Compound, composition, method for expressing sensitizing effect, and production method
Patent Information
- Application Number
- JP2025539186
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Priority Date
- 2023-10-11
- Filing Date
- 2024-06-28
- Publication Date
- 2025-02-13
Abstract
Description
Compound, composition, method for exhibiting sensitizing effect, and production method
[0001] The present invention relates to compounds, compositions, methods for exerting a sensitizing effect, and production methods.
[0002] In recent years, advances in lithography technology have led to rapid miniaturization of semiconductors (patterns) and pixels in the manufacture of semiconductor elements and liquid crystal display elements. Therefore, materials that can accommodate this miniaturization are desired. For example, Patent Document 1 discloses a resist composition containing a compound having a structure in which multiple aromatic rings are crosslinked and containing an iodine atom. This resist composition has excellent etching resistance. Furthermore, Patent Document 2 discloses a compound having a polymerizable group and an iodine atom. A resist composition containing this compound is said to be capable of forming a resist pattern with excellent CD uniformity.
[0003] International Publication No. 2020 / 040161 Japanese Patent Application Laid-Open No. 2021-188040
[0004] There is a need for the development of a compound useful for a lithography composition, preferably a resist composition, that can accommodate miniaturization. In view of the above circumstances, an object of the present invention is to provide a compound useful as a lithography composition, a composition containing the compound, a method for achieving a sensitizing effect using the compound, and a method for producing the compound.
[0005] The inventors have discovered that a compound having a specific structure can solve the above problems.
[0006] That is, the present invention includes the following aspects: [1] A compound represented by the following formula (1): (Wherein, RG is a group containing at least one cyclic structure, I is an iodine atom, and R １ are the same or different monovalent functional groups having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, n is an integer of 1 to 5, and m is an integer of 1 to 5. [2] A compound represented by the formula (1), wherein RG is a group derived from benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring, or a polycyclic alicyclic ring, which may have a substituent, and R １R is selected from the group consisting of a hydroxyl group and an ether group having a protecting group. ｆ and a hydrocarbon group R having 0 to 30 carbon atoms which may have a substituent. ｇ [3] The compound described above, wherein R ｆ 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, alkali, or heat; ｆ [4] The compound, wherein RG is a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, or adamantane, which may have a substituent. [5] The compound, wherein RG is a group derived from benzene, naphthalene, or adamantane, which may have a substituent. [6] R １ Ga-OR ２ , -COOR ３ , -CH ２ -OR ４ or —CHO, wherein R ２ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an aryl group having 1 to 30 carbon atoms, ３ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms which may have a substituent, or an aryl group having 1 to 29 carbon atoms, ４ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms which may have a substituent, or an aryl group having 1 to 29 carbon atoms. [7] The compound described above, １ [8] The compound represented by any one of the following formulae: (Wherein, Z is I, R １ or a linking group for forming a dimer, １ is defined the same as in formula (1), A is a group having a protecting group, R is an organic group that is not a functional group, and R １ , A, and R are bonded to available positions, r1 to r4 are integers of 0 to 5, and the sum of r1 to r4 in one benzene is equal to or less than the valence of the benzene. (In the formula, I, A, R １is defined as above, R″ is a hydrogen atom or R １ s1 is an integer of 1 to 7, s2 and s3 are an integer of 0 to 7, and s4 is an integer of 1 to 7. However, the total of s1 to s4 is equal to or less than the valence of naphthalene, and at least either s2 or s3 is selected to be 1 or greater.) (In the formula, I, R １ , R″ is defined as above, t1 is an integer of 1 to 10, t2 is an integer of 1 to 9, and t3 is an integer of 1 to 14, provided that the sum of t1 to t3 is equal to or less than the valence of adamantane.) [9] The compound represented by any of the following formulas: (In the formula, I, Z, R, R １ , A is defined the same as in formula (Bz). (In the formula, I, R １ , A, and R" are defined the same as in formula (N); x and y are 0 or 1, provided that at least one of them is 1; and s4' represents the number of R"s that can be bonded to the 1st, 7th, and 8th positions of naphthalene, and is an integer of 1 to 3. (In the formula, I, R １ , R″ is defined the same as in formula (Ad), one of D is I, and the other of D is R １
[10] The compound represented by any one of the following formulas: (In the formula, I, Z, R, R １ , A is defined the same as in formula (Bz). (In the formula, I, R １ , R″, A, x, y, and s4′ are defined the same as in formula (n). (In the formula, I, R １ , R″ is defined the same as in formula (Ad).
[11] The R １ is a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group, and A is -O-R ａ -O-R ｂ In the case of A' represented by (R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂis a monovalent linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.), and the compound contains one or more of A'.
[12] The compound wherein RG is a group derived from benzene which may have a substituent.
[13] The compound wherein RG is a group containing benzene, and R １ If there are multiple R １ does not include a combination of an alkoxy group (excluding those having a protecting group) and an aldehyde group, a combination of the alkoxy group and a hydroxyl group, or a combination of a hydroxyl group and an aldehyde group, RG is a group containing naphthalene, and R １ If there are multiple R １ The compound represented by the following formula (Bz4): (In the formula, I, R, A, and Z are defined the same as in formula (Bz). R １’ are monovalent functional groups, which may be the same or different, having 0 to 30 carbon atoms and containing no polymerizable unsaturated bond, excluding hydroxyl groups, and r1', r2', and r4' are integers of 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.)
[15] The compound represented by the following formula (Bz4-1): (Wherein I, R, Z and R １’ are defined the same as in formula (Bz4). r1', r2', and r4' are integers of 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.)
[16] The compound represented by the following formula (Bz4-2): (wherein I is defined the same as in formula (Bz4), r4' is an integer of 0 to 4, and r5' is an integer of 0 to 4).
[17] The compound represented by any one of the following formulas:
[18] The compound represented by any one of the following formulas: (Wherein I, R, Z, A and R １ is defined the same as in formula (Bz), A' is a group having a protecting group, -O-R ａ -O-Rｂ , -O-CO-OR ｂ , or -O-R ａ -CO-O-R ｂ It is expressed as: R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.)
[19] The compound represented by any of the following formulas: (In the formula, I, R １ A is defined as in formula (Bz), A' is a group having a protecting group, -O-R ａ -O-R ｂ , -O-CO-OR ｂ , or -O-R ａ -CO-O-R ｂ It is expressed as: R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom. Z' is I, R １ or a hydrogen atom.)
[20] The compound above, wherein RG is a group derived from naphthalene which may have a substituent.
[21] The compound above, represented by any of the following formulas: (In the formula, I, R １ , R″, A, x, y, and s4′ are defined the same as in formula (n).
[22] The compound represented by any one of the following formulas: (In the formula, I, R １ , R″ is defined the same as in formula (n), A′ is a group having a protecting group, —O—R ａ -O-R ｂ , -O-CO-OR ｂ , or -O-R ａ -CO-O-R ｂ It is expressed as: R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂis a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group, which forms a ring together with the adjacent oxygen atom. １ is a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group.
[24] The compound represented by any one of the following formulas: (In the formula, I, R １ , A, A', x, and y are defined the same as in formula (n).
[25] The compound above, wherein RG is a group derived from adamantane which may have a substituent.
[26] The compound above, represented by any of the following formulas: (In the formula, I, R １ , R″ is defined the same as in formula (Ad).
[27] The R １ is a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group.
[28] The compound represented by any one of the following formulas: (In the formula, I, R １ is defined the same as in formula (Ad).)
[29] A composition comprising the compound.
[30] The composition for use in lithography.
[31] The composition comprising two or more compounds represented by formula (1).
[32] The composition further comprising a compound represented by formula (DM0-1) below, or a compound represented by formula (BP0-1) below, or a combination thereof. (wherein, RG, I, R １ is defined the same as in formula (1), Q is a group resulting from a group bonding between molecules or a single bond, n' is an integer from 0 to 5 and not more than n, m' is an integer from 1 to 5 and not more than m, and b is an integer from 1 to 4.)
[33] The above composition, wherein the compound represented by formula (DM0-1) is a compound represented by the following formula (DM1a), (Dn1), or (Da1), and the compound represented by formula (BP0-1) is a compound represented by the following formula (BP1a), (Bn1), or (Ba1). (Wherein, Z is I, R １ or a linking group for forming a dimer, １is defined the same as in formula (1), A is a group having a protecting group, R is an organic group that is not a functional group, and R １ , A, and R are bonded to available positions, r1 to r4 are integers of 0 to 5, and the sum of r1 to r4 in one benzene is equal to or less than the valence of the benzene. (In the formula, I, R １ , A is defined as in formula (DM1a), R″ is a hydrogen atom or R １ an organic group other than I, R １ , A, and R" are bonded to available positions, Q is defined the same as in formula (DM0-1), s1 is an integer of 1 to 7, s2 and s3 are an integer of 0 to 7, and s4 is an integer of 1 to 7, provided that the total of s1 to s4 is equal to or less than the valence of naphthalene, and either s2 or s3 is selected to be 1 or greater, and nd is an integer of 1 to 4.) (In the formula, I, R １ is defined the same as in formula (Dn1), R″ is a hydrogen atom or R １ is an organic group other than ｄ is a single bond or -O- (ether bond), t1 is an integer of 1 to 10, t2 is an integer of 1 to 9, and t3 is an integer of 1 to 13, provided that the sum of t1 to t3 is equal to or less than the valence of adamantane. (In the formula, I, Z, R, R １ , A is defined 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, where r4 is defined the same as in formula (DM1a). (In the formula, I, R １ , R", and A are defined the same as in formulas (Dn1) and (Da1), s2 to s4 are defined the same as in formula (Dn1), and s1b is an integer from 0 to 6 that satisfies s1b≦(s1-1), where s1 is defined the same as in formula (Dn1). (In the formula, I, R １, R" are defined the same as in formulas (Dn1) and (Da1), t2 and t3 are defined the same as in formula (Da1), t1b is an integer of 0 to 9, and is an integer that satisfies t1b≦(t1-1). Here, t1 is defined the same as in formula (Da1).)
[34] The composition comprising the compound represented by formula (DM0-1).
[35] The composition, wherein the compounds represented by formula (1) and formula (DM0-1) satisfy the following relationship: 0.1≧[amount (mol) of compound of formula (DM0-1)]÷[amount (mol) of compound of formula (1)]≧0.000001
[36] The composition comprising the compound represented by formula (BP0-1).
[37] The composition, 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 a compound represented by formula (Ba1).
[38] The composition, wherein the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relationship: 0.1≧([total amount (mol) of the compound of formula (DM0-1) and the compound of formula (BP0-1)])÷[amount (mol) of the compound of formula (1)]≧0.000001
[39] The composition, wherein the compound represented by formula (DM0-1) is a compound represented by the following formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb), and the compound represented by formula (BP0-1) is a compound represented by the following formula (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt). (In the formula, Z, R, R １ , A, r1, r2, r3, and r4a are defined the same as in formula (BP1a). (In the formula, Z, I, R １ , A, R, r1 to r4 are defined the same as in formula (DM1a). (In the formula, Z, R １ , A, R, r1 to r4 are defined the same as in formula (DM1a). (In the formula, R １ , R″, A, s2 to s4 are defined the same as in formula (Bn1).) (In the formula, I, R １, A, R″, Q, s1 to s4 are defined the same as in formula (Dn1).) (In the formula, R １ , A, R″, Q, s2 to s4 are defined the same as in formula (Dn1). (In the formula, R １ , R″, t2, and t3 are defined the same as in formula (Ba1).) (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1). (In the formula, R １ , R”, R ｄ , t2 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1).)
[40] The composition, wherein RG in formula (1) is a group derived from benzene which may have a substituent.
[41] The composition, wherein RG in formula (1) is a group derived from naphthalene which may have a substituent.
[42] The composition, wherein RG in formula (1) is a group derived from adamantane which may have a substituent.
[43] The composition, which exhibits a sensitizing effect upon irradiation with radiation.
[44] The composition, wherein the content of metal impurities is less than 1 ppm.
[45] A method for exhibiting a sensitizing effect upon irradiation of a composition for lithography, using the compound.
[46] The method according to
[45] , wherein two or more of the compounds are used.
[47] A compound containing the RG group, wherein an iodine atom or R １
[48] A method for producing the compound represented by formula (1), comprising a step of introducing a group into the compound represented by formula (1), wherein the compound represented by formula (1) is represented by formula (Bz): (In the formula, I, Z, R １, A, R, and r1 to r4 are defined as in formula (DM1a). 1) preparing a compound represented by formula (MB); (In the formula, I, R １ , R, r1, and r2 are defined the same as in formula (Bz), and R １ , R and OH are bonded to any available positions.) 2) an iodination step of iodinating 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 producing the compound according to
[48] , wherein the protecting group introduction step comprises a step of introducing a protecting group to the hydroxy group of formula (MB) using an inorganic base.
[50] A method for producing the compound represented by formula (1), wherein the compound represented by formula (1) is represented by formula (Bz), (In the formula, I, Z, R １ , A, R, and r1 to r4 are defined the same as in formula (DM1a). 1) preparing a compound represented by formula (Bz4); (Wherein, I, R, A, and Z are defined as in formula (Bz), R １’ are the same or different functional groups having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding a monovalent hydroxyl group, and r1', r2', and r4' are integers of 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.) 2) a step of carrying out an iodination step of iodinating the compound once or twice or more times.
[51] A method for producing a compound represented by formula (1), comprising: (In the formula, I, Z, R １ , A, R, and r1 to r4 are defined the same as in formula (DM1a). 1) preparing a compound represented by formula (Bz5); (In the formula, I, Z, R １, A, R, and r1 to r4 are defined the same as in formula (DM1a). 2) A step of esterifying a carboxylic acid of a compound represented by formula (Bz5), and 3) A step of reducing the obtained ester group to convert it into a hydroxymethyl group.
[52] A method for producing a compound represented by formula (1), wherein the compound represented by formula (1) is represented by formula (N), (In the formula, I, R １ , A, and R″ are defined the same as in formulas (Dn1) and (Bn1), where I, R １ , R″, and A are bonded to any bondable position, s1 is an integer of 1 to 7, s2 and s3 are an integer of 0 to 7, and s4 is an integer of 1 to 7, provided that the sum of s1 to s4 is equal to or less than the valence of naphthalene, and either s2 or s3 is selected to be 1 or greater.) 1) a step of preparing a compound represented by formula (MN), (In the formula, R １ , R", s3, and s4 are defined the same as in formula (N). 2) an iodination step of iodinating 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 producing a compound represented by formula (1), comprising: (In the formula, I, R １ , R″ are defined the same as in formula (Da1), and I, R １ t1 is an integer of 1 to 10, t2 is an integer of 1 to 9, and t3 is an integer of 1 to 14, provided that the sum of t1 to t3 is equal to or less than the valence of adamantane. 1) preparing a compound represented by formula (MA), (In the formula, R １, R, t2, and t3 are defined the same as in formula (Ad). 2) an iodination step of iodinating the compound.
[54] A method for producing the compound according to any of
[48] to
[53] , wherein the iodination step comprises a step of performing iodination in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent.
[55] A method for producing the compound according to any of
[48] to
[53] , wherein the iodination step comprises a step of concentrating the reaction solution while distilling off water during the reaction.
[56] A method for producing the compound according to any of
[48] to
[53] , wherein the iodination step comprises a step of charging a substrate and an iodinating agent and then allowing the mixture to stand for 1 to 48 hours.
[57] A method for producing the compound, comprising one or more steps selected from: 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] 1) preparing a compound represented by formula (Ad-A-3-0);
[58] A method for producing the compound according to
[57] , further comprising the steps of: 1) oxidizing a compound represented by formula (Ad-A-3-0), 2) oxidizing a compound represented by formula (Ad-A-3-0), 3) esterifying a carboxylic acid of the compound obtained, 4) hydrolyzing the ester group of the compound obtained to convert it to a carboxylic acid, and 5) iodinating the compound.
[59] A method for producing the compound according to any one of
[47] to
[58] , further comprising a step of treating the compound with an adsorbent.
[60] The compound represented by the following formula (Ad-A-3):
[61] The compound represented by the following formula (Ad-A-4):
[0007] The present invention provides a compound useful as a composition for lithography, a composition containing the compound, a method for producing the compound using the compound, and a method for producing the compound. Furthermore, the compound and composition of the present invention can be used in a lithography process to obtain a sensitization effect.
[0008] The present invention will be described in detail below. In the present invention, "to" such as "X to Y" includes the extreme values X and Y.
[0009] 1. Compound The compound according to this embodiment is represented by the following formula (1):
[0010]
[0011] [RG] In the formula, RG is a group containing at least one cyclic structure. The valence of RG is determined by the I and R groups described below. １ , R １ The number of substituents other than the above is appropriately adjusted. The group containing a cyclic structure may contain an aromatic ring, an alicyclic ring, or a heterocyclic ring, but is preferably a group having 6 to 60 carbon atoms, and is more preferably a group derived from an aromatic ring, a heteroaromatic ring, such as benzene, naphthalene, biphenyl, anthracene, phenanthrene, pyrene, or fluorene, which may have a substituent, or a polycyclic alicyclic ring, such as cyclohexane, cyclododecane, dicyclopentane, tricyclodecane, or adamantane. RG does not necessarily have to contain a ring assembly in which single rings are bonded by a single bond (e.g., biphenyl, binaphthyl, bicyclopropyl, etc.). In this case, RG is preferably a group having at least one cyclic structure selected from a monocyclic aromatic ring structure, a fused-ring aromatic structure, and a polycyclic alicyclic structure.
[0012] Among these, from the viewpoint of availability and the like, RG is preferably a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, or a polycyclic alicyclic ring, which may have a substituent; more preferably a group derived from benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring, or a polycyclic alicyclic ring, which may have a substituent; still more preferably a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, or adamantane, which may have a substituent; still more preferably a group derived from benzene, naphthalene, or adamantane, which may have a substituent; and particularly preferably a group derived from benzene, naphthalene, or adamantane.
[0013] [I] In the formula, I is an iodine atom. n represents the number of I and is an integer of 1 to 5. From the viewpoints of the sensitizing effect, solubility in solvents, and chemical stability, n is preferably an integer of 1 to 3, and more preferably 1 or 2. When n is greater than 1, the sensitizing effect can be obtained, and when n is 5 or less, the solubility of the compound in solvent components commonly used for semiconductors and the stability of the compound itself can be ensured.
[0014] [R １ ] In the formula, R １ R may be the same or different and are monovalent functional groups having 0 to 30 carbon atoms and containing no polymerizable unsaturated bonds. １ By converting R to another group or bonding it to another group, a derivative of the compound of formula (1) can be produced. The polymerizable unsaturated bond is an ethylenic double bond or triple bond. １ When the above is true, the stability and solubility are excellent.
[0015] R １ is a functional group and is not an alkyl group. １ is, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxyl group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 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. １From the viewpoint of sensitizing effect, etc., 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, those that can have a substituent may have a substituent. Unless otherwise defined, "substituted" means that one or more hydrogen atoms in the functional group are substituted with a substituent. The "substituent" is not particularly limited, but examples thereof include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an acyl group having 1 to 30 carbon atoms (preferably an alkyloyloxy group having 1 to 20 carbon atoms, an aryloyloxy group having 7 to 30 carbon atoms), an alkoxycarbonyl group having 2 to 20 carbon atoms, or an alkylsilyl group having 1 to 20 carbon atoms. These groups may be groups within a substituent, a group having a substituent, or other R １ Suitable examples of the group that may form a ring structure include a glycidyl group, a cyclic acetal group, and a group in which two adjacent hydroxyl groups are protected by an acetal protecting group structure.
[0016] Among them, R １ is preferably a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group, and more preferably —OR ２ an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aldehyde group, and for example, R １ -OR ２ , -COOR ３ , -CH ２ -OR ４ or —CHO, where R ２is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, or a cyclic alkyl ether group having 1 to 5 carbon atoms. The carboxyl group or carboxylic acid ester group is more preferably —COOR ３ where R ３ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms. The alkoxyalkyl group or hydroxyalkyl group is more preferably —CH ２ -OR ４ where R ４ is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms. The alkyl group or aryl group may have a substituent. Examples of the substituent include an alkoxy group. Therefore, the -OR ２ R ２ In one embodiment, is —CH ２ -OC ２ H ５ It is possible.
[0017] The R ２ ~R ４ The alkyl group in the formula (I) is preferably a methyl group, an ethyl group, or a propyl group (including isomers, the same applies hereinafter). The aryl group is preferably a phenyl group or a naphthyl group.
[0018] R １ may have a protecting group. A protecting group is a group that dissociates under specific conditions and is also called a dissociable group. The protecting group is preferably an acid-dissociable group that dissociates in the presence of an acid. Preferred examples of such groups include a 1-substituted ethyl group, a 1-substituted-n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, or an alkoxycarbonylalkyl group. In one embodiment, R １ may be a hydroxyl group or a carboxyl group protected by a protecting group. For example, R １ Ha -O-CH ２ -O-R'. R' is, for example, an alkyl group having 1 to 5 carbon atoms. In this embodiment, R １ Ga-OR ２(However, R ２ is CH ３ ) and R ２ has an alkoxy group (—O—R′) as a substituent. １ is a group having a protecting group, as described below, R １ is sometimes written as A or A'.
[0019] In the formula, m is R １ and is an integer of 1 to 5. From the viewpoint of solubility in a solvent, m is preferably 4, 3, 2, or 1. When m is 2 or 3, a plurality of R １ may be different or the same. m is more preferably 2 or 3, and even more preferably 2. The total number of m and n is adjusted appropriately depending on the valence of RG.
[0020] The compound may optionally contain R １ The compound may have an organic group other than R. The organic group may be an alkyl group having 1 to 30 carbon atoms. A plurality of such groups may be present. However, the compound may have an organic group other than R. １ It is preferable that the iodine atom does not contain any organic groups other than the iodine atom.
[0021] RG is a group containing benzene, and R １ If there are multiple R １ Preferably, R does not include a combination of an alkoxy group and an aldehyde group, an alkoxy group and a hydroxyl group, or an aldehyde group and a hydroxyl group. The alkoxy group here does not include those having a protecting group. The alkoxy group is, for example, a methoxy group or an ethoxy group. When RG is a group containing naphthalene, and R １ If there are multiple R １ It is preferable that the combination of hydroxyl and carboxyl groups is not included.
[0022] When RG is a group derived from benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring, or a polycyclic alicyclic ring, R １ is preferably one or more R ｆ and 0 or more R ｇ It is one selected from R１ is one or more R ｆ ' and zero or more R ｇ It is one of the types selected from. ｆ is selected from the group consisting of a hydroxyl group and an ether group having a protecting group. ｆ R' is selected from the group consisting of a hydroxyl group and an ether group having a protecting group that can be removed by an acid, an alkali, or heat. ｇ is a hydrocarbon group having 0 to 30 carbon atoms which may have a substituent. In particular, when RG is a benzene or naphthalene structure, R １ is one or more R selected from the group consisting of a hydroxyl group and an ether group having a protecting group; ｆ and 0 or more hydrocarbon groups R having 0 to 30 carbon atoms which may have a substituent. ｇ , and R ｆ 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, alkali, or heat; ｆ It is more preferred that the compound of formula (1) is R １ When the compound has these groups as the substituent, the reaction of linking the compound with other compounds can proceed smoothly.
[0023] As mentioned above, the compound of formula (1) can be linked to other compounds. For example, the compound of formula (1) can be made into a dimer to a pentamer. Multimers will be described later.
[0024] 1-2. Preferred Embodiments (1) First Embodiment In the first embodiment, RG is benzene. In this embodiment, the compound represented by formula (1) (hereinafter referred to as "compound of formula (1)") is preferably represented by formula (Bz) from the viewpoints of sensitizing effect, availability, etc.
[0025]
[0026] In the formula, A is a group having a protecting group. A becomes a functional group by removing the protecting group, so R １As mentioned above, the protecting group is preferably an acid-labile group. Therefore, the group having a protecting group is preferably a group in which a hydroxyl group or a carboxyl group is protected with an acid-labile group. A is -O-R ａ -O-R ｂ In this case, it is preferable that the compound of formula (Bz) contains one or more of the A'. ａ and R ｂ will be discussed later.
[0027] In the formula, R is a non-functional organic group, such as an alkyl group having 1 to 30 carbon atoms.
[0028] In the formula, Z is I, R １ , or a linking group for forming a dimer. When Z is a linking group for forming a dimer, two molecules are bonded by a single bond to form a dimer. Dimers are included in compounds represented by formula (DM1a) described below. Z does not necessarily have to contain a linking group for forming a dimer. When Z does not contain a linking group for forming a dimer, Z will be particularly represented as Z'.
[0029] wherein I and R １ is defined as above. From the viewpoint of the sensitizing effect, R １ 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.
[0030] R １ , R, and A are bonded to any available position. r1 to r4 are integers of 0 to 5, and the sum of r1 to r4 is equal to or less than the valence of benzene. Furthermore, r1 to r4 are preferably integers of 1 to 4, more preferably integers of 1 to 3, and particularly preferably an integer of 1 or 2. However, it is preferable that at least one of r2 and r3 is 1 or greater. Below, preferred embodiments of the compound will be described from the viewpoints of sensitizing effect, ease of availability, etc.
[0031] [Bz1 Series] The compound of formula (Bz) is preferably represented by formula (Bz1). The compound of formula (Bz1) is preferably represented by formula (Bz1) in which R not derived from Z is １In the present disclosure, unless otherwise specified, each substituent of a compound is defined the same as in the compound group to which the compound belongs.
[0032]
[0033] (Bz1-1 series) The compound of formula (Bz1) is preferably represented by formula (Bz1-1). The compound of formula (Bz1-1) has R not derived from Z at the meta position of I. １ It has one.
[0034]
[0035] The compound of formula (Bz1-1) is preferably represented by formula (1b), more preferably by formula (1b-3). Z' is I, R １ or a hydrogen atom, and A and Z, or A and Z', together with the protecting group, may form a cyclic structure.
[0036]
[0037] The compound of formula (Bz1-1) is preferably represented by formula (1b-1), more preferably by formula (1b-4).
[0038]
[0039] (Bz1-2 series) The compound of formula (Bz1) is preferably represented by formula (Bz1-2). The compound of formula (Bz1-2) has R which is not derived from Z at the para position of I. １ A and Z may form a cyclic structure together with a protecting group. １ may form a cyclic structure together with the protecting group.
[0040]
[0041] The compound of formula (Bz1-2) is preferably represented by formula (Bz1-2-1), more preferably by formula (Bz1-2-2): A and Z, or A and Z', together with the protecting group, may form a cyclic structure.
[0042]
[0043] (Bz1-3 series) Furthermore, the compound of formula (Bz1) is preferably represented by formula (Bz1-3). The compound has R not derived from Z at the ortho position of I. １ A and Z may form a cyclic structure together with a protecting group.
