that vanillin (4-hydroxy-3-methoxybenzaldehyde) was used to replace 4-hydroxybenzaldehyde, and the iodination step was set as described in [Iodination Step L3] below, the [iodination step], [protecting group introduction step], and [reduction step] were performed in the same manner as in Synthesis Example L1 to obtain the target compounds (1-5). The formation was confirmed by NMR and LC-MS. The molecular weight before and after the reduction step changed from 336 to 338.

[0517]

[0518] [Iodization Step L3] In a 30L glass reaction vessel, 1300g (8.55mol) of vanillin (4-hydroxy-3-methoxybenzaldehyde) and 5.6L of methanol were introduced. Nitrogen was blown into the reaction vessel at a flow rate of 200mL / min and stirring was started. After confirming that the vanillin was dissolved, 2.6L of deionized water and 635g (6mol) of sodium carbonate were introduced, and the mixture was stirred at room temperature (22°C) for 3 hours. Iodine 2600g (10.3mol) was added in portions, and the mixture was stirred at room temperature (22°C) for 20 hours. Then, 16.6% sodium sulfite aqueous solution was added until both the solution was decolorized and the system became alkaline. After that, 4.3L of water was added and the mixture was stirred for 1 hour. The precipitated solid was filtered through a suction filter, washed, reslurried, and dried to obtain 1900g of white solid. Analysis by liquid chromatography-mass spectrometry (LC-MS) confirmed a molecular weight of 278. Furthermore, 1H-NMR analysis under the aforementioned conditions confirmed the presence of the chemical structure 4-hydroxy-5-iodo-3-methoxybenzaldehyde. The LC purity at 254 nm was 99.8%, and the GPC purity was 99.9%. The molecular weight was 338, confirmed by NMR and LC-MS.

[0519] (Synthesis Example L4) Except that 1300g of vanillin was replaced with 1420g of ethyl vanillin, the [iodination step], [protecting group introduction step] and [reduction step] were carried out in the same manner as in Synthesis Example L3 to obtain compounds (1-6).

[0520]

[0521] (Synthesis Example L5)

[0522] Other than replacing 4-hydroxybenzaldehyde with 3-hydroxybenzaldehyde, the [iodination step], [protecting group introduction step] and [reduction step] were carried out in the same manner as in Synthesis Example L1 to obtain compounds (1-7).

[0523]

[0524] [Iodization Step] Using a 100L glass-lined reaction vessel connected to a reflux duct, 700g of 3-hydroxybenzaldehyde, 4900ml of methanol, and 1260mL of pure water were added and stirred at 220rpm for 1 hour under a nitrogen flow to dissolve the iodine. Then, 730g of sodium bicarbonate was gradually added in 10 portions over 10 minutes, followed by 1480g of iodine in 10 portions over 40 minutes. At this point, the liquid temperature rose to 47°C, and foaming was observed. The internal temperature was maintained at 46°C in a hot water bath, and the mixture was stirred for 8 hours. An additional 300g of iodine was added after 5 hours of stirring. The mixture was then stirred at 24°C and 70rpm for 24 hours. Finally, 21L of 6M hydrochloric acid aqueous solution was added dropwise over 1 hour at 120rpm, followed by stirring for 30 minutes. Next, while stirring, 2.3 L of a 20 wt.% sodium sulfite aqueous solution was added, followed by 3.5 L of pure water. The precipitate formed by filtration was then separated and recovered. After washing with 2 L of methanol, the product was dried to obtain 1237 g of 3-hydroxy-4-iodobenzaldehyde in a yield of 86%.

[0525] [Protective Group Introduction Procedure] Using a 100L glass-lined reaction vessel connected to a reflux duct, under nitrogen flow and an ice bath, 1237g of 3-hydroxy-4-iodobenzaldehyde and 3650mL of dehydrated dimethylformamide (DMF) were added and stirred with a stirrer blade until dissolved. Then, under an ice bath, 689g of potassium carbonate (1.0 equivalent relative to the matrix) was added while stirring for 60 minutes. 565g of chloromethyl ethyl ether (1.2 equivalent relative to the matrix) was added dropwise to the stirred reaction solution over 60 minutes using a dropping funnel, followed by stirring under an ice bath for 30 minutes. Afterwards, 7.2L of pure water was added under an ice bath, and after stirring for 60 minutes, the precipitate was filtered and recovered. The recovered solid was suspended in 5.8L of methanol under an ice bath and stirred for 30 minutes, then filtered to obtain the protected group, a white solid (1511g), as the target compound. The yield was 99%. The formation was confirmed by NMR and LC-MS. The molecular weight was 306.

[0526] [Reduction Step] Using a 20L separable flask, fill with 5L of ethanol under ice bath conditions, then slowly add 1511g of the protective medium obtained in the previous step and suspend it. Under nitrogen flow and stirring, add 50g of sodium borohydride in 5g increments over 60 minutes. Then, after stirring for 1 hour under ice bath conditions, add 842g of 5% ammonium chloride aqueous solution dropwise over 15 minutes. Under ice cooling, slowly add the obtained reaction solution to 21L of pure water and stir for 30 minutes. After filtering to separate the precipitate that gradually forms during stirring, wash with 5L of pure water. Dissolve the obtained precipitate in 10.5L of ethyl acetate and wash three times with 3.5L of 10% NaCl aqueous solution. After recovering the obtained ethyl acetate solution, add 200g of magnesium sulfate and suspend for 30 minutes. Concentrate the filtrate obtained by filtration to a concentration of approximately 50% ± 5% by mass, and then add 9L of heptane for crystallization. The filtered crystals were then washed with cold heptane and dried to obtain 1171 g of compound (1-7), yield 77%, LC purity 99.8%. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 306 to 308 before and after the reduction step.

[0527] (Synthesis Example L6) Using 3,4-dihydroxybenzaldehyde as a starting material, the protecting group introduction step of Synthesis Example L3 was performed. However, the amounts of diisopropylmethylamine and chloromethyl ethyl ether relative to 3,4-dihydroxybenzaldehyde were set to twice the amount. Then, the [iodination step L6] described below was performed. Next, the [reduction step] was performed in the same manner as in Synthesis Example L3 to obtain compounds (1-8). The formation was confirmed by NMR and LC-MS. The molecular weight before and after the reduction step changed from 380 to 382.

[0528] [Iodination step L6]

[0529] In a 30L glass reaction vessel, 2172g (8.55mol) of 3,4-diethoxymethoxybenzaldehyde and 5.6L of methanol were introduced as raw materials. Nitrogen was introduced and stirred at a flow rate of 200mL / min. After confirming the dissolution of the raw materials, 2.6L of deionized water and 634g (5.99mol) of sodium carbonate were added, and the mixture was stirred at room temperature (22°C) for 3 hours. Then, 2609g (10.3mol) of iodine was added, and the mixture was stirred at room temperature (22°C) for 12 hours. A 16.6% sodium sulfite aqueous solution was added until the solution was decolorized. Then, 4.3L of water was added and the mixture was stirred for 1 hour. The precipitated solid was filtered through a suction filter, washed, reslurried, and dried to obtain 2438g of a white solid. Analysis by liquid chromatography-mass spectrometry (LC-MS) confirmed a molecular weight of 380. Furthermore, 1H-NMR analysis under the aforementioned conditions confirmed the presence of the chemical structure 3,4-diethoxymethoxy-5-iodobenzaldehyde. The LC purity at 254 nm was 99.5%, and the GPC purity was 99.9%.

[0530]

[0531]

[0532] (Synthesis Example L7) Using 2,4,6-trihydroxybenzaldehyde as a starting material, the protecting group introduction step of Synthesis Example L3 was performed. However, the amounts of diisopropylmethylamine and chloromethyl ethyl ether relative to 2,4,6-dihydroxybenzaldehyde were set to 3 times. Then, the [iodination step] was performed in the same manner as in Synthesis Example L3. Next, the [reduction step] was performed in the same manner as in Synthesis Example L3 to obtain compounds (1-9). The formation was confirmed by NMR and LC-MS. The molecular weight before and after the reduction step changed from 580 to 582.

[0533]

[0534] (Synthesis Example L8) Using 3,5-dihydroxybenzaldehyde as a starting material, the protecting group introduction step of Synthesis Example L3 was performed. However, the amounts of diisopropylmethylamine and chloromethyl ethyl ether relative to 3,5-dihydroxybenzaldehyde were set to twice the amount. Then, the [iodination step] was performed in the same manner as in Synthesis Example L3. Next, the [reduction step] was performed in the same manner as in Synthesis Example L3 to obtain compounds (1-10). The formation was confirmed by NMR and LC-MS. The molecular weight changed from 380 to 382 before and after the reduction step.

[0535]

[0536] (Synthesis Example L9) 4-hydroxybenzaldehyde was replaced with 2,4-dihydroxybenzaldehyde, and the [iodination step], [protecting group introduction step], and [reduction step] were performed in the same manner as in Synthesis Example L1 to obtain compound (1-11). The formation was confirmed by NMR and LC-MS.

[0537]

[0538] [Iodization Step L9] In a 500 mL four-necked flask connected to a reflux tube, 6.91 g (50 mmol) of 2,4-dihydroxybenzaldehyde, 69.74 g of methanol, 10.14 g (40 mmol) of iodine, and 7.2 g of water were added and stirred for 30 minutes to dissolve the iodine. Then, under ice cooling, 10.1 g (19.5 mmol based on iodic acid) of 34% by mass aqueous solution was slowly added dropwise over 30 minutes. After that, the mixture was heated to room temperature and stirred for 1 hour. Then, while stirring, 1 g of 5% by mass sodium bisulfite aqueous solution was added, followed by 27.6 g of pure water. The precipitate formed by filtration was separated and recovered. After rinsing twice with 27.6 g of pure water, the mixture was dried to obtain 15.6 g (1,4-dihydroxy-3,5-diiodobenzaldehyde) in 80% yield.

[0539] [Protective Group Introduction Step L9] In a 500 mL four-necked flask connected to a reflux tube, 20 g (51 mmol) of 2,4-dihydroxy-3,5-diiodobenzaldehyde and 140 g of DMF obtained in the previous step were added and stirred under a nitrogen stream to dissolve. Then, under ice cooling, 17.75 g of potassium carbonate (2.5 equivalents relative to the matrix) was added and stirred for 30 minutes. Next, while stirring, 12.12 g of chloromethyl ethyl ether (2.5 equivalents relative to the matrix) was added dropwise using a dropping funnel, and the mixture was stirred in an ice bath for 3 hours. After the reaction was complete, 140 g of water was added, and the precipitate was filtered. The mixture was then washed with 40 g of pure water, followed by 60 g of 2-propanol, to obtain 35.9 g of wet crystals.

[0540] [Reduction Step L9] In a 500mL four-necked flask connected to a reflux tube, 182g of ethanol and 0.485g of sodium borohydride were added and stirred under a nitrogen stream to dissolve them. 35.9g of the wet crystals obtained in the previous step were added under ice-cooling, and the reaction was directly stirred under ice-cooling for 40 minutes. After the reaction was complete, the reaction solution was transferred to a 1L pear-shaped flask. 78g of 0.2M hydrochloric acid was added while stirring under ice-cooling, followed by two additions of 0.77g of 2M hydrochloric acid and 133g of pure water. The precipitate was filtered. The mixture was then rinsed with 100g of pure water to obtain 13.21g of the target compound represented by formula (1-11) (the total yield of 2,4-dihydroxy-3,5-diiodobenzaldehyde introduced in [Protecting Group Introduction Step L9] was 51%).

[0541] (Synthesis Example BPL1) [Protective Group Introduction Step BPL1P]

[0542]

[0543] Using a 100L glass-lined reaction vessel connected to a reflux pipe, under nitrogen flow and an ice bath, 700g of 4-hydroxybenzaldehyde and 3650mL of dehydrated dimethylformamide (DMF) were added and stirred with a stirrer blade until dissolved. Then, under an ice bath, 822g of diisopropylethylamine was added dropwise over 30 minutes with stirring, followed by 60 minutes of stirring. 553g of chloromethyl ethyl ether (1.2 times the amount of matrix) was added dropwise over 60 minutes with a dropping funnel, followed by 30 minutes of stirring under an ice bath. Afterwards, 7.2L of pure water was added under an ice bath, and after stirring for 60 minutes, the precipitate was filtered and recovered. The recovered solid was suspended in 5.8L of methanol under an ice bath and stirred for 30 minutes, followed by filtration to obtain the target compound (BPL1P) (1012g), a white solid. The yield was 98%. The formation was confirmed by NMR and LC-MS. The molecular weight was 180.

[0544] [Restore Steps BPL1R]

[0545]

[0546] Using a 20L separable flask, after filling with ethanol (5L) under ice bath conditions, slowly add 1012g of the aforementioned protective agent BPL1P and suspend it. Under nitrogen flow and stirring, add 50g of sodium borohydride in 5g increments over 60 minutes. Then, after stirring for 1 hour under ice bath conditions, add 842g of 5% ammonium chloride aqueous solution dropwise over 15 minutes. Under ice cooling, slowly add the obtained reaction solution to 21L of pure water and stir for 30 minutes. After filtering to separate the precipitate that gradually formed during stirring, wash with 5L of pure water. Dissolve the obtained precipitate in 10.5L of ethyl acetate and wash three times with 3.5L of 10% NaCl aqueous solution. After recovering the obtained ethyl acetate solution, add 200g of magnesium sulfate and suspend for 30 minutes. Concentrate the filtrate obtained by filtration to a concentration of approximately 50% ± 5% and then add 9L of heptane for crystallization. The filtered crystals were then washed with cold heptane and dried to obtain compound (BPL1R) (716 g), yield 70%, purity 99.6%. The formation was confirmed by NMR and LC-MS. The molecular weight was 182.