[0044]
[0045] The compound of formula (Bz1-3) is preferably represented by formula (Bz1-3-1), more preferably by formula (Bz1-3-2).
[0046]
[0047] A' is a group having a protecting group, -O-R ａ -O-R ｂ , -O-CO-OR ｂ , -O-R ａ -CO-O-R ｂ , or -O-R ａ -O-CO-R ｂ It is expressed as: R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear or branched alkyl group 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. ａ and R ｂ A' may form a cyclic structure containing the following: wherein A' is present at one or more.
[0048] [Bz2 Series] The compound of formula (Bz) is preferably represented by formula (Bz2). The compound has two R groups not derived from Z. １ are located in positions that are not adjacent to each other.
[0049]
[0050] The compound (Bz2) is preferably represented by the formula (Bz2-1).
[0051]
[0052] [Bz3 Series] The compound of formula (Bz) is preferably represented by formula (Bz3). The compound has two R groups not derived from Z.１ are adjacent to each other. A' is defined as above and may occur at least once.
[0053]
[0054] [Particularly preferred embodiment] Among the above, from the viewpoint of sensitization effect, the compound of formula (Bz1) is particularly preferably the compound of formula (1b-1). １ and two iodine atoms and one or more A'. The compound of formula (1b-1) will be described below.
[0055] R １ is preferably a hydroxyalkyl group or an aldehyde group, and particularly preferably a hydroxyalkyl group. The method for introducing a hydroxyalkyl group into benzene is not limited. For example, R １ As an example, a method in which a carboxyl group is introduced and then reduced can be mentioned. The reduction method can be carried out by a known method.
[0056] In formula (1b-1), A′ is a group having a protecting group, and —O—R ａ -O-R ｂ , -O-CO-OR ｂ , -O-R ａ -CO-O-R ｂ , or -O-R ａ -O-CO-R ｂ It is represented by R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear or branched alkyl group 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. ａ and R ｂ A' may form a cyclic structure containing the following: wherein A' is present at one or more.
[0057] R ｂIn another embodiment, R is a linear, branched, or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a linear, branched, or cyclic aliphatic group having 1 to 30 carbon atoms containing a heteroatom, or a linear, branched, or cyclic aromatic group having 1 to 30 carbon atoms containing a heteroatom. The aliphatic group, aromatic group, aliphatic group containing a heteroatom, or aromatic group containing a heteroatom may further have a substituent. Examples of the substituent here include those mentioned above, but a linear, branched, or cyclic aliphatic group having 1 to 20 carbon atoms and an aromatic group having 6 to 20 carbon atoms are preferred. R ｂ Among these, an aliphatic group is preferable. ｂ The aliphatic group in the formula (I) 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. The aliphatic group is not particularly limited, but examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group, and an adamantyl group. Among these, a tert-butyl group, a cyclohexyl group, or an adamantyl group is preferred.
[0058] Other R ｂ As the aryl group, a group having the following structure can be used.
[0059]
[0060] A' may alternatively be -CO-O-R ｂ Or represented by -C-CyE, where CyE is a cyclic ester group which may have a substituent. A' is preferably, for example, a group represented by the following formula:
[0061]
[0062] In the compound belonging to formula (Bz), R １ If there are multiple １ does not include a combination of an alkoxy group (excluding those having a protecting group) and an aldehyde group, a combination of an alkoxy group (excluding those having a protecting group) and a hydroxyl group, or a combination of an aldehyde group and a hydroxyl group.
[0063] In the formula (1b-1), R １ is preferably a hydroxyl group, a carboxyl group, an ester group, an aldehyde group, or a hydroxyalkyl group. A' is preferably -O-R ａ -O-R ｂ It is expressed as:
[0064] Specific examples of compounds represented by formula (1b-1) or (1b-4) are shown below, but the invention is not limited thereto.
[0065]
[0066] Specific examples of compounds represented by formula (1b) or (1b-3) are shown below, but the invention is not limited thereto.
[0067]
[0068] Specific examples of the compound represented by formula (Bz1-3-2) are shown below, but the compound is not limited thereto.
[0069]
[0070] Specific compounds belonging to the formula (Bz) are shown below.
[0071]
[0072] [Bz4 Series] The compound of formula (Bz) is preferably represented by formula (Bz4) from the viewpoint of suppressing defects in the resist pattern.
[0073]
[0074] In the formula, I, R, A, and Z are defined as above.
[0075] R １’ R may be the same or different and are functional groups having 0 to 30 carbon atoms, not containing a polymerizable unsaturated bond, excluding a monovalent hydroxyl group, and are preferably not alkyl groups. １’is, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxyl group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 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. １’ is preferably a carboxyl group, an ester group, or a hydroxyalkyl group from the viewpoint of sensitizing effect, etc. Among these groups, groups that can have a substituent may have a substituent other than a hydroxyl group. 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 of 0 to 5, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 3. The sum of r1', r2', and r4' is equal to or less than the valence of benzene.
[0076] [Particularly Preferred Aspects] Among the above, 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). ２ It is preferred that no iodine atoms are bonded to the two ortho positions relative to the OH group.
[0077]
[0078] In the formula, I, R, Z, and R1' are defined the same as in formula (Bz4). r1', r2', and r4' are integers of 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene. The compound of formula (Bz4-1) is particularly preferably represented by formula (Bz4-2). This compound has a hydroxymethyl group and an iodine atom.
[0079]
[0080] In the formula, I is defined the same as in formula (Bz4), r4' is an integer of 0 to 4, and r5' is an integer of 0 to 4. From the viewpoint of the effect of improving resist sensitivity, r4' is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3. r5' is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.
[0081] Specific compounds belonging to the compounds of formula (Bz4), formula (Bz4-1), and formula (Bz4-2) are shown below.
[0082] (2) Second Aspect In the second aspect, RG is naphthalene. In the second aspect, the compound is preferably represented by formula (N) from the viewpoints of sensitizing effect, availability, etc.
[0083]
[0084] In the formula, R １ R may be the same or different and are monovalent functional groups having 0 to 30 carbon atoms and containing no polymerizable unsaturated bonds. １ is defined in the same way as in the first embodiment, but from the viewpoint of the sensitizing effect, R １ is preferably a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group. As explained in the first embodiment, A is a group having a protecting group. A is -O-R ａ -O-R ｂ In this case, it is preferable that the compound of formula (N) contains one or more of the A'. R" is a hydrogen atom or R １ I, R are organic groups other than １, R", and A are bonded to any available position. s1 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. s2 and s3 are preferably integers of 0 to 7, more preferably integers of 0 to 5, and particularly preferably 1 to 3. s4 is preferably an integer of 1 to 7, and more preferably an integer of 1 to 6, with the proviso that s4 is a number that satisfies s4≦8−s1−s2−s3. The sum of s1 to s4 is equal to or less than the valence number of naphthalene, with the proviso that at least one of s2 and s3 is 1 or greater. Preferred compounds from the viewpoints of sensitizing effect, ease of availability, etc. will be described below.
[0085] In another embodiment, a compound in which RG is naphthalene may have a linking group Z for forming a dimer. The compound is represented by formula (N'). In the formula, each substituent is defined as above, and its bonding position is also optional. s1 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. s2 and s3 are preferably integers of 0 to 7, more preferably integers of 0 to 5, and particularly preferably 1 to 3. s4 is preferably an integer of 1 to 7, more preferably an integer of 1 to 6. s5 is preferably an integer of 1 or 2. However, the sum of s1 to s5 is equal to or less than the valence number of naphthalene, and at least one of s2 and s3 is 1 or greater.
[0086]
[0087] The compound of formula (N) is preferably represented by formula (n), formula (2n), or formula (3n). １ , A, and R" are defined the same as in formula (N). x and y are 0 or 1, provided that at least one of them is 1. s4' represents the number of R"s that can be bonded to the 1st, 7th, and 8th positions of naphthalene (where the carbon atom on the top of the right ring is considered to be the 1st position, and the same applies below), and is an integer of 1 to 3.
[0088]
[0089] [(n) Series] The compound of formula (n) is preferably represented by formula (1n), more preferably (1n-1). As described above, R １ If there are multiple R １ does not include a combination of a hydroxyl group and a carboxyl group.
[0090]
[0091] The compound of formula (n) is preferably represented by formula (1n'), more preferably by formula (1n'-1). １ If there are multiple R １ does not include a combination of a hydroxyl group and a carboxyl group.
[0092]
[0093] [(2n) Series] The compound of formula (2n) is preferably represented by formula (2n-1), more preferably (2n-1-1). As described above, R １ If there are multiple R １ does not include a combination of a hydroxyl group and a carboxyl group.
[0094]
[0095] [(3n) Series] The compound of formula (3n) is preferably represented by formula (3n-1), more preferably (3n-1-1). As described above, R １ If there are multiple R １ does not include a combination of a hydroxyl group and a carboxyl group.
[0096]
[0097] The compound of formula (3n) is preferably represented by formula (3n-2), more preferably by formula (3n-2-1). １ If there are multiple R １ does not include a combination of a hydroxyl group and a carboxyl group.
[0098]
[0099] Specific examples of the compound of formula (N) are shown below.ｃ is a monovalent group having 0 to 29 carbon atoms and containing no polymerizable unsaturated bonds.
[0100]
[0101]
[0102]
[0103]
[0104] Non-limiting specific examples of compounds belonging to formula (N) are disclosed below.
[0105]
[0106]
[0107]
[0108]
[0109]
[0110]
[0111]
[0112] In the above formula, A is a group having a protecting group. A is, for example, but not limited to, the following:
[0113]
[0114] (3) Third Aspect In the third aspect, RG is an alicyclic ring having a polycyclic structure with 3 to 30 carbon atoms. I and R in the alicyclic ring １ The substituents such as may be present at any position. Specific examples of the alicyclic ring include the following structures: These alicyclic rings may further have an alicyclic structure.
[0115]
[0116] From the viewpoint of sensitization effect and availability, RG is preferably adamantane. Therefore, in this embodiment, the compound of formula (1) is preferably represented by formula (Ad).
[0117]
[0118] In the formula, I, R １ , and R" are defined as above, where I, R １ , and R″ are bonded to any position of the adamantane. R １ When R is a group having a protecting group, the protecting group is preferably an acid-labile group as described above. Therefore, the group having a protecting group is preferably a group in which a hydroxyl group or a carboxyl group is protected with an acid-labile group. １ is preferably a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group from the viewpoint of sensitization effect, etc. In this case, another R １ can be A, -O-R ａ -O-R ｂ The compound of formula (Ad) preferably contains one or more As. t1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. t2 is preferably an integer of 1 to 9, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. t3 is preferably an integer of 1 to 14, more preferably an integer of 5 to 14, and particularly preferably an integer of 8 to 14. However, t3 is a number that satisfies the relationship t3≦16−t1−t2. The sum of t1 to t3 is equal to or less than the valence of adamantane. Below, preferred compounds will be described from the viewpoints of sensitizing effect, ease of availability, and the like. A compound in which RG is adamantane may have a linking group Z at any position to form a dimer.
[0119] The compound of formula (Ad) is preferably represented by formula (Ad1): In one embodiment, one of D is I and the other of D is R １ In another embodiment, two D's are R １ is.
[0120]
[0121] The compound of formula (Ad) is preferably represented by formula (1a), (2a) or (3a).
[0122]
[0123] The compounds of formula (1a), (2a) and (3a) are preferably represented by the following formula:
[0124]
[0125] The compound of formula (Ad1) is preferably represented by the following formula:
[0126]
[0127] wherein I and R １ is defined as above. The organic group is as described in the first or second aspect. Preferably, the compound has 1 to 2 iodine atoms.
[0128] In formulas (1a) to (3a), preferably, R １ is a hydroxyl group, a carboxyl group, an ester group (which may have a substituent other than iodine atom such as a halogen atom), or a hydroxyalkyl group.
[0129] Non-limiting specific examples of the compound represented by formula (Ad1) are shown below.
[0130]
[0131]
[0132] For example, the above-described tetra-substituted adamantane having iodine and a carboxylic acid group can be synthesized from the following compound as a raw material.
[0133]
[0134]
[0135]
[0136] 1-3. Polymers As mentioned above, the compound of formula (1) may be a polymer. In this case, it is preferable that RG does not include a ring assembly in which single rings are bonded by a single bond (for example, biphenyl, binaphthyl, bicyclopropyl, etc.). Specifically, it is preferable that RG is a group having at least one cyclic structure selected from a monocyclic aromatic ring structure, a fused ring aromatic structure, and a polycyclic alicyclic structure. In this case, at least a part of R １ is preferably the following group, which links two or more molecules: an alcohol group, an acetal group, a carbonate ester group, a glycidyl group, a carboxyl group, a carboxylic acid halide group, an aldehyde group; or an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 1 to 30 carbon atoms, wherein the substituent is an alcohol group, an acetal group, a carbonate ester group, a glycidyl group, a carboxyl group, or a carboxylic acid halide group. The carbonate ester group may be an optionally substituted alkoxycarbonyloxy group or an aryloxycarbonyloxy group.
[0137] When the compound of formula (1) is a polymer, the compound is preferably represented by the following formula:
[0138]
[0139] In the formula, RG, I, R １ is defined the same as in formula (1). n' is an integer of 0 to 5 and not more than n, preferably an integer of 1 to 3. m' is an integer of 1 to 5 and not more than m, preferably an integer of 1 to 4. b is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably an integer of 1 or 2. Q is a group derived from a group bonding between molecules or a single bond. A group derived from a group bonding between molecules is a single bond that is derived from an R bonding between molecules. １ When Q is derived from Z, Q is a single bond, meaning that the repeating units are bonded by a single bond. １ When the compound is derived from the above, Q is, for example, an ester group.
[0140] [Bz Series] In a preferred embodiment, the compound of formula (DM0-1) is represented by formula (DM1a).
[0141]
[0142] In the formula, R, R １ , A, Z, r1 to r4 are defined the same as in the compounds of the formula (Bz) series. In the compounds, Z is preferably R １ is.
[0143] The compound of formula (DM1a) is preferably a compound represented by formula (DM1b).
[0144]
[0145] In the formula, I, R, R １ , A, and Z are defined the same as in formula (DM1a).
[0146] The compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c1).
[0147]
[0148] In the formula, I, R, R １ , A, and Z are defined the same as in formula (DM1a).
[0149] The compound represented by formula (DM1c1) is preferably a compound represented by formula (DM1d11).
[0150]
[0151] In the formula, I, R, R １ , A, and Z are defined the same as in formula (DM1a).
[0152] The compound represented by formula (DM1c1) is preferably a compound represented by formula (DM1d12).
[0153]
[0154] In the formula, I, R, R １ , Z is defined as in formula (DM1a). A′ is a group having a protecting group, —O—R ａ -O-R ｂ , -O-CO-ORｂ , or -O-R ａ -CO-O-R ｂ In, or, -O-R ａ -O-CO-R ｂ It is expressed as: R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear or branched alkyl group 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. ａ and R ｂ A' may form a cyclic structure containing the following:
[0155] The compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c2).
[0156]
[0157] In the formula, I, R, R １ , A, and Z are defined the same as in formula (DM1a).
[0158] The compound represented by formula (DM1c2) is preferably a compound represented by formula (DM1d21) below.
[0159]
[0160] In the formula, I, R, R １ , A, and Z are defined the same as in formula (DM1a).
[0161] The compound represented by formula (DM1c1) is preferably a compound represented by formula (DM1d22).
[0162]
[0163] In the formula, I, R, R １ , Z is defined the same as in formula (DM1a), A' is defined the same as in formula (DM1d12).
[0164] The compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c3).
[0165]
[0166] In the formula, I, R, R １ , A, and Z are defined the same as in formula (DM1a).
[0167] The compound represented by formula (DM1c3) is preferably a compound represented by formula (DM1d31).
[0168]
[0169] In the formula, I, R, R １ , A, and Z are defined the same as in formula (DM1a).
[0170] The compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c4).
[0171]
[0172] In the formula, I, R, R １ , A, and Z are defined the same as in formula (DM1a).
[0173] The compound represented by formula (DM1c4) is preferably a compound represented by formula (DM1d41).
[0174]
[0175] In the formula, I, R, R １ , A, and Z are defined the same as in formula (DM1a). A' is defined the same as in formula (DM1d12).
[0176] The compound of formula (DM1a) is preferably a compound represented by formula (DM1e).
[0177]
[0178] In the formula, I, R, A, and Z are defined as in formula (DM1a), and R １’ , r1', r2', and r4' are defined the same as in formula (Bz4).
[0179] The compound of formula (DM1e) is preferably a compound represented by formula (DM1e1).
[0180]
[0181] The compound of formula (DM1e1) is preferably a compound represented by formula (DM1e2).
[0182]
[0183] An example of a dimer compound is shown below: １ and A is defined the same as in formula (Bz). This compound corresponds to the compound of formula (1b) in which Z is a linking group for forming a dimer.
[0184]
[0185] Specific dimer compounds are shown below.
[0186]
[0187] [N Series] In another preferred embodiment, the compound of formula (DM0-1) is represented by formula (Dn1).
[0188]
[0189] Each substituent and the like are defined the same as in formula (N). nd is an integer of 1 to 4, and preferably an integer of 1 or 2. Q is a single bond, and nd is preferably 1.
[0190] The compound represented by formula (Dn1) is preferably a compound represented by formula (Dn1a).
[0191]
[0192] In formula (Dn1a), I, R １ , R", A, and nd are defined the same as in formula (Dn1). x and y each represent 0 or 1, and at least one of x and y represents 1. s4' represents the number of R"s bonded to the 1-, 7-, and 8-positions of naphthalene.
[0193] The compound represented by formula (Dn1a) is preferably a compound represented by formula (Dn1b1).
[0194]
[0195] In formula (Dn1b1), I, R １, R", A, and nd are defined as in formula (Dn1), x and y are each 0 or 1, and at least one of x and y is 1. s4' is defined as in formula (Dn1a).
[0196] The compound represented by formula (Dn1b1) is preferably a compound represented by formula (Dn1c11).
[0197]
[0198] In formula (Dn1c11), I, R １ , R″, A, and nd are defined the same as in formula (Dn1), x and y are each 0 or 1, and at least one of x and y is 1. nd is preferably 2.
[0199] The compound represented by formula (Dn1b1) is preferably a compound represented by formula (Dn1c12).
[0200]
[0201] In formula (Dn1c12), I, R １ , R″, and nd are defined the same as in formula (Dn1). A′ is a group having a protecting group, and is —O—R ａ -O-R ｂ , -O-CO-OR ｂ , or -O-R ａ -CO-O-R ｂ Preferably, nd is 2.
[0202] The compound represented by formula (Dn1a) is preferably a compound represented by formula (Dn1b2).
[0203]
[0204] In formula (Dn1b2), I, R １ , R″, A, and nd are defined the same as in formula (Dn1), x is 0 or 1, and at least one x is 1. s4′ is defined the same as in formula (Dn1a).
[0205] The compound represented by formula (Dn1b2) is preferably a compound represented by formula (Dn1c21).
[0206]
[0207] In formula (Dn1c21), I, R １ , R″, A, and nd are defined the same as in formula (Dn1), and Z is defined the same as in formula (DM1a). A′ is a group having a protecting group, and is —O—R ａ -O-R ｂ , -O-CO-OR ｂ , or -O-R ａ -CO-O-R ｂ where R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom. nd is preferably 2.
[0208] The compound represented by formula (Dn1a) is preferably a compound represented by formula (Dn1b3).
[0209]
[0210] In formula (Dn1b3), I, R １ , R″, A, and nd are defined the same as in formula (Dn1), each y is 0 or 1, and at least one of x and y is 1. nd is preferably 2.
[0211] The compound represented by formula (Dn1b3) is preferably a compound represented by formula (Dn1c31).
[0212]
[0213] In formula (Dn1c31), I, R １ , R″, and nd are defined the same as in formula (Dn1), and Z is defined the same as in formula (DM1a). A′ is a group having a protecting group, and is —O—R ａ -O-R ｂ , -O-CO-OR ｂ , or -O-R ａ -CO-O-R ｂ where R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms.ｂ is a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom. nd is preferably 2.
[0214] The compound represented by formula (Dn1b3) is preferably a compound represented by formula (Dn1c32).
[0215]
[0216] In formula (Dn1c32), I, R １ , R″, and nd are defined the same as in formula (Dn1), and Z is defined the same as in formula (DM1a). A′ is a group having a protecting group, and is —O—R ａ -O-R ｂ , -O-CO-OR ｂ , or -O-R ａ -CO-O-R ｂ where R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom. nd is preferably 2. Non-limiting specific examples of formula (Dn1) are shown below.
[0217]
[0218] [Ad Series] In yet another preferred embodiment, the compound of formula (DM0-1) is represented by formula (Da1): The compound of formula (Da1) is more preferably represented by formula (Da2).
[0219]
[0220] Each substituent is defined the same as in formula (Ad).
[0221] The compound represented by formula (Da1) is preferably a compound represented by formula (Da1a).
[0222]
[0223] In formula (Da1a), I, R, R１ , R”, R ｄ is defined the same as in formula (Da1).
[0224] The compound represented by formula (Da1a) is preferably a compound represented by formula (Da1b).
[0225]
[0226] In formula (Da1b), I, R, R １ , R”, R ｄ is defined the same as in formula (Da1a).
[0227] In yet another preferred embodiment, the compound of formula (DM0-1) is represented by formula (Da1c11).
[0228]
[0229] In formula (Da1c11), I, R", R １ is defined the same as in formula (Da1a), and ba is an integer of 2 to 5.
[0230] The compound represented by formula (Da1b) is preferably a compound represented by formula (Da1c12).
[0231]
[0232] In formula (Da1c12), I, R, R'', R １ is the same as defined in formula (Da1a).
[0233] 1-4. Production Method The compound can be produced by any method as long as its effects are not impaired. However, if an iodine atom or an R group is added to the compound containing the R group, １ For example, the step of introducing an iodine atom into a compound having an aromatic ring may be carried out by reacting the compound having an aromatic ring with iodine I. ２This can be carried out by reacting the compounds under acidic or alkaline conditions. This reaction can produce compounds and dimers with different numbers of iodine atoms. The production ratios of these compounds can be adjusted by the reaction conditions. In particular, lowering the reaction temperature or shortening the reaction time tends to increase the number of compounds with fewer iodine atoms and decrease the number of dimers. Increasing the reaction temperature or lengthening the reaction time tends to decrease the number of compounds with fewer iodine atoms and increase the number of dimers. Furthermore, the step of introducing iodine atoms into a compound having an alicyclic ring can be carried out by reacting the compound having an alicyclic ring with HI (hydrogen iodide). A preferred method for producing the compound comprises reacting RG with a functional group capable of substituting an iodine atom by a substitution reaction, and, if necessary, R １ Another method for producing the compound may include an iodination step of introducing iodine atoms into a raw material containing RG and, if necessary, R １ The method may include an iodination step of introducing iodine into a raw material containing the above in the form of a radical or as a cation or anion.
[0234] [Iodination Step] The iodination step can be appropriately selected from a method of introducing a halogen from an amino group by the Sandmeyer reaction or the like, a method of reacting with iodine chloride in an organic solvent (e.g., JP 2012-180326 A, JP 2000-256231 A, JP 2010-159233 A, J. Chem. Soc. 636, 1943), a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of β-cyclodextrin under alkaline conditions (JP 63-101342 A, JP 2003-64012 A), and the like.
[0235] The iodinating agent is not particularly limited, and examples thereof include iodine chloride, iodine, N-iodosuccinimide, iodic acid, hydrogen iodide (including hydroiodic acid and aqueous hydrogen iodide solutions), etc. In the iodination step, the ratio of the iodinating agent to the substrate is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and even more preferably 2.0 molar times or more.
[0236] The iodination introduction reaction can be carried out by reacting at least an iodinating agent with a substrate. For example, the target compound can be obtained under known iodination reaction conditions using methods described in non-patent documents such as Adv. Synth. Catal. 2007, 349, 1159-1172, Organic Letters; Vol. 6; (2004); pp. 2785-2788, "Organic Synthesis of Bromine and Iodine Compounds: Reagents and Synthesis Methods" (edited by Suzuki Hitomi, published by Manac Corporation Research Institute, Maruzen Publishing), and patent documents such as US Pat. No. 5,300,506, US Pat. No. 5,434,154, US Pat. No. 2009 / 281114, EP1,439,164, and WO2006 / 101318. Examples of iodinating agents that can be used include, but are not limited to, iodine compounds, iodide monochloride, N-iodosuccinimide, benzyltrimethylammonium dichloroiodate, tetraethylammonium iodide, tetra-normal-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodine fluoride, tert-butylhypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetylhypoiodide, iodine-iodic acid, iodine-periodic acid, iodine-hydrogen peroxide, 1-iodoheptafluoropropane, triphenylphosphate-methyl iodide, iodine-thallium(I) acetate, 1-chloro-2-iodoethane, iodine-copper(II) acetate, and the like.
[0237] One or more additives can be added to the iodination reaction for the purpose of promoting the reaction or suppressing by-products. Examples of additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, copper chloride, antimony pentachloride, silver sulfate, silver nitrate, and silver trifluoroacetate; bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, and potassium bicarbonate; oxidizing agents such as cerium (IV) ammonium nitrate and sodium peroxodisulfate; inorganic compounds such as sodium chloride, potassium chloride, mercury (II) oxide, and cerium oxide; organic compounds such as acetic anhydride; and porous substances such as zeolites. In the iodination step, the ratio of the additive to the iodinating agent is preferably 1.0 molar amount, more preferably 1.2 molar amounts or more, even more preferably 1.5 molar amounts or more, and even more preferably 2.0 molar amounts or more.
[0238] In the iodination step, iodine is preferably introduced into the mother nucleus using at least an iodine source and an oxidizing agent. Using an iodine source and an oxidizing agent is preferred from the viewpoints of reaction efficiency and improved purity. Examples of the iodination source include the iodinating agents described above. Examples of the oxidizing agent 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 having a carboxylic acid group or a nitro group, the iodination reaction can also be carried out using an iodine cation species formed by combining an iodine source such as iodine with a silver salt or fuming sulfuric acid. Furthermore, for other relatively inert aromatic compounds, the iodination reaction can be carried out by combining an iodine source with an inorganic salt to form hypoiodous acid and an iodine cation species. An example of an inorganic salt that can be used as appropriate is potassium peroxodisulfate. A method of introducing iodine into an aliphatic alcohol group by a substitution reaction can also be used as appropriate. Examples of iodinating agents that can be used include hydrogen halides, phosphorus halides, sulfonyl halides (a combination of NaI / acetone), thionyl halides, trimethylsilane halides, Vilsmeier reagents, and the Abbel reaction (a combination of triphenylphosphine and an iodine source).