[0547] (Synthesis Example BPL1b) 4-Hydroxybenzyl alcohol was added to THF, stirred and dissolved. Phosgene (2 equivalents relative to the starting material, 20% toluene solution, Merck) was added dropwise under nitrogen and ice-cooling, and the mixture was stirred for 2 hours under ice-cooling. Then, it was stirred at 25°C for 12 hours. After 2 hours of nitrogen bubbling, the carbonate (1be0) was obtained by vacuum concentration. The obtained carbonate (1be0) was added to chloroform and stirred and dissolved under ice-cooling. Then, 1-methylcyclopentanol (1.2 equivalents relative to the aforementioned (1be0)) was added dropwise under ice-cooling and stirred. Pyridine (1.2 equivalents relative to the aforementioned (1be0)) was added dropwise under ice-cooling and stirred. After stirring for 1 hour, the mixture was stirred at 25°C for 12 hours. Then, deionized water was added, and the organic phase was recovered. The organic phase was washed with 5% sodium bicarbonate solution, followed by five washes with deionized water. The compound (BPL1b) was then concentrated under reduced pressure. The formation was confirmed by NMR and LC-MS. The molecular weight was 250.

[0548]

[0549] (Synthesis Example BPL2) (BPL2P) and (BPL2R) were synthesized in the same manner as in Synthesis Examples BPL1-4, except that salicylaldehyde was used instead of 4-hydroxybenzaldehyde as a starting material. The formation of (BPL2R) was confirmed by NMR and LC-MS. The molecular weight was 182.

[0550]

[0551] (Synthesis Example BPL3) Except that 3-hydroxybenzaldehyde was used as a starting material, (BPL3P) and (BPL3R) were obtained in the same manner as in Synthesis Example BPL1. The formation of (BPL3R) was confirmed by NMR and LC-MS. The molecular weight was 182.

[0552]

[0553] (Synthesis Example DML1) [Iodination Step DML1D]

[0554]

[0555] Using a 100L stainless steel reaction vessel connected to a reflux pipe, 700g of 4-hydroxybenzaldehyde and 4900ml of methanol were fed in and stirred at 220rpm for 1 hour under a nitrogen flow to dissolve them. The reaction vessel was ice-cooled, and a sodium hydroxide aqueous solution prepared by dissolving 757g of sodium hydroxide in 1260mL of pure water was slowly added to the reaction vessel. Iodine 3200g was gradually added in 10 portions over 60 minutes. The internal temperature was maintained at 60°C by a hot water bath and the mixture was stirred for 8 hours. Then, 21L of 6M hydrochloric acid aqueous solution was added dropwise at 120rpm for 1 hour under ice-cooling, and the mixture was stirred for 30 minutes. Then, while stirring, 2.3L of 20wt.% sodium sulfite aqueous solution was added, followed by 3.5L of pure water. The precipitate formed by filtration was filtered and recovered. The obtained solid was purified by column chromatography using silica gel, thereby obtaining DML1D (840 g) in 30% yield. The formation was confirmed by NMR and LC-MS. The molecular weight was 494.

[0556] [Protective Base Import Steps DML1P]

[0557]

[0558] Using a 100L glass-lined reaction vessel connected to a reflux pipe, under nitrogen flow and an ice bath, 840g of DML1D and 1680mL of dehydrated dimethylformamide (DMF) were added and stirred with a stirrer blade until dissolved. Then, under an ice bath, 380g of diisopropylethylamine was added dropwise over 30 minutes with stirring, followed by 60 minutes of stirring. 255g of chloromethyl ethyl ether (1.2 times the amount of matrix) was added dropwise over 60 minutes with a dropping funnel, followed by 30 minutes of stirring under an ice bath. Afterwards, 7.2L of pure water was added under an ice bath, and after stirring for 60 minutes, the precipitate was filtered and recovered. The recovered solid was suspended in 5.8L of methanol under an ice bath and stirred for 30 minutes, then filtered to obtain 996g of the white solid used as the protected form of the target compound, DML1P. The yield was 96%. The formation was confirmed by NMR and LC-MS. The molecular weight was 610.

[0559] [Restore Steps DML1R]

[0560]

[0561] Using a 20L separable flask, after filling with 5L of ethanol in an ice bath, 996g of the prepared protective body DML1P was slowly added and suspended. Under a nitrogen flow and stirring, 19g of sodium borohydride was added in 3g increments over 60 minutes. Then, after stirring in an ice bath for 1 hour, 350g of a 5wt.% ammonium chloride aqueous solution was added dropwise over 15 minutes. Under ice cooling, the obtained reaction solution was slowly added to 8L of pure water and stirred for 30 minutes. After filtering to separate the precipitate that gradually formed during stirring, it was washed with 2L of pure water. The obtained precipitate was dissolved in 4L of ethyl acetate and washed three times with 1.5L of a 10wt.% NaCl aqueous solution. After recovering the obtained ethyl acetate solution, 80g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of approximately 50wt.% ± 5% and then added to 9L of heptane for crystallization. The filtered crystals were then washed with cold heptane and dried to obtain compound DML1R 701g, yield 70%, purity 99.2%. The formation was confirmed by NMR and LC-MS. The molecular weight was 614.

[0562] (Synthesis Example DML2R)

[0563] Except for using 4-hydroxybenzaldehyde as a raw material, setting the type of protecting agent to ethyl vinyl ether, and changing the [protecting group introduction step] to the method described below, DML2R was synthesized in the same manner as in synthesis example DML1. The formation was confirmed by NMR and LC-MS. The molecular weight was 642.

[0564]

[0565] [Protective Group Introduction Procedure] Using a 100L glass-lined reaction vessel connected to a reflux duct, under nitrogen flow and an ice bath, 840g of DML1D and 1680mL of dehydrated tetrahydrofuran (THF) were added and stirred with a stir bar to dissolve them. Then, under an ice bath, 80g of PPTS (pyridinium p-toluenesulfonic acid) was added over 30 minutes with stirring, followed by 60 minutes of stirring. 294g of ethyl vinyl ether (1.2 equimolar amounts relative to the functional group) was added dropwise to the stirred reaction solution over 60 minutes, followed by stirring at 35°C for 60 minutes. Afterwards, 7.2L of pure water was added under an ice bath and stirred for 60 minutes. The recovered organic phase was then reacted with 2L of ethyl acetate and 5L of pure water, stirred, and the organic phase was recovered. The mixture was concentrated under reduced pressure to obtain the protected form DML2P, with 833g of a white solid as the target compound. The yield was 81%. The formation was confirmed by NMR and LC-MS. The molecular weight is 638.

[0566]

[0567] (Synthesis Example DML3R) DML3R was synthesized in the same manner as in Synthesis Example DML2, except that 4-hydroxybenzaldehyde was used as the starting material, 3,4-dihydropyran was used as the protecting agent, and the [protecting group introduction step] was changed to the method described below. The formation was confirmed by NMR and LC-MS. The molecular weight was 666.

[0568]

[0569] (Synthesis Example DML4R) Except for using 4-hydroxybenzaldehyde as a raw material, setting the type of protecting agent, and changing the [protecting group introduction step] to the method described below, DML4R was synthesized in the same manner as in Synthesis Example DML1. The formation was confirmed by NMR and LC-MS. The molecular weight was 698.

[0570]

[0571] [Protective Group Introduction Step] Using a 100L glass-lined reaction vessel connected to a reflux pipe, under a nitrogen flow and ice bath, 840g of DML1D and 1680mL of dehydrated tetrahydrofuran (THF) were added and stirred with a stirrer blade until dissolved. Next, under ice bath conditions, 10g of DMAP (dimethylaminopyridine) (0.05 equimolar to the matrix) was added over 10 minutes with stirring, and then stirred for 30 minutes. 890g of di-tert-butyldicarbonate (1.2 equimolar to the functional group) was added dropwise to the stirred reaction solution over 60 minutes, and then stirred under ice cooling for 120 minutes. After confirming the disappearance of the starting material by TLC (thin-layer chromatography), 1000mL of n-heptane was added under cooling, and while confirming the internal temperature was below 10°C under ice cooling, 2800mL of 1N hydrochloric acid was added dropwise, and then stirred for 30 minutes. After recovering the upper organic phase, the sample was washed with 7L of 5% sodium bicarbonate solution (once) and 7L of ion-exchanged water (three times). Then, 50g of silica gel was added for dispersion, and the organic phase was recovered by filtration. 200ppm of MQ (methoxyphenol) was added to the matrix, followed by concentration using n-heptane (40°C) to confirm no THF effluent. Further concentration was then performed using high-purity IPA (Kanto Chemical EL-IPA). High-purity IPA was then added at 40°C and dissolved until the target compound dissolved. An equal volume of ion-exchanged water was added dropwise, and crystallization was performed at ice-cold for approximately 1 hour to recover the target compound. 811g of a white solid, DML4P, was obtained as the protected form of the target compound. The yield was 69%. The formation was confirmed by NMR and LC-MS. The molecular weight was 694.

[0572]

[0573] (Synthesis Example DML5R) DML5R was synthesized in the same manner as in Synthesis Example DML1, except that 3-hydroxybenzaldehyde was used as a starting material. The formation was confirmed by NMR and LC-MS. The molecular weight was 614.

[0574]

[0575] (Synthesis Example DML6R) DML6R was synthesized in the same manner as in Synthesis Example DML1, except that vanillin was used as a starting material. The formation was confirmed by NMR and LC-MS. The molecular weight was 674.

[0576]

[0577] (Synthesis Example DML7R) DML7 was synthesized in the same manner as in Synthesis Example DML1, except that 3,4-dihydroxybenzaldehyde was used as the starting material. However, the amount of diisopropylmethylamine and chloromethyl ethyl ether used as the starting material in the protecting group introduction step was set to twice that of 3,4-dihydroxybenzaldehyde. The formation was confirmed by NMR and LC-MS. The molecular weight was 762.

[0578]

[0579] (Synthesis Example DML8R) DML8R was synthesized in the same manner as in Synthesis Example DML1, except that ethyl vanillin was used as a starting material. The formation was confirmed by NMR and LC-MS. The molecular weight was 702.

[0580]

[0581] (Synthesis Example DML9R) DML9R was synthesized in the same manner as in Synthesis Example DML1, except that 2-hydroxybenzaldehyde was used as a starting material. The formation was confirmed by NMR and LC-MS. The molecular weight was 614.

[0582]

[0583] (Synthetic Example DML10R) The compound was prepared as follows. The reaction was carried out under a nitrogen atmosphere to obtain DML10R. The formation was confirmed by NMR and LC-MS. The molecular weight was 496.

[0584] Using a 200L glass-lined reaction vessel connected to a reflux duct, 10 kg of 4-aminobenzyl alcohol and 100 L of methanol were added, and the mixture was stirred at 220 rpm for 1 hour under a nitrogen flow to dissolve it. 21 kg of iodine was added. 10 L of water was added, and the mixture was ice-cooled. 9.2 kg of 30 wt% hydrogen peroxide was added dropwise. The mixture was then stirred at 24°C and 70 rpm for 24 hours. Afterward, 10 L of 10 wt.% sodium sulfite aqueous solution was added while stirring at 120 rpm, followed by 3.5 L of pure water. The precipitate formed was filtered and recovered. The obtained solid was purified by column chromatography using silica gel to obtain 1 kg of DML10R.

[0585] (Synthetic Example DML11R) The compound was prepared as follows. The reaction was carried out under a nitrogen atmosphere to obtain DML11R. The formation was confirmed by NMR and LC-MS. The molecular weight was 718.

[0586] Using a 200L glass-lined reaction vessel connected to a reflux pipe, add 10kg of DML10R and 20L of methanol, and stir for 1 hour under a nitrogen flow at 220rpm to dissolve it. Add 1.2aq. concentrated hydrochloric acid, ice-cool, and dropwise add 1.1aq. 40wt% sodium nitrite aqueous solution. Then, stir at 24°C and 70rpm for 24 hours. Afterward, add potassium iodide aqueous solution at 120rpm, followed by 7.0L of pure water. Filter the precipitate formed and separate and recover it. Dry to obtain 4kg of DML11R.

[0587] (Synthetic Example DML1e) Using compounds (1-4) obtained in Synthetic Example L2, the [reduction step] of Synthetic Example L1 was performed to obtain compound (1-4a). The formation was confirmed by NMR and LC-MS. The molecular weight was 376. In a 200 mL container connected to a reflux tube, 5 g (13.3 mmol) of the obtained compound (1-4a) and 100 mL of toluene were added. The mixture was reacted under reflux for 1 hour, and separated by column chromatography to obtain 0.4 g (0.55 mmol) of compound 1-4b. The formation was confirmed by NMR and LC-MS. The molecular weight was 734. Next, using compound 1-4b, the [protecting group introduction step] of Synthetic Example L1 was performed to obtain compound (DML1e). The formation was confirmed by NMR and LC-MS. The molecular weight was 850.