[0239] The reaction in the iodination step can be carried out neat without a solvent, but examples of usable reaction solvents include halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; alkyl-based solvents such as hexane, cyclohexane, heptane, pentane, and octane; aromatic hydrocarbon-based solvents such as benzene and toluene; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; ether-based solvents such as diethyl ether, diisopropyl ether, and tetrahydrofuran; acetic acid, dimethylformamide, dimethyl sulfoxide, and water.
[0240] The reaction temperature of the iodination step is not particularly limited and may be any temperature between the freezing point and the boiling point of the solvent used in the reaction, but is preferably 0°C to 150°C, more preferably 20°C to 150°C, and even more preferably 50°C to 120°C. The reaction time of the iodination step is also not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours. The reaction system may be refluxed to more efficiently proceed with iodination. Furthermore, in order to control the concentration of the iodinating agent in the reaction system, a reflux tube equipped with a Dean-Stark or the like may be used to control the concentration of the iodinating agent in the reaction solution.
[0241] The iodine substitution reaction in the iodination step can proceed by reacting at least an iodinating agent with a substrate. For example, the target compound can be obtained under known iodine substitution reaction conditions such as a Sandmeyer reaction using the method described in Chemistry - A European Journal, 24(55), 14622-14626; 2018, Synthesis (2007)(1), 81-84, etc.
[0242] [Protective Group Introduction Step] In the preferred method for producing the compound, the protective group represented by A' can be introduced into RG by a known method, for example, a method appropriately selected from those described in Green's Protective Groups in Organic Synthesis (Peter G.M. Wuts, Wiley), pp. 17 to 553.
[0243] In the protecting group introduction step, the ratio of the protecting group introduction agent to the substrate is not particularly limited, but is preferably 0.5 molar equivalents or more, more preferably 1.0 molar equivalents or more, and even more preferably 1.5 molar equivalents or more. The reaction temperature in the protecting group introduction step is not particularly limited, but 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, a temperature of 25°C to 150°C is more preferred, and a temperature of 50°C to 100°C is even more preferred. In the reaction of this embodiment, the preferred temperature range is 0°C to 100°C. The reaction time in the protecting group introduction step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.
[0244] [Reduction Step] In the compound of the formula (1), R １ is a hydroxyalkyl group or an aldehyde group, for example, R １ The compound can be obtained by introducing a carboxyl group, an ester group, or an aldehyde group into the compound and then reducing the resulting compound.
[0245] Known methods can be used for the reduction, including, for example, methods using metal hydride complexes such as sodium borohydride, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride (SBMEA), and diisobutylaluminum hydride (DIBAL); methods using metal hydrides such as aluminum hydride; and methods using these reducing agents together with reduction promoters such as aluminum chloride and ethanedithiol. The reducing ability of the reducing agent may be adjusted by modifying a portion of its structure with an alkoxy group or a hydrocarbon group, or by using it in combination with a Lewis acid. Known solvents such as methanol, ethanol, 2-propanol, DMF, and DMSO can be used as the solvent for the reduction reaction. The reaction temperature can be performed at room temperature or under heated conditions, or may be cooled to adjust the reactivity. The reaction temperature is not particularly limited, but is preferably −20°C to 150°C, more preferably 0°C to 150°C, and even more preferably 20°C to 120°C. The ratio of the reducing agent to the substrate in the reduction step is not particularly limited, but is preferably 0.5 molar equivalent or more, more preferably 1.0 molar equivalent or more, and even more preferably 1.5 molar equivalent or more. The reaction time in the reduction step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.
[0246] The compound of this embodiment is preferably obtained as a crude product by the reaction, and then further purified to remove any remaining metal impurities. In other words, it is preferable to avoid residual metal impurities from the viewpoints of preventing deterioration of the resin over time and preservation stability, as well as from the viewpoints of process suitability and production yield due to defects when the resin is applied to a semiconductor manufacturing process. Metal impurities may originate from reaction aids in the compound manufacturing process, or from the reaction vessel or other manufacturing equipment used in the manufacturing process.
[0247] The residual amount of the above-mentioned metal impurities is preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb, relative to the compound. In particular, for metal species 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 interaction with other compounds may cause denaturation or deterioration of the material over time. Furthermore, for alkali metals and alkalinity metals, such as Na, K, Ca, and Mg, contained in the resin, if the residual metal amount is 1 ppm or more, the residual metal amount cannot be sufficiently reduced when using the compound to produce a resin for semiconductor processing, which may cause defects and performance degradation due to residual metals in the semiconductor manufacturing process, resulting in a decrease in yield, and there is a concern that the doping effect of metal elements on the substrate may cause a decrease in characteristics.
[0248] The purification method is not particularly limited, but the method described in International Publication No. 2015 / 080240 or International Publication No. 2018 / 159707 can be used. Specifically, this purification method includes dissolving the 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 an extraction process, thereby transferring metal components contained in the organic phase containing the compound and the organic solvent to the aqueous phase, and then separating the organic phase from the aqueous phase. The organic solvent that is immiscible with water is typically an organic solvent classified as a non-aqueous 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.
[0249] Specific examples of the organic solvent to be used include those described in International Publication No. 2015 / 080240. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, etc. are preferred, with cyclohexanone and propylene glycol monomethyl ether acetate being particularly preferred.
[0250] The acidic aqueous solution can be appropriately selected from aqueous solutions prepared by dissolving commonly known organic or inorganic compounds in water. Examples include those described in International Publication No. 2015 / 080240. These acidic aqueous solutions can be used alone or in combination of two or more. Examples of the acidic aqueous solution include mineral acid aqueous solutions and organic acid aqueous solutions. Examples of the mineral acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of the organic acid aqueous solution include an aqueous solution 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, and more preferably approximately 0 to 3.
[0251] Other production methods that can be used appropriately include a method using a filter as described below, a method using an adsorptive ion exchange resin, passing a liquid through a column, a method of dispersing and suspending an ion exchange resin in a container, and a method using distillation.
[0252] In the method for producing the compound represented by formula (1), the order and number of the iodination step, the protecting group introduction step, and the reduction step are not particularly limited and can be appropriately selected depending on the structure of the target compound.
[0253] 1-5. Purification Method [Filter Purification Step (Liquid Passage Step)] In the filter passage step, a commercially available filter for liquid filtration can be used as the filter used to remove metals from a solution containing the compound and a solvent. The filtration accuracy of the filter is not particularly limited, but the nominal pore size of the filter is preferably 0.2 μm or less, more preferably less than 0.2 μm, even more preferably less than 0.1 μm, even more preferably less than 0.1 μm, and even more preferably 0.05 μm or less. The lower limit of the nominal pore size of the filter is not particularly limited, but is typically 0.005 μm. The nominal pore size here refers to the nominal pore size that indicates the separation performance of the filter, and is determined by a test method specified by the filter manufacturer, such as a bubble point test, a mercury intrusion porosimetry test, or a standard particle capture test. When a commercially available product is used, the value is that listed in the manufacturer's catalog data. By setting the nominal pore size to 0.2 μm or less, the metal content after a solution has been passed through the filter once can be effectively reduced. In the second embodiment, the filter passing step may be carried out two or more times in order to further reduce the content of each metal component in the solution.
[0254] As the form of the filter, hollow fiber membrane filter, membrane filter, pleated membrane filter, and filter filled with filter material such as nonwoven fabric, cellulose, and diatomaceous earth can be used. Among the above, it is preferable that the filter is one or more selected from the group consisting of hollow fiber membrane filter, membrane filter, and pleated membrane filter. In addition, it is particularly preferable to use hollow fiber membrane filter because of its particularly high filtration accuracy and high filtration area compared to other forms.
[0255] The filter material can be exemplified by polyolefins such as polyethylene and polypropylene, polyethylene-based resins with functional groups having ion exchange capacity by graft polymerization, polar group-containing resins such as polyamide, polyester, and polyacrylonitrile, and fluorine-containing resins such as fluorinated polyethylene (PTFE).Among the above, it is preferable that the filter material of the filter is one or more selected from the group consisting of polyamide, polyolefin resin, and fluororesin.In addition, polyamide is particularly preferable from the viewpoint of reducing heavy metals such as chromium.In addition, it is preferable to use a filter material other than sintered metal material from the viewpoint of preventing metal elution from the filter material.
[0256] Examples of polyamide filters (hereinafter referred to as trademarks) include, but are not limited to, the Polyfix Nylon series manufactured by Kitz Microfilter Co., Ltd., Ultipleat P-Nylon 66 and Ultipore N66 manufactured by Nippon Pall Co., Ltd., and the LifeAsure PSN series and LifeAsure EF series manufactured by 3M Limited. Examples of polyolefin filters include, but are not limited to, Ultipleat PE Clean and Ion Clean manufactured by Nippon Pall Co., Ltd., and the Protego series, Microguard Plus HC10, and Optimizer D manufactured by Nippon Entegris Co., Ltd. Examples of polyester filters include, but are not limited to, Gelaflow DFE manufactured by Central Filter Kogyo Co., Ltd., and Bleats Type PMC manufactured by Nippon Filter Co., Ltd. Examples of polyacrylonitrile filters include, but are not limited to, Ultrafilter AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantec Toyo Co., Ltd. Examples of fluororesin filters include, but are not limited to, Enflon HTPFR manufactured by Nippon Pall Co., Ltd. and the Lifesure FA series manufactured by 3M Ltd. These filters may be used alone or in combination of two or more types.
[0257] The filter may also contain an ion exchanger such as a cation exchange resin, or a cationic charge regulator that generates a zeta potential in the organic solvent solution being filtered. Examples of filters containing an ion exchanger include, but are not limited to, the Protego series manufactured by Nippon Entegris Co., Ltd. and Clangraft manufactured by Kurashiki Seni Kako Co., Ltd. Examples of filters containing a substance with a positive zeta potential, such as a polyamide polyamine epichlorohydrin cationic resin, include, but are not limited to, Zeta Plus 40QSH (registered trademark), Zeta Plus 020GN (registered trademark), and the LifeAsure EF (registered trademark) series manufactured by 3M Limited.
[0258] [Treatment step with ion exchange resin] Another purification method is to treat a solution containing the compound with an ion exchange resin. As the ion exchange resin, a known ion exchange resin having a function corresponding to the target metal element can be used as appropriate. Purification using an ion exchange resin is a step in which the material to be purified containing the compound is subjected to ion exchange or ion adsorption by a chelating group. Components removed by the treatment step with an ion exchange resin include, but are not limited to, acid components and metal ions contained in the metal components.
[0259] The method for carrying out the ion exchange method is not particularly limited, and known methods can be used. A typical example is a method in which a solution containing the compound is passed through a packing filled with an ion exchange resin. Another example is a method in which an ion exchange resin is added to a solution containing the compound in a treatment vessel, followed by dispersion and suspension treatment, and then the ion exchange resin is separated and removed by a method such as filtration to obtain a purified solution. In the treatment step with an ion exchange resin, the product to be purified may be treated with the same ion exchange resin multiple times, or the product may be treated with different ion exchange resins.
[0260] Examples of ion exchange resins include cation exchange resins and anion exchange resins, and it is preferable to use at least a cation exchange resin because it is easy to adjust the content of the metal component and thereby make the mass ratio of the content of the acid component to the content of the metal component fall within the above range, and it is more preferable to use an anion exchange resin together with a cation exchange resin because it is possible to adjust the content of the acid component. When both a cation exchange resin and an anion exchange resin are used, the liquid may be passed through a packed section filled with a mixed resin containing both resins, or may be passed through multiple packed sections filled with each resin.
[0261] As the cation exchange resin, known cation exchange resins can be used, among which gel-type cation exchange resins are preferred, specifically sulfonic acid-type cation exchange resins and carboxylic acid-type cation exchange resins. As the cation exchange resin, commercially available products can be used, such as Amberlite IR-124, Amberlite IR-120B, Amberlite IR-200CT, ORLITE DS-1, ORLITE DS-4 (all manufactured by Organo Corporation), Duolite C20J, Duolite C20LF, Duolite C255LFH, Duolite C-433LF (all manufactured by Sumika Chemtex Co., Ltd.), DIAION SK-110, DIAION SK1B, and DIAION SK1BH (all manufactured by Mitsubishi Chemical Corporation), Purolite S957, and Purolite S985 (all manufactured by Purolite Co., Ltd.), and the like.
[0262] As the anion exchange resin, known anion exchange resins can be used, and among them, it is preferable to use a gel-type anion exchange resin. Here, examples of acid components present as ions in the product to be purified include inorganic acids derived from catalysts used in the production of the product to be purified, and organic acids (e.g., reaction raw materials, isomers, and by-products) generated after the reaction in the production of the product to be purified. Such acid components are classified as hard acids to medium-hard acids in terms of the HSAB (Hard and Soft Acids and Bases) rule. Therefore, it is preferable to use an anion exchange resin containing a hard base to a medium-hard base in order to increase the removal efficiency of these acid components through interaction with the anion exchange resin. The anion exchange resin containing such a hard base to a moderately hard base is preferably at least one anion exchange resin selected from the group consisting of a strong base type I anion exchange resin having a trimethylammonium group, a slightly weakly strong base type II anion exchange resin having a dimethylethanolammonium group, and a weak base type anion exchange resin such as dimethylamine or diethylenetriamine. Among acid components, for example, organic acids are hard acids, and among inorganic acids, sulfate ions are moderately hard acids. Therefore, by using the above-mentioned strong base type or slightly weakly strong base type anion exchange resin in combination with a weak base type anion exchange resin of moderate hardness, it becomes easy to reduce the content of acid components to a suitable range.
[0263] As the anion exchange resin, commercially available products can be used, and examples thereof include Amberlite IRA-400J, Amberlite IRA-410J, Amberlite IRA-900J, Amberlite IRA67, ORLITE DS-2, ORLITE DS-5, and ORLITE DS-6 (manufactured by Organo Corporation), Duolite A113LF, Duolite A116, and Duolite A-375LF (manufactured by Sumika Chemtex), and DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, and DIAION WA10 (manufactured by Mitsubishi Chemical Corporation). Among these, examples of anion exchange resins containing the above-mentioned hard base to medium hardness base include ORLITE DS-6 and ORLITE DS-4 (all manufactured by Organo Corporation), DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, and DIAION WA10 (all manufactured by Mitsubishi Chemical Corporation), Purolite A400, Purolite A500, and Purolite A850 (all manufactured by Purolite Co., Ltd.), and the like.
[0264] Ion adsorption by chelating groups can be performed, for example, using a chelating resin having a chelating group. Chelate resins do not release substitute ions when capturing ions, and by not using chemically highly active functional groups such as strong acidity or strong basicity, they can suppress side reactions, such as hydrolysis and condensation reactions, in the organic solvent being purified. This allows for more efficient purification. Examples of chelating resins include resins having chelating groups or chelating ability, such as amidoxime groups, thiourea groups, thiouronium groups, iminodiacetic acid, amide phosphoric acid, phosphonic acid, amino phosphoric acid, aminocarboxylic acid, N-methylglucamine, alkylamino groups, pyridine rings, cyclic cyanines, phthalocyanine rings, and cyclic ethers. As the chelating resin, commercially available products can be used, such as Duolite ES371N, Duolite C467, Duolite C747UPS, Sumikelate MC760, Sumikelate MC230, Sumikelate MC300, Sumikelate MC850, Sumikelate MC640, and Sumikelate MC900 (all manufactured by Sumika Chemtex Co., Ltd.), Purolite S106, Purolite S910, Purolite S914, Purolite S920, Purolite S930, Purolite S950, Purolite S957, and Purolite S985 (all manufactured by Purolite Co., Ltd.).
[0265] The method for ion adsorption is not particularly limited, and known methods can be used. A typical example is a method in which the material to be purified is passed through a packed section filled with a chelating resin. In the treatment step using an ion exchange resin, the material to be purified may be passed through the same chelating resin multiple times, or may be passed through different chelating resins.
[0266] The packed section usually includes a container and the above-mentioned ion exchange resin packed in the container. Examples of the container include a column, a cartridge, and a packed tower, but other containers than those exemplified above may also be used as long as they are capable of passing the product to be purified after being packed with the ion exchange resin.
[0267] [Distillation Step] Another purification method is to distill the compound itself. The distillation method is not particularly limited, and known methods such as atmospheric distillation, reduced pressure distillation, molecular distillation, and steam distillation can be used.
[0268] [Preferred Production Method] (Compound in which RG is benzene) A method for producing the compound of formula (Bz) will be specifically explained. The compound of formula (Bz) is preferably produced by using the compound represented by formula (MB) as a raw material. The substituents and r1, r2, etc. in the compound are defined as above. R １ , R, and OH are bonded to any available positions. However, r1 and r2 in formula (MB) are selected so that when formula (Bz) is obtained, the sum of r1 to r4 is equal to or less than the valence of benzene. Examples of compounds of formula (MB) include hydroxybenzaldehyde.
[0269]
[0270] The compound of formula (Bz) can be produced by various methods, but from the viewpoint of availability of raw materials and yield, it is preferably produced by a method including the following steps: a preparation step of preparing a compound of formula (MB), an iodination step of introducing an iodine atom into the compound, a protecting group introduction step of introducing a protecting group into the compound, and a reduction step of reducing the compound.
[0271] From the viewpoint of suppressing by-products, the preparation step, the iodination step, the protecting group introduction step, and the reduction step are preferably carried out in this order.
[0272] 1) Iodination Step Solvents that can be used in the iodination step include a wide variety of solvents, including polar aprotic solvents and protic polar solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used. Polar protic solvents or mixtures thereof are preferred, and a mixture of polar protic solvents and water is preferred from the viewpoint of suppressing side reactions. A solvent is effective but not required. Suitable polar aprotic solvents include, but are not limited to, ether-based solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester-based solvents such as ethyl acetate and γ-butyrolactone; nitrile-based solvents such as acetonitrile; hydrocarbon-based solvents such as toluene and hexane; amide-based solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; ketone-based solvents such as acetone and ethyl methyl ketone; chlorine-based solvents such as dichloromethane and chloroform; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, water, alcohol-based solvents such as methanol, ethanol, propanol, and butanol; di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.
[0273] The raw material compounds, catalyst, and solvent are added to a reactor to form a reaction mixture. Any suitable reactor can be used. The reaction can be carried out by a known method, such as batchwise, semi-batchwise, or continuous. The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the catalyst selected, 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, a reaction temperature of 0°C to 70°C is more preferred, and a reaction temperature of 0°C to 50°C is even more preferred. In the reaction of this embodiment, the preferred reaction temperature range is 0°C to 100°C. In the iodination step, the ratio of the iodinating agent to the substrate is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and even more preferably 1.5 molar times or more. The reaction pressure is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the catalyst selected, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen or by using a suction pump. For reactions at high pressure, conventional pressure reactors, including but not limited to shaker vessels, rocker vessels, and stirred autoclaves, can be used. In the reaction of this embodiment, the preferred reaction pressure is between reduced pressure and atmospheric pressure, with reduced pressure being preferred. The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the catalyst selection, and the desired yield. However, most reactions are carried out in less than 6 hours, with reaction times of 15 to 600 minutes being typical. In the reaction of this embodiment, the reaction time ranges from 15 to 600 minutes, preferably from 15 to 600 minutes, and more preferably from 15 to 360 minutes. Isolation and purification can be carried out after completion of the reaction using appropriate methods known in the art. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure.The desired high-purity compound can be isolated and purified by separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination of these methods.
[0274] When synthesizing a compound represented by the following formula (1), (Bz4), (Bz4-1), or (Bz4-2), from the viewpoint of improving productivity, it is preferable to perform the iodination step once or twice or more, and it is preferable to perform it twice. Furthermore, when the iodination step is performed once or more, the iodinating agent is not particularly limited, and examples thereof include iodine chloride, iodine, N-iodosuccinimide, iodic acid, and hydrogen iodide (including hydroiodic acid and aqueous hydrogen iodide solutions). It is preferable to use iodine or iodic acid. In the iodination step, the ratio of the iodinating agent to the substrate is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and even more preferably 2.0 molar times or more. Furthermore, in the second iodination step, it is preferable to use a method of introducing a halogen from an amino group by a Sandmeyer reaction or the like. (Wherein, RG is a group containing at least one cyclic structure, I is an iodine atom, and R １ are the same or different monovalent functional groups having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, n is an integer of 1 to 5, and m is an integer of 1 to 5. (In the formula, I, R, A, and Z are defined the same as in formula (Bz). R １’ are monovalent functional groups, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding hydroxyl groups; r1', r2', and r4' are integers of 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.
[0275] In formula (Bz4), I, R, A, and Z are defined as above, and R １’ R may be the same or different and are functional groups having 0 to 30 carbon atoms, not containing a polymerizable unsaturated bond, excluding a monovalent hydroxyl group, and are preferably not alkyl groups. １’is preferably, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxyl group having 1 to 30 carbon atoms, a carboxylic acid ester group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 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. １’ is preferably a carboxyl group, an ester group, or a hydroxyalkyl group from the viewpoint of sensitizing effect, etc. Among these groups, groups that can have a substituent may have a substituent other than a hydroxyl group. 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 of 0 to 5, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 3. However, the sum of r1', r2', and r4' is equal to or less than the valence of benzene. (Wherein I, R, Z and R １’ are defined the same as in formula (Bz4). r1', r2', and r4' are integers of 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene. (wherein I is defined the same as in formula (Bz4), r4' is an integer of 0 to 4, and r5' is an integer of 0 to 4.)
[0276] 2) Protecting Group Introduction Step A wide variety of solvents can be used in this step, including polar aprotic solvents and protic polar solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred. A solvent is effective but not essential. Suitable polar aprotic solvents include, but are not limited to, ether-based solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester-based solvents such as ethyl acetate and γ-butyrolactone; nitrile-based solvents such as acetonitrile; hydrocarbon-based solvents such as toluene and hexane; amide-based solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; ketone-based solvents such as acetone and ethyl methyl ketone; chlorine-based solvents such as dichloromethane and chloroform; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, water, alcohol-based solvents such as methanol, ethanol, propanol, and butanol; di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited, but is generally 0 to 10,000 parts by mass relative to 100 parts by mass of the reaction raw materials, and from the viewpoint of yield, 100 to 2,000 parts by mass is preferable. As the protecting agent, a wide variety of protecting agents that function under the reaction conditions of this embodiment can be used.Examples of suitable protecting agent include, but are not limited to, activated carboxylic acid derivative compounds such as acid halides, acid anhydrides, dicarbonates, alkyl halides, vinyl alkyl ethers, dihydropyrans, and alkyl halocarboxylic acid esters. The ratio of the protecting agent to the substrate in the protecting group introduction step is not particularly limited, but is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and even more preferably 1.5 molar times or more. A wide variety of protecting catalysts that function under the reaction conditions of this embodiment can be used as catalysts in the protecting step. Acid catalysts or base catalysts are preferred. Examples of suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid. These acid catalysts may be used alone or in combination of two or more. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of production, such as ease of availability and handling. Examples of suitable base catalysts include, but are not limited to, amine-containing catalysts such as pyridine, diisopropylethylamine, and ethylenediamine, and non-amine base catalysts such as inorganic bases, preferably metal salts, particularly potassium salts or acetate salts, and suitable catalysts include, but are not limited to, potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide. All of the non-amine base catalysts of this embodiment are commercially available, for example, from EM Science (Gibbstown) or Aldrich (Milwaukee).The amount of catalyst used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 1 to 5,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 50 to 3,000 parts by mass is preferable.
[0277] When a protecting group is introduced into a hydroxy group of a compound having a hydroxy group in the protecting group introduction step, from the viewpoint of improving yield and scaling up, it is preferable to introduce the protecting group into the hydroxy group using an inorganic base, and it is more preferable to combine an amide solvent with an inorganic base. Examples of inorganic bases include, but are not limited to, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, potassium metasilicate, etc., and among these, sodium carbonate and potassium carbonate are preferred. Examples of amide solvents include, but are not limited to, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), etc., and among these, DMF is preferred. These solvents may be used alone or in combination of two or more. Although not intended to be particularly limiting, the present inventors speculate that HCl, which is by-produced in the protecting group introduction step, contributes to the decomposition reaction of the product, and that by using an inorganic base, the reaction between the inorganic base and HCl suppresses the decomposition of the product. Furthermore, it is presumed that by combining an inorganic base with an amide solvent, the component produced by the reaction of the inorganic base with HCl is insoluble in the amide solvent and is released from the reaction system, thereby suppressing decomposition of the product. １ is a hydroxy group. １ is a hydroxy group, R １ A protecting group may be introduced into the
[0278] The protecting compound, catalyst, and solvent are added to a reactor to form a reaction mixture. Any suitable reactor can be used. The reaction can be carried out by any known method, such as batch, semi-batch, or continuous. The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the catalyst selected, and the desired yield. Generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 10°C to 190°C is preferred, a temperature of 25°C to 150°C is more preferred, and a temperature of 50°C to 100°C is even more preferred. In the reaction of this embodiment, 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 substrate, the stability of the formed product, the catalyst selected, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen or using a suction pump. For reactions at high pressure, conventional pressure reactors, including but not limited to, shaker vessels, rocker vessels, and stirred autoclaves, can be used. In the reaction of this embodiment, the preferred reaction pressure is reduced to atmospheric pressure, with reduced pressure being preferred. The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the catalyst selection, and the desired yield. However, most reactions are carried out in less than 6 hours, with reaction times of 15 to 600 minutes being typical. In the reaction of this embodiment, the preferred reaction time range is 15 to 600 minutes. Isolation and purification can be carried out after completion of the reaction using an appropriate method known in the art. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity monomer can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, or a combination thereof.
[0279] 3) Reduction Step A wide variety of solvents can be used in the reduction step, including polar aprotic solvents and protic polar solvents. A single protic polar solvent or a single polar aprotic solvent can be used. Furthermore, a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used. Polar aprotic solvents or mixtures thereof are preferred, and from the viewpoint of suppressing side reactions, a mixture of polar aprotic solvents and polar protic solvents is preferred. As polar protic solvents, water, alcoholic solvents such as methanol, ethanol, propanol, and butanol are more preferred. A solvent is effective but not essential. Suitable polar aprotic solvents include, but are not limited to, ether-based solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester-based solvents such as ethyl acetate and γ-butyrolactone; nitrile-based solvents such as acetonitrile; hydrocarbon-based solvents such as toluene and hexane; amide-based solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; ketone-based solvents such as acetone and ethyl methyl ketone; chlorine-based solvents such as dichloromethane and chloroform; and dimethyl sulfoxide. Dimethyl sulfoxide is preferred. Suitable protic polar solvents include, but are not limited to, water, alcohol-based solvents such as methanol, ethanol, propanol, and butanol; di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol. The amount of solvent used can be appropriately set depending on the substrate, reducing agent, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.
[0280] A wide variety of reducing agents that function under the reaction conditions of this embodiment can be used as the reducing agent. Suitable reducing agents include, but are not limited to, metal hydrides, metal hydrogen complex compounds, etc., such as borane dimethyl sulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-s-butylborohydride, potassium tri-s-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-t-butoxyaluminum hydride, and sodium bis(methoxyethoxy)aluminum hydride.
[0281] The amount of the reducing agent used can be appropriately set depending on the substrate and reducing agent used, the reaction conditions, and the like, and is not particularly limited. Generally, however, an amount of 1 to 500 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 10 to 200 parts by mass is preferable.
[0282] As the quenching agent, a wide variety of quenching agents that function under the reaction conditions of this embodiment can be used. The quenching agent has the function of deactivating the reducing agent. The quenching agent is effective but not an essential component. Suitable quenching agents include, but are not limited to, ethanol, aqueous ammonium chloride, water, hydrochloric acid, sulfuric acid, and the like. The amount of the quenching agent used can be appropriately set depending on the amount of the reducing agent used and is not particularly limited, but generally, 1 to 500 parts by mass per 100 parts by mass of the reducing agent is suitable, and from the viewpoint of yield, 50 to 200 parts by mass is preferable.
[0283] The compound to be reduced, the reducing agent, and the solvent are added to a reactor to form a reaction mixture. Any suitable reactor can be used. The reaction can be carried out by any known method, such as batch, semi-batch, or continuous. The reaction temperature is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the selection 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, a temperature of 0°C to 70°C is more preferred, and a temperature of 0°C to 50°C is even more preferred. 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 substrate, the stability of the formed product, the selection of the reducing agent, and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen or by using a suction pump. For reactions at high pressure, conventional pressure reactors, including but not limited to, shaker vessels, rocker vessels, and stirred autoclaves, can be used. In the reaction of this embodiment, the preferred reaction pressure is reduced to atmospheric pressure, with reduced pressure being preferred. The reaction time is not particularly limited. The preferred range varies depending on the concentration of the substrate, the stability of the formed product, the selection of the reducing agent, and the desired yield. However, most reactions are carried out in less than 6 hours, with reaction times of 15 to 600 minutes being typical. In the reaction of this embodiment, the reaction time range is preferably 15 to 600 minutes, more preferably 15 to 360 minutes. Isolation and purification can be carried out after completion of the reaction using an appropriate method known in the art. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation under reduced pressure. The desired high-purity compound can be isolated and purified using separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination thereof.
[0284] In formula (Bz), R １When R is a carboxylic acid, the reduction step preferably includes a step of esterifying the carboxylic acid and a step of reducing the resulting ester group to convert it into a hydroxymethyl group, from the viewpoint of improving productivity. For example, when an alkyl ester group is obtained in the step of esterifying the carboxylic acid, the ester group has a structure consisting of a carbonyl group derived from the carboxylic acid and an alkoxy group derived from an alcohol. In the esterification step, it is preferable to use an esterifying agent from the viewpoint of productivity. A carboxylic acid halide or a carboxylic acid anhydride can also be used as the carboxylic acid. Furthermore, in the formula (Bz), when R １ As the compound in which is a carboxylic acid, a compound represented by the following formula (Bz5) is preferred. Also preferred is a carboxylic acid connected to an electrically attractive group, and examples thereof include a compound represented by the following formula (Bz5), which is an aromatic carboxylic acid having an iodine atom as a substituent. (In the formula, I, Z, R １ , A, R, r1 to r4 are defined the same as in formula (DM1a).
[0285] Specific examples of the compound represented by the following formula (Bz5) are as follows.
[0286] The esterification agent used in the esterification step is not particularly limited, but examples thereof include acid catalysts, base catalysts, carbodiimide condensing agents, and phosgene derivative condensing agents, and it is preferable to use an acid catalyst, base catalyst, or carbodiimide condensing agent. The acid catalyst and base catalyst are not particularly limited, and the same as those described above can be used. The solvent is not particularly limited, but examples thereof include THF, DMSO, chloroform, toluene, and it is preferable to use THF.
[0287] The reducing agent used in the step of reducing the ester group to convert it to a hydroxy group is not particularly limited, but examples thereof include boron-based reducing agents and lithium-based reducing agents, and it is preferable to use a boron-based reducing agent such as sodium borohydride or borane, and it is more preferable to use the reducing agent in combination with calcium chloride or lithium chloride. The solvent is not particularly limited, but examples thereof include THF, DMSO, chloroform, toluene, etc., and it is preferable to use toluene, and it is more preferable to use it in combination with methanol. Furthermore, after the step of esterifying the carboxylic acid, a step of reducing the ester group to convert it to a hydroxy group may be carried out without purification.
[0288] (Compound where RG is naphthalene) A method for producing the compound of formula (N) will be specifically described. The compound of formula (N) is preferably produced by using the compound represented by formula (MN) as a raw material. In this formula, the substituents s3, s4, etc. are defined as above. However, s3 and s4 in formula (MN) are selected so that the sum of s1 to s4 is equal to or less than the valence of naphthalene when formula (N) is obtained. R １ is not limited to, but includes a hydroxyl group, an amino group, a nitro group, a halogen atom other than an iodine atom, an aldehyde group, etc. Specific examples of the compound of formula (MN) are not limited to, but include (di)hydroxynaphthaldehyde, aminosinaphthaldehyde, nitronaphthaldehyde, naphthaldehyde chloride, etc.
[0289]
[0290] The compound of formula (N) can be produced by various methods, but from the viewpoints of availability of raw materials and yield, it is preferably produced by a method comprising the following steps: a preparation step of preparing a compound of formula (MN), an iodination step of introducing an iodine atom into the compound, a protecting group introduction step of introducing a protecting group into the compound, and a reduction step of reducing the compound.
[0291] From the viewpoint of suppressing by-products, the steps are preferably carried out in the order of the preparation step, the iodination step, the protecting group introduction step, and the reduction step, or in the order of the preparation step, the protecting group introduction step, the iodination step, and the reduction step. The solvents and reaction conditions that can be used in each step can be the same as those described in the method for producing a compound in which RG is benzene.
[0292] (Compound where RG is adamantane) A method for producing the compound of formula (Ad) will be specifically described. In this method, it is preferable to use a compound represented by formula (MA) as a raw material. In formula (MA), １ , R″, t2, and t3 are defined the same as in formula (Ad). However, t2 and t3 in formula (MA) are selected so that when formula (Ad) is obtained, the sum of t1 to t3 is equal to or less than the valence of adamantane. The compound is not limited, but examples thereof include adamantanetriol.
[0293]
[0294] The compound of formula (Ad) can be produced by various methods, but from the viewpoint of availability of raw materials and yield, it is preferably produced by a method including the following steps: a preparation step of preparing a compound of formula (MA), and an iodination step of introducing an iodine atom.
[0295] In addition, as another embodiment of the method for producing a compound represented by formula (1), in order to improve productivity, it is preferable that the method comprises any one or more steps selected from: 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).
[0296] In addition, when the method includes a step of preparing a compound represented by formula (Ad-A-3-0), the method includes: 1) a step of preparing a compound represented by formula (Ad-A-3-0); 2) an oxidation step of oxidizing the compound represented by formula (Ad-A-3-0), 3) a step of esterifying the carboxylic acid of the obtained compound, 4) an iodination step of converting the ester group of the obtained compound into a carboxyl group by hydrolysis.
[0297] The oxidation step for oxidizing the compound represented by formula (Ad-A-3-0) is not particularly limited, but examples thereof include a method using an oxidizing agent, a method of hydrolyzing a bromide, and a method of oxygen oxidation using an imide compound. Examples of the oxidizing agent include, but are not limited to, air, oxygen, ozone, nitric acid, halogens (chlorine, bromine, iodine), potassium nitrate, hypochlorous acid, permanganate, cerium ammonium nitrate, chromic acid, peroxide, Tollens' reagent, and ruthenium compounds. It is desirable to use a ruthenium compound. Examples of the ruthenium compound include, but are not limited to, ruthenium metal, ruthenium dioxide, ruthenium tetroxide, ruthenium hydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium sulfate, and hydrates thereof. These compounds can be used alone or in combination. Among ruthenium compounds, ruthenium chloride, ruthenium dioxide, or hydrates thereof are particularly preferred, as they readily react with periodate or hypochlorite used as a co-oxidant to produce highly oxidized ruthenium having a highly active catalytic function. As the periodate, potassium periodate, sodium periodate, or calcium periodate is preferred, with sodium periodate being more preferred. One or more types of oxidizing agents or co-oxidizing agents can be used.
[0298] The step of esterifying the carboxylic acid of the obtained compound may be the same as the esterification step in formula (Bz).
[0299] The step of hydrolyzing the ester group of the obtained compound to convert it to a carboxyl group is not particularly limited, but preferably involves hydrolysis using an acid catalyst or a base catalyst to convert it to a carboxyl group, and from the viewpoint of selectivity of hydrolysis, it is preferable to use a base catalyst. The acid catalyst is not particularly limited, 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, iron chloride, and boron trifluoride; and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid. From the viewpoint of production, such as ease of availability and ease of handling, it is preferable to use hydrochloric acid or sulfuric acid. The base catalyst is not particularly limited, and examples thereof include organic base catalysts such as pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N,N-dimethylaniline, and N,N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate, with inorganic salt catalysts being preferred, and potassium hydroxide and sodium hydroxide being more preferred. Furthermore, one or more types of acid catalysts or base catalysts can be used.
[0300] The iodination step for iodinating the compound represented by formula (Ad-A-3-0) may be the same as the above-mentioned iodination step.
[0301] As another embodiment of the method for producing a compound represented by formula (1), it is preferable to further include the step of: 4) preparing a compound represented by formula (Ad-A-3) in order to improve productivity.
[0302]
[0303] In addition, when the method includes a step of preparing a compound represented by formula (Ad-A-3), the method includes: 1) a step of preparing a compound represented by formula (Ad-A-3); 2) a reduction step of reducing the compound represented by formula (Ad-A-3).
[0304] The reduction step of reducing the obtained compound may be the same as the reduction step described above.
[0305] The solvents that can be used in the iodination step include those mentioned in the method for producing a compound in which RG is benzene. In this step, a raw material compound, a catalyst, and a solvent are added to a reactor to form a reaction mixture. The reaction conditions can also be the same as those described in the method for producing a compound in which RG is benzene.
[0306] Furthermore, the iodination step preferably includes concentrating the reaction solution by distilling off water in the reaction to obtain an alkyl iodide using an aqueous hydrogen iodide solution and an adamantane alcohol as raw materials. The hydrogen iodide concentration of 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. When the reaction solution is separated into two or more phases, it is preferable that the hydrogen iodide concentration of the aqueous phase containing hydrogen iodide is within the above range.
[0307] The adamantane alcohol may have only one hydroxy group in the molecule, or two or more hydroxy groups. The hydroxy group to be iodized may be primary, secondary, or tertiary, but is preferably secondary or tertiary, and more preferably tertiary.
[0308] The adamantane alcohol is preferably represented by the following formula (MA-1): １ , R″ are defined the same as in formula (Ad), except that R １ is -OH, -NO ２ Preferably, the functional group is a monovalent group having 1 to 12 carbon atoms which may contain at least one functional group. The functional group may be a hydroxyl group, an ether group, an ester group, a carboxyl group, a halogen atom, or —NO ２and NLL', where L and L' are each independently a hydrogen atom, a hydroxyl group, or a monovalent group having 1 to 12 carbon atoms which may contain at least one functional group.
[0309]
[0310] The amount of hydrogen iodide is preferably 1.01 equivalents or more, more preferably 1.1 equivalents or more, even more preferably 1.3 equivalents or more, and particularly preferably 1.5 equivalents or more, relative to the hydroxy groups to be iodinated, in terms of the substance ratio.
[0311] When the compound of formula (MA-1) has two or more hydroxy groups in the molecule, all of the hydroxy groups may be iodinated, or one or more hydroxy groups may remain. A method for selectively leaving one or more hydroxy groups may include, for example, a step of performing iodination in a multiphase system containing an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent. Examples of organic solvents include hydrophobic solvents, and the hydrophobic solvent refers to a solvent that is immiscible with water in any proportion. When the aqueous phase is derived from an aqueous hydrogen halide solution, in a reaction system in which the aqueous hydrogen halide solution and the hydrophobic solvent undergo liquid-liquid two-phase separation into an aqueous phase and a hydrophobic solvent phase, iodination of the hydroxy groups proceeds in the aqueous phase. It is possible to obtain an alkyl iodide with one or more remaining hydroxy groups by extracting an alkyl iodide with one or more remaining hydroxy groups from an alcohol having two or more hydroxy groups into the hydrophobic solvent phase. Furthermore, by extracting the resulting alkyl iodide into the hydrophobic solvent phase, yield reduction due to side reactions can be suppressed, so the use of a hydrophobic solvent is also effective when all hydroxy groups are to be iodinated.
[0312] The hydrophobic solvent may or may not form an azeotropic mixture with water, but a hydrophobic solvent that forms an azeotropic mixture with water is preferred. Examples of hydrophobic solvents that form an azeotropic mixture 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, cyclopentyl methyl ether, and cyclohexanone, with hexane, toluene, o-xylene, m-xylene, and p-xylene being preferred. The hydrophobic solvent may be used alone, or two or more hydrophobic solvents may be used in combination.
[0313] The amount of the hydrophobic solvent is preferably 50 equivalents or less, more preferably 30 equivalents or less, and even more preferably 20 equivalents or less, based on the mass ratio of the raw material alcohol.
[0314] An acid may be used in the reaction, such as 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, or boric acid.
[0315] During the reaction, metal iodides can be used in combination. For example, LiI, NaI, KI, MgI ２ , CaI ２ , AlI ３ The combination of these is effective.
[0316] During the reaction, it is preferable to stir the reaction solution to prevent bumping. Stirring blades of various shapes can be suitably used, such as flat paddle blades, inclined paddle blades, turbine blades, disk turbine blades, propeller blades, three-bladed swept blades, anchor blades, helical ribbon blades, screw blades, anchor blades, Max Blend, Full Zone, Twin Star, etc.
[0317] The stirring speed can be any speed. When a hydrophobic solvent is used and the reaction solution is separated into two liquid-liquid phases, the stirring speed may be set to a level that causes the interface to fluctuate, a stirring speed that generates and disperses some oil droplets or water droplets, or a stirring speed that results in a completely dispersed state. Furthermore, the reaction time for iodination can be shortened by allowing the mixture to stand and then stirring after charging the substrate and iodinating agent. The standing time is preferably 1 to 48 hours, more preferably 4 to 24 hours, and even more preferably 8 to 12 hours.
[0318] The reaction temperature is preferably 0 to 150°C, more preferably 20 to 150°C, and even more preferably 50 to 120°C. On the other hand, in order to obtain an iodine alkyl in high yield, it is preferable to concentrate the reaction solution by distilling off water during the reaction. In order to distill off water, the reaction temperature must be the boiling point of the reaction solution. If the boiling point fluctuates due to the use of a hydrophobic solvent, the reaction temperature can be controlled by reducing or increasing the pressure of the reaction.
[0319] The reaction temperature can also be controlled by changing the stirring speed. Generally, when a hydrophobic solvent forms an azeotrope with water, the azeotropic point is lower than the boiling point of the solvent. When a hydrophobic solvent that forms an azeotrope with water is used and the reaction liquid is separated into two liquid-liquid phases, as the stirring speed increases, the two phases approach a completely dispersed state, and accordingly the boiling point approaches the azeotropic point, so the reaction temperature can be controlled by the stirring speed.
[0320] When concentrating the reaction solution, all of the water distilled by simple distillation may be distilled off, or a required amount may be distilled off using a Dean-Stark apparatus or the like, but it is preferable to distill off the required amount using a Dean-Stark apparatus or the like.
[0321] The amount of water to be distilled off is preferably determined so as to maintain the hydrogen iodide concentration at a predetermined concentration or higher. The concentration is preferably at least 15% lower than the hydrogen iodide concentration in the feed, more preferably at least 10% lower than the hydrogen halide concentration in the feed, even more preferably at least 5% lower than the hydrogen iodide concentration in the feed, and particularly preferably at least the hydrogen iodide concentration in the feed. A fixed amount of water may be distilled off continuously, or may be distilled off all at once at predetermined time intervals. After completion of the reaction, the alkyl iodide is purified and isolated.
[0322] During the reaction, hydrogen iodide is oxidized to produce elemental iodine. If elemental iodine remains, it can cause coloration, etc., so it is preferable to reduce it to hydrogen iodide using a reducing agent. The type of reducing agent is not particularly limited, but examples include sodium sulfite, sodium hydrogen sulfite, and phosphinic acid.
[0323] Another preferred method for removing elemental iodine is to add an iodide salt to the reaction solution and remove the elemental iodine by transferring it to the aqueous layer. Potassium iodide or the like can be used as the iodide salt.
[0324] The reducing agent may be added directly to the reaction solution or may be added as an aqueous solution. The reducing agent may be added in a state where hydrogen iodide remains in the reaction solution, or may be added after neutralizing the hydrogen iodide with a base. The base used in the neutralization step is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate.
[0325] The iodination step is also preferably a method using a combination of trimethylsilyl chloride and sodium iodide or potassium iodide, and adamantane alcohol as raw materials. The solvent is preferably a polar aprotic solvent, and is not limited thereto. Examples include ether solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme; ester solvents such as ethyl acetate and γ-butyrolactone; nitrile solvents such as acetonitrile; hydrocarbon solvents such as toluene and hexane; amide solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide; ketone solvents such as acetone and ethyl methyl ketone; chlorine-based solvents such as dichloromethane and chloroform; and dimethyl sulfoxide. Acetonitrile is most preferred. The ratio of trimethylsilyl chloride to sodium iodide used is preferably 1.0 molar amount or more, more preferably 1.5 molar amount or more, and even more preferably 2.0 molar amount or more. When acetonitrile is used as a solvent, the reaction temperature is preferably reflux condition.
[0326] In the iodination reaction using a combination of trimethylsilyl chloride and sodium iodide or potassium iodide, the concentration method, type of reducing agent, stirring speed, form of filter, etc. can be the same as those in the above-mentioned iodination reaction using hydrogen iodide.
[0327] When an adamantane polyol is used as a raw material, it is preferable to use hydrogen iodide as an iodinating agent when introducing multiple iodine atoms, and it is preferable to use a combination of trimethylsilyl chloride and sodium iodide or potassium iodide as an iodinating agent when introducing one iodine atom.
[0328] When a hydrophobic solvent is used, purification is possible by washing the hydrophobic solvent phase with water. For example, pure water, a sodium chloride aqueous solution, a nitric acid aqueous solution, an oxalic acid aqueous solution, a sulfuric acid aqueous solution, or a hydrogen chloride aqueous solution can be suitably used for washing with water. Furthermore, after completion of the reaction, a hydrophobic solvent can be added and washed with water. The hydrophobic solvent added after completion of the reaction may be the same as or different from the hydrophobic solvent used in the reaction.
[0329] Generally, washing with water is carried out at around room temperature, but if the product precipitates when washing with water at room temperature, washing with water can be carried out while heating. The temperature for washing with water is preferably not higher than the azeotropic temperature of the hydrophobic solvent and water.
[0330] As described above, purification can also be performed by passing the liquid through an ion exchange resin, a chelating resin, a metal removal filter, a particulate removal filter, etc. The ion exchange resin, the chelating resin, the metal removal filter, and the particulate removal filter may be used alone during purification, or may be used in combination with an operation such as washing with water.
[0331] The compound of formula (Ad) can be isolated by distillation or crystallization. When isolating by distillation, the distillation method is not particularly limited, and for example, methods such as batch simple distillation, equilibrium flash distillation, batch rectification, and continuous rectification can be suitably applied. In addition, the compound of formula (Ad) may be recovered by distillation, or may be recovered as a bottoms liquid or a bottom product.
[0332] When isolating by crystallization, the hydrophobic solvent used in the reaction may be used as is, or a new solvent may be added. The solvent may be a single solvent or a combination of two or more solvents.
[0333] The amount of the solvent used during crystallization is preferably 20 equivalents or less, more preferably 10 equivalents or less, even more preferably 5 equivalents or less, and particularly preferably 3 equivalents or less, in terms of mass ratio relative to the compound of formula (Ad). The ratio of the solvent to the compound of formula (Ad) can also be adjusted by distilling off the solvent.
[0334] Crystals may be precipitated by adding seed crystals, or by cooling the solution without adding seed crystals. After crystal precipitation, the slurry is cooled to improve 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.
[0335] The temperature at which the slurry is subjected to solid-liquid separation after cooling is preferably −50 to 40° C., more preferably −20 to 30° C., and even more preferably −20 to 10° C. The holding time from when the slurry temperature reaches the temperature at which solid-liquid separation occurs until solid-liquid separation is not particularly limited, but is preferably within 24 hours, and more preferably within 10 hours.
[0336] The method of solid-liquid separation is not particularly limited, but for example, methods such as Nutsche filtration, centrifugation, and pressure filtration can be suitably applied.
[0337] Furthermore, a base or an oxidizing agent can be used when iodinating compound (MA). When the base or oxidizing agent has high activity, compound (Da2) can be synthesized. Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, and potassium bicarbonate. Examples of the oxidizing agent include, but are not limited to, periodic acid, hydrogen peroxide, and predetermined additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, etc.). Furthermore, compound (Da2) can also be synthesized by condensing the hydroxyl groups of compound (MA) together using a strong acid or the like.
[0338] The method for producing compound (B) according to the present invention preferably further comprises a step of treatment using an adsorbent. The method for producing compound (B) may involve removing impurities using an adsorbent, or multiple types of filter filtration and adsorbents may be used in appropriate combination. Examples of adsorbents include known adsorbents, such as inorganic adsorbents such as alumina, activated alumina, silica gel, silica-alumina, zeolite (synthetic zeolite, etc.), mica, and organic adsorbents such as activated carbon, molecular sieves, and ion exchange resins. When a target organism comes into contact with a clean solid surface, the target component is adsorbed to the surface due to the interaction between the solid surface atoms and the target component, and this adsorption action can be used to adsorb and remove specific components. Depending on the type of interaction, adsorption phenomena can be classified into two types: physical adsorption and chemical adsorption. Physical adsorption is a phenomenon in which atoms or molecules adsorb onto a solid surface, where the adsorption is primarily due to van der Waals forces between gas molecules and surface atoms. Its characteristics include little substance specificity, a fast adsorption rate, a small heat of adsorption (up to 20 kJ mol-1), multilayer adsorption, and reversible desorption without dissociation. On the other hand, chemical adsorption is a phenomenon in which atoms or molecules adsorb onto a solid surface, where the adsorption is due to chemical bond formation or charge transfer interactions. Many gas molecules and gas atoms are chemically adsorbed onto metals and metal oxides. Its characteristics include strong substance specificity, a slow adsorption rate, a large heat of adsorption (several hundred kJ mol-1), and only monolayer adsorption occurs.
[0339] 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, but examples thereof include adding the adsorbent to the reaction solution (also called silica dispersion), passing the reaction solution through a column packed with an 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 packed with an adsorbent.From the viewpoint of productivity, it is preferable to add an adsorbent to the reaction solution.Furthermore, from the viewpoint of selectively removing impurities from the compound (B) and suppressing the incorporation of impurities from the adsorbent, it is preferable to use alumina, activated alumina, silica gel, or silica-alumina as the adsorbent, and it is more preferable to use silica gel or silica-alumina.
[0340] 2. Composition The compound is useful as a composition. The compound is particularly useful as a composition for lithography, and may be a composition for use in lithography. Hereinafter, a composition containing the compound will be described using a composition for lithography as an example.
[0341] The compound exhibits a sensitizing effect on the lithography composition containing the compound upon irradiation with radiation. Therefore, one aspect of this embodiment may be a method for exhibiting a sensitizing effect on the lithography composition upon irradiation with radiation using the compound, and preferably uses two or more of the compounds. The reason for this is thought to be, but is not limited to, that the compound promotes radiation absorption. This effect is particularly pronounced when irradiated with extreme ultraviolet (EUV) light. The sensitizing effect can take multiple forms. When a photosensitive layer formed using the lithography composition is used as a resist film for lithography, the sensitizing effect can be confirmed, for example, as follows: 1) Using a patternless surface exposure method, the film thickness is measured after exposure, optionally followed by a PEB process (a process of performing a post-exposure heat treatment) and optionally a development process (a process of dissolving and removing exposed or unexposed areas with a developer). 2) The exposure dose is changed, the film thickness is measured, and the exposure dose at which the film thickness changes drastically is defined as the sensitivity in the surface exposure method. 3) If sensitivity is confirmed on the low exposure dose side, the sensitizing effect can be confirmed. In addition, in a method of forming a pattern by exposure, 1) a pattern is formed by varying the exposure dose, and the exposure dose at which a specified line width is obtained after exposure is defined as the sensitivity. 2) If sensitivity is confirmed on the lower exposure dose side, it can be determined that a sensitization effect has been achieved. Furthermore, lithography compositions containing the above-mentioned compound are useful for suppressing defects in resist patterns. In particular, in pattern evaluation using extreme ultraviolet (EUV) light, this can also be confirmed by a reduction in defects such as pitting and bridging. These defects are caused by fluctuations in the optical exposure dose or by exposure conditions at low exposure doses that are essentially similar to defects. However, if the resist film has a sensitization effect, the aforementioned fluctuations and defects are avoided by promoting absorption, thereby reducing the defects. When the above-mentioned compound is used in a lithography composition, the compound can be used directly as a component of the composition. Alternatively, the compound can be processed into a resin (substrate (A)) containing the compound as a partial structure, or additives (acid generator (C), crosslinker (G), acid diffusion inhibitor (E), other components (F), etc.), and used as a lithography composition containing these resins and additives as components.
[0342] The composition for lithography according to this embodiment contains a compound represented by formula (1) (hereinafter also referred to as "compound (B)"), and may contain other components, such as a base material (A), a solvent (S), an acid generator (C), a crosslinking agent (G), and an acid diffusion controller (E), as necessary. Each component will be described below.
[0343] [Compound (B)] The composition of this embodiment contains one or more compounds (B). Although not limited thereto, it is preferable that the composition contains two or more compounds (B). When two or more compounds (B) are contained, etching defects tend to be reduced as shown in the examples described below. The reason for the reduction in etching defects is unclear, but it is thought that, for example, the compatibility of compound (B) in the composition is improved, which may reduce fine defects when a film is formed. RG of compound B is preferably a group derived from benzene, naphthalene, or adamantane, which may have a substituent. When two or more compounds B are contained, the groups derived from RG may be the same or different.