[0588]

[0589] [Example 2] A compound was prepared using naphthalene as the parent nucleus as described below. The reaction was carried out under a nitrogen flow.

[0590]

[0591] (Synthesis of Compound 2-2) In a flask equipped with a stirrer and cooling tube, 50 g of Compound 2-1 (manufactured by Fujifilm and Kazuhiro Pure Chemical Co., Ltd.), 600 mL of ethanol, and 2.8 mL of 98% sulfuric acid (0.2 equivalents relative to Compound 2-1) were added. The contents were stirred under reflux for 14 hours to carry out the esterification reaction. Then, the mixture was neutralized with 10.6 g of sodium bicarbonate (a reagent manufactured by Fujifilm and Kazuhiro Pure Chemical Co., Ltd.), and the ethanol was distilled off. Ethyl acetate was then added and the organic phase was extracted with water. After washing with sodium bicarbonate, the mixture was dehydrated with sodium sulfate, the solvent was distilled off, and the mixture was suspended and washed with acetone and dried to obtain Compound 2-2. The yield was 64%.

[0592] (Synthesis of Compound 2-3) In a flask equipped with a stirrer and cooling tube, 34 g of compound 2-2, 48 g (1.2 equivalents of compound 2-2) of iodine, 20 g of sodium bicarbonate, 160 mL of methanol, and 16 mL of water were added. The contents were stirred at room temperature for 5 hours to carry out the iodination reaction. Then, 50 mL of methanol was added, followed by sodium bisulfite until the iodine color disappeared. The mixture was filtered, washed with water, suspended in methanol, filtered again, and dried to obtain compound 2-3. The yield was 97%. The formation was confirmed by NMR and LC-MS. The molecular weight was 342.

[0593] (Synthesis of Compounds 2-4) A flask equipped with a stirrer and cooling tube was immersed in an ice-water bath. 50 g of compound 2-3 and 150 mL of acetone were added to the flask and stirred. The internal temperature was 4°C. Next, 20.8 g (1.1 equivalents relative to compound 2-3) of diisopropylethylamine was added dropwise to the flask. After the addition of diisopropylethylamine was complete, 14.7 g of chloromethyl ethyl ether was added dropwise, and the reaction was allowed to proceed for 1 hour. After the reaction was complete, 300 g of ethyl acetate and 500 g of water were added to extract the organic phase. The solvent in the extracted organic phase was distilled off, and the mixture was separated by column chromatography to obtain compound 2-4. The yield was 70%. The formation was confirmed by NMR and LC-MS. The molecular weight was 400.

[0594] (Synthesis of Na-1) Except that 4-hydroxybenzaldehyde was replaced with 6,7,8-trimethoxynaphthalene-2-carboxaldehyde, the iodination and reduction steps were performed in the same manner as in Synthesis Example L1 to obtain compound Na-1. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 372 to 374 before and after the reduction step.

[0595]

[0596] (Synthesis of Na-2) Compound Na-2 was obtained in the same manner as in Synthesis Example L1, except that 2-hydroxy-1-naphthaldehyde was used to replace 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-2-1) was 298. Furthermore, the molecular weight of (Na-2) before and after the reduction step was changed from 356 to 358.

[0597]

[0598] (Synthesis of Na-3) Compound Na-3 was obtained in the same manner as in Synthesis Example L1, except that 4-hydroxybenzaldehyde was replaced with 2-hydroxynaphthalene-6-carboxaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-3-1) was 298. Furthermore, the molecular weight of (Na-3) before and after the reduction step was changed from 356 to 358.

[0599]

[0600] (Synthesis of Na-4) Compound Na-4-3 was obtained in the same manner as in Example 2, except that 3-hydroxy-2-naphthoic acid was substituted for compound 2-1. The procedure is shown below. The formation was confirmed by NMR and LC-MS. The molecular weights (Na-4-2) are 342 and (Na-4-3) are 400.

[0601]

[0602] (Synthesis of Na-5) Compound Na-5 was obtained in the same manner as in Synthesis Example L1, except that 1-hydroxy-2-naphthaldehyde was used to replace 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-5) changed from 356 to 358 before and after the reduction step.

[0603]

[0604] (Synthesis of Na-6) Compound Na-6 was obtained in the same manner as in Synthesis Example L1, except that 4-hydroxy-2-naphthal was substituted for 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-6) changed from 356 to 358 before and after the reduction step.

[0605]

[0606] (Synthesis of Na-7) Compound Na-7 was obtained in the same manner as in Synthesis Example L1, except that 4-hydroxy-2-naphthaldehyde was substituted for 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-7) changed from 356 to 358 before and after the reduction step.

[0607]

[0608] (Synthesis of Na-8) Compound Na-8 was obtained in the same manner as in Synthesis Example L1, except that 4-hydroxy-1-naphthal was substituted for 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-8) changed from 356 to 358 before and after the reduction step.

[0609]

[0610] (Synthesis of Na-9) Compound Na-9 was obtained in the same manner as in Synthesis Example L1, except that 5-hydroxy-2-naphthal was used to replace 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-9) changed from 356 to 358 before and after the reduction step.

[0611]

[0612] (Synthesis of Na-10) Compound Na-10 was obtained in the same manner as in Synthesis Example L1, except that 8-hydroxy-2-naphthaldehyde was used to replace 4-hydroxybenzaldehyde. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-10) before and after the reduction step changed from 356 to 358.

[0613]

[0614] (Synthesis of Na-11) Compound Na-11 was obtained in the same manner as in Synthesis Example L1, except that 4-hydroxybenzaldehyde was replaced with 8-hydroxy-1-naphthal. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-11) before and after the reduction step changed from 356 to 358.

[0615]

[0616] (Synthesis of Na-12) Compound Na-12 was obtained in the same manner as in Example 2 (Synthesis of Compounds 2-4), except that 1-hydroxy-2-naphthoic acid was substituted for compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. By introducing a protecting group to form (Na-12), the molecular weight was changed from 342 to 400.

[0617]

[0618] (Synthesis of Na-13) Compound Na-13 was obtained in the same manner as in Example 2 (Synthesis of Compounds 2-4), except that 4-hydroxy-2-naphthoic acid was substituted for compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. By introducing a protecting group to form (Na-13), the molecular weight was changed from 342 to 400.

[0619]

[0620] (Synthesis of Na-14) Compound Na-14 was obtained in the same manner as in Example 2 (Synthesis of Compounds 2-4), except that 4-hydroxy-2-naphthoic acid was substituted for compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. By introducing a protecting group to form (Na-14), the molecular weight was changed from 342 to 400.

[0621]

[0622] (Synthesis of Na-15) Compound Na-15 was obtained in the same manner as in Example 2 (Synthesis of Compounds 2-4), except that 5-hydroxy-1-naphthoic acid was substituted for compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. By introducing a protecting group into the formation (Na-15), the molecular weight was changed from 342 to 400.

[0623]

[0624] (Synthesis of Na-16) Compound Na-16 was obtained in the same manner as in Example 2 (Synthesis of Compounds 2-4), except that 5-hydroxy-2-naphthoic acid was substituted for compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. By introducing a protecting group into the formation of (Na-16), the molecular weight was changed from 342 to 400.

[0625]

[0626] (Synthesis of Na-17) Compound Na-17 was obtained in the same manner as in Example 2 (Synthesis of Compounds 2-4), except that 8-hydroxy-2-naphthoic acid was substituted for compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. By introducing a protecting group to form (Na-17), the molecular weight was increased from 342 to 400.

[0627]

[0628] (Synthesis of Na-18) Compound Na-18 was obtained in the same manner as in Example 2 (Synthesis of Compounds 2-4), except that 8-hydroxy-1-naphthoic acid was substituted for compound 2-1. The process is shown below. The formation was confirmed by NMR and LC-MS. By introducing a protecting group to form (Na-18), the molecular weight was increased from 342 to 400.

[0629]

[0630] (Synthesis of Na-19) Compound Na-19 was obtained in the same manner as in Synthesis Example L1, except that 4-hydroxybenzaldehyde was replaced with 6-hydroxy-2-naphthal. The process is shown below. The formation was confirmed by NMR and LC-MS. The molecular weight of (Na-19) before and after the reduction step changed from 356 to 358.

[0631]

[0632] [Synthesis Example DMN2-3P] The following reaction was carried out.

[0633]

[0634] (Synthesis of Compound 2-2) Compound 2-2 was obtained by the same method as in Example 2. Its formation was confirmed by NMR and LC-MS. The molecular weight was 216.

[0635] (Synthesis of compound DMN2-3) In a flask equipped with a stirrer and cooling tube, 34 g of compound 2-2, 48 g (1.2 equivalents of compound 2-2) of iodine, 10 g of sodium bicarbonate, 160 mL of methanol, and 16 mL of water were added. The contents were stirred at 40 °C for 5 hours to carry out the iodination reaction. Then, 50 mL of methanol was added, followed by sodium bisulfite until the iodine color disappeared. The mixture was filtered, washed with water, suspended in methanol, filtered again, and dried to obtain compound DMN2-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 682.

[0636] (Synthesis of Compound DMN2-3P) A flask equipped with a stirrer and cooling tube was immersed in an ice-water bath. 50 g of compound DMN2-3 and 150 mL of acetone were added to the flask and stirred. The internal temperature was 4°C. Next, 20.8 g (1.1 equivalents relative to DMN2-3) of diisopropylethylamine was added dropwise to the flask. After the addition of diisopropylethylamine was complete, 14.7 g of chloromethyl ethyl ether was added dropwise, and the reaction was allowed to proceed for 1 hour. After the reaction was complete, 300 g of ethyl acetate and 500 g of water were added to extract the organic phase. The solvent in the extracted organic phase was distilled off, and the mixture was separated by column chromatography to obtain compound DMN2-3P. The formation was confirmed by NMR and LC-MS. The molecular weight was 798.

[0637] [Synthesis Example BPN2-3P] The following reaction was carried out.

[0638]

[0639] (Synthesis of Compound 2-2) Compound 2-2 was obtained by the same method as in Example 2.

[0640] (Synthesis of compound BPN2-3P) A flask equipped with a stirrer and cooling tube was immersed in an ice-water bath. 15.8 g of compound 2-2 and 150 mL of acetone were added to the flask and stirred. The internal temperature was 4°C. Next, 20.8 g (1.1 equivalents relative to compound 2-2) of diisopropylethylamine was added dropwise to the flask. After the addition of diisopropylethylamine was complete, 14.7 g of chloromethyl ethyl ether was added dropwise, and the reaction was allowed to proceed for 1 hour. After the reaction was complete, 300 g of ethyl acetate and 500 g of water were added to extract the organic phase. The solvent in the extracted organic phase was distilled off, and the mixture was separated by column chromatography to obtain compound BPN2-3P. The formation was confirmed by NMR and LC-MS. The molecular weight was 274.

[0641] (Synthesis of DMNa-1-1) Compound DMNa-1-1 was synthesized in the same manner as in Synthesis Example DMN2-3, except that compound 2-2 was substituted with 6,7,8-trimethoxynaphthalene-2-carboxaldehyde. The formation was confirmed by NMR and LC-MS. The molecular weight was 744.

[0642]

[0643] [Synthesis Example DMNa2-1R] Compound DMNa-2-1 was synthesized in the same manner as in Synthesis Example DMN2-3, except that 2-hydroxy-3-naphthal was substituted for compound 2-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 594. Next, compound DMNa2-1P was synthesized in the same manner as in the synthesis of compound DMN2-3P, except that compound DMNa-2-1 was substituted for compound DMN2-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 710. Furthermore, compound DMNa-2-1R was obtained in the same manner as in the synthesis of compound 1-3, except that compound DMNa2-1P was substituted for compound 1-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 714.

[0644]

[0645] [Synthetic Example BPNa2-1R] Compound BPNa2-1P was obtained in the same manner as compound DMN2-3P, except that 2-hydroxy-3-naphthaldehyde was substituted for compound DMN2-3. Its formation was confirmed by NMR and LC-MS. The molecular weight was 230. Furthermore, compound BPNa-2-1R was obtained in the same manner as compound 1-3, except that compound BPNa2-1P was substituted for compound 1-2. Its formation was confirmed by NMR and LC-MS. The molecular weight was 232.

[0646]

[0647] (Synthesis of Compound DMNa-3-1R) Compound DMNa-3-1 was obtained in the same manner as in Synthesis Example DMN2-3, except that 2-hydroxynaphthalene-6-carboxaldehyde was substituted for compound 2-2. Its formation was confirmed by NMR and LC-MS. The molecular weight was 594. Next, compound DMNa-3-1P was obtained in the same manner as in the synthesis of compound DMN2-3P, except that compound DMNa-3-1 was substituted for compound DMN2-3. Its formation was confirmed by NMR and LC-MS. The molecular weight was 710. Furthermore, compound DMNa-3-1R was obtained in the same manner as in the synthesis of compound 1-3, except that compound DMNa-3-1P was substituted for compound 1-2. Its formation was confirmed by NMR and LC-MS. The molecular weight was 714.

[0648]

[0649] [Synthesis Example DMNa-2b-1R] The following reaction was carried out.