[0344] The amount of compound (B) is not limited, but when a small amount of compound (B) is present (this compound is referred to as compound (B')), the amount of compound (B') is preferably 1 ppm or more, and more preferably 10 ppm or more, of the total amount of compounds (B), from the viewpoint of improving etching defects. Furthermore, when a compound (B) is present in the largest amount (this compound is referred to as compound (B")), the content of compound (B'"), which has a lower iodine atom content in its molecule than compound (B"), is preferably 40% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less, of the total amount of compounds (B), from the viewpoint of improving sensitivity.
[0345] In one embodiment, when the monomer compound having a large number of iodine atoms is H, the monomer compound having a small number of iodine atoms is L, and the dimer compound is D in compound (B), the following combinations can be exemplified: H / L (mass ratio, the same applies hereinafter) = (97 to 99.999): (3 to 0.001) H / D = (97 to 99.999): (3 to 0.001) H / L / D = (95 to 99.999): (2.5 to 0.0005): (2.5 to 0.0005) Furthermore, the following combinations are more preferable. H / L = (98 to 99.99): (2 to 0.01) H / D = (98 to 99.99): (2 to 0.01) H / L / D = (97 to 99.99): (1.5 to 0.005): (1.5 to 0.005) Furthermore, the following combinations are more preferred: H / L = (99 to 99.9): (1 to 0.1) H / D = (99 to 99.9): (1 to 0.1) H / L / D = (98 to 99.9): (1 to 0.05): (1 to 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)
[0346] The method for mixing two or more types of compound (B) is not limited, and two or more types of compound (B) may be mixed, or may be simultaneously synthesized as a mixture in the process of synthesizing compound (B).
[0347] More preferred embodiments of compound B include the following. 1) A combination of a reference compound represented by formula (1) and a compound represented by formula (1) but having fewer iodine atoms than the reference compound (preferably a compound represented by formula (BP0-1) described below). 2) A combination of a reference compound represented by formula (1) and a multimer of a compound represented by formula (1) (preferably a compound represented by formula (DM0-1) described above). 3) A combination of a reference compound represented by formula (1), the compound having fewer iodine atoms, and the multimer. The compound having fewer iodine atoms may also be a compound that does not contain iodine atoms.
[0348] By including the compound represented by formula (DM0-1), the composition is expected to be highly effective in ensuring stability over time, particularly due to inorganic substances and inorganic components, and the high trapping effect of the causative components is expected to lead to improved stability over time. In another preferred embodiment, by including the compound represented by formula (BP0-1), the mechanism caused by the difference in redox potential with the compound represented by formula (1) is expected to be effective in ensuring stability over time, leading to improved stability over time caused by natural oxidation and deterioration of coexisting substances over time.
[0349] The compound represented by formula (DM0-1) is as described above. The compound represented by formula (DM0-1) is preferably a compound represented by the above formula (DM1a), (Dn1), or (Da1), or the following formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb). (In the formula, Z, I, R １ , A, R, r1 to r4 are defined the same as in formula (DM1a). (In the formula, Z, R １ , A, R, r1 to r4 are defined the same as in formula (DM1a). (In the formula, I, R １ , A, R″, Q, s1 to s4 are defined the same as in formula (Dn1).) (In the formula, R １ , A, R″, Q, s2 to s4 are defined the same as in formula (Dn1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1). (In the formula, R １ , R”, R ｄ , t2 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ, t1 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1).
[0350] An example of the compound having a small number of iodine atoms is a compound represented by formula (BP0-1).
[0351]
[0352] R.G., I.R. １ is defined the same as in formula (1). n' is an integer from 0 to 5 and not more than n, and is preferably an integer from 0 to 3. When the composition contains compounds represented by formula (DM0-1) and formula (BP0-1), n' in formula (BP0-1) is preferably an integer obtained by subtracting 1 from the value of n' in formula (DM0-1). m' is an integer from 1 to 5 and not more than m. When n' is 1 to 5, the compound of formula (BP0-1) is a type of compound represented by formula (1).
[0353] The compound represented by formula (BP0-1) is preferably represented by the following formula: １ , R", A, r1 to r4, s2 to s3, and t2 to t3 are defined as above. a1 and r4a are integers of 0 to 4, and a1 and r4a are numbers satisfying a1+r4a≦r4. r4 is defined as above, but preferably has the same meaning as r4 in formula (Bz). s1b is an integer of 0 to 6 and is an integer that satisfies s1b≦(s1−1). s1 is defined as above, but preferably has the same meaning as s1 in formula (N). t1b is an integer of 0 to 9 and is an integer that satisfies t1b≦(t1−1). t1 is defined as above, but preferably has the same meaning as t1 in formula (Ad).
[0354]
[0355] The compound represented by formula (BP0-1) is preferably represented by the following formula (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt). (In the formula, Z, R, R １, A, r1, r2, r3, and r4a are defined the same as in formula (BP1a). (In the formula, R １ , R″, A, s2 to s4 are defined the same as in formula (Bn1).) (In the formula, R １ , R″, t2, and t3 are defined the same as in formula (Ba1).
[0356] Compositions using a compound represented by formula (1) in combination with a compound represented by formula (DM0-1) or formula (BP0-1) have excellent storage stability. The reason for this is not limited, but it is presumed that the compound represented by formula (DM0-1) or formula (BP0-1) sterically or electronically captures causative substances or components that deteriorate storage stability. From this perspective, the lower limit of the total amount of the compounds represented by formula (DM0-1) and formula (BP0-1) relative to the entire 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 the 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.
[0357] When the composition further contains a compound represented by formula (DM0-1), it is preferable that the compounds represented by formula (1) and formula (DM0-1) satisfy the following relationship: 0.1 ≥ [amount (mol) of compound of formula (DM0-1)] ÷ [amount (mol) of compound of formula (1)] ≥ 0.000001
[0358] When the composition further contains a compound represented by formula (DM0-1) and a compound represented by formula (BP0-1), it is preferable that the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relational expression: 0.1≧([total amount (mol) of the compound of formula (DM0-1) and formula (BP0-1)])÷[amount (mol) of the compound of formula (1)]≧0.000001
[0359] In addition to the above effects, from the viewpoint of enhancing the heat resistance of the compound, it is preferable to use a compound represented by formula (DM0-1), and more preferable are compounds represented by formula (DM1a), (Dn1), (Da1), (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb). Among these, dimers are particularly preferable.
[0360] In addition to the above effects, from the viewpoint of compatibility, when the composition contains a compound B different from the compound represented by formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), (Ba1-eb), formula (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt), it is preferable that the compound represented by formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), (Ba1-eb), formula (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt), have the same mother nucleus as compound B.
[0361] In addition to the above effects, from the viewpoint of enhancing the dissolution stability of the compound, it is preferable to use a compound represented by formula (BP0-1), and it is preferable to use a compound having a small number of iodine atoms, such as a compound represented by formula (BP1a), (Bn1), or (Ba1). Even if the compounds represented by formula (BP1a), (Bn1), or (Ba1) do not contain iodine atoms, the desired effects can be achieved. In this embodiment, Z in formula (BP1a) may not contain I. Preferred compounds will be described below.
[0362] The compound represented by formula (BP1a) is preferably a compound represented by formula (BP1b).
[0363]
[0364] In formula (BP1b), I, R, R １, A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers of 0 to 2 that satisfy a11 + a12 ≦ r4. r4 is defined as above, but preferably has the same meaning as r4 in formula (Bz) (the same applies hereinafter).
[0365] The compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c1).
[0366]
[0367] In formula (BP1c1), I, R, R １ , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.
[0368] The compound represented by formula (BP1c1) is preferably a compound represented by formula (BP1d11).
[0369]
[0370] In formula (BP1d11), I, R, R １ , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.
[0371] The compound represented by formula (BP1c1) is preferably a compound represented by formula (BP1d12).
[0372]
[0373] In formula (BP1d12), I, R, R １ Z is defined the same as in formula (BP1a), and a11 and a12 are integers of 0 to 1 satisfying a11+a12≦r4. A′ is a group having a protecting group, and —O—R ａ -O-R ｂ , -O-CO-OR ｂ or —O—Ra—CO—O—R ｂ , or —O—Ra—O—CO—R ｂ It is expressed as: R ａ is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂis a monovalent linear or branched alkyl group 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. ａ and R ａ A' may form a cyclic structure containing the following:
[0374] The compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c2).
[0375]
[0376] In formula (BP1c2), I, R, R １ , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.
[0377] The compound represented by formula (BP1c2) is preferably a compound represented by formula (BP1d21).
[0378]
[0379] In formula (BP1d21), I, R, R １ , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.
[0380] The compound represented by formula (BP1c1) is preferably a compound represented by formula (BP1d22).
[0381]
[0382] In formula (BP1dd22), I, R, R １ is defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4. A′ is defined the same as in formula (BP1d12).
[0383] The compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c3).
[0384]
[0385] In formula (BP1c3), I, R, R １, A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.
[0386] The compound represented by formula (BP1c3) is preferably a compound represented by formula (BP1d31).
[0387]
[0388] In formula (BP1d31), I, R, R １ , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.
[0389] The compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c4).
[0390]
[0391] In formula (BP1c4), I, R, R １ , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4.
[0392] The compound represented by formula (BP1c4) is preferably a compound represented by formula (BP1d41).
[0393]
[0394] In formula (BP1d41), I, R, R １ is defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 that satisfy a11+a12≦r4. A′ is defined the same as in formula (BP1d12).
[0395] The compound represented by formula (Bn1) is preferably a compound represented by formula (Bn1a).
[0396]
[0397] In formula (Bn1a), I, R １ , R", and A are defined the same as in formula (Bn1). x' and y' are each 0 or 1, and satisfy (x'+y')≦(x+y−1) for x and y in formula (1n).
[0398] The compound represented by formula (Bn1a) is preferably a compound represented by formula (Bn1b1).
[0399]
[0400] In formula (Bn1b1), I, R １ , R", and A are defined the same as in formula (Bn1). x' and y' are each 0 or 1, and satisfy (x'+y')≦(x+y−1) for x and y in formula (1n). s4' is defined as above.
[0401] The compound represented by formula (Bn1b1) is preferably a compound represented by formula (Bn1c11).
[0402]
[0403] In formula (Bn1c11), I, R １ , R", and A are defined the same as in formula (Bn1). x' and y' are each 0 or 1, and satisfy (x'+y')≦(x+y−1) for x and y in formula (1n).
[0404] The compound represented by formula (Bn1b1) is preferably a compound represented by formula (Bn1c12).
[0405]
[0406] In formula (Bn1c12), R １ , R″ is defined the same as in formula (Bn1), and A′ is defined the same as in formula (BP1d12).
[0407] The compound represented by formula (Bn1a) is preferably a compound represented by formula (Bn1b2).
[0408]
[0409] In formula (Bn1b2), I, R １ , R″ and A are defined the same as in formula (Bn1). x″ is 0 or 1. s4′ is defined as above.
[0410] The compound represented by formula (Bn1b2) is preferably a compound represented by formula (Bn1c21).
[0411]
[0412] In formula (Bn1c21), R １ , R″ is defined the same as in formula (Bn1), and A′ is defined the same as in formula (BP1d12).
[0413] The compound represented by formula (Bn1a) is preferably a compound represented by formula (Bn1b3).
[0414]
[0415] In formula (Bn1b3), I, R １ , R", and A are defined the same as in formula (Bn1). x' and y' are each 0 or 1, and satisfy (x'+y')≦(x+y−1) for x and y in formula (1n). s4' is defined as above.
[0416] The compound represented by formula (Bn1b3) is preferably a compound represented by formula (Bn1c31).
[0417]
[0418] In formula (Bn1c31), R １ , R″ is defined the same as in formula (Bn1), and A′ is defined the same as in formula (BP1d12).
[0419] The compound represented by formula (Bn1b3) is preferably a compound represented by the following formula (Bn1c32).
[0420]
[0421] In formula (Bn1c32), R １ , R″ is defined the same as in formula (Bn1), and A′ is defined the same as in formula (BP1d12).
[0422] The compound represented by formula (Ba1) is preferably a compound represented by formula (Ba1a).
[0423]
[0424] In formula (Ba1a), I, R １, R″ are defined the same as in formula (Ba1). 1c1, 1c2, and 1c3 are integers of 0 or 1 that satisfy (1c1 + 1c2 + 1c3)≦t1b. t1b is defined as above, but preferably has the same meaning as t1b in formula (Ba1) (the same applies hereinafter).
[0425] The compound represented by formula (Ba1a) is preferably a compound represented by formula (Ba1b).
[0426]
[0427] In formula (Ba1b), I, R'', R １ is defined the same as in formula (Ba1a). 1c1, 1c2, and 1c3 are integers of 0 or 1 that satisfy (1c1 + 1c2 + 1c3) ≦ t1b.
[0428] The compound represented by formula (Ba1b) is preferably a compound represented by the following formula (Ba1c11).
[0429]
[0430] In formula (Ba1c11), I, R'', R １ , are defined the same as in formula (Ba1a). 1d1 and 1d2 are integers of 0 or 1 that satisfy (1d1 + 1d2) ≦ t1b.
[0431] The compound represented by formula (Ba1b) is preferably a compound represented by the following formula (Ba1c12).
[0432]
[0433] (In formula (Ba1c12), I, R'', R １ is defined as in formula (Ba1a), and 1e1, 1e2, and 1e3 are integers of 0 or 1 that satisfy (1e1+1e2+1e3)≦t1b.
[0434] It is also preferable that the composition contains a compound to which a solvent has been added as compound B. Examples of the compound to which a solvent has been added include compounds represented by the following formula (Ba1-tl), (Ba1-x), or (Ba1-eb). (In the formula, I, R １ , R”, R ｄ, t1 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1).
[0435] Examples of compounds represented by formula (DM0-1) and formula (BP0-1) that do not contain an iodine atom are shown below.
[0436] [Substrate (A)] In this embodiment, the substrate (A) refers to a compound other than the compound (B) that can be used as a resist. The substrate (A) may be a resin. For example, the substrate (A) refers to a substrate (e.g., a substrate for lithography or a substrate for resist) that can be used as a resist for g-line, i-line, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm), or electron beam (EB). Examples of the substrate (A) include phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof. Among these, from the viewpoint of the shape of the resist pattern that can be obtained, preferred are phenol novolac resins, cresol novolac resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives of these.
[0437] From the viewpoints of reducing defects in a film formed using the composition and achieving a good pattern shape, the weight average molecular weight of the substrate (A) is preferably 2000 to 49900, more preferably 2000 to 29900, and even more preferably 2000 to 14900. The weight average molecular weight can be a value obtained by measuring the weight average molecular weight in terms of polystyrene using GPC.
[0438] [Solvent (S)] The solvent in this embodiment may be any solvent that dissolves compound (B), and known solvents may be used as appropriate. Specific examples of the solvent 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; lactate esters; aliphatic carboxylic acid esters; other esters; aromatic hydrocarbons; ketones; 3:9 amides; lactones; and the like. Specific examples of these solvents include those disclosed in Patent Document 1.
[0439] The solvent used in the present 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.
[0440] In this embodiment, the amounts of the solid components and the solvent are not particularly limited, but are preferably 1 to 80% by mass of the solid components and 20 to 99% by mass of the solvent, more preferably 1 to 50% by mass of the solid components and 50 to 99% by mass of the solvent, even more preferably 2 to 40% by mass of the solid components and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid components and 90 to 98% by mass of the solvent, relative to the total mass of the solid components and the solvent. The total mass of the solid components (the sum of the solid components including optional components such as the base material (A), the compound (B), the acid generator (C), the crosslinking agent (G), the acid diffusion controller (E), and other components (F); the same applies hereinafter) is defined as the amount of the solid components.
[0441] [Acid Generator (C)] The composition of the present embodiment preferably contains one or more acid generators (C). The acid generator (C) is a material that generates an acid directly or indirectly when irradiated with 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, those described in WO 2013 / 024778 can be used. Two or more types of acid generators (C) can also be used in combination.
[0442] The amount of the acid generator (C) used is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, still more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass, of the total mass of the solid components. By using the acid generator (C) within the above range, a pattern profile with high sensitivity and low edge roughness tends to be obtained.
[0443] [Crosslinking Agent (G)] The composition of this embodiment preferably contains one or more crosslinking agents (G). The crosslinking agent (G) can crosslink at least either the substrate (A) or the compound (B). The crosslinking agent (G) intramolecularly or intermolecularly crosslinks the substrate (A) in the presence of the acid generated from the acid generator (C). Examples of such acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") capable of crosslinking the substrate (A). Examples of the crosslinking agent (G) having the crosslinkable group include those described in WO 2013 / 024778. Two or more crosslinking agents (G) can also be used in combination.
[0444] In this embodiment, the amount of crosslinking agent (G) used is preferably 0.5 to 50% by mass, more preferably 0.5 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass, of the total mass of the solid components. When the blending ratio of the crosslinking agent (G) is 0.5% by mass or more, the effect of suppressing the solubility of the resist film in an alkaline developer tends to be improved, and a decrease in the residual film rate and the occurrence of swelling or meandering of the pattern tend to be suppressed. On the other hand, when the blending ratio is 50% by mass or less, a decrease in the heat resistance of the resist tend to be suppressed.
[0445] [Acid Diffusion Controller (E)] The composition of this embodiment may contain an acid diffusion controller (E). The acid diffusion controller (E) controls the diffusion of the acid generated from the acid generator upon irradiation in the resist film, thereby preventing undesirable chemical reactions in unexposed areas. The use of the acid diffusion controller (E) tends to improve the storage stability of the composition of this embodiment. Furthermore, the use of the acid diffusion controller (E) can improve the resolution of the film formed using the composition of this embodiment. In addition, the use of the acid diffusion controller (E) can suppress changes in the line width of the resist pattern due to variations in the waiting time before and after irradiation, which tends to improve process stability. Examples of the acid diffusion controller (E) include radiation-decomposable basic compounds such as those described in WO 2013 / 024778. Two or more types of acid diffusion controllers (E) can also be used in combination.
[0446] The amount of the acid diffusion controller (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass, based on the total mass of the solid components. When the amount of the acid diffusion controller (E) is within the above range, degradation of resolution, pattern shape, dimensional fidelity, and the like tends to be prevented. Furthermore, even if the exposure time between electron beam irradiation and post-exposure heating is long, degradation of the shape of the upper layer of the pattern can be suppressed. Furthermore, when the amount is 10% by mass or less, degradation of sensitivity, developability of unexposed areas, and the like tends to be prevented. Furthermore, the use of such an acid diffusion controller improves the storage stability and resolution of the resist composition, and also suppresses changes in the line width of the resist pattern due to variations in exposure time before and after radiation exposure, tending to improve process stability.
[0447] [Other Components (F)] The composition of this embodiment may contain one or more of the following additives as the other component (F). (Dissolution Promoter) When the solubility of a solid component in a developer is too low, the dissolution promoter increases the solubility and appropriately increases the dissolution rate of the compound during development. The dissolution promoter is preferably a low-molecular-weight compound, and examples of such a compound include low-molecular-weight phenolic compounds. Examples of low-molecular-weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. Two or more dissolution promoters may also be used in combination.
[0448] The amount of the dissolution promoter to be added is adjusted appropriately depending on the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
[0449] (Dissolution Controller) When the solubility of a solid component in a developer is too high, the dissolution controller controls the solubility and appropriately reduces the dissolution rate during development. Such a dissolution controller is preferably one that does not undergo chemical changes during processes such as baking, irradiation, and development of the resist film.
[0450] The dissolution controller is not particularly limited, but examples thereof include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone; and sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. Two or more dissolution controllers can also be used in combination. The amount of the dissolution controller is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
[0451] (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 produced and improving the apparent sensitivity of the resist. Examples of such sensitizers include benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. Two or more sensitizers can also be used in combination. The amount of sensitizer added is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
[0452] (Surfactant) The surfactant improves the coatability, striation, resist developability, and other properties of the composition of this embodiment. The surfactant may be an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant. Preferred surfactants include nonionic surfactants. Nonionic surfactants have good affinity with the solvent used in producing the composition of this embodiment, further enhancing the effects of the composition of this embodiment. Examples of nonionic surfactants include, but are not limited to, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol. Commercially available surfactants such as those described in Patent Document 1 can also be used. The amount of surfactant added is adjusted appropriately depending on the type of solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
[0453] (Organic Carboxylic Acid, or Phosphorus Oxo Acid, or Derivative of the Oxo Acid) Organic carboxylic acids, phosphorus oxo acids, or derivatives of the oxo acids (hereinafter also referred to as "acids or derivatives") have effects such as preventing sensitivity degradation, improving resist pattern shape, or improving post-deposition stability. Examples of organic carboxylic acids include malonic acid as described in Patent Document 1. Examples of phosphorus oxo acids or derivatives thereof include phosphonic acid or derivatives such as esters thereof as described in Patent Document 1, and among these, phosphonic acid is particularly preferred.
[0454] The amount of the acid or derivative may be adjusted appropriately depending on the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
[0455] (Other Additives) Furthermore, the composition of the present embodiment may contain additives other than the components described above, as necessary. Examples of such additives include dyes, pigments, and adhesion promoters. For example, the incorporation of a dye or pigment is preferable because it can visualize the latent image in the exposed area and mitigate the effects of halation during exposure. Furthermore, the incorporation of an adhesion promoter is preferable because it can improve adhesion to the substrate. Further examples of other additives include antihalation agents, storage stabilizers, antifoaming agents, shape modifiers, and the like, specifically 4-hydroxy-4'-methylchalcone.
[0456] [Ratio of Components 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 mass of the solid components of the composition. In this disclosure, the total mass of the solid components refers to the sum of the solid components, including the base material (A), compound (B), acid generator (C), crosslinking agent (G), acid diffusion controller (E), and other optional components (F). The mass ratio of base material (A) to compound (B) is preferably 3:97 to 99.5:0.5, and more preferably 10:90 to 99:1. A mass ratio within this range tends to provide high sensitivity and minimize variation in exposure in the depth direction. The mass ratio is more preferably 30:70 to 98:2, and even more preferably 50:50 to 97:3.
[0457] In the composition of this embodiment, the total amount of the base material (A) and the compound (B) is preferably 50 to 99.4 mass % of the total mass of the solid components, more preferably 55 to 95 mass %, even more preferably 60 to 95 mass %, and particularly preferably 70 to 95 mass %. When the total amount of the base material (A) and the compound (B) is within the above range, the resolution tends to be further improved and the line edge roughness (LER) tends to be further reduced.
[0458] In the composition of this embodiment, the (A) / (B) / (C) / (G) / (E) / (F) mass ratio (mass%) relative to the total mass of solids in the composition of this embodiment is preferably: 1.5 to 99.0 / 0.2 to 96.4 / 0.001 to 49 / 0 to 49 / 0.001 to 49 / 0 to 49, more preferably 5 to 98.5 / 0.5 to 89 / 1 to 40 / 0 to 40 / 0.01 to 10 / 0 to 5, even more preferably 15 to 97.5 / 1 to 69 / 3 to 30 / 0 to 30 / 0.01 to 5 / 0 to 1, and particularly preferably 25 to 96.5 / 1.5 to 50 / 3 to 30 / 0 to 30 / 0.01 to 3 / 0.
[0459] The blending ratio of each component is selected from each range so that the total sum adds up to 100% by mass. This blending ratio tends to result in excellent performance in terms of sensitivity, resolution, developability, etc. "Solid content" refers to the components excluding the solvent, and "total mass of solid content" refers to the sum of the components constituting the composition excluding the solvent, which is 100% by mass.
[0460] The composition of the present embodiment is usually prepared at the time of use by dissolving each component in a solvent to form a homogeneous solution, and then filtering the solution, if necessary, using a filter with a pore size of about 0.2 μm, for example.
[0461] [Physical Properties of the Composition] The composition of this embodiment can form an amorphous film by spin coating. The composition of this embodiment can be applied to general semiconductor manufacturing processes. The composition of this embodiment can also produce either a positive resist pattern or a negative resist pattern, depending on the type of developer used.
[0462] Lithography compositions containing compound (B) exhibit excellent sensitization effects in EUV exposure. Therefore, the present invention also provides a method for increasing the sensitivity of lithography compositions in EUV exposure. As described above, the sensitization method preferably uses two or more types of compound (B).
[0463] The residual amount of metal impurities in the composition is preferably less than 1 ppm, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb. In particular, for transition metals such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al, if the residual amount of the metal is 1 ppm or more, there is a concern that the interaction with other compounds may cause denaturation or deterioration of the material over time. Furthermore, if the residual amount of alkali metals or alkalinity metals such as Na, K, Ca, and Mg is 1 ppm or more, the residual metal amount cannot be sufficiently reduced when the compound is used to produce a resin for semiconductor processing, and there is a concern that this may cause defects due to residual metals or performance degradation in the semiconductor manufacturing process, resulting in a decrease in yield.
[0464] [Measurement Methods] [Nuclear Magnetic Resonance (NMR)] The structure of the compound was confirmed by NMR measurement using a nuclear magnetic resonance spectrometer "Avance500III spectrometer" (product name, manufactured by Bruker) under the following conditions: [1H-NMR Measurement] Frequency: 500 MHz Solvent: CDCl3 or d6-DMSO Internal standard: TMS Measurement temperature: 23°C [13C-NMR Measurement] Frequency: 125 MHz Solvent: CDCl3 or d6-DMSO Internal standard: Use the solvent used Measurement temperature: 23°C
[0465] [Molecular Weight] The molecular weight of the compound was measured by liquid chromatography-mass spectrometry (LC-MS) using Acquity UPLC / MALDI-Synapt HDMS manufactured by Waters.
[0466] Example 1 Compound Having Benzene as Mother Nucleus The compound was produced according to the following scheme: The reaction was carried out under a nitrogen stream.
[0467]
[0468] (Synthesis of Compound 1-2) A flask equipped with a stirrer and a condenser was immersed in an ice-water bath, and 40 g (0.11 mol) of Compound 1-1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 120 mL of acetone were charged into the flask and stirred. The internal temperature at this time 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 dropwise 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 for 2 hours under a nitrogen stream. After the reaction was completed, 120 mL of water was added to the flask to obtain a precipitate. This was followed by filtration and washing with water, followed by further washing with methanol, filtration, and drying to obtain Compound 1-2. The yield was 84%. The formation was confirmed by NMR and LC-MS. The molecular weight was 432.
[0469] (Synthesis of Compound 1-2 2) A flask equipped with a stirrer and a condenser was immersed in an ice-water bath, and 40 g (0.11 mol) of Compound 1-1 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 80 mL of dimethylformamide were charged into the flask and stirred. The internal temperature at this time 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 complete, 12.3 g (1.2 equivalents relative to Compound 1-1) of chloromethyl ethyl ether was added dropwise, and the reaction was carried out for 1 hour under a nitrogen stream. After the reaction was complete, 180 mL of water was added to the flask to obtain a precipitate. This was followed by filtration and washing with water, followed by further washing with methanol, filtration, and drying to obtain Compound 1-2. The yield was 89%.
[0470] (Synthesis of Compound 1-3) A flask equipped with a stirrer and a condenser was immersed in an ice-water bath, and 33 g of Compound 1-2 and 100 mL of dehydrated ethanol were placed in the flask. The internal temperature at this time was 3°C. Next, 2.88 g (less than 1.0 equivalent relative to Compound 1-2) of NaBH ４was added in portions over 1 hour. The reaction was then continued for 45 minutes under a nitrogen stream. 78 g of 5% ammonium chloride (a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 100 g of water were then added, followed by filtration, washing with water, and drying to obtain Compound 1-3. The yield was 85%. The formation was confirmed by NMR and LC-MS. The molecular weight was 434.
[0471] Example 1a: Compound 2 having a benzene core: To 16 g (65 mmol) of 5-iodovanillin, 60 ml of acetone was added and the mixture was ice-cooled. Under nitrogen, 8.2 g (63 mmol) of diisopropylethylamine was added, and then 6.4 ml (0.84 mol) of chloromethyl ethyl ether was added dropwise at 12°C or below. The mixture was stirred at 3°C for 15 minutes, and 100 ml of water was slowly added. The precipitate was collected by filtration and washed with water. The resulting solid was suspended in 70 ml of methanol, stirred, and filtered. The solid was dried at room temperature and used in the next step. 15 ml of ethanol was added to 2 g of the solid, and the mixture was ice-cooled. 225 mg (5.9 mmol) of sodium borohydride was added in portions over 5 minutes. The mixture was allowed to react for 30 minutes, and then 20 ml of water was added. 400 mg (7.5 mmol) of ammonium chloride was added, and then 20 ml of water was added dropwise. Ethyl acetate was added for extraction, and the mixture was then dried over sodium sulfate and the organic solvent was removed using an evaporator to obtain Compound 2. The production was confirmed by NMR and LC-MS. The molecular weight was 338.
[0472]
[0473] [Example 1b] Compound 3 with a Benzene Core Compound 3 was obtained in the same manner as in Example 1, except that 9.38 g of ethyl vinyl ether was used instead of 12.3 g of chloromethyl ethyl ether. Alternatively, 100 ml of methylene chloride was added to 22 g (60 mmol) of 4-hydroxy-3,5-diiodobenzaldehyde and the mixture was ice-cooled. 43.2 g (600 mmol) of ethyl vinyl ether was added under a nitrogen atmosphere, and then 1.5 g (6 mmol) of pyridinium paratoluenesulfonate was added at 10°C or below. The mixture was then stirred at 20°C for 24 hours, and 100 ml of water was added. After extraction with methylene chloride, the organic layer was dried over sodium sulfate, and the organic solvent was removed using an evaporator to obtain an ethoxyethyl-protected compound. 25 ml of ethanol was added to 4.5 g (10 mmol) of the protected compound and the mixture was ice-cooled. 113 mg (3 mmol) of sodium borohydride was added in portions over 5 minutes. The mixture was allowed to react for 30 minutes, and 20 ml of water was added. After adding 240 mg (4.5 mmol) of ammonium chloride, 20 ml of water was added dropwise. Ethyl acetate was added and the mixture was extracted, then dried over sodium sulfate and the organic solvent was removed using an evaporator to obtain Compound 3. The production was confirmed by NMR and LC-MS. The molecular weight was 448.
[0474]
[0475] [Example 1c] Compound 4 having a benzene core In the same manner as in Example 1b, compound 4 was obtained using 50.5 g of 3,4-dihydro-2H-pyran instead of 43.2 g of ethyl vinyl ether. The production was confirmed by NMR and LC-MS. The molecular weight was 460.
[0476]
[0477] [Example 1d] Compound 5 having a benzene core Compound 5 was obtained in the same manner as in Example 1, except that 14.2 g of di-tert-butyl dicarbonate was used instead of 12.3 g of chloromethyl ethyl ether. The production was confirmed by NMR and LC-MS. The molecular weight was 474.
[0478]
[0479] [Example 1e] Compound 6 having a benzene core 3,5-diiodo-4-hydroxybenzyl alcohol was obtained in the same manner as in Example 1. 3,5-diiodo-4-hydroxybenzyl alcohol and THF were added and stirred to dissolve, and then phosgene (2 equivalents relative to the starting material, 20% toluene solution, manufactured by Merck) was added dropwise under ice-cooling in a nitrogen atmosphere, and the mixture was stirred for another 2 hours under ice-cooling. The mixture was further stirred at 25°C for 12 hours. Nitrogen bubbling was then performed for 2 hours, and the mixture was then concentrated under reduced pressure to obtain a carbonate ester compound (1e0). The obtained carbonate ester compound (1e0) was added to chloroform and dissolved by stirring under ice-cooling. 1-Methylcyclopentanol (1.2 equivalents relative to the (1e0)) was then added dropwise under ice-cooling, and the mixture was stirred. Pyridine (1.2 equivalents relative to the (1e0)) was then added dropwise under ice-cooling, and the mixture was stirred. After stirring for 1 hour, the mixture was stirred at 25°C for 12 hours. Thereafter, ion-exchanged water was added, and the organic phase was recovered. The obtained organic phase was washed with 5% sodium bicarbonate water, and then washed five times with ion-exchanged water, and then concentrated under reduced pressure to obtain Compound 6. The production was confirmed by NMR and LC-MS. The molecular weight was 502.
[0480]
[0481] [Example 1f] Compound 7 having a benzene core Compound 7 was obtained in the same manner as in Example 1, except that 10.5 g of chloromethyl methyl ether was used instead of 12.3 g of chloromethyl ethyl ether. The production was confirmed by NMR and LC-MS. The molecular weight was 420.
[0482]
[0483] [Example 1g] Compound 8 having a benzene core The compound was produced according to the following scheme: The reaction was carried out under a nitrogen stream.
[0484]
[0485] A 200 L glass-lined reaction vessel equipped with a reflux condenser was used to add 10 kg of 4-aminobenzyl alcohol and 100 L of methanol, which were dissolved by stirring at 220 rpm for 1 hour under a nitrogen flow. 21 kg of iodine was added. 10 L of water was added, and the mixture was cooled on ice. 9.2 kg of 30 wt. % hydrogen peroxide was added dropwise. Stirring was then continued for 24 hours at 24°C and 70 rpm. Subsequently, 10 L of a 10 wt. % aqueous sodium sulfite solution was added with stirring at 120 rpm, followed by 3.5 L of purified water. The precipitate formed was collected by filtration. After drying, 5 kg of Compound 8 was obtained. The formation of the compound was confirmed by NMR and LC-MS. The molecular weight was 249.
[0486] [Example 1h] Compound 9 having a benzene core The compound was produced according to the following scheme: The reaction was carried out under a nitrogen stream.
[0487]
[0488] Using a 200 L glass-lined reaction vessel connected to a reflux condenser, 10 kg of compound (8) was added to 20 L of methanol and stirred at 220 rpm for 1 hour under a nitrogen flow to dissolve the compound. 1.2 aq. of concentrated hydrochloric acid was added, and the mixture was ice-cooled. 1.1 aq. of a 40 wt % aqueous solution of sodium nitrite was added dropwise. Stirring was then carried out for 24 hours at 24°C and 70 rpm. An aqueous solution of potassium iodide was then added at 120 rpm, and 7.0 L of purified water was further added. The precipitate formed was collected by filtration. 5 kg of compound 9 was obtained by drying. The formation of the compound was confirmed by NMR and LC-MS. The molecular weight was 360.
[0489] [Example 1i] Compound 10(1) having a benzene core The compound was produced according to the following scheme: The reaction was carried out under a nitrogen stream.
[0490]
[0491] A 200 mL flask equipped with a reflux condenser was charged with 760 mg of lithium aluminum hydride and 100 mL of ultra-dehydrated THF, and the mixture was stirred at 220 rpm for 1 hour under a nitrogen flow. 10 g of 2,3,5-triiodobenzoic acid was then gradually added in 10 portions over 40 minutes. The mixture was then stirred at 24°C and 70 rpm for 24 hours. 3,500 mL of purified water was added, and the precipitate formed was collected by filtration. After drying, 0.4 g of compound 10 (4% yield) was obtained. The formation of the compound was confirmed by NMR and LC-MS. The molecular weight was 486.
[0492] Example 1j Compound 10 (2) Having Benzene as Mother Nucleus 0.1 g (yield 1%) of compound 10 was obtained in the same manner as in Example 1i, except that sodium borohydride was used instead of lithium aluminum hydride.
[0493] [Example 1k] Compound 10(3) having a benzene core The compound was produced according to the following scheme: The reaction was carried out under a nitrogen stream.
[0494]
[0495] [Esterification Step] A flask connected to a reflux condenser was charged with 5 g of 2,3,5-triiodobenzoic acid, 50 mL of toluene, and 0.01 mL of dimethylformamide and cooled with ice. Then, 2.38 g (2.0 equivalents) of thionyl chloride was added dropwise, and the mixture was warmed to room temperature and stirred at room temperature for 2 hours. The mixture was then warmed to 60°C and stirred for 2 hours. Subsequently, 3.2 g (10 equivalents) of methanol was added, and the reaction was continued for 2 hours. The reaction solution was concentrated under reduced pressure, and 25 mL of water and sodium carbonate were added to make the mixture 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. The aqueous layer was removed, and the organic layer was concentrated. Hexane was added, and the mixture was filtered and dried to obtain 4.6 g (90% yield) of 2,3,5-triiodobenzoic acid methyl ester. The product was confirmed by NMR and LC-MS. The molecular weight was 514. [Reduction Step] 0.90 g (1.05 equivalents) of calcium chloride and 30 mL of ethanol were placed in a vessel connected to a reflux condenser, and 0.64 g (2.2 equivalents) of sodium borohydride was added under ice-cooling. 4 g of methyl 2,3,5-triiodobenzoate obtained in the esterification step was added thereto, and the mixture was stirred at room temperature for 1.5 hours and at 40°C for 1.5 hours. After the reaction was completed, 90 mL of water was added, and hydrochloric acid was further added to adjust the pH to 3-4. Ethyl acetate was then added to extract the organic layer, which was then dehydrated and concentrated. After addition of hexane, the mixture was filtered, washed with chloroform, and dried to obtain crude compound 10. This crude compound was purified by column chromatography to obtain 3.0 g (yield 80%) of compound 10. The yield of compound 10 was significantly improved compared to Example 1i.
[0496] [Example 11] Compound 10 (4) with a benzene core The esterification step of Example 1k was carried out under reflux conditions by placing 15 g of 2,3,5-triiodobenzoic acid, 150 mL of toluene, 20 g (20 equivalents) of methanol, and 1.8 g (0.6 equivalents) of sulfuric acid in a vessel connected to a reflux condenser. After 8 hours, 1.8 g (0.6 equivalents) of sulfuric acid was added, and the reaction was continued for 16 hours. After cooling, the mixture was washed with 100 mL of water, 100 mL of 10% aqueous sodium carbonate solution was added, and then washed with another 100 mL of water. After concentration, hexane was added, and the mixture was filtered and dried. The resulting mixture was changed to 7.2 g (46.7% yield) of 2,3,5-triiodobenzoic acid methyl ester, yielding 3.2 g (85%) of compound 10.
[0497] Example 1m Compound 10 (5) having a benzene core In the same manner as in Example 1k, except that lithium chloride was used instead of calcium chloride, 2.1 g of compound 10 was obtained (yield 55%).
[0498] Example 1n Compound 10 (6) Having a Benzene Core Similar to Example 1k, 1.4 g of compound 10 was obtained (yield 40%) without using calcium chloride and adding 2 mL of methanol.
[0499] [Example 1o] Compound 10 (7) having a benzene core: In the same manner as in Example 1k, 0.6 g of compound 10 was obtained (yield 15%), except that calcium chloride was not used and lithium aluminum hydride was used instead of sodium borohydride.
[0500] (Synthesis Example L1) [Iodination Step]
[0501]
[0502] A 100 L glass-lined reaction vessel connected to a reflux condenser was charged with 700 g of 4-hydroxybenzaldehyde, 4900 ml of methanol, and 1260 mL of pure water, and the mixture was dissolved by stirring at 220 rpm for 1 hour under a nitrogen flow. 1590 g of sodium bicarbonate was then gradually added in 10 portions over 10 minutes, followed by 3200 g of iodine in 10 portions over 40 minutes. During this time, the liquid temperature rose to 47°C, and bubbling was observed. The mixture was stirred for 8 hours while maintaining the internal temperature at 46°C using a water bath. An additional 300 g of iodine was added at the 5-hour mark. Stirring was then continued for 24 hours at 24°C and 70 rpm. Subsequently, 21 L of 6 M aqueous hydrochloric acid solution was added dropwise at 120 rpm over 1 hour, followed by 30 minutes of stirring. Next, 20 wt. 2.3 L of a 5% aqueous solution of sodium sulfite was added with stirring, and then 3.5 L of pure water was further added, and the precipitate formed was collected by filtration. After rinsing with 2 L of methanol, the mixture was dried to obtain 4-hydroxy-3,5-diiodobenzaldehyde (1,880 g) in a yield of 87%.
[0503] [Protecting group introduction step]
[0504]
[0505] Using a 100 L glass-lined reaction vessel equipped with a reflux condenser, 1822 g of 4-hydroxy-3,5-diiodobenzaldehyde was dissolved in 3650 mL of dehydrated dimethylformamide (DMF) under nitrogen flow in an ice bath. 673 g of potassium carbonate (1.0 equivalent relative to the substrate) was then added with stirring in the ice bath, followed by stirring for an additional 60 minutes. 553 g of chloromethyl ethyl ether (1.2 equivalent relative to the substrate) was added dropwise to the stirred reaction solution using a dropping funnel over 60 minutes, followed by stirring for an additional 30 minutes in the ice bath. 7.2 L of purified water was then added in the ice bath, and after stirring for 60 minutes, the resulting precipitate was collected by filtration. The collected solid was suspended and stirred in 5.8 L of methanol in the ice bath for 30 minutes, after which the desired protected product was obtained as a white solid (2450 g) by filtration. The yield was 99%. The production was confirmed by NMR and LC-MS. The molecular weight was 432.
[0506] [Reduction process]
[0507]
[0508] A 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 2,450 g of the protected compound obtained in the previous step was gradually added and suspended. Under a nitrogen flow, 50 g of sodium borohydride was added in 5 g increments over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 842 g of a 5 wt% aqueous ammonium chloride solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 21 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off and then rinsed with 5 L of pure water. The resulting precipitate was dissolved in 10.5 L of ethyl acetate and washed three times with 3.5 L of a 10 wt% aqueous NaCl solution. The resulting ethyl acetate solution was recovered, and 200 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of approximately 50% by mass ± 5%, and 9 L of heptane was added to perform crystallization. The filtered crystals were further rinsed with cold heptane and then dried to obtain 1,680 g of compound (1-3) in a yield of 77% and an LC purity of 99.8%. The production was confirmed by NMR and LC-MS. The molecular weight was 434.
[0509] 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 to carry out silica gel dispersion, followed by an additional step of recovering the organic phase by filtration. The same operations as in Synthesis Example L1 were otherwise carried out to obtain 1,660 g of compound (1-3) with a high purity of 76% yield and LC purity of >99.9%.
[0510] (Synthesis Example L2)
[0511] The same procedures as in Synthesis Example L1 were carried out for the [Iodination Step], [Protective Group Introduction Step], and [Reduction Step] to obtain compound (1-4), except that salicylaldehyde was used instead of 4-hydroxybenzaldehyde and the iodination step was performed as in Iodination Step L2 described below. The formation of compound (1-4) was confirmed by NMR and LC-MS. The molecular weight changed from 432 to 434 before and after the reduction step.
[0512]
[0513] [Iodination Step L2] Using a 100 L glass-lined reaction vessel connected to a reflux condenser, 700 g of salicylaldehyde, 5700 ml of ethanol, and 1164 g of iodine were charged. Under a nitrogen flow, the mixture was heated in a water bath to an internal temperature of 40 ° C. and stirred at 220 rpm for 1 hour to dissolve the mixture. 2490 g of a 20 mass% aqueous iodic acid solution was then slowly added dropwise over 60 minutes. The internal temperature was then raised to 50 ° C. and stirring was continued for 2 hours. Next, 2.3 L of a 20 wt. % aqueous sodium sulfite solution was added with stirring, followed by the addition of 7.6 L of pure water. The precipitate formed was collected by filtration. After rinsing with 5 L of pure water, the mixture was dried to obtain 2-hydroxy-3,5-diiodobenzaldehyde (2046 g) in a yield of 95.5%.
[0514]
[0515] (Synthesis Example L3) The [Iodination Step], [Protective Group Introduction Step], and [Reduction Step] were carried out in the same manner as in Synthesis Example L1, except that vanillin (4-hydroxy-3-methoxybenzaldehyde) was used instead of 4-hydroxybenzaldehyde and the iodination step was performed as described below in [Iodination Step L3], to obtain the target compound (1-5). The production was confirmed by NMR and LC-MS. The molecular weight changed from 336 before to 338 after the reduction step.
[0516]
[0517] [Iodination Step L3] A 30 L glass reaction vessel was charged with 1,300 g (8.55 mol) of vanillin (4-hydroxy-3-methoxybenzaldehyde) and 5.6 L of methanol, and nitrogen was introduced into the reaction vessel at a flow rate of 200 mL / min and stirring was initiated. After confirming the dissolution of vanillin, 2.6 L of ion-exchanged water and 635 g (6 mol) of sodium carbonate were charged and stirred at room temperature 22 ° C. for 3 hours. 2,600 g (10.3 mol) of iodine was added in portions and stirred at room temperature 22 ° C. for 20 hours. After stirring, a 16.6% aqueous sodium sulfite solution was added until both the solution was decolorized and the system reached basicity, and then 4.3 L of water was added and stirred for 1 hour. The precipitated solid was filtered using a suction filter, rinsed, reslurried, and dried to obtain 1,900 g of a white solid. Analysis by liquid chromatography-mass spectrometry (LC-MS) confirmed that the molecular weight was 278. １ H-NMR measurement confirmed that the product had the chemical structure of 4-hydroxy-5-iodo-3-methoxybenzaldehyde. LC purity at 254 nm was 99.8%, and GPC purity was 99.9%. Production was confirmed by NMR and LC-MS. The molecular weight was 338.
[0518] Synthesis Example L4 Compound (1-6) was obtained by performing the [iodination step], [protecting group introduction step], and [reduction step] in the same manner as in Synthesis Example L3, except that 1,420 g of ethyl vanillin was used instead of 1,300 g of vanillin.
[0519]
[0520] (Synthesis Example L5)
[0521] The [iodination step], [protecting group introduction step], and [reduction step] were carried out in the same manner as in Synthesis Example L1, except that 3-hydroxybenzaldehyde was used instead of 4-hydroxybenzaldehyde, to obtain compound (1-7).
[0522]
[0523] [Iodination Step] A 100 L glass-lined reaction vessel connected to a reflux condenser was charged with 700 g of 3-hydroxybenzaldehyde, 4900 ml of methanol, and 1260 mL of pure water, and the mixture was stirred at 220 rpm for 1 hour under a nitrogen flow to dissolve the 3-hydroxybenzaldehyde. Then, 730 g of sodium bicarbonate was gradually added in 10 portions over 10 minutes, followed by 1480 g of iodine in 10 portions over 40 minutes. During this time, the liquid temperature rose to 47°C, and bubbling was observed. The mixture was stirred for 8 hours while maintaining the internal temperature at 46°C using a water bath. An additional 300 g of iodine was added at the 5-hour mark. Stirring was then continued for 24 hours at 24°C and 70 rpm. Subsequently, 21 L of 6 M aqueous hydrochloric acid solution was added dropwise at 120 rpm over 1 hour, followed by 30 minutes of stirring. Next, 20 wt. After adding 2.3 L of a 5% aqueous solution of sodium sulfite with stirring, 3.5 L of pure water was further added, and the precipitate formed was collected by filtration. After rinsing with 2 L of methanol, the mixture was dried to obtain 3-hydroxy-4-iodobenzaldehyde (1,237 g) in a yield of 86%.
[0524] [Protecting Group Introduction Step] Using a 100 L glass-lined reaction vessel connected to a reflux condenser, 1237 g of 3-hydroxy-4-iodobenzaldehyde was added to 3650 mL of dehydrated dimethylformamide (DMF) in an ice bath under nitrogen flow and stirred with a stirring blade until dissolved. Next, 689 g of potassium carbonate (1.0 equivalent relative to the substrate) was added while stirring in the ice bath, and the mixture was stirred for an additional 60 minutes. 565 g of chloromethyl ethyl ether (1.2 equivalents relative to the substrate) was added dropwise to the stirred reaction solution using a dropping funnel over 60 minutes, followed by stirring for an additional 30 minutes in the ice bath. Subsequently, 7.2 L of pure water was added in the ice bath, and after stirring for 60 minutes, the formed precipitate was collected by filtration. The collected solid was suspended and stirred in 5.8 L of methanol in the ice bath for 30 minutes, and then filtered to obtain the desired protected compound as a white solid (1511 g). The yield was 99%. The production was confirmed by NMR and LC-MS. The molecular weight was 306.
[0525] [Reduction Step] A 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 1511 g of the protected compound obtained in the previous step was gradually added and suspended. Under a nitrogen flow, 50 g of sodium borohydride was added in 5 g increments over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 842 g of a 5 wt% aqueous ammonium chloride solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 21 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off and then rinsed with 5 L of pure water. The resulting precipitate was dissolved in 10.5 L of ethyl acetate and washed three times with 3.5 L of a 10 wt% aqueous NaCl solution. The resulting ethyl acetate solution was recovered, and 200 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of approximately 50% by mass ± 5%, and 9 L of heptane was added to perform crystallization. The filtered crystals were further rinsed with cold heptane and dried to obtain 1,171 g of compound (1-7) in a yield of 77% and an LC purity of 99.8%. The formation was confirmed by NMR and LC-MS. The molecular weight changed from 306 to 308 after the reduction step.
[0526] (Synthesis Example L6) Using 3,4-dihydroxybenzaldehyde as a starting material, the protecting group introduction step of Synthesis Example L3 was carried out. However, the amounts of diisopropylmethylamine and chloromethyl ethyl ether relative to 3,4-dihydroxybenzaldehyde were doubled. Then, the following [Iodination Step L6] was carried out. Next, the [Reduction Step] was carried out in the same manner as in Synthesis Example L3 to obtain compound (1-8). The production was confirmed by NMR and LC-MS. The molecular weight changed from 380 before to 382 after the reduction step.
[0527] [Iodination step L6]
[0528] A 30 L glass reactor was charged with 2,172 g (8.55 mol) of 3,4-diethoxymethoxybenzaldehyde as raw materials and 5.6 L of methanol, and nitrogen was blown into the reactor at a flow rate of 200 mL / min and stirring was initiated. After confirming dissolution of the raw materials, 2.6 L of ion-exchanged water and 634 g (5.99 mol) of sodium carbonate were charged and stirred at room temperature of 22°C for 3 hours. Next, 2,609 g (10.3 mol) of iodine was charged, and the reactor was stirred at room temperature of 22°C for 12 hours. After that, a 16.6% aqueous solution of sodium sulfite was added until the solution was decolorized, followed by the addition of 4.3 L of water and stirring for 1 hour. The precipitated solid was filtered using a suction filter, rinsed, reslurried, and dried to obtain 2,438 g of a white solid. Analysis by liquid chromatography-mass spectrometry (LC-MS) confirmed a molecular weight of 380. Furthermore, under the above measurement conditions, １ H-NMR measurement confirmed that the compound had the chemical structure of 3,4-diethoxymethoxy-5-iodobenzaldehyde. The LC purity at 254 nm was 99.5%, and the GPC purity was 99.9%.
[0529]
[0530]
[0531] (Synthesis Example L7) Using 2,4,6-trihydroxybenzaldehyde as a starting material, the protecting group introduction step of Synthesis Example L3 was carried out. However, the amounts of diisopropylmethylamine and chloromethyl ethyl ether relative to the amount of 2,4,6-dihydroxybenzaldehyde were three times the amount. Thereafter, the [iodination step] was carried out in the same manner as in Synthesis Example L3. Next, the [reduction step] was carried out in the same manner as in Synthesis Example L3 to obtain compound (1-9). The production was confirmed by NMR and LC-MS. The molecular weight changed from 580 before the reduction step to 582.
[0532]
[0533] (Synthesis Example L8) Using 3,5-dihydroxybenzaldehyde as a starting material, the protecting group introduction step of Synthesis Example L3 was carried out. However, the amounts of diisopropylmethylamine and chloromethyl ethyl ether relative to 3,5-dihydroxybenzaldehyde were doubled. Thereafter, the [iodination step] was carried out in the same manner as in Synthesis Example L3. Next, the [reduction step] was carried out in the same manner as in Synthesis Example L3 to obtain compound (1-10). The production was confirmed by NMR and LC-MS. The molecular weight changed from 380 before the reduction step to 382.
[0534]
[0535] (Synthesis Example L9) Using 2,4-dihydroxybenzaldehyde instead of 4-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 compound (1-11). The production was confirmed by NMR and LC-MS.
[0536]
[0537] [Iodination Step L9] 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 charged into a 500 mL four-neck flask connected to a reflux condenser and stirred for 30 minutes to dissolve. Further, under ice cooling, 10.1 g of a 34% by mass aqueous solution of iodic acid (19.5 mmol as iodic acid) was slowly added dropwise over 30 minutes. The mixture was then warmed to room temperature and stirred for 1 hour. Next, 1 g of a 5% by mass aqueous solution of sodium hydrogen sulfite was added with stirring, followed by 27.6 g of pure water. The precipitate formed was collected by filtration. After rinsing twice using 27.6 g of pure water, the mixture was dried to obtain 2,4-dihydroxy-3,5-diiodobenzaldehyde (15.6 g) in an 80% yield.
[0538] [Protecting Group Introduction Step L9] A 500 mL four-neck flask equipped with a reflux condenser was charged with 20 g (51 mmol) of 2,4-dihydroxy-3,5-diiodobenzaldehyde obtained in the previous section and 140 g of DMF. After stirring and dissolving under a nitrogen flow, 17.75 g of potassium carbonate (2.5 equivalents relative to the substrate) was added under ice cooling and stirred for 30 minutes. Further, 12.12 g of chloromethyl ethyl ether (2.5 equivalents relative to the substrate) was added dropwise using a dropping funnel while stirring, and the mixture was further stirred in an ice bath for 3 hours. After completion of the reaction, 140 g of water was added, and the precipitate was collected by filtration. Rinsing was further performed with 40 g of pure water and then with 60 g of 2-propanol, yielding 35.9 g of wet crystals.