[0650]

[0651] Except for replacing 4-hydroxybenzaldehyde with 2-hydroxy-3-naphthaldehyde, compound DMNa-2b-1 was obtained in the same manner as in the iodination step DML1D. Its formation was confirmed by NMR and LC-MS. The molecular weight was 594. Next, except for replacing 5-iodovanillin with compound DMNa-2b-1, compound Na-2b-1P was obtained in the same manner as in the protecting group introduction step DML1P. Its formation was confirmed by NMR and LC-MS. The molecular weight was 710. Furthermore, except for replacing DML1P with compound DMNa-2b-1P, compound DMNa-2b-1R was obtained in the same manner as in the reduction step DML1R. Its formation was confirmed by NMR and LC-MS. The molecular weight was 714.

[0652] [Synthesis Example: Synthesis of DMNa-3-2R] The following reaction was carried out.

[0653]

[0654] Except that 2-hydroxy-3-naphthaldehyde was substituted for 2-hydroxy-6-carboxaldehyde as a raw material, the iodination step, protecting group introduction step, and reduction step were performed in the same manner as in the synthesis example DMNa-2-1 to obtain compound DMNa-3-2R. The formation was confirmed by NMR and LC-MS. The molecular weight was 714.

[0655] (Synthesis of DMNa-4-2P) Compound Na-4-1 was obtained in the same manner as the synthesis of compound 2-2, except that 3-hydroxy-2-naphthoic acid was substituted for compound 2-1. Next, compound DMNa-4-2 was obtained in the same manner as the iodination step in synthesis example DMNa-2-1, except that compound Na-4-1 was substituted for compound 2-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 682. Furthermore, for this compound, a protecting group introduction step was performed in the same manner as in synthesis example DMNa-2-1 to obtain compound DMNa-4-2P. The formation was confirmed by NMR and LC-MS. The molecular weight was 798.

[0656]

[0657] [Example 3] The compound with adamantane as the parent nucleus (synthesis 1 of compound 3-2) was manufactured as follows.

[0658]

[0659] Immerse a flask equipped with a stirrer and cooling tube in an oil bath. Add 80g of compound 3-1 (manufactured by Mitsubishi Gas Chemical Co., Ltd., 0.43mol) and 2.5L of toluene to the flask and stir. Then add 400g (1.72mol) of a 55% hydrogen iodide aqueous solution to the flask. Set the internal temperature to 83-89°C and react for 32 hours. Further, add 50g of a 55% hydrogen iodide aqueous solution to the flask. Set the internal temperature to 83-89°C and react for 16 hours.

[0660] In another container, add 22.5 mL of a 10% sodium sulfite aqueous solution and 1720 mL of water, and then slowly pour in the aforementioned reaction solution. Upon further addition of 2 g of sodium sulfite and 1 L of ethyl acetate, separate the solution into an organic phase and an aqueous phase. Add more water and separate the solution to obtain the organic phase (oil phase). Concentrate this organic phase, add 500 mL of toluene, and store in a freezer overnight.

[0661] The organic phase was filtered and washed with ice-cold toluene and hexane to obtain a wet cake of 145 g. The wet cake was dried under reduced pressure at 40 °C for 2.5 hours to obtain 138 g of pale red crystals. The crystals were then mixed with 1.3 L of ethyl acetate and heated to 70 °C to dissolve them. The ethyl acetate solution was cooled to room temperature. 650 mL of 0.5% sodium sulfite aqueous solution was added to the solution and stirred. The mixture was separated, and the ethyl acetate phase was collected.

[0662] 650 mL of water was added to the ethyl acetate phase and stirred, followed by separation. The ethyl acetate phase was removed again, magnesium sulfate was added and stirred for 30 minutes, and the mixture was allowed to stand in a refrigerator for two nights. Crystals precipitated after standing, so they were heated to dissolve and then cooled to room temperature. The cooled mixture was filtered to obtain magnesium sulfate and a filtrate. The magnesium sulfate was then washed with ethyl acetate. The resulting filtrate was concentrated and further dried under reduced pressure at 40°C for 9 hours to obtain 128 g of white crystalline compound 3-2 with a purity of 99.2% (yield 72%). The formation was confirmed by NMR and LC-MS. The molecular weight was 404. At the end of the reflux reaction, the yield of the compound 3-1 with only one hydroxyl group converted to iodine was <1%, and the yield of the compound with three hydroxyl groups converted to iodine was <1%.

[0663] (Synthesis 2 of Compound 3-2) A flask equipped with a stirrer, cooling tube, and Dean-Stark tube was immersed in an oil bath. 21 g of 1,3,5-adamantanetriol was added to 308 g of toluene, followed by 78.6 g of 55 wt% aqueous hydrogen iodide solution. The mixture was refluxed at 105-110 °C using a Dean-Stark tube for 3 hours, while simultaneously removing 26 g of distilled water. The mixture was then cooled to room temperature. 177.5 g of water was added, followed by 10 g of 10% sodium sulfite aqueous solution. Then, 61.4 g of 6% sodium hydroxide aqueous solution was added and neutralized. The reaction mixture was then filtered. After separating the toluene solution and 31 g of crystals, the toluene solution was washed twice with 88 g of 3 wt% oxalic acid, followed by five separate washes with 88 g of water, yielding 255 g of toluene solution. 31g of the filtered crystals were dissolved in 341g of ethyl acetate, followed by the addition of 85g of water and 0.4g of a 10% sodium sulfite aqueous solution for separation and washing. This was further repeated six times with 85g of water to obtain 316g of ethyl acetate solution. 255g of toluene solution and the 316g of dissolved ethyl acetate solution were concentrated under reduced pressure. After filtration to separate the precipitated crystals, they were dried under reduced pressure at 50°C to obtain 40.9g of white crystalline compound 3-2 with a purity of 99.3% and a yield of 89%. At the end of the reflux reaction, the yield of the compound 3-1 with only one hydroxyl group converted to iodine was <1%, and the yield of the compound with three hydroxyl groups converted to iodine was <1%.

[0664] (Synthesis 3 of Compound 3-2) A flask equipped with a stirrer, cooling tube, and Dean-Stark tube was immersed in an oil bath. 7 g of 1,3,5-adamantanetriol was added to 102 g of toluene, followed by 26.6 g of 55 wt% aqueous hydrogen iodide solution. The mixture was allowed to stand for 12 h. Then, the mixture was refluxed at 102–108 °C using a Dean-Stark tube for 1 h, while simultaneously removing 8.5 g of distilled water. The mixture was then cooled to room temperature. 59 g of water was added, followed by 8 g of 10% sodium sulfite aqueous solution. The reaction mixture was then filtered. After separating the toluene solution and 12 g of crystals, the toluene solution was washed five times with 29 g of water to obtain 85 g of toluene solution. 122 g of ethyl acetate was added to the filtered crystals to dissolve them, followed by 28 g of water and 0.4 g of 10% sodium sulfite aqueous solution for further washing. The mixture was further washed six times with 85g of water to obtain 105g of ethyl acetate solution. 85g of toluene solution and 105g of ethyl acetate solution were concentrated under reduced pressure. After filtration to separate the precipitated crystals, they were dried under reduced pressure at 50°C to obtain 13.7g of white crystalline compound 3-2 with a purity of 99.3% (yield 91%). At the end of the reflux reaction, the yield of the compound 3-1 with only one hydroxyl group converted to iodine was <1%, and the yield of the compound with three hydroxyl groups converted to iodine was 2%.

[0665] (Synthesis of Compound 3-2 3-2) 105g of the obtained ethyl acetate solution was added to 50g of silica gel for silica gel dispersion. An additional step of recovering the organic phase by filtration was performed. The other operations were the same as in Synthesis 2 of Compound 3-2. 13.5g of compound (3-2) was obtained with high purity, yield 90%, and LC purity > 99.9%.

[0666] (Synthesis 4 of Compounds 3-2) A flask equipped with a stirrer, cooling tube, and Dean-Stark tube was immersed in an oil bath. 21 g of 1,3,5-adamantanetriol was added to 17.8 g of water, followed by 78.6 g of a 55 wt% aqueous hydrogen iodide solution, and the mixture was stirred. The mixture was refluxed at 115-120°C using a Dean-Stark tube for 2 hours, while simultaneously removing 28 g of distilled water. The mixture was then cooled to room temperature. 100 g of water was added, followed by 15 g of a 10% sodium sulfite aqueous solution. The reaction mixture was then filtered, and 45 g of crystals were separated. 220 g of ethyl acetate was added to the 45 g of filtered crystals to dissolve them. Then, 110 g of water and 4.8 g of a 10% sodium sulfite aqueous solution were added for separation and washing. The mixture was further washed eight times with 110 g of water to obtain 165 g of ethyl acetate solution. The ethyl acetate solution obtained by vacuum concentration was filtered to separate the precipitated crystals, and then dried under reduced pressure at 50°C to obtain 41.9 g of white crystalline compound 3-2 with a purity of 99.1% and a yield of 91%. At the end of the reflux reaction, the yield of the compound 3-1 with only one hydroxyl group converted to iodine was 1%, and the yield of the compound with three hydroxyl groups converted to iodine was 2%.

[0667] (Synthesis of Compounds 3-2 5) The obtained precipitate was dissolved in 10.5 L of ethyl acetate, and then 50 g of silica gel was added for silica gel dispersion. The organic phase was recovered by filtration. The rest of the operation was the same as in Synthesis Example L1, and 1660 g of compound (1-3) was obtained with high purity, yield 76%, and purity >99.9%.

[0668] (Synthesis of Ad-A-1) 1278 g of acetonitrile was added to 150 g of 1,3,5-adamantanetriol and stirred. 177 g of trimethylsilyl chloride was added at room temperature under nitrogen, followed by the addition of 244 g of sodium iodide (equivalent to 2 equivalents of 1,3,5-adamantanetriol) in portions. The reaction was carried out at 85°C for 6 hours, then allowed to cool overnight. 1625 g of water was added, followed by 79 g of a 10% sodium sulfite aqueous solution. The mixture was concentrated under reduced pressure using an evaporator to a volume of 2.2 kg, and then 700 g of toluene was added. The mixture was stirred at room temperature for 14 hours and then filtered. The solid was washed twice with 150 ml of acetonitrile. The solid was dried under reduced pressure at 30°C to obtain 132 g of solid. The formation was confirmed by NMR and LC-MS. The molecular weight was 294.

[0669]

[0670] (Synthesis of Ad-A-2) 24 g of 1-iodoadaramane-3,5-diol was added to 100 ml of dehydrated N-methylpyrrolidone (NMP) and the mixture was ice-cooled. 10 g of chloroacetyl chloride was added dropwise at below 5°C. The reaction bath was set to 60°C and reacted for 1 hour. The reaction mixture was added to ice containing 4% hydrochloric acid while stirring. Extraction was performed with 200 ml of ethyl acetate, followed by washing with 100 ml of 2% hydrochloric acid and 100 ml of water. After dehydration with saturated brine and sodium sulfate, the solvent was removed by distillation using an evaporator, and the mixture was purified by silica gel column chromatography. 18.8 g of solid was obtained. The formation was confirmed by NMR and LC-MS. The molecular weight was 371.

[0671]

[0672] (Synthesis of Ad-2-2) Compound Ad-2-2 was obtained in the same manner as in Example 1, except that compound 3-1 was replaced by compound Ad-2-1. The formation was confirmed by NMR and LC-MS. The molecular weight was 420.

[0673]

[0674] (Synthesis of Ad-2-3) 10 g of Ad2-2 was dissolved in 30 ml of THF, and after ice cooling, 7.7 g of succinate chloride was added dropwise. After the addition was complete, the reaction was carried out at 60 °C for 2 hours. THF was distilled off from the reaction solution, and toluene was added to the residue. The precipitated solid was filtered to obtain 11 g of Ad-2-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 657.

[0675]

[0676] (Synthesis of Ad-2-4) 10 g of Ad-2-2 was dissolved in 50 ml of THF and cooled on ice. Then, 7.7 g of succinate chloride was added dropwise. After the addition was complete, the reaction mixture was reacted at 60 °C for 2 hours. After the reaction mixture was brought to room temperature, 40 ml of 15% sodium carbonate was added dropwise, and the mixture was stirred for 1 hour. 7 ml of concentrated hydrochloric acid was added dropwise to the reaction mixture, and the precipitated solid was filtered to obtain 10 g of Ad-2-4. The formation was confirmed by NMR and LC-MS. The molecular weight was 620.

[0677]

[0678] (Synthesis of Ad-A-3) The compound is prepared as follows.

[0679] (Synthesis of Ad-A-3-1) In a suspension of 30 g (153 mmol) of Ad-A-3-0 (3-hydroxy-1-adamantanecarboxylic acid) in acetonitrile-water (1:1, 300 mL), 600 mg (2.54 mmol, 1.7 mol%) of ruthenium(III) chloride hydrate (ruthenium content: 42.8%), 1.2 mL (15 mmol, 10 mol%) of pyridine, and 60.0 g (280 mmol, 1.8 equivalents) of sodium periodate were added sequentially. After stirring at 70 °C for 15 hours, acetone was added to the reaction mixture and the mixture was filtered. The filtrate was concentrated, and the resulting residue was washed with acetone to obtain 20.0 g (GC purity 68%) of crude Ad-A-3-1. This crude product was not purified and was used in the next step.