[0539] [Reduction Step L9] A 500 mL four-neck flask equipped with a reflux condenser was charged with 182 g of ethanol and 0.485 g of sodium borohydride, and the mixture was stirred and dissolved under a nitrogen flow. 35.9 g of the wet crystals obtained in the previous section was added under ice cooling, and the mixture was stirred and reacted for 40 minutes while still cooling on ice. After completion of the reaction, the reaction solution was transferred to a 1 L recovery flask, and 78 g of 0.2 M hydrochloric acid was added while stirring under ice cooling. Then, 0.77 g of 2 M hydrochloric acid was added twice, and 133 g of pure water was added, and the precipitate was filtered. The mixture was further rinsed with 100 g of pure water, yielding 13.21 g of the target product represented by formula (1-11) (51% yield in total from 2,4-dihydroxy-3,5-diiodobenzaldehyde in [Protecting Group Introduction Step L9]).
[0540] (Synthesis Example BPL1) [Protecting Group Introduction Step BPL1P]
[0541]
[0542] Using a 100 L glass-lined reaction vessel connected to a reflux condenser, 700 g of 4-hydroxybenzaldehyde was dissolved in 3650 mL of dehydrated dimethylformamide (DMF) under nitrogen flow in an ice bath with stirring using a stirring blade. Next, 822 g of diisopropylethylamine was added using a dropping funnel over 30 minutes while stirring in the ice bath, and the mixture was stirred for an additional 60 minutes. 553 g of chloromethyl ethyl ether (1.2 equivalents relative to the substrate) was added dropwise to the stirred reaction solution using a dropping funnel over 60 minutes and stirred for an additional 30 minutes in the ice bath. Subsequently, 7.2 L of purified water was added in an ice bath, and after stirring for 60 minutes, the formed precipitate was collected by filtration. The collected solid was suspended and stirred in 5.8 L of methanol in an ice bath for 30 minutes, and then filtered to obtain the target compound (BPL1P) (1012 g) as a white solid. The yield was 98%. The production was confirmed by NMR and LC-MS. The molecular weight was 180.
[0543] [Reduction step BPL1R]
[0544]
[0545] A 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 1,012 g of the protected BPL1P was gradually added and suspended. Under a nitrogen flow, 50 g of sodium borohydride was added in 5 g increments over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 842 g of a 5 wt% aqueous ammonium chloride solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 21 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off and then rinsed with 5 L of pure water. The resulting precipitate was dissolved in 10.5 L of ethyl acetate and washed three times with 3.5 L of a 10 wt% aqueous NaCl solution. The resulting ethyl acetate solution was recovered, and 200 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of approximately 50% by mass ± 5%, and 9 L of heptane was added to perform crystallization. The filtered crystallized product was further rinsed with cold heptane and then dried to obtain compound (BPL1R) (716 g) with a yield of 70% and a purity of 99.6%. The production was confirmed by NMR and LC-MS. The molecular weight was 182.
[0546] (Synthesis Example BPL1b) THF was added to 4-hydroxybenzyl alcohol and the mixture was stirred to dissolve it. Then, under a nitrogen atmosphere and ice-cooling, phosgene (2 equivalents relative to the starting material, 20% toluene solution, manufactured by Merck) was added dropwise, and the mixture was further stirred for 2 hours under ice-cooling. Stirring was then continued for 12 hours at 25°C. Nitrogen bubbling was then performed for 2 hours, and the mixture was then concentrated under reduced pressure to obtain a carbonate ester (1be0). The obtained carbonate ester (1be0) was added to chloroform and dissolved by stirring under ice-cooling. 1-Methylcyclopentanol (1.2 equivalents relative to the (1be0)) was then added dropwise under ice-cooling, and the mixture was further stirred. Pyridine (1.2 equivalents relative to the (1be0)) was then added dropwise under ice-cooling, and the mixture was further stirred. Stirring was continued for 1 hour, and then stirring was continued for 12 hours at 25°C. Ion-exchanged water was then added, and the organic phase was recovered. The resulting organic phase was washed with 5% sodium bicarbonate water, then washed five times with ion-exchanged water, and concentrated under reduced pressure to obtain compound (BPL1b). The production was confirmed by NMR and LC-MS. The molecular weight was 250.
[0547]
[0548] (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 the raw material. The production of (BPL2R) was confirmed by NMR and LC-MS. The molecular weight was 182.
[0549]
[0550] (Synthesis Example BPL3) (BPL3P) and (BPL3R) were obtained in the same manner as in Synthesis Example BPL1, except that 3-hydroxybenzaldehyde was used as the raw material. The production of (BPL3R) was confirmed by NMR and LC-MS. The molecular weight was 182.
[0551]
[0552] (Synthesis Example DML1) [Iodination Step DML1D]
[0553]
[0554] A 100 L stainless steel reaction vessel equipped with a reflux condenser was charged with 700 g of 4-hydroxybenzaldehyde and 4900 ml of methanol, which were dissolved under nitrogen flow and stirred at 220 rpm for 1 hour. The reaction vessel was ice-cooled, and an aqueous sodium hydroxide solution prepared by dissolving 757 g of sodium hydroxide in 1260 mL of purified water was gradually added to the reaction vessel, followed by the gradual addition of 3200 g of iodine in 10 portions over 60 minutes. The mixture was stirred for 8 hours while maintaining the internal temperature at 60°C using a water bath. Subsequently, 21 L of 6 M aqueous hydrochloric acid was added dropwise over 1 hour at 120 rpm under ice cooling, followed by 30 minutes of stirring. Next, 2.3 L of a 20 wt. % aqueous sodium sulfite solution was added with stirring, followed by 3.5 L of purified water. The precipitate formed was collected by filtration. The resulting solid was purified by column chromatography using silica gel to obtain DML1D (840 g) in a yield of 30%. The production was confirmed by NMR and LC-MS. The molecular weight was 494.
[0555] [Protecting group introduction step DML1P]
[0556]
[0557] Using a 100 L glass-lined reaction vessel equipped with a reflux condenser, 840 g of DML1D was dissolved in 1680 mL of dehydrated dimethylformamide (DMF) under nitrogen flow in an ice bath. The mixture was then stirred with a stirring blade. Next, 380 g of diisopropylethylamine was added over 30 minutes using a dropping funnel while stirring in the ice bath, followed by an additional 60 minutes of stirring. 255 g of chloromethyl ethyl ether (1.2 equivalents relative to the substrate) was added dropwise to the stirred reaction solution over 60 minutes using a dropping funnel, followed by an additional 30 minutes of stirring in the ice bath. Subsequently, 7.2 L of purified water was added in an ice bath, and after 60 minutes of stirring, the resulting precipitate was collected by filtration. The collected solid was suspended and stirred in 5.8 L of methanol in an ice bath for 30 minutes, after which 996 g of the desired protected DML1P was obtained by filtration as a white solid. The yield was 96%. The formation was confirmed by NMR and LC-MS. The molecular weight was 610.
[0558] [Reduction step DML1R]
[0559]
[0560] A 20 L separable flask was charged with ethanol (5 L) in an ice bath, and 996 g of the prepared protected DML1P isomer was gradually added and suspended. Under a nitrogen flow, 19 g of sodium borohydride was added in 3 g increments over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 350 g of a 5 wt. % aqueous ammonium chloride solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 8 L of purified water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off and rinsed with an additional 2 L of purified water. The resulting precipitate was dissolved in 4 L of ethyl acetate and washed three times with 1.5 L of a 10 wt. % aqueous NaCl solution. The resulting ethyl acetate solution was recovered, and 80 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of approximately 50 wt. % ± 5%, and 9 L of heptane was added to perform crystallization. The filtered crystallized product was further rinsed with cold heptane and then dried to obtain 701 g of compound DML1R with a yield of 70% and a purity of 99.2%. The production was confirmed by NMR and LC-MS. The molecular weight was 614.
[0561] (Synthesis Example DML2R)
[0562] DML2R was synthesized in the same manner as in Synthesis Example DML1, except that 4-hydroxybenzaldehyde was used as the raw material, the type of protecting agent was ethyl vinyl ether, and the [protecting group introduction step] was changed to the method described below. The production was confirmed by NMR and LC-MS. The molecular weight was 642.
[0563]
[0564] [Protecting Group Introduction Step] Using a 100 L glass-lined reaction vessel connected to a reflux condenser, 840 g of DML1D was dissolved in 1680 mL of dehydrated tetrahydrofuran (THF) in an ice bath under nitrogen flow and stirred with a stirring blade. Next, 80 g of PPTS (pyridinium-p-toluenesulfonic acid) was added over 30 minutes while stirring in the ice bath, and the mixture was stirred for an additional 60 minutes. 294 g of ethyl vinyl ether (1.2 equivalents relative to the functional group equivalent) was added dropwise to the stirred reaction solution over 60 minutes and stirred for an additional 60 minutes at 35°C. Subsequently, 7.2 L of pure water was added in an ice bath, and after stirring for 60 minutes, 2 L of ethyl acetate and 5 L of pure water were added to the recovered organic phase, followed by stirring. The organic phase was recovered and concentrated under reduced pressure to obtain 833 g of the desired white solid, the protected DML2P. The yield was 81%. The production was confirmed by NMR and LC-MS. The molecular weight was 638.
[0565]
[0566] (Synthesis Example DML3R) DML3R was synthesized in the same manner as in Synthesis Example DML2, except that 4-hydroxybenzaldehyde was used as the raw material, the type of protecting agent was 3,4-dihydropyran, and the [protecting group introduction step] was changed to the method described below. The production was confirmed by NMR and LC-MS. The molecular weight was 666.
[0567]
[0568] (Synthesis Example DML4R) DML4R was synthesized in the same manner as in Synthesis Example DML1, except that 4-hydroxybenzaldehyde was used as the raw material, the type of protecting agent was changed, and the [protecting group introduction step] was changed to the method described below. The production was confirmed by NMR and LC-MS. The molecular weight was 698.
[0569]
[0570] [Protecting Group Introduction Step] Using a 100 L glass-lined reaction vessel connected to a reflux condenser, 840 g of DML1D isomer was dissolved in 1680 mL of dehydrated tetrahydrofuran (THF) in an ice bath under nitrogen flow and stirred with a stirring blade. Next, 10 g of DMAP (dimethylaminopyridine) (0.05 equivalents relative to the substrate) was added over 10 minutes while stirring in an ice bath, and the mixture was stirred for an additional 30 minutes. 890 g of di-tert-butyl dicarbonate (1.2 equivalents relative to the functional group equivalents) was added dropwise to the stirred reaction solution over 60 minutes, and the mixture was stirred for an additional 120 minutes under ice cooling. After confirming the disappearance of the raw materials by TLC (thin layer chromatography), 1000 mL of n-heptane was added under cooling, and 2800 mL of 1N hydrochloric acid was added dropwise while ensuring the internal temperature was below 10°C under ice cooling, and the mixture was stirred for an additional 30 minutes. After recovering the upper organic phase, the mixture was washed with 7 L of 5% sodium bicarbonate water (once) and 7 L of ion-exchanged water (three times). 50 g of silica gel was then added to the mixture to disperse the silica gel, and the organic phase was recovered by filtration. MQ (methoquinone) was added at 200 ppm relative to the substrate, followed by a drive-off concentration with n-heptane (40°C) to confirm that no THF was leaking out. This was followed by further drive-off concentration using high-purity IPA (Kanto Chemical EL-IPA). High-purity IPA was added at 40°C until the target compound dissolved, after which an equal amount of ion-exchanged water was added dropwise. Crystallization was carried out by ice cooling for approximately 1 hour, and the target compound was recovered. 811 g of a white solid was obtained as the target protected compound DML4P. The yield was 69%. The product was confirmed by NMR and LC-MS. The molecular weight was 694.
[0571]
[0572] (Synthesis Example DML5R) DML5R was synthesized in the same manner as in Synthesis Example DML1, except that 3-hydroxybenzaldehyde was used as the raw material. The production was confirmed by NMR and LC-MS. The molecular weight was 614.
[0573]
[0574] (Synthesis Example DML6R) DML6R was synthesized in the same manner as in Synthesis Example DML1, except that vanillin was used as the raw material. The production was confirmed by NMR and LC-MS. The molecular weight was 674.
[0575]
[0576] (Synthesis Example DML7R) DML7 was synthesized in the same manner as in Synthesis Example DML1, except that 3,4-dihydroxybenzaldehyde was used as the raw material. However, in the protecting group introduction step, the amounts of diisopropylmethylamine and chloromethyl ethyl ether were doubled relative to the amount of the raw material 3,4-dihydroxybenzaldehyde. The product was confirmed by NMR and LC-MS. The molecular weight was 762.
[0577]
[0578] (Synthesis Example DML8R) DML8R was synthesized in the same manner as in Synthesis Example DML1, except that ethyl vanillin was used as the raw material. The production was confirmed by NMR and LC-MS. The molecular weight was 702.
[0579]
[0580] (Synthesis Example DML9R) DML9R was synthesized in the same manner as in Synthesis Example DML1, except that 2-hydroxybenzaldehyde was used as the raw material. The production was confirmed by NMR and LC-MS. The molecular weight was 614.
[0581]
[0582] (Synthesis Example DML10R) The compound was produced according to the following scheme. The reaction was carried out under a nitrogen stream to obtain DML10R. The production was confirmed by NMR and LC-MS. The molecular weight was 496.
[0583] Using a 200 L glass-lined reaction vessel connected to a reflux condenser, 10 kg of 4-aminobenzyl alcohol and 100 L of methanol were added and dissolved under nitrogen flow with stirring at 220 rpm for 1 hour. 21 kg of iodine was added. 10 L of water was added, and the mixture was cooled with ice and 9.2 kg of 30 wt. % hydrogen peroxide was added dropwise. Stirring was then continued for 24 hours at 24°C and 70 rpm. Subsequently, 10 L of a 10 wt. % aqueous sodium sulfite solution was added with stirring at 120 rpm, followed by 3.5 L of purified water. The precipitate formed was collected by filtration. The resulting solid was purified by column chromatography using silica gel to obtain 1 kg of DML10R.
[0584] (Synthesis Example DML11R) The compound was produced according to the following scheme. The reaction was carried out under a nitrogen stream to obtain DML11R. The production was confirmed by NMR and LC-MS. The molecular weight was 718.
[0585] Using a 200 L glass-lined reaction vessel connected to a reflux condenser, 10 kg of DML10R was added to 20 L of methanol and stirred at 220 rpm for 1 hour under a nitrogen flow to dissolve. 1.2 aq. of concentrated hydrochloric acid was added, and the mixture was ice-cooled. 1.1 aq. of a 40 wt% aqueous solution of sodium nitrite was added dropwise. Stirring was then carried out for 24 hours at 24 °C and 70 rpm. An aqueous solution of potassium iodide was then added at 120 rpm, and 7.0 L of pure water was further added. The precipitate formed was collected by filtration. After drying, 4 kg of DML11R was obtained.
[0586] (Synthesis Example DML1e) The [reduction step] of Synthesis Example L1 was carried out using compound (1-4) obtained in Synthesis Example L2, to obtain compound (1-4a). The production was confirmed by NMR and LC-MS. The molecular weight was 376. 5 g (13.3 mmol) of the obtained compound (1-4a) and 100 mL of toluene were placed in a 200 mL container connected to a reflux condenser, and the mixture was reacted under reflux conditions for 1 hour. The mixture was separated by column chromatography to obtain 0.4 g (0.55 mmol) of compound 1-4b. The production was confirmed by NMR and LC-MS. The molecular weight was 734. Next, the [protecting group introduction step] of Synthesis Example L1 was carried out using compound 1-4b, to obtain compound (DML1e). The production was confirmed by NMR and LC-MS. The molecular weight was 850.
[0587]
[0588] [Example 2] Compound having naphthalene as a parent nucleus The compound was produced according to the following scheme: The reaction was carried out under a nitrogen stream.
[0589]
[0590] (Synthesis of Compound 2-2) 50 g of Compound 2-1 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 600 mL of ethanol, and 2.8 mL of 98% sulfuric acid (0.2 equivalents relative to Compound 2-1) were placed in a flask equipped with a stirrer and a condenser. The contents were stirred under reflux for 14 hours to carry out an esterification reaction. Next, the contents were neutralized with 10.6 g of sodium bicarbonate (a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the ethanol was distilled off. Ethyl acetate and water were then added to extract the organic phase, which was then washed with sodium bicarbonate, dehydrated with sodium sulfate, and the solvent was distilled off. Compound 2-2 was obtained by suspension washing in acetone and drying. The yield was 64%.
[0591] (Synthesis of Compound 2-3) In a flask equipped with a stirrer and a condenser, 34 g of Compound 2-2, 48 g of iodine (1.2 equivalents relative to Compound 2-2), 20 g of sodium bicarbonate, 160 mL of methanol, and 16 mL of water were charged. The contents were stirred at room temperature for 5 hours to carry out an iodination reaction. Next, 50 mL of methanol was added, and sodium hydrogen sulfite was added until the color of iodine disappeared. The mixture was filtered, washed with water, suspended and washed in methanol, filtered, 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.
[0592] (Synthesis of Compound 2-4) A flask equipped with a stirrer and a condenser was immersed in an ice-water bath, and 50 g of Compound 2-3 and 150 mL of acetone were charged into the flask and stirred. The internal temperature at this time 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 dropwise addition of diisopropylethylamine was completed, 14.7 g of chloromethyl ethyl ether was added dropwise, and the reaction was carried out for 1 hour. After the reaction was completed, 300 g of ethyl acetate and 500 g of water were added to extract the organic phase. The solvent from 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 production was confirmed by NMR and LC-MS. The molecular weight was 400.
[0593] (Synthesis of Na-1) The iodination step and reduction step were carried out in the same manner as in Synthesis Example L1, except that 6,7,8-trimethoxynaphthalene-2-carbaldehyde was used instead of 4-hydroxybenzaldehyde, to obtain compound Na-1. The scheme is shown below. The production was confirmed by NMR and LC-MS. The molecular weight changed from 372 before to 374 after the reduction step.
[0594]
[0595] (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 instead of 4-hydroxybenzaldehyde. The synthesis scheme is shown below. The production was confirmed by NMR and LC-MS. The molecular weight of (Na-2-1) was 298. Furthermore, the molecular weight changed from 356 to 358 before and after the reduction step to produce (Na-2).
[0596]
[0597] (Synthesis of Na-3) Compound Na-3 was obtained in the same manner as in Synthesis Example L1, except that 2-hydroxynaphthalene-6-carbaldehyde was used instead of 4-hydroxybenzaldehyde. The synthesis scheme is shown below. The production was confirmed by NMR and LC-MS. The molecular weight of (Na-3-1) was 298. Furthermore, the molecular weight changed from 356 to 358 before and after the reduction step to produce (Na-3).
[0598]
[0599] (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 used instead of compound 2-1. The synthesis scheme is shown below. The production was confirmed by NMR and LC-MS. The molecular weights of (Na-4-2) and (Na-4-3) were 342 and 400, respectively.
[0600]
[0601] (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 instead of 4-hydroxybenzaldehyde. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-5) changed from 356 to 358 after the reduction step.
[0602]
[0603] (Synthesis of Na-6) Compound Na-6 was obtained in the same manner as in Synthesis Example L1, except that 4-hydroxy-2-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-6) changed from 356 to 358 after the reduction step.
[0604]
[0605] (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 used instead of 4-hydroxybenzaldehyde. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-7) changed from 356 to 358 after the reduction step.
[0606]
[0607] (Synthesis of Na-8) Compound Na-8 was obtained in the same manner as in Synthesis Example L1, except that 4-hydroxy-1-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-8) changed from 356 to 358 after the reduction step.
[0608]
[0609] (Synthesis of Na-9) Compound Na-9 was obtained in the same manner as in Synthesis Example L1, except that 5-hydroxy-2-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-9) changed from 356 to 358 after the reduction step.
[0610]
[0611] (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 instead of 4-hydroxybenzaldehyde. The scheme is shown below. The production was confirmed by NMR and LC-MS. The molecular weight changed from 356 to 358 before and after the reduction step to produce (Na-10).
[0612]
[0613] (Synthesis of Na-11) Compound Na-11 was obtained in the same manner as in Synthesis Example L1, except that 8-hydroxy-1-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-11) changed from 356 to 358 after the reduction step.
[0614]
[0615] (Synthesis of Na-12) Compound Na-12 was obtained in the same manner as in Example 2 (Synthesis of Compound 2-4), except that 1-hydroxy-2-naphthalenecarboxylic acid was used instead of compound 2-1. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-12) increased from 342 to 400 by introducing a protecting group.
[0616]
[0617] (Synthesis of Na-13) Compound Na-13 was obtained in the same manner as in Example 2 (Synthesis of Compound 2-4), except that 4-hydroxy-2-naphthalenecarboxylic acid was used instead of compound 2-1. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-13) increased from 342 to 400 by introducing a protecting group.
[0618]
[0619] (Synthesis of Na-14) Compound Na-14 was obtained in the same manner as in Example 2 (Synthesis of Compound 2-4), except that 4-hydroxy-2-naphthalenecarboxylic acid was used instead of compound 2-1. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-14) increased from 342 to 400 by introducing a protecting group.
[0620]
[0621] (Synthesis of Na-15) Compound Na-15 was obtained in the same manner as in Example 2 (Synthesis of Compound 2-4), except that 5-hydroxy-1-naphthalenecarboxylic acid was used instead of compound 2-1. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-15) increased from 342 to 400 by introducing a protecting group.
[0622]
[0623] (Synthesis of Na-16) Compound Na-16 was obtained in the same manner as in Example 2 (Synthesis of Compound 2-4), except that 5-hydroxy-2-naphthalenecarboxylic acid was used instead of compound 2-1. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-16) increased from 342 to 400 by introducing a protecting group.
[0624]
[0625] (Synthesis of Na-17) Compound Na-17 was obtained in the same manner as in Example 2 (Synthesis of Compound 2-4), except that 8-hydroxy-2-naphthalenecarboxylic acid was used instead of compound 2-1. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-17) increased from 342 to 400 by introducing a protecting group.
[0626]
[0627] (Synthesis of Na-18) Compound Na-18 was obtained in the same manner as in Example 2 (Synthesis of Compound 2-4), except that 8-hydroxy-1-naphthalenecarboxylic acid was used instead of compound 2-1. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-18) increased from 342 to 400 by introducing a protecting group.
[0628]
[0629] (Synthesis of Na-19) Compound Na-19 was obtained in the same manner as in Synthesis Example L1, except that 6-hydroxy-2-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The synthesis scheme is shown below. The synthesis was confirmed by NMR and LC-MS. The molecular weight of (Na-19) changed from 356 to 358 after the reduction step.
[0630]
[0631] Synthesis Example DMN2-3P The following reaction was carried out.
[0632]
[0633] (Synthesis of Compound 2-2) Compound 2-2 was obtained in the same manner as in Example 2. The production was confirmed by NMR and LC-MS. The molecular weight was 216.
[0634] (Synthesis of Compound DMN2-3) In a flask equipped with a stirrer and a condenser, 34 g of Compound 2-2, 48 g of iodine (1.2 equivalents relative to Compound 2-2), 10 g of sodium bicarbonate, 160 mL of methanol, and 16 mL of water were charged. The contents were stirred at 40°C for 5 hours to carry out an iodination reaction. Next, 50 mL of methanol was added, and sodium hydrogen sulfite was added until the color of iodine disappeared. The mixture was filtered, washed with water, suspended and washed in methanol, then filtered and dried to obtain Compound DMN2-3. The production was confirmed by NMR and LC-MS. The molecular weight was 682.
[0635] (Synthesis of Compound DMN2-3P) A flask equipped with a stirrer and a condenser was immersed in an ice-water bath, and 50 g of Compound DMN2-3 and 150 mL of acetone were charged into the flask and stirred. The internal temperature at this time was 4°C. Next, 20.8 g (1.1 equivalents relative to DMN2-3) of diisopropylethylamine was added dropwise to the flask. After the dropwise addition of diisopropylethylamine was completed, 14.7 g of chloromethyl ethyl ether was added dropwise, and the reaction was carried out for 1 hour. After the reaction was completed, 300 g of ethyl acetate and 500 g of water were added to extract the organic phase. The solvent from the extracted organic phase was distilled off, and the mixture was separated by column chromatography to obtain Compound DMN2-3P. The production was confirmed by NMR and LC-MS. The molecular weight was 798.
[0636] [Synthesis Example BPN2-3P] The following reaction was carried out.
[0637]
[0638] (Synthesis of Compound 2-2) Compound 2-2 was obtained in the same manner as in Example 2.
[0639] (Synthesis of Compound BPN2-3P) A flask equipped with a stirrer and a condenser was immersed in an ice-water bath, and 15.8 g of Compound 2-2 and 150 mL of acetone were charged into the flask and stirred. The internal temperature at this time 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 dropwise addition of diisopropylethylamine was completed, 14.7 g of chloromethyl ethyl ether was added dropwise, and the reaction was carried out for 1 hour. After the reaction was completed, 300 g of ethyl acetate and 500 g of water were added to extract the organic phase. The solvent from the extracted organic phase was distilled off, and the mixture was separated by column chromatography to obtain Compound BPN2-3P. The production was confirmed by NMR and LC-MS. The molecular weight was 274.
[0640] (Synthesis of DMNa-1-1) Compound DMNa-1-1 was synthesized in the same manner as in Synthesis Example DMN2-3, except that 6,7,8-trimethoxynaphthalene-2-carbaldehyde was used instead of compound 2-2. The production was confirmed by NMR and LC-MS. The molecular weight was 744.
[0641]
[0642] [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-naphthaldehyde was used instead of compound 2-2. Production 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 used instead of compound DMN2-3. Production 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 used instead of compound 1-2. Production was confirmed by NMR and LC-MS. The molecular weight was 714.
[0643]
[0644] [Synthesis Example BPNa2-1R] Compound BPNa2-1P was obtained in the same manner as in the synthesis of compound DMN2-3P, except that 2-hydroxy-3-naphthaldehyde was used instead of compound DMN2-3. The production was confirmed by NMR and LC-MS. The molecular weight was 230. Furthermore, compound BPNa-2-1R was obtained in the same manner as in the synthesis of compound 1-3, except that compound BPNa2-1P was used instead of compound 1-2. The production was confirmed by NMR and LC-MS. The molecular weight was 232.