[0680] (Synthesis of Ad-A-3-2) 20.0 g of the crude Ad-A-3-1 was dissolved in 300 mL of methanol, and 18 mL (289 mmol) of iodomethane and 25 mL (167 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene were added. The mixture was stirred at 60 °C for 5 hours, and then the reaction solution was concentrated. The residue was subjected to silica gel column chromatography to obtain 18.7 g (82.6 mmol) of Ad-A-3-2.

[0681] (Synthesis of Ad-A-3) 4.6 g (115 mmol, 1.2 equivalent) of an aqueous solution of sodium hydroxide (100 mL) was added to a methanol (100 mL) solution of 21.4 g (94.5 mmol) of Ad-A-3-2. After stirring at 60 °C for 12 hours, the reaction solution was concentrated. 200 mL of 57% hydroiodic acid was added to the residue, and the mixture was stirred at 60 °C for 18 hours. After cooling to room temperature, the reaction solution was added to an aqueous solution of sodium sulfite. The solid was obtained by filtration and washed with water and toluene. It was then redeprecipitated from methanol-water to obtain 22.8 g (70.8 mmol) of Ad-A-3. The formation was confirmed by NMR and LC-MS. 1H-NMR: δ(ppm)(d-DMSO): 12.3(1H, -COOH), 4.9(1H, -OH), 1.2~2.5 (13H, =CH-, -CH 2-), molecular weight 322.

[0682] (Synthesis of Ad-A-4)

[0683] Using a 300 mL flask connected to a reflux tube, 0.4 mg of lithium aluminum hydride and 100 mL of superhydrated THF were added, and the mixture was stirred at 220 rpm for 1 hour under a nitrogen flow. Then, 3.2 g of Ad-A-3 was gradually added in 10 portions over 40 minutes. The mixture was then stirred at 24°C and 70 rpm for 24 hours. 100 mL of pure water was added, and the precipitate formed was filtered and recovered. The precipitate was dried to obtain 0.3 g of Ad-A-4 (yield 10%). The formation was confirmed by NMR and LC-MS. 1H-NMR: δ(ppm)(d-DMSO): 4.9 (1H, -OH), 4.2 (1H, -CH 2OH), 1.0~2.5 (15H, =CH-, -CH 2-), molecular weight 308.

[0684] (Synthesis of Ad-A-5)

[0685] 57% hydroiodic acid (300 mL) was added to Ad-A-3-2 (20.4 g, 90.1 mmol) obtained from the aforementioned synthesis of Ad-A-3, and the mixture was heated to 110 °C. The methanol produced was distilled off while the mixture was stirred for 9 hours. After cooling to room temperature, water was added to the reaction mixture. Then, an aqueous solution of sodium sulfite was added until the red color disappeared. The solid was filtered and washed with water. It was recrystallized from acetonitrile to obtain Ad-A-5 (27.5 g, 63.7 mmol, 71%). The formation was confirmed by GC-MS and LC-MS.

[0686] In addition, the GC-MS and LC-MS conditions for the synthesis of Ad-A-5 are as follows. [GC-MS] ・Agilent GC column DB-5ms was used, with an inner diameter of 0.25 mm, a length of 30 m, and a film thickness of 0.25 μm. ・Pretreatment: Approximately 5 mg of the obtained (Ad-A-5) was added to 1 mL of TMS-HT (hexamethyldisilazane and trimethylchlorosilane in anhydrous pyridine), mixed for about 30 seconds, allowed to stand for 5 minutes, and then the supernatant was measured for extension. • Temperature conditions: Ing.Temp.: 300℃ Det.Temp.: 300℃ 200℃ (4 min hold) - (20℃ / min) → 320℃ (4 min hold) • Split ratio: 50:1 • Injection volume: 1 μL [LC-MS (ESI-MS)] Prepare the obtained (Ad-A-5) acetonitrile (approximately 1 mg / mL) solution, inject 3 μL of this solution, and deliver acetonitrile-0.1% formic acid aqueous solution (ratio 9:1) at 0.2 mL / min. Do not pass through the column, and introduce into ESI-MS (electrospray ionization mass spectrometer).

[0687] (A synthesis of Ad-A-6-0 and Ad-A-6-1)

[0688] In an acetonitrile-water (1:1, 30 mL) suspension of 3.0 g (15.3 mmol) of Ad-A-3-0 (3-hydroxy-1-adamantane carboxylic acid), 62 mg (0.26 mmol, 1.7 mol%) of ruthenium(III) chloride hydrate (ruthenium content: 42.8%), 62 μL (0.77 mmol, 5 mol%) of pyridine, and 5.88 g (27.5 mmol, 1.8 equivalent) of sodium periodate were added sequentially. After stirring at 70 °C for 15 hours, the reaction solution was filtered, and 10 mL of acetonitrile was added. Then, 5 mL of 35% sodium bisulfite aqueous solution was added dropwise under ice cooling. Acetone was then added, and the mixture was filtered. The filtrate was concentrated, and 15 mL of acetonitrile was added to obtain 2.11 g of white precipitate. The white precipitate was purified by silica gel column chromatography to obtain Ad-A-6-0 (0.17 g, yield 5.2%).

[0689] To a methanol (20 mL) solution of the obtained Ad-A-6-0: 1.8 g (7.4 mmol), 1.8 mL (29 mmol) of iodomethane and 2.5 mL (17 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene were added. After stirring at 60 °C for 5 hours, the reaction solution was concentrated. The residue was subjected to silica gel column chromatography to obtain Ad-A-6-1: 1.5 g (6.2 mmol). The formation was confirmed by GC-MS and LC-MS under the same conditions as the synthesis of Ad-A-5.

[0690] (Synthesis of Ad-A-6a and Ad-A-6b)

[0691] 1 g (4.38 mmol) of Ad-A-6-0 was suspended in toluene (5 mL), 2.0 mL (15 mmol) of 57% hydroiodic acid was added, followed by 5 mL of toluene, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, the resulting suspension was added to pure water (25 mL), followed by 1 mL of 35% sodium bisulfite aqueous solution for decolorization. The precipitate obtained by filtration was subjected to silica gel column chromatography to obtain 0.75 g (2.2 mmol) of Ad-A-6a and 0.43 g (0.96 mmol) of Ad-A-6b. The formation was confirmed by GC-MS and LC-MS under the same conditions as the synthesis of Ad-A-5.

[0692] (Synthesis of Ad-A-6c)

[0693] 1 g (4.03 mmol) of Ad-A-6-1 was added to 57% hydroiodic acid (5.0 mL, 37.9 mmol), and the mixture was stirred at 60 °C for 7 hours. After cooling to room temperature, the resulting suspension was added to pure water (25 mL), followed by the addition of 35% sodium bisulfite aqueous solution (1 mL) for decolorization. The filtered precipitate was subjected to silica gel column chromatography to obtain 0.11 g (0.20 mmol) of Ad-A-6c. The formation was confirmed by GC-MS and LC-MS under the same conditions as the synthesis of Ad-A-5.

[0694] [Synthesis Example DMA1P] The compound was prepared by using adamantane as the parent nucleus as described below.

[0695]

[0696] Immerse a flask equipped with a reflux duct and a Dean-Stark apparatus in an oil bath. Add 80 g of compound 3-1 (manufactured by Mitsubishi Gas Chemical Co., Ltd., 0.43 mol) and 2.5 L of o-xylene to the flask and stir. Then add 400 g (1.72 mol) of 55% hydrogen iodide aqueous solution to the flask. Set the internal temperature to 125°C and react for 3 hours. Afterward, stir for 1 hour in a water bath at 25°C.

[0697] 2.5 L of ion-exchanged water was added to the reaction vessel to separate the organic and aqueous phases. After recovering the organic phase, it was washed three times with 1 L of 5% sodium bicarbonate solution, followed by 1 L of ion-exchanged water. The recovered organic phase was then concentrated to obtain 35 g of a white solid (DMA1a). The formation was confirmed by NMR and LC-MS. The molecular weight was 570.

[0698] In a 3L flask connected to a reflux tube and a Dean-Stark apparatus, 35g of DMA1a (0.06mol) and 182.5mL of dehydrated toluene were added under a nitrogen flow and stirred with a stirrer blade until dissolved. Then, while stirring, 12g of methanesulfonic acid was added and dissolved over 30 minutes. Next, 7.4g of succinic anhydride (1.2 times the amount of matrix) was added to the stirred reaction mixture over 60 minutes, and the mixture was stirred at 100°C for 2 hours. Afterward, the mixture was cooled to room temperature, 360mL of pure water was added, and the toluene phase was recovered after separation. The mixture was then washed three times with 350mL of 0.5% sodium bicarbonate aqueous solution and ion-exchanged water. The recovered toluene phase was concentrated under reduced pressure to obtain 20.6g of a white solid as the protected form of the target compound, DMA1aP. The yield was 50%. The formation was confirmed by NMR and LC-MS. The molecular weight was 670.

[0699]

[0700] [Synthesis Example DMA2] The compound was prepared using adamantane as the parent compound according to the following procedure. (Synthesis of DMA2a)

[0701]

[0702] A flask equipped with a reflux duct and a Dean-Stark apparatus was immersed in an oil bath. 87.9 g of compound Ad-2-1 (0.43 mol) and 2.5 L of toluene were added to the flask and stirred. Then, 400 g (1.72 mol) of a 55% hydrogen iodide aqueous solution was added to the flask. The reaction was carried out at 100°C for 3 hours. Afterward, the reaction was carried out in a water bath at 25°C for 1 hour with stirring.

[0703] 2.5 L of ion-exchanged water was added to the reaction vessel to separate the organic and aqueous phases. After recovering the organic phase, it was washed three times with 1 L of 5% sodium bicarbonate solution, followed by 1 L of ion-exchanged water. The recovered organic phase was then concentrated to obtain 37 g of a white solid (DMA2a). The formation was confirmed by NMR and LC-MS. The molecular weight was 602.

[0704] (Synthesis of DMA2aP)

[0705]

[0706] Using a 3L flask connected to a Dean-Stark apparatus and a reflux flask, 37g (0.06mol) of (DMA1a) and 182.5mL of dehydrated toluene were added under a nitrogen flow and stirred with a stirrer blade until dissolved. Then, 12g of methanesulfonic acid was added and dissolved over 30 minutes while stirring. Next, 7.4g of succinic anhydride (1.2 equivalence to the matrix) was added to the stirred reaction mixture over 60 minutes, and the mixture was stirred at 100°C for 2 hours. Afterward, the mixture was cooled to room temperature, 360mL of pure water was added, and the toluene phase was recovered after separation. The mixture was then washed three times with 350mL of deionized water after washing with 360mL of 0.5% sodium bicarbonate aqueous solution. The recovered toluene phase was concentrated under reduced pressure to obtain the target compound (DMA2aP), with 23.8g of white solid. The yield was 55%. The formation was confirmed by NMR and LC-MS. The molecular weight was 702.

[0707] (Synthesis of DMA1aP2)

[0708]

[0709] 47.1 g of DMA1a was added to 140 ml of dehydrated NMP and cooled on ice. 10 g of chloroacetyl chloride was added dropwise at below 5°C. The bath temperature was set to 60°C and the reaction was carried out for 1 hour. The reaction mixture was added to ice containing 4% hydrochloric acid while stirring. Extraction was performed with 200 ml of ethyl acetate, followed by washing with 100 ml of 2% hydrochloric acid and 100 ml of water. After dehydration with saturated brine and sodium sulfate, the solvent was removed by distillation using an evaporator, and the product was purified by silica gel column chromatography. 29.6 g of solid was obtained in 79.7% yield as the target DMA1aP2. The formation was confirmed by NMR and LC-MS. The molecular weight was 679.

[0710] (Synthesis of DMA2aP2)

[0711]

[0712] 49.1 g of DMA2a was added to 140 ml of THF and cooled on ice. 14 g of succinate chloride was added dropwise at below 5°C. The bath temperature was set to 60°C and the reaction was carried out for 2 hours. After the addition was completed, the reaction was carried out at 60°C for 2 hours. THF was distilled off from the reaction solution, and toluene was added to the residue. The precipitated solid of 46.9 g was recovered by filtration, and DMA2aP2 was obtained as the target compound in a yield of 79.8%. The formation was confirmed by NMR and LC-MS. The molecular weight was 721.

[0713] (Synthesis of DMA3a)

[0714] DMA3-2 was obtained in the same manner as the synthesis of Ad-A-3-2, except that 60 g (258 mmol) of 55% hydrogen iodide aqueous solution was used instead of 18 mL (289 mmol) of iodomethane. Then, DMA3a was obtained by replacing AdA-3-2 with DMA3-2 in the same manner as the synthesis of Ad-A-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 626.

[0715]

[0716] (Synthesis of DMA4a)

[0717] DMA4a was obtained by replacing AdA-3 with DMA3a in the same manner as the synthesis of Ad-A-4. The formation was confirmed by NMR and LC-MS. The molecular weight was 598.

[0718]

[0719] (Synthesis of DAMA1-tl) DAMA1-tl was obtained in the same manner as (Synthesis 2 of Compounds 3-2), except that hydrogen iodide and sulfuric acid were substituted in a 1:1 ratio. The formation was confirmed by NMR and LC-MS. The molecular weight was 384.

[0720]

[0721] (Synthesis of DAMA1-mx) DAMA1-mx was obtained in the same manner as DAMA1-tl, except that m-xylene was used to replace toluene. The formation was confirmed by NMR and LC-MS. The molecular weight was 398.

[0722]

[0723] (Synthesis of DAMA1-eb) DAMA1-eb was obtained in the same manner as DAMA1-tl, except that ethylbenzene was substituted for toluene. The formation was confirmed by NMR and LC-MS. The molecular weight was 398.

[0724]

[0725] [Examples 4-7, 7A-7C] Photolithography Composition (Substrate A): 0.5 g of 4-hydroxystyrene, 4.0 g of 2-methyl-2-adamantyl methacrylate, 0.9 g of γ-butyrolactone methacrylate, and 1.5 g of hydroxyadamantyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. After reflux for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain a white powder, represented by the following formula (MAR). The polymer has a weight-average molecular weight (Mw) of 11,500 and a dispersion (Mw / Mn) of 1.90. Furthermore, the 13C-NMR results showed that the composition ratio (molar ratio) in the following formula (MA1) was a:b:c:d = 60:10:15:15. Furthermore, the following formula (MAR) is a simplified representation of the ratio of each constituent unit, but the arrangement of the constituent units is random, and does not mean that each constituent unit independently forms a block copolymer. For units containing benzene, the molar ratio is calculated based on the integral ratio of the carbon atoms directly bonded to the benzene backbone. For methacrylate-based units (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate), the molar ratio is calculated based on the integral ratio of the carbonyl carbon atoms of the ester bond.

[0726]

[0727] (Composition) Compounds 1-3 synthesized in Example 1, compounds 2-3 and 2-4 synthesized in Example 2, compound 3-2 synthesized in Example 3, compound 8 synthesized in Example 1g, compound 9 synthesized in Example 1h, and compound 10 synthesized in Example 1i were used as compound B to prepare the composition shown in Table 1. The following were used for the acid generating agent, acid diffusion inhibitor, and organic solvent: Acid generating agent: Triphenyls(2-fluorobutane)sulfonate (TPS-109) manufactured by Midori Kagaku Co., Ltd. Acid diffusion control agent: Tri-n-octylamine (TOA) manufactured by Kanto Chemical. Organic solvent: Propylene glycol monomethyl ether acetate (PGMEA) manufactured by Kanto Chemical.

[0728]

[0729] [Evaluation Method] (Evaluation of EB Resist Pattern (Pattern Formation)) After modifying the resist composition according to the composition in Table 1, it was spin-coated onto a clean silicon wafer and pre-exposure baked (PB) on a heated plate at 110°C to form a resist film with a thickness of 50 nm. Using an EB drawing apparatus (ELS-7500, manufactured by ELIONIX INC.), the obtained resist film was irradiated with an electron beam set to a 1:1 line and gap spacing of 50 nm. After irradiation, the resist film was heated at 110°C for 90 seconds and then developed by immersion in TMAH 2.38% by mass alkaline developer for 60 seconds. Afterward, the resist film was washed with ultrapure water for 30 seconds and dried to form a resist pattern.

[0730] (Resistant Pattern Shape Evaluation) The cross-sectional shape of the obtained 50 nml / S (1:1) resistant pattern was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd. Regarding the resistant pattern shape after development, patterns with a width less than +10% of the half-width relative to the half-width of the pattern cross-section from the surface of the silicon wafer to 10% of the pattern height were evaluated as "A", and those with a width greater than +10% of the half-width were evaluated as "C". (Resistant Pattern Defects) Furthermore, regarding resistant pattern defects after development, the number of spherical foreign objects in a 1 μm length resistant pattern was used as an indicator. (Evaluation Criteria) S: Number of spherical foreign objects = 0 A: 0 < Number of spherical foreign objects ≤ 5 C: 5 < Number of spherical foreign objects (Electron Beam Drawing Sensitivity) The minimum electron beam energy that can draw a shape without a pattern collapse is used as the "Electron Beam Drawing Sensitivity". Those that are equal to or better than Comparative Example 1 are rated as "A", and those that are worse than Comparative Example 1 are rated as "C".

[0731]

[0732] [Examples 8-11] EUV Exposure Sensitivity and Etching Defects (EUV Exposure Sensitivity) After spin-coating the compositions prepared in Examples 4-7 and 7A-7C onto a silicon wafer, a photoresist layer with a film thickness of 100 nm was formed by baking at 110°C for 60 seconds. In Comparative Example 3, compound 3-1 was used instead of compound 1-3 in Example 4. Next, the wafer was exposed to extreme ultraviolet (EUV) light using an EUVES-7000 (manufactured by Litho Tech Japan Corporation) with an exposure amount increasing by 1 mJ / cm² each time until reaching 80 mJ / cm² without a mask. After baking (PEB) at 110°C for 90 seconds, the wafer was developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain a wafer that had undergone 80 minutes of exposure. For each irradiated area, the film thickness was measured using an optical interferometer "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.) to obtain film thickness profile data relative to the exposure amount. The exposure amount at which the slope of the film thickness variation relative to the exposure amount becomes the largest was used as the sensitivity value (mJ / cm 2) to calculate the EUV sensitivity of the resist.

[0733] ​​(Etching Defect Evaluation) The composition used in EUV exposure sensitivity measurement was coated onto an 8-inch silicon wafer with a 100nm thick oxide film on the outermost layer, and baked at 110°C for 60 seconds to form a 100nm thick photoresist layer. Next, the wafer was fully exposed using an extreme ultraviolet (EUV) exposure apparatus "EUVES-7000" (product name, manufactured by Litho Tech Japan Corporation) with an exposure amount reduced by 10% compared to the EUV sensitivity value obtained by the above EUV sensitivity evaluation. Then, it was baked at 110°C for 90 seconds (PEB) and developed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain a wafer that has been fully exposed for 80 minutes.

[0734] (Etching Defects) For the exposed wafers produced, etching is performed using a "Telius SCCM" etching apparatus (manufactured by Tokyo Powertech Co., Ltd.) with CF 4 / Ar gas until the oxide film is etched to 50nm. For wafers produced by etching, defects are evaluated using a "Surfscan SP5" defect inspection device (manufactured by KLA Corporation), and the number of taper defects above 19nm is used as the indicator of etching defects. (Evaluation Criteria) A: Number of taper defects ≤ 10 B: 10 < Number of taper defects ≤ 80 C: 80 < Number of taper defects ≤ 400 D: 400 < Number of taper defects

[0735] (Etching Defect Evaluation over Time) The components used in the aforementioned etching defect evaluation were placed at room temperature for 7 days, and the etching defect evaluation was performed again. Conditions with a change in EUV sensitivity of less than 6% before and after placement were evaluated as "G", and conditions with a change of more than 6% were evaluated as "N".

[0736]

[0737] [Example 12] Purification of Compound 3-2 using acid (Treatment 1: Purification using acid) 150 g of a solution (10% by mass) of Compound 3-2 dissolved in PGMEA was added to a 1000 mL four-necked flask (bottomless type). The mixture was heated to 80°C while stirring. Then, 37.5 g of oxalic acid aqueous solution (pH 1.3) was added, and the mixture was stirred for 5 minutes and then allowed to stand for 30 minutes. This separated the oil phase and the aqueous phase, which was then removed. This operation was repeated once. Then, 37.5 g of ultrapure water was added to the obtained oil phase, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes to remove the aqueous phase. This operation was repeated three times. The pressure in the flask was reduced to below 200 hPa while heating to 80°C, thereby concentrating and distilling off residual water and PGMEA. Next, the EL grade PGMEA (a reagent manufactured by Kanto Chemical Co., Ltd.) was diluted to adjust the concentration to 10% by mass, thereby obtaining a PGMEA solution of compound 3-2 with reduced metal content.

[0738] (Treatment 2: Treatment without acid) Except that ultrapure water was used instead of oxalic acid aqueous solution, a PGMEA solution of compound 3-2 with a concentration adjusted to 10% by mass was obtained by the same method as in Example 12.

[0739] The contents of various metals in a 10% PGMEA solution of compound 3-2 without treatment, a 10% PGMEA solution of compound 3-2 treated with treatment 1, and a 10% PGMEA solution of compound 3-2 treated with treatment 2 were determined by ICP-MS. The results are shown in the table below.

[0740]

[0741] (EUV exposure sensitivity, etching defects) EUV exposure sensitivity and etching defects were measured using the purified compound 3-2 in the same manner as in Example 8. The measurement results are shown in the table below.

[0742]

[0743] [Example 13] The synthesis of aldehydes with benzene as the parent nucleus was carried out by the following process. The reaction was carried out under a nitrogen flow.

[0744]

[0745] (Synthesis of Compounds 1-1, 1-1a, and 1-1b) In a 3L three-necked flask equipped with a stirrer and a nitrogen flow, 150g (1.2mol) of 4-hydroxybenzaldehyde and 1L of methanol (Kanto Chemical) were measured and added. The flask was immersed in a water bath at 40°C, and heated while stirring under a nitrogen flow. 200mL of water was added. At the point when the internal temperature reached 34°C, 309.4g (3.7mol) of sodium bicarbonate (NaHCO3) was added.

[0746] At the point when the internal temperature reaches 38°C, while paying attention to foaming, add 654.5g (2.6mol) of iodine (I₂) in portions and stir at 40°C for 3 hours. Afterward, cool the flask with ice and add sodium sulfite aqueous solution (Na₂SO₃) dropwise until the color of the reaction solution turns yellowish-white.

[0747] Add 3L of water to a container equipped with a stirrer, pour in the aforementioned reaction solution, and stir for 15 minutes. Filter the precipitate and wash with 500mL of water. Add the filtered material to a container equipped with a stirrer, add 1L of water, and stir for 15 minutes. Filter the precipitate and wash with 300mL of water.

[0748] The filter extract was added to a container equipped with a stirrer, and 500 mL of methanol was added and stirred for 15 minutes. The precipitate was filtered and washed with 150 mL of methanol. Column chromatography (spherical silicon dioxide 60N manufactured by Kanto Chemical Co., Ltd.) was used to separate the precipitate by forming a gradient with an ethyl acetate:hexane ratio of 1:9 to 9:1 as the developing solvent, yielding compounds 1-1, 1-1a, and 1-1b, with a relative ratio of approximately 1:0.9:0.5. The molecular weights of the components of the mixture were determined by LC-MS: compound 1-1 was 374, compound 1-1a was 248, and compound 1-1b was 494.

[0749] (Synthesis of compounds 1-3a and 1-3b) Compound 1-3a was obtained from compound 1-1a via compound 1-2a by the same method as in Example 1. Compound 1-3b was obtained from compound 1-1b via compound 1-2b.

[0750]

[0751] (Synthesis of a mixture of compounds 1-2, 1-2a, 1-2b, 1-3, 1-3a, and 1-3b) Using the same method as in Example 1, a mixture of compounds 1-2, 1-2a, and 1-2b was obtained from a mixture of compounds 1-1, 1-1a, and 1-1b. Furthermore, a mixture of compounds 1-3, 1-3a, and 1-3b was obtained from a mixture of compounds 1-2, 1-2a, and 1-2b. The molecular weights of each component of the mixtures were determined by LC-MS: compound 1-2a was 306, compound 1-3a was 308, compound 1-2b was 610, and compound 1-3b was 614.

[0752] [Examples 14-18] Evaluation of EUV exposure sensitivity and etching defects: The composition was prepared using the following compound as compound B in the same manner as in Example 4. The table shows the mass ratio of each compound contained in the composition. EUV exposure sensitivity and etching defects were evaluated in the same manner as in Example 8. However, regarding etching defects, the following criteria were used for evaluation. (Evaluation Criteria) S: Number of conical defects ≤ 6 A': 6 < Number of conical defects ≤ 10 B: 10 < Number of conical defects ≤ 80 C: 80 < Number of conical defects ≤ 400 D: 400 < Number of conical defects

[0753]

[0754] (Synthesis Example BPL1Rc) Using a 100L glass-lined reaction vessel connected to a reflux duct, 700g of 4-hydroxybenzaldehyde and 1600mL of dehydrated tetrahydrofuran (THF) were added under a nitrogen flow and ice bath conditions, and stirred with a stir bar to dissolve them. Next, 80g of PPTS (pyridinium p-toluenesulfonic acid) was added over 30 minutes with stirring in an ice bath, followed by stirring for 60 minutes. 500g of ethyl vinyl ether (1.2 equimolar amounts relative to the functional groups) was added dropwise to the stirred reaction mixture over 60 minutes, and then stirred at 35°C for 60 minutes. Afterward, 7.2L of pure water was added under ice bath conditions, and after stirring for 60 minutes, the organic phase was recovered. The recovered organic phase was then treated with 2L of ethyl acetate and 5L of pure water, stirred, and the organic phase was recovered again. The recovered organic phase was concentrated under reduced pressure to obtain the protected form BPL1Rc, with 840g of a white solid as the target compound. The yield was 75%. The formation was confirmed by NMR and LC-MS. The molecular weight was 194.

[0755]

[0756] Using the obtained BPL1Pc as a starting material, BPL1c was obtained in the same manner as in the reduction step BPL1R. The formation was confirmed by NMR and LC-MS. The molecular weight was 196.