[0645]
[0646] (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-carbaldehyde was used instead of compound 2-2. The production was confirmed by NMR and LC-MS. The molecular weight was 594. Next, compound DMNa3-1P was obtained in the same manner as in the synthesis of compound DMN2-3P, except that compound DMNa-3-1 was used instead of compound DMN2-3. The production 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 DMNa3-1P was used instead of compound 1-2. The production was confirmed by NMR and LC-MS. The molecular weight was 714.
[0647]
[0648] [Synthesis Example DMNa-2b-1R] The following reaction was carried out.
[0649]
[0650] Compound DMNa-2b-1 was obtained in the same manner as in the iodination step DML1D, except that 2-hydroxy-3-naphthaldehyde was used instead of 4-hydroxybenzaldehyde. The formation was confirmed by NMR and LC-MS. The molecular weight was 594. Next, compound Na-2b-1P was obtained in the same manner as in the protecting group introduction step DML1P, except that compound DMNa-2b-1 was used instead of 5-iodovanillin. The formation was confirmed by NMR and LC-MS. The molecular weight was 710. Furthermore, compound DMNa-2b-1R was obtained in the same manner as in the reduction step DML1R, except that compound DMNa-2b-1P was used instead of DML1P. The formation was confirmed by NMR and LC-MS. The molecular weight was 714.
[0651] [Synthesis Example: Synthesis of DMNa-3-2R] The following reaction was carried out.
[0652]
[0653] The iodination step, the protecting group introduction step, and the reduction step were carried out in the same manner as in Synthesis Example DMNa-2-1, except that 2-hydroxynaphthalene-6-carbaldehyde was used instead of 2-hydroxy-3-naphthaldehyde as the starting material, to obtain compound DMNa-3-2R. The production was confirmed by NMR and LC-MS. The molecular weight was 714.
[0654] (Synthesis of DMNa-4-2P) Compound Na-4-1 was obtained in the same manner as in the synthesis of compound 2-2, except that 3-hydroxy-2-naphthoic acid was used instead of compound 2-1. Next, compound DMNa-4-2 was obtained in the same manner as in the iodination step in Synthesis Example DMNa-2-1, except that compound Na-4-1 was used instead of compound 2-2. The production was confirmed by NMR and LC-MS. The molecular weight was 682. Furthermore, this compound was subjected to a protecting group introduction step in the same manner as in Synthesis Example DMNa-2-1, to obtain compound DMNa-4-2P. The production was confirmed by NMR and LC-MS. The molecular weight was 798.
[0655]
[0656] Example 3 Compound Having Adamantane as Mother Nucleus (Synthesis 1 of Compound 3-2) The compound was produced according to the following scheme.
[0657]
[0658] A flask equipped with a stirrer and a condenser was immersed in an oil bath, and 80 g of compound 3-1 (manufactured by Mitsubishi Gas Chemical Company, Inc., 0.43 mol) and 2.5 L of toluene were charged into the flask and stirred. Next, 400 g (1.72 mol) of 55% aqueous hydrogen iodide solution was added to the flask. The internal temperature was kept at 83 to 89°C and the reaction was carried out for 32 hours. Furthermore, 50 g of 55% aqueous hydrogen iodide solution was added to the flask. The internal temperature was kept at 83 to 89°C and the reaction was carried out for 16 hours.
[0659] In a separate container, 22.5 mL of 10% aqueous sodium sulfite solution and 1,720 mL of water were charged, and the reaction solution was slowly poured into the container. 2 g of sodium sulfite and 1 L of ethyl acetate were added, resulting in separation into an organic phase and an aqueous phase. Further water was added, and the mixture was separated to obtain an organic phase (oil phase). The organic phase was concentrated, 500 mL of toluene was added, and the mixture was left in a freezer overnight.
[0660] The organic phase was filtered and washed with chilled toluene and hexane to obtain 145 g of a wet cake. 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. The ethyl acetate solution was cooled to room temperature. 650 mL of 0.5% aqueous sodium sulfite solution was added to the liquid, stirred, and the mixture was separated, and the ethyl acetate phase was removed.
[0661] To the ethyl acetate phase, 650 mL of water was added, stirred, and the mixture was separated. The ethyl acetate phase was again removed, magnesium sulfate was added, and the mixture was stirred for 30 minutes and allowed to stand in a refrigerator for two nights. After standing, crystals precipitated, which were dissolved by heating and cooled to room temperature again. The cooled mixture was filtered to obtain magnesium sulfate and a filtrate. The magnesium sulfate was washed with ethyl acetate. The filtrate thus obtained 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 in which only one of the hydroxy groups of compound 3-1 was converted to iodine was <1%, and the yield of the compound in which all three hydroxy groups were converted to iodine was <1%.
[0662] (Synthesis of Compound 3-2 2) A flask equipped with a stirrer, a condenser, and a Dean-Stark tube was immersed in an oil bath, and 308 g of toluene was added to 21 g of 1,3,5-adamantanetriol, followed by 78.6 g of 55 wt % aqueous hydrogen iodide solution. The mixture was refluxed at 105-110°C for 3 hours while 26 g of distilled water was removed using a Dean-Stark tube, after which it was cooled to room temperature. 177.5 g of water was added, followed by 10 g of 10% aqueous sodium sulfite solution. 61.4 g of 6% aqueous sodium hydroxide solution was then added for neutralization. The reaction mixture was then filtered, and 31 g of the toluene solution and crystals were separated. The toluene solution was then 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. 341 g of ethyl acetate was added to 31 g of the filtered crystals and dissolved, followed by separation and washing with 85 g of water and 0.4 g of a 10% aqueous sodium sulfite solution. Separation and washing were further performed six times with 85 g of water, yielding 316 g of an ethyl acetate solution. 255 g of the toluene solution and 316 g of the ethyl acetate solution in which the crystals had been dissolved were concentrated under reduced pressure, and the precipitated crystals were filtered and then dried under reduced pressure at 50 ° C. to obtain 40.9 g 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 in which only one hydroxy group of compound 3-1 was converted to iodine was <1%, and the yield of the compound in which three hydroxy groups were converted to iodine was <1%.
[0663] (Synthesis of Compound 3-2 3) A flask equipped with a stirrer, a condenser, and a Dean-Stark tube was immersed in an oil bath, and 102 g of toluene was added to 7 g of 1,3,5-adamantanetriol. 26.6 g of a 55 wt % aqueous hydrogen iodide solution was then added, and the mixture was allowed to stand for 12 hours. The mixture was then refluxed for 1 hour at 102-108°C while 8.5 g of distilled water was removed using a Dean-Stark tube, and then cooled to room temperature. 59 g of water was added, followed by 8 g of a 10% aqueous sodium sulfite solution. The reaction mixture was then filtered, and 12 g of the toluene solution and crystals were separated by filtration. The toluene solution was then washed five times with 29 g of water, yielding 85 g of a toluene solution. 12 g of the separated crystals were added and dissolved in 122 g of ethyl acetate, and then 28 g of water and 0.4 g of a 10% aqueous sodium sulfite solution were added for separation and washing. Six more separate washings were performed with 85 g of water, yielding 105 g of an ethyl acetate solution. 85 g of the toluene solution and 105 g of the ethyl acetate solution were concentrated under reduced pressure, and the precipitated crystals were filtered and dried under reduced pressure at 50° C. to obtain 13.7 g of compound 3-2 as a white crystal with a purity of 99.3% (yield 91%). At the end of the reflux reaction, the yield of compound 3-1 in which only one hydroxy group was converted to iodine was <1%, and the yield of compound 3-1 in which all three hydroxy groups were converted to iodine was 2%.
[0664] (Synthesis 3-2 of Compound 3-2) The same operations as in Synthesis 2 of Compound 3-2 were carried out except for adding 50 g of silica gel to 105 g of the obtained ethyl acetate solution to carry out silica gel dispersion and recovering the organic phase by filtration, thereby obtaining 13.5 g of compound (3-2) in a high purity with a yield of 90% and an LC purity of >99.9%.
[0665] (Synthesis of Compound 3-2 4) A flask equipped with a stirrer, a condenser, and a Dean-Stark tube was immersed in an oil bath, and 17.8 g of water was added to 21 g of 1,3,5-adamantanetriol. 78.6 g of 55 wt % aqueous hydrogen iodide solution was then added and stirred. The mixture was refluxed at 115-120°C for 2 hours while 28 g of distilled water was removed using a Dean-Stark tube, and then cooled to room temperature. 100 g of water was added, followed by 15 g of 10% aqueous sodium sulfite solution. The reaction solution was then filtered, and 45 g of crystals were separated. 220 g of ethyl acetate was added to the separated 45 g of crystals and dissolved, followed by separation washing with 110 g of water and 4.8 g of 10% aqueous sodium sulfite solution. Eight separate washings with 110 g of water were then performed, yielding 165 g of ethyl acetate solution. The resulting ethyl acetate solution was concentrated under reduced pressure, and the precipitated crystals were filtered and dried under reduced pressure at 50°C to obtain 41.9 g of compound 3-2 as white crystals with a purity of 99.1% and a yield of 91%. At the end of the reflux reaction, the yield of compound 3-1 in which only one hydroxy group was converted to iodine was 1%, and the yield of compound 3-1 in which three hydroxy groups were converted to iodine was 2%.
[0666] (Synthesis of Compound 3-2 5) The obtained precipitate was dissolved in 10.5 L of ethyl acetate, and then 50 g of silica gel was added to carry out silica gel dispersion, followed by an additional step of recovering the organic phase by filtration. The same operations as in Synthesis Example L1 were otherwise carried out to obtain 1,660 g of compound (1-3) with a high purity of >99.9% and a yield of 76%.
[0667] (Synthesis of Ad-A-1) 1278 g of acetonitrile was added to 150 g of 1,3,5-adamantanetriol and stirred. At room temperature under nitrogen, 177 g of trimethylsilyl chloride was added, followed by the addition of 244 g of sodium iodide (2 equivalents relative to 1,3,5-adamantanetriol) in portions. The bath temperature was set to 85°C, and the reaction was continued for 6 hours, followed by cooling overnight. 1625 g of water was added, followed by 79 g of a 10% aqueous solution of sodium sulfite. The mixture was concentrated under reduced pressure using an evaporator until the volume reached 2.2 kg, and 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. It was dried under reduced pressure at 30°C, yielding 132 g of solid. The product was confirmed by NMR and LC-MS. The molecular weight was 294.
[0668]
[0669] (Synthesis of Ad-A-2) 100 ml of dehydrated N-methylpyrrolidone (NMP) was added to 24 g of 1-iodoadamantane-3,5-diol and the mixture was cooled with ice. 10 g of chloroacetyl chloride was added dropwise at 5°C or below. The bath temperature was set to 60°C and the reaction was carried out for one hour. The reaction solution was added to ice containing 4% hydrochloric acid with stirring. The mixture was extracted with 200 ml of ethyl acetate and washed with 100 ml of 2% hydrochloric acid and 100 ml of water. After dehydration with saturated saline and sodium sulfate, the solvent was removed using an evaporator and the mixture was purified by silica gel column chromatography. 18.8 g of solid was obtained. The product was confirmed by NMR and LC-MS. The molecular weight was 371.
[0670]
[0671] (Synthesis of Ad-2-2) Compound Ad-2-2 was obtained in the same manner as in Example 1, except that compound Ad-2-1 was used instead of compound 3-1. The production was confirmed by NMR and LC-MS. The molecular weight was 420.
[0672]
[0673] (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 succinic acid chloride was added dropwise. After the dropwise addition was completed, the reaction was carried out at 60°C for 2 hours. THF was distilled off from the reaction solution, toluene was added to the residue, and the precipitated solid was filtered to obtain 11 g of Ad-2-3. The production was confirmed by NMR and LC-MS. The molecular weight was 657.
[0674]
[0675] (Synthesis of Ad-2-4) 10 g of Ad-2-2 was dissolved in 50 ml of THF and cooled on ice, after which 7.7 g of succinyl chloride was added dropwise. After the addition was complete, the reaction was carried out at 60°C for 2 hours. After the reaction solution 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 solution, and the precipitated solid was filtered to obtain 10 g of Ad-2-4. The production was confirmed by NMR and LC-MS. The molecular weight was 620.
[0676]
[0677] (Synthesis of Ad-A-3) The compound was produced according to the following scheme.
[0678] (Synthesis of Ad-A-3-1) To 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 solution and the mixture was filtered. The filtrate was concentrated, and the resulting residue was washed with acetone to obtain 20.0 g of crude Ad-A-3-1 (GC purity 68%). This was used in the next step without purification.
[0679] (Synthesis of Ad-A-3-2) To a solution of 20.0 g of the crude product of Ad-A-3-1 in methanol (300 mL) were added 18 mL (289 mmol) of iodomethane and 25 mL (167 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene. After stirring at 60°C for 5 hours, 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.
[0680] (Synthesis of Ad-A-3) To a solution of 21.4 g (94.5 mmol) of Ad-A-3-2 in methanol (100 mL) was added 4.6 g (115 mmol, 1.2 equivalents) of sodium hydroxide in water (100 mL). After stirring at 60°C for 12 hours, the reaction solution was concentrated. To the residue was added 200 mL of 57% hydroiodic acid, and the mixture was stirred at 60°C for 18 hours. After cooling to room temperature, the reaction solution was added to an aqueous sodium sulfite solution. The solid was collected by filtration and washed with water and toluene. This was reprecipitated from methanol-water to obtain 22.8 g (70.8 mmol) of Ad-A-3. Formation was confirmed by NMR and LC-MS. １ H-NMR: δ (ppm) (d-DMSO): 12.3 (1H, -COOH), 4.9 (1H, -OH), 1.2 to 2.5 (13H, =CH-, -CH ２ -,) and the molecular weight was 322.
[0681] (Synthesis of Ad-A-4)
[0682] A 300 mL flask equipped with a reflux condenser was charged with 0.4 mg of lithium aluminum hydride and 100 mL of ultra-dehydrated THF, and the mixture was stirred at 220 rpm for 1 hour under a nitrogen flow. 3.2 g of Ad-A-3 was then gradually added in 10 portions over 40 minutes. The mixture was then stirred for 24 hours at 24°C and 70 rpm. 100 mL of purified water was added, and the precipitate formed was collected by filtration. After drying, 0.3 g of Ad-A-4 was obtained (yield 10%). The formation of the product was confirmed by NMR and LC-MS. １ H-NMR: δ (ppm) (d-DMSO): 4.9 (1H, -OH), 4.2 (1H, -CH ２ OH), 1.0 to 2.5 (15H, =CH-, -CH ２-,) and the molecular weight was 308.
[0683] (Synthesis of Ad-A-5)
[0684] 57% hydroiodic acid (300 mL) was added to Ad-A-3-2 (20.4 g, 90.1 mmol) obtained in the synthesis of Ad-A-3, and the mixture was heated to 110°C. The mixture was heated and stirred for 9 hours while distilling off the resulting methanol. After cooling to room temperature, water was added to the reaction mixture. Then, an aqueous sodium sulfite solution was added until the red color disappeared. The solid was collected by filtration and washed with water. This 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.
[0685] The conditions for GC-MS and LC-MS in the synthesis of Ad-A-5 are as follows. [GC-MS] Column used: Agilent GC column DB-5ms, inner diameter: 0.25 mm, length: 30 m, film thickness: 0.25 μm Pretreatment: 1 mL of TMS-HT (Hexamethyldisilazane and Trimethylchlorosilane in Anhydrous Pyridine) was added to approximately 5 mg of the obtained (Ad-A-5), kneaded for about 30 seconds, and then allowed to stand for 5 minutes, after which the mixture was stretched and the supernatant was measured. Temperature conditions: Ing. Temp.: 300°C, Det. Temp.: 100°C. : 300°C 200°C (4 min hold) - (20°C / min) → 320°C (4 min hold) Split ratio: 50:1 Injection volume: 1 μL [LC-MS (ESI-MS)] An acetonitrile (approximately 1 mg / mL) solution of the obtained (Ad-A-5) was prepared, and 3 μL of this solution was injected. An acetonitrile-0.1% formic acid aqueous solution (ratio 9:1) was delivered at 0.2 mL / min and introduced into an ESI-MS (electrospray ionization mass spectrometer) without passing through a column.
[0686] (Synthesis of Ad-A-6-0 and Ad-A-6-1)
[0687] To a suspension of 3.0 g (15.3 mmol) of Ad-A-3-0 (3-hydroxy-1-adamantanecarboxylic acid) in acetonitrile-water (1:1, 30 mL), 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 equivalents) 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, 35% by mass aqueous sodium bisulfite solution (5 mL) was added dropwise under ice cooling. Further, acetone was added, and the filtered filtrate was concentrated, and acetonitrile (15 mL) was added to obtain 2.11 g of a white precipitate. This white precipitate was purified by silica gel column chromatography to obtain Ad-A-6-0 (0.17 g, yield 5.2%).
[0688] To a solution of 1.8 g (7.4 mmol) of the obtained Ad-A-6-0 in methanol (20 mL) were added 1.8 mL (29 mmol) of iodomethane and 2.5 mL (17 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene. 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 in the synthesis of Ad-A-5.
[0689] (Synthesis of Ad-A-6a and Ad-A-6b)
[0690] 1 g (4.38 mmol) of Ad-A-6-0 was suspended in toluene (5 mL), 57% hydroiodic acid (2.0 mL, 15 mmol) was added, and then toluene (5 mL) was added. The mixture was heated to reflux for 2 hours. After cooling to room temperature, the reaction suspension was added to purified water (25 mL), and 35% aqueous sodium hydrogen sulfite solution (1 mL) was added for decolorization. The precipitate collected 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 in the synthesis of Ad-A-5.
[0691] (Synthesis of Ad-A-6c)
[0692] 57% hydroiodic acid (5.0 mL, 37.9 mmol) was added to 1 g (4.03 mmol) of Ad-A-6-1, and the mixture was stirred at 60°C for 7 hours. After cooling to room temperature, the suspension after the reaction was added to pure water (25 mL), and 35% aqueous sodium hydrogen sulfite solution (1 mL) was added for decolorization. The precipitate collected by filtration 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 in the synthesis of Ad-A-5.
[0693] [Synthesis Example DMA1P] Compound having adamantane as a parent nucleus The compound was produced according to the following scheme.
[0694]
[0695] A flask equipped with a reflux condenser and a Dean-Stark tube was immersed in an oil bath, and 80 g of compound 3-1 (manufactured by Mitsubishi Gas Chemical Company, Inc., 0.43 mol) and 2.5 L of o-xylene were charged into the flask and stirred. Next, 400 g (1.72 mol) of a 55% aqueous hydrogen iodide solution was added to the flask. The internal temperature was set to 125°C and the reaction was carried out for 3 hours. Thereafter, the mixture was stirred for 1 hour in a water bath at 25°C.
[0696] An additional 2.5 L of ion-exchanged water was added to the reaction vessel, and the mixture was separated into an organic phase and an aqueous phase. After collecting the organic phase, it was washed three times with 1 L of 5% sodium bicarbonate water and then with 1 L of ion-exchanged water. After collecting the organic phase, it was concentrated to obtain 35 g of a white solid (DMA1a). The production was confirmed by NMR and LC-MS. The molecular weight was 570.
[0697] A 3L flask equipped with a reflux condenser and a Dean-Stark tube was charged with 35 g of DMA1a (0.06 mol) and 182.5 mL of dehydrated toluene under nitrogen flow, and the mixture was dissolved by stirring with a stirring blade. Next, 12 g of methanesulfonic acid was added over 30 minutes while stirring, and the mixture was dissolved. 7.4 g of succinic anhydride (1.2 equivalents relative to the substrate) was then added to the stirred reaction solution over 60 minutes, after which the internal temperature was raised to 100°C and the mixture was stirred for 2 hours. The mixture was then cooled to room temperature, 360 mL of pure water was added, and the toluene phase was recovered after separation. The mixture was then washed with 360 mL of 0.5% aqueous sodium bicarbonate solution, followed by three washes with 350 mL of ion-exchanged water. The recovered toluene phase was concentrated under reduced pressure to obtain 20.6 g of a white solid, the desired protected DMA1aP form. The yield was 50%. The product was confirmed by NMR and LC-MS. The molecular weight was 670.
[0698]
[0699] [Synthesis Example DMA2] Compound having adamantane as a parent nucleus The compound was produced according to the following scheme. (Synthesis of DMA2a)
[0700]
[0701] A flask equipped with a reflux condenser and a Dean-Stark tube was immersed in an oil bath, and 87.9 g of compound Ad-2-1 (0.43 mol) and 2.5 L of toluene were charged into the flask and stirred. Next, 400 g (1.72 mol) of 55% aqueous hydrogen iodide solution was added to the flask. The internal temperature was raised to 100°C and the reaction was carried out for 3 hours. After that, the mixture was stirred for 1 hour in a water bath at 25°C.
[0702] An additional 2.5 L of ion-exchanged water was added to the reaction vessel, and the mixture was separated into an organic phase and an aqueous phase. After collecting the organic phase, it was washed three times with 1 L of 5% sodium bicarbonate water and then with 1 L of ion-exchanged water. After collecting the organic phase, it was concentrated to obtain 37 g of a white solid (DMA2a). The production was confirmed by NMR and LC-MS. The molecular weight was 602.
[0703] (Synthesis of DMA2aP)
[0704]
[0705] Using a 3 L flask connected to a reflux condenser and Dean-Stark tube, 37 g (0.06 mol) of (DMA1a) was added to 182.5 mL of dehydrated toluene under nitrogen flow and dissolved with stirring using a stirring blade. Next, 12 g of methanesulfonic acid was added over 30 minutes while stirring and dissolved. 7.4 g of succinic anhydride (1.2 equivalents relative to the substrate) was added to the stirred reaction solution over 60 minutes, after which the internal temperature was raised to 100 °C and the mixture was stirred for 2 hours. The mixture was then cooled to room temperature, 360 mL of pure water was added, and the toluene phase was recovered after separation. After further washing with 360 mL of 0.5% aqueous sodium bicarbonate solution, the mixture was washed three times with 350 mL of ion-exchanged water. The recovered toluene phase was concentrated under reduced pressure to obtain 23.8 g of a white solid (DMA2aP). The yield was 55%. The product was confirmed by NMR and LC-MS. The molecular weight was 702.
[0706] (Synthesis of DMA1aP2)
[0707]
[0708] 140 ml of dehydrated NMP was added to 47.1 g of DMA1a and the mixture was cooled with ice. 10 g of chloroacetyl chloride was added dropwise at 5°C or below. The bath temperature was set to 60°C and the reaction was allowed to proceed for one hour. The reaction mixture was added to ice containing 4% hydrochloric acid with stirring. The mixture was extracted with 200 ml of ethyl acetate and washed with 100 ml of 2% hydrochloric acid and 100 ml of water. After dehydration with saturated brine and sodium sulfate, the solvent was removed using an evaporator and the mixture was purified by silica gel column chromatography. 29.6 g of solid was obtained as the target product, DMA1aP2, in a yield of 79.7%. Production was confirmed by NMR and LC-MS. The molecular weight was 679.
[0709] (Synthesis of DMA2aP2)
[0710]
[0711] 140 ml of THF was added to 49.1 g of DMA2a and the mixture was cooled on ice. 14 g of succinic acid chloride was added dropwise at 5°C or below. The bath temperature was set to 60°C and the reaction was carried out for 2 hours. After the dropwise addition was completed, the reaction was carried out for 2 hours at 60°C. THF was distilled off from the reaction solution, toluene was added to the residue, and 46.9 g of the precipitated solid was recovered by filtration, obtaining the target product, DMA2aP2, in a yield of 79.8%. The production was confirmed by NMR and LC-MS. The molecular weight was 721.
[0712] (Synthesis of DMA3a)
[0713] DMA3-2 was obtained in the same manner as in the synthesis of Ad-A-3-2, except that 60 g (258 mmol) of 55% aqueous hydrogen iodide solution was used instead of 18 mL (289 mmol) of iodomethane. Next, DMA3a was obtained in the same manner as in the synthesis of Ad-A-3, except that DMA3-2 was used instead of AdA-3-2. The production was confirmed by NMR and LC-MS. The molecular weight was 626.
[0714]
[0715] (Synthesis of DMA4a)
[0716] DMA4a was obtained in the same manner as in the synthesis of Ad-A-4, except that DMA3a was used instead of AdA-3. The production was confirmed by NMR and LC-MS. The molecular weight was 598.
[0717]
[0718] (Synthesis of DAMA1-tl) DAMA1-tl was obtained in the same manner as in (Synthesis 2 of Compound 3-2), except that hydrogen iodide:sulfuric acid = 1:1 was used instead of hydrogen iodide. The production was confirmed by NMR and LC-MS. The molecular weight was 384.
[0719]
[0720] (Synthesis of DAMA1-mx) DAMA1-mx was obtained in the same manner as in the synthesis of DAMA1-tl, except that meta-xylene was used instead of toluene. The production was confirmed by NMR and LC-MS. The molecular weight was 398.
[0721]
[0722] (Synthesis of DAMA1-eb) DAMA1-eb was obtained in the same manner as in the synthesis of DAMA1-tl, except that ethylbenzene was used instead of toluene. The production was confirmed by NMR and LC-MS. The molecular weight was 398.
[0723]
[0724] [Examples 4 to 7, 7A to 7C] Lithography 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 refluxing 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 polymer MAR represented by the following formula (MAR) in the form of a white powder. The weight-average molecular weight (Mw) of this polymer was 11,500, and the dispersity (Mw / Mn) was 1.90. In addition, １３ As a result of C-NMR measurement, the composition ratio (molar ratio) in the following formula (MA1) was found to be a:b:c:d = 60:10:15:15. Note that, although the following formula (MAR) is written in a simplified form to indicate the ratio of each structural unit, the arrangement order of the structural units is random, and it is not a block copolymer in which each structural unit forms an independent block. The molar ratio was determined based on the integral ratio of the main chain carbon directly bonded to benzene for units having benzene, and the carbonyl carbon of the ester bond for methacrylate-based units (2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, and hydroxyadamantyl methacrylate).
[0725]
[0726] (Compositions) 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 compositions shown in Table 1. The acid generator, acid diffusion inhibitor, and organic solvent used were as follows: Acid generator: triphenylsulfonium nonafluorobutanesulfonate (TPS-109) manufactured by Midori Chemical Co., Ltd. Acid diffusion controller: tri-n-octylamine (TOA) manufactured by Kanto Chemical Co., Ltd. Organic solvent: propylene glycol monomethyl ether acetate (PGMEA) manufactured by Kanto Chemical Co., Ltd.
[0727]
[0728] [Evaluation Method] (Pattern Evaluation of EB Resist Pattern (Pattern Formation)) After preparing a resist composition according to the composition shown in Table 1, the resist composition was spin-coated on a clean silicon wafer and then pre