[0757]

[0758] (Synthesis Example BPL3R) BPL3R was obtained from 4-hydroxy-3-methoxybenzaldehyde in the same manner as in Synthesis Example BPL1. The formation was confirmed by NMR and LC-MS. The molecular weight was 212.

[0759]

[0760] (Synthesis Example BPL4R) BPL4R was obtained from 4-hydroxy-3-ethoxybenzaldehyde in the same manner as in Synthesis Example BPL1. The formation was confirmed by NMR and LC-MS. The molecular weight was 226.

[0761]

[0762] (Synthesis Example DML1bR) DML1bR was obtained by replacing iodine with iodic acid in the same manner as in Synthesis Example DML1. The formation was confirmed by NMR and LC-MS. The molecular weight was 362.

[0763]

[0764] (Synthesis Example Na-Ob) In Example L1, 4-hydroxy-3,5-diiodobenzaldehyde was replaced with 6-hydroxy-2-naphthal in a [protecting group introduction step], followed by a [reduction step], thereby obtaining compound Na-Ob. The formation was confirmed by NMR and LC-MS. The molecular weight was 232.

[0765]

[0766] (Synthesis Example Na-0c) In the synthesis of compounds 2-4 in Example 2, compound 2-3 was replaced by compound 2-2 to obtain compound Na-0c. The formation was confirmed by NMR and LC-MS. The molecular weight was 274.

[0767]

[0768] (Synthesis Example Na-2b) In Example L1, 4-hydroxy-3,5-diiodobenzaldehyde was replaced with 2-hydroxy-1-naphthal in a [protecting group introduction step], followed by a [reduction step], thereby obtaining compound Na-2b. The formation was confirmed by NMR and LC-MS. The molecular weight was 232.

[0769]

[0770] (Synthesis Example DMNa2-1bR) DMNa2-1bR was obtained by replacing iodine with iodic acid in the same manner as in Synthesis Example DMN2-1. The formation was confirmed by NMR and LC-MS. The molecular weight was 463.

[0771]

[0772] (Synthesis Example DMN2-3cP) DMN2-3c was obtained by replacing iodine with iodic acid in the same manner as in Synthesis Example DMN2-3. Then, DMN2-3 was replaced with DMN2-3c in the same manner as in DMN2-3P to obtain compound DMN2-3cP. The formation was confirmed by NMR and LC-MS. The molecular weight was 547.

[0773]

[0774] (Synthesis Example Ad-A-2b) Ad-A-2b was obtained by replacing 1-iodoadaramane-3,5-diol with 1,3,5-adamantanetriol in the same manner as the synthesis of Ad-A-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 414.

[0775]

[0776] (Synthetic Example Ad-A-2c) Ad-A-2c was obtained by replacing Ad2-2 with 1,3,5-adamantanetriol in the same manner as the synthesis of Ad-2-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 540.

[0777]

[0778] (Synthetic Example Ad-A-2d) Ad-A-2d was obtained by replacing Ad2-2 with 1,3,5-adamantanetriol in the same manner as the synthesis of Ad-2-4. The formation was confirmed by NMR and LC-MS. The molecular weight was 484.

[0779]

[0780] (Synthetic Example Ad-2-3b) Ad-2-3b was obtained by replacing Ad-A-1 with 1,3,5,7-adamantetrol in the same manner as the synthesis of Ad-A-2. The formation was confirmed by NMR and LC-MS. The molecular weight was 506.

[0781]

[0782] (Synthetic Example DMA1bP) DMA1b was obtained by replacing hydrogen iodide with iodic acid in the same manner as the synthesis of DMA1a. The formation was confirmed by NMR and LC-MS. The molecular weight was 350. Next, DMA1a was replaced with DMA1b in the same manner as the synthesis of DMA1aP to obtain a mixture of DMA1bP and DMA1bP2. This mixture was purified and separated by column chromatography to obtain DMA1bP and DMA1bP2. The formation was confirmed by NMR and LC-MS. The molecular weights of DMA1bP and DMA1bP2 were 656 and 194, respectively.

[0783]

[0784] As a result of the above, the compound of this embodiment can provide, for example, a lithography composition that maintains good pattern shape and has high sensitivity and few defects under EUV exposure, and is industrially usable.

[0785] [Example 19-1] Except that compound B as described in the table below was used instead of compounds 1-3 as described in Example 14, and the baking temperature after exposure was set to 100°C for 120 seconds as an evaluation condition, the evaluation was conducted in the same manner as in Examples 4 and 8. The results are shown in the table below, confirming that the resist pattern and EUV exposure sensitivity are as good as those in Examples 4 and 8.

[0786]

[0787] [Example 19-2] Except that compound B1 as described in the table below was used instead of compounds 1-3 as described in Example 14, and the baking temperature after exposure was set to 100°C for 120 seconds as an evaluation condition, the evaluation was conducted in the same manner as in Examples 4 and 8. The results are shown in the table below, confirming that the resist pattern and EUV exposure sensitivity are as good as those in Examples 4 and 8.

[0788]

[0789] [Examples 19-3] Except that compounds B1 as described in the table below were used instead of compounds 1-3 as described in Example 14, and the baking temperature after exposure was set to 100°C for 120 seconds as an evaluation condition, the evaluation was conducted in the same manner as in Examples 4 and 8. The results are shown in the table below, confirming that the resist pattern and EUV exposure sensitivity are as good as those in Examples 4 and 8.

[0790]

[0791]

[0792] [Example 20-1] Except that compounds 1-3 and 1-3a were replaced with compounds B1 and B2 as described in the table below at the ratios described below, the evaluation of EUV sensitivity and etching defects was performed in the same manner as in Examples 14-18.

[0793]

[0794]

[0795] [Example 20-2] Except that compounds 1-3 and 1-3a were replaced with compounds B1 and B2 as described in the table below at the ratios described below, the evaluation of EUV sensitivity and etching defects was performed in the same manner as in Examples 14-18.

[0796]

[0797]

[0798] [Example 20-3] Except that compounds 1-3 and 1-3a were replaced with compounds B1 and B2 as described in the table below at the ratios described below, the evaluation of EUV sensitivity and etching defects was performed in the same manner as in Examples 14-18.

[0799]

[0800]

[0801] [Example 21] Except that compounds 3-2 were replaced with compounds shown in the table below, compounds treated with treatment 1 or treatment 2 were obtained in the same manner as in Example 12, and EUV sensitivity and etching defects were evaluated. The results were the same as in Example 12, confirming that the compounds showed good results in both EUV sensitivity and etching defect evaluation.

[0802]

[0803]

[0804] [Example 22] The following composition was prepared according to the method of Example 4. (Values: parts by mass)

[0805]

[0806] For the above-mentioned components, an end-of-life test was conducted under the following conditions, and the state of the liquid after the test was evaluated by measuring the absorbance using a spectrophotometer. Specifically, the visible light spectrum of the sample after the end-of-life test was measured, and the average absorbance A1 at 450 nm, 550 nm, and 650 nm was calculated. The difference ΔA between this average absorbance A0 and the average absorbance A0 at 450 nm, 550 nm, and 650 nm before the start of the test was evaluated.

[0807]

[0808] The results showed that by using a specified amount of compound B2 in any of the components, the increase in absorbance in the spectrophotometer after the time test could be suppressed. The ΔA value was lower than that of the L1-NA composition using only one compound and a specified amount of compound B2. From these results, it was found that by using this composition, the time-dependent stability was improved.

[0809] [Example 23] The following composition (numerical value: parts by mass) was prepared according to the method of Example 4. The long-term stability of the composition was evaluated using the same method as in Example 22.

[0810]

[0811]

[0812] The results showed that by using a specified amount of compound B2 in any component, the increase in absorbance in the spectrophotometer after the time test could be suppressed. From these results, it was found that by using this component, the time stability was improved.

[0813] [Example 24] The following composition (numerical value: parts by mass) was prepared according to the method of Example 4. The long-term stability of the composition was evaluated using the same method as in Example 22.

[0814]

[0815]

[0816] The results showed that by using a specified amount of compound B2 in any component, the increase in absorbance in the spectrophotometer after the time test could be suppressed. From these results, it was found that by using this component, the time stability was improved.

[0817] [Example 25]

[0818] The following composition (numerical value: parts by mass) was prepared according to the method of Example 4. The long-term stability of the composition was evaluated using the same method as in Example 22.

[0819]

[0820] The results showed that by using a specified amount of compound B2 in any component, the increase in absorbance in the spectrophotometer after the time test could be suppressed. From these results, it was found that by using this component, the time stability was improved.

[0821] [Example 26] The following composition (numerical value: parts by mass) was prepared according to the method of Example 4. The long-term stability of the composition was evaluated using the same method as in Example 22.

[0822]

[0823]

[0824] The results showed that by using a specified amount o...

Claims

1. A compound represented by the following formula (1), (where RG is a group containing at least one cyclic structure, I is an iodine atom, R1 may be the same or different monovalent functional group with 0 to 30 carbon atoms that does not contain polymerizable unsaturated bonds, n is an integer from 1 to 5, and m is an integer from 1 to 5).

2. The compound of claim 1, wherein the aforementioned RG is derived from a group of benzene, naphthalene, anthracene, pyrene, heteroaromatic ring or polycyclic alicyclic ring that may have substituents, and the aforementioned R1 is one selected from Rf selected from the group consisting of hydroxyl and ether group having a protecting group, and hydrocarbon group Rg having 0 to 30 carbon atoms that may have substituents.

3. The compound of claim 2, wherein the aforementioned Rf is an Rf' belonging to the group consisting of one or more ether groups selected from hydroxyl groups and having a protecting group that can be removed by acid, base or heat.

4. The compound of claim 1, wherein RG is derived from a group of benzene, naphthalene, anthracene, phenanthrene, pyrene, fumarate, or adamantane that may have substituents.

5. The compound of claim 4, wherein RG is derived from a group of benzene, naphthalene or adamantane that may have substituents.

6. The compound of claim 1, wherein R1 is selected from -OR2, -COOR3, -CH2-OR4 or -CHO, wherein R2 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 1 to 30 carbon atoms that may have a substituent, R3 is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms or an aryl group having 1 to 29 carbon atoms that may have a substituent, and R4 is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms or an aryl group having 1 to 29 carbon atoms that may have a substituent.

7. The compound of claim 1, wherein R1 has a protecting group.

8. The compound of claim 1 is represented by any of the following formulas, (where Z is I, R1, or a linking group used to form a dimer; the definitions of I and R1 are the same as in formula (1); A is a group with a protecting group; R is a non-functional organic group; R1, A, and R are bonded to bondable positions; r1 to r4 are integers from 0 to 5; and the sum of r1 to r4 in one benzene is less than or equal to the valence of benzene) (where the definitions of I, A, and R1 are the same as above; R” is a hydrogen atom or an organic group other than R1; s1 is 1 to 7; s2 to s3 are 0 to 7; and s4 is an integer from 1 to 7; however, the sum of s1 to s4 is less than or equal to the valence of naphthalene; and the selection is made such that at least one of s2 and s3 is 1 or more) (where the definitions of I, R1, and R” are the same as above). t1 is an integer from 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 14; however, the sum of t1 to t3 is less than or equal to the valence of adamantane.

9. The compound of claim 8 is represented by any of the following formulas (where I, Z, R, R1, A are defined as in formula (Bz)) (where I, R1, A, R” are defined as in formula (N), x and y are 0 or 1, but at least one of them is 1, s4' represents the number of R” that can be bonded to the 1st, 7th, and 8th positions of naphthalene, and is an integer from 1 to 3) (where I, R1, R” are defined as in formula (Ad), one of D is I, and the other of D is R1).

10. The compound of claim 9 is represented by any of the following formulas (where I, Z, R, R1, A are defined as in formula (Bz)) (where I, R1, R”, A, x, y, s4’ are defined as in formula (n)) (where I, R1, R” are defined as in formula (Ad)).

11. The compound of claim 8, wherein the aforementioned R 1 is a hydroxyl, carboxyl, ester or hydroxyalkyl group, and the aforementioned A is an A' represented by -OR aOR b (R a is a straight-chain or branched alkyl group having 1 to 3 carbon atoms; R b is a straight-chain, branched or cyclic alkyl group having 1 to 3 carbon atoms in a monovalent state, or a divalent cyclic alkyl group that forms a ring together with an adjacent oxygen atom), comprises one or more of the aforementioned A'.

12. The compound of claim 5, wherein RG is derived from a benzene group that may have substituents.

13. The compound of claim 1, wherein RG is a phenyl group and there is a plurality of R1, wherein R1 does not contain a combination of an alkoxy group (except for those with a protecting group) and an aldehyde group, a combination of an alkoxy group and a hydroxyl group, or a combination of a hydroxyl group and an aldehyde group; wherein RG is a naphthalene group and there is a plurality of R1, wherein R1 does not contain a combination of a hydroxyl group and a carboxyl group.

14. The compound of claim 12 is represented by the following formula (Bz4), (where I, R, A and Z are defined as in formula (Bz), R1' is a monovalent functional group with 0 to 30 carbon atoms excluding hydroxyl groups, which may be the same or different, and r1', r2' and r4' are integers from 0 to 5, and the sum of r1', r2' and r4' is less than or equal to the valence of benzene).

15. The compound of claim 14 is represented by the following formula (Bz4-1), (where I, R, Z and R1' are defined as in formula (Bz4), r1', r2' and r4' are integers from 0 to 5, and the sum of r1', r2' and r4' is less than or equal to the valence of benzene).

16. The compound of claim 15 is represented by the following formula (Bz4-2), (where I is defined as in formula (Bz4), r4' is an integer from 0 to 4, and r5' is an integer from 0 to 4).

17. The compound of claim 15 is represented by any of the following formulas.

18. The compound of claim 12 is represented by any of the following formulas (where I, R, Z, A and R1 are defined as in formula (Bz), A' is a protecting group and is represented by -OR aOR b, -O-CO-OR b or -OR a-CO-OR b; Ra is a straight-chain or branched alkyl group having 1 to 3 carbon atoms; Rb is a monovalent straight-chain, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group that forms a ring together with the adjacent oxygen atom).

19. The compound of claim 12 is represented by any of the following formulas (where I, R1, and A are defined as in formula (Bz); A' is a protecting group and is represented by -OR aOR b, -O-CO-OR b, or -OR a-CO-OR b; Ra is a straight-chain or branched alkyl group having 1 to 3 carbon atoms; Rb is a monovalent straight-chain, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group forming a ring with an adjacent oxygen atom; Z' is I, R1, or a hydrogen atom).

20. The compound of claim 5, wherein RG is derived from a naphthalene group that may have substituents.

21. The compound of claim 20 is represented by any of the following formulas (where I, R1, R”, A, x, y, s4’ are defined in the same way as in formula (n).

22. The compound of claim 21 is represented by any of the following formulas (where I, R1, and R" are defined as in formula (n), A' is a protecting group and is represented by -OR aOR b, -O-CO-OR b, or -OR a-CO-OR b; Ra is a straight-chain or branched alkyl group having 1 to 3 carbon atoms; Rb is a monovalent straight-chain, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group that forms a ring together with the adjacent oxygen atom).

23. The compound of claim 22, wherein the aforementioned R 1 is a hydroxyl, carboxyl, ester or hydroxyalkyl group.

24. The compound of claim 21 is represented by any of the following formulas (where I, R1, A, A', x, and y are defined as in formula (n)).

25. The compound of claim 5, wherein RG is derived from an adamantane group that may have substituents.

26. The compound of claim 25 is represented by any of the following formulas (where I, R1, R" are defined as in formula (Ad)).

27. The compound of claim 26, wherein the aforementioned R 1 is a hydroxyl, carboxyl, ester or hydroxyalkyl group.

28. The compound of claim 27 is represented by any of the following formulas (where I and R1 are defined as in formula (Ad)).

29. A composition comprising the compound as claimed in claim 1.

30. As a component of claim 29, which is used in lithography.

31. The composition of claim 30 comprises two or more compounds represented by the aforementioned formula (1).

32. The composition of claim 29 further comprises a compound represented by the following formula (DM0-1) or the following formula (BP0-1), or a combination thereof, (wherein, RG, I, and R1 are defined as in formula (1), Q is a base or single bond derived from the intermolecular bond, n' is 0 to 5 and is an integer less than n, m' is 1 to 5 and is an integer less than m, and b is an integer from 1 to 4).

33. The composition of claim 32, wherein the compound represented by the aforementioned formula (DM0-1) is a compound represented by the following formula (DM1a), (Dn1) or (Da1), and the compound represented by the aforementioned formula (BP0-1) is a compound represented by the following formula (BP1a), (Bn1) or (Ba1), (where Z is I, R1, or a linking group used to form a dimer; the definitions of I and R1 are the same as in formula (1); A is a group with a protecting group; R is a non-functional organic group; R1, A, and R are bonded to bondable positions; r1 to r4 are integers from 0 to 5, and the sum of r1 to r4 in one benzene is less than or equal to the valence of benzene) (where the definitions of I, R1, and A are the same as in formula (DM1a); R” is a hydrogen atom or an organic group other than R1; I, R1, A, and R” are bonded to bondable positions; and the definition of Q is the same as in formula (DM0-1). s1 is 1~7, s2~s3 are 0~7, and s4 is an integer from 1 to 7; however, the sum of s1~s4 is less than or equal to the valence of naphthalene, and is selected such that either s2 or s3 is 1 or higher; nd is an integer from 1 to 4 (where I and R1 are defined the same as in formula (Dn1), R” is a hydrogen atom or an organic group other than R1, Rd is a single bond or -O- (ether bond), t1 is 1~10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 13; however, regarding t1~t3, the sum of t1~t3 is less than or equal to the valence of adamantane) (where I, Z, R, R1, and A are defined the same as in formula (DM1a), r1, r2, and r3 are integers from 0 to 5, and a1 and r4a are integers from 0 to 4). a1 and r4a satisfy a1+r4a≦r4; here the definition of r4 is the same as in equation (DM1a) (where I, R1, R”, and A are defined as in equations (Dn1) and (Da1), s2~s4 are defined as in equation (Dn1), s1b is an integer from 0 to 6, and is an integer satisfying s1b≦(s1-1); here the definition of s1 is the same as in equation (Dn1) (where I, R1, and R” are defined as in equations (Dn1) and (Da1), t2 and t3 are defined as in equation (Da1), t1b is an integer from 0 to 9, and is an integer satisfying t1b≦(t1-1); here the definition of t1 is the same as in equation (Da1)).

34. A composition of claim 32 comprising a compound represented by the aforementioned formula (DM0-1).

35. The composition of claim 34, wherein the compounds represented by formula (1) and formula (DM0-1) satisfy the following relationship: 0.1 ≧ [amount (mol) of compound (DM0-1)] ÷ [amount (mol) of compound (1)] ≧ 0.000001.

36. The composition of claim 32, comprising a compound represented by formula (BP0-1).

37. The composition of claim 36, wherein the compound represented by formula (BP0-1) is a compound represented by formula (BP1a) and Z is not I, or a compound represented by formula (Bn1) or formula (Ba1).

38. The composition of claim 32, wherein the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relationship: 0.1 ≧ ([total amount of the compound of formula (DM0-1) and the compound of formula (BP0-1) (mol)]) ÷ [amount of the compound of formula (1) (mol)] ≧ 0.000001.

39. The composition of claim 33, wherein the compound represented by the aforementioned formula (DM0-1) is a compound represented by the following formulas (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb), and the compound represented by the aforementioned formula (BP0-1) is a compound represented by the following formulas (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt), (wherein, the definitions of Z, R, R1, A, r1, r2, r3, r4a are the same as those in formula (BP1a)) (wherein, the definitions of Z, I, R1, A, R, r1~r4 are the same as those in formula (DM1a)) (wherein, the definitions of Z, R1, A, R, r1~r4 are the same as those in formula (DM1a)) (wherein, R 1. The definitions of R1, A, s2~s4 are the same as in equation (Bn1) (where I, R1, A, R1", Q, s1~s4 are the same as in equation (Dn1) (where R1, A, R1", Q, s2~s4 are the same as in equation (Dn1) (where R1, R1", t2, t3 are the same as in equation (Ba1) (where I, R1, R1", Rd, t1~t3 are the same as in equation (Da1) (where R1, R1", Rd, t2~t3 are the same as in equation (Da1) (where I, R1, R1", Rd, t1~t3 are the same as in equation (Da1) (where I, R1, R1", Rd, t1~t3 are the same as in equation (Da1)) (where I, R1, R1", R1", Rd, t1~t3 are the same as in equation (Da1)) The definitions of d and t1~t3 are the same as those in equation (Da1).

40. The composition of claim 30, wherein RG of the aforementioned formula (1) is derived from a benzene group that may have substituents.

41. The composition of claim 30, wherein RG of the aforementioned formula (1) is derived from a naphthalene group that may have substituents.

42. The composition of claim 30, wherein RG of formula (1) is derived from adamantane that may have substituents.

43. The composition of claim 29 exhibits a sensitizing effect upon exposure to radiation.

44. The composition of claim 29, wherein the content of metallic impurities is less than 1 ppm.

45. A method for exhibiting a sensitizing effect on a composition for photolithography under radiation, wherein the compound of claim 1 is used.

46. ​​The method of claim 45, which uses two or more of the aforementioned compounds.

47. A method for manufacturing a compound as claimed in claim 1, comprising the step of introducing an iodine atom or an R1 group into a compound containing the aforementioned RG group.

48. A method for manufacturing a compound as claimed in claim 1, wherein the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, the definitions of I, Z, R1, A, R, r1 to r4 are the same as those of formula (DM1a)); the aforementioned manufacturing method comprises: 1) a step of preparing a compound represented by formula (MB), (wherein, the definitions of I, R1, R, r1, r2 are the same as those of formula (Bz), and R1, R, OH are bonded at any bondable position) 2) an iodination step of iodizing the compound, 3) a protecting group introduction step of introducing a protecting group into the compound, and 4) a reduction step of reducing the compound.

49. A method for manufacturing the compound of claim 48, wherein the aforementioned protecting group introduction step includes the step of introducing a protecting group using an inorganic basic (MB) hydroxyl group.

50. A method for manufacturing a compound as claimed in claim 1, wherein the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, the definitions of I, Z, R1, A, R, r1 to r4 are the same as those of formula (DM1a)); the aforementioned manufacturing method comprises: 1) a step of preparing a compound represented by formula (Bz4), (wherein, the definitions of I, R, A, Z are the same as those of formula (Bz), R1' may be the same or different and may be a 1-valent functional group excluding hydroxyl groups with 0 to 30 carbon atoms that do not contain polymerizable unsaturated bonds, r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is less than or equal to the valence of benzene) 2) a step of performing an iodination step of iodizing the compound once or twice or more.

51. A method for manufacturing the compound of claim 1, wherein the compound represented by the aforementioned formula (1) is represented by formula (Bz), (wherein, the definitions of I, Z, R1, A, R, r1 to r4 are the same as those of formula (DM1a)) The aforementioned manufacturing method comprises: 1) a step of preparing the compound represented by formula (Bz5), (wherein, the definitions of I, Z, R1, A, R, r1 to r4 are the same as those of formula (DM1a)) 2) a step of esterifying the carboxylic acid of the compound represented by formula (Bz5) 3) a step of reducing the obtained ester group to convert it into a hydroxymethyl group.

52. A method for manufacturing the compound of claim 1, wherein the compound represented by the aforementioned formula (1) is represented by formula (N), (wherein, the definitions of I, R1, A, and R” are the same as those of formulas (Dn1) and (Bn1), but I, R1, R” and A are bonded at any bondable position, s1 is 1 to 7, s2 to s3 are 0 to 7, and s4 is an integer from 1 to 7; but the sum of s1 to s4 is less than the valence of naphthalene, and is selected such that either s2 or s3 is 1 or more) The aforementioned manufacturing method comprises: 1) a step of preparing the compound represented by formula (MN), (wherein, the definitions of R1, R”, s3, and s4 are the same as those of formula (N)) 2) an iodination step of iodizing the compound, 3) a protecting group introduction step of introducing a protecting group into the compound, and 4) a reduction step of reducing the compound.

53. A method for manufacturing the compound as claimed in claim 1, wherein the compound represented by the aforementioned formula (1) is represented by formula (Ad), (wherein, the definitions of I, R1, and R” are the same as those of formula (Da1), I, R1, and R” are bonded at any bondable position, t1 is 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 14; however, regarding t1 to t3, the sum of t1 to t3 is less than or equal to the valence of adamantane); the aforementioned manufacturing method comprises: 1) a step of preparing the compound represented by formula (MA), (wherein, the definitions of R1, R, t2, and t3 are the same as those of formula (Ad)) 2) an iodination step of iodizing the compound.

54. A method for manufacturing the compound of claim 53, wherein the aforementioned iodination step comprises a step of iodizing in a system composed of a multiphase, wherein the multiphase comprises an organic phase comprising an organic solvent as a solvent and an aqueous phase comprising water as a solvent.

55. A method for producing the compound of claim 53, wherein the aforementioned iodination step includes a step of simultaneously distilling off water and concentrating the reaction solution during the reaction.

56. A method for manufacturing the compound of claim 53, wherein the aforementioned iodination step includes a step of allowing the substrate and iodizing agent to stand for 1 hour to 48 hours after feeding them into the substrate and iodizing agent.

57. A method for manufacturing the compound as claimed in claim 1, comprising one or more steps selected from any one of the following 1) to 3): 1) a step of preparing a compound represented by formula (Ad-A-3-0), 2) a step of preparing a compound represented by formula (Ad-A-3-1), and 3) a step of preparing a compound represented by formula (Ad-A-3-2); 58. A method for manufacturing the compound of claim 57, comprising: 1) a step of preparing the compound represented by formula (Ad-A-3-0), 2) an oxidation step of the compound represented by oxidative formula (Ad-A-3-0), 3) a step of esterifying the carboxylic acid of the compound obtained by esterification, 4) a step of hydrolyzing the ester group of the compound obtained by hydrolysis to convert it into a carboxylic acid, and 5) an iodination step of iodination.

59. The manufacturing method of any of claims 47 to 58 further includes a step of treating with an adsorbent.

60. The compound of claim 1 is represented by the following formula (Ad-A-3).

61. The compound of claim 1 is represented by the following formula (Ad-A-4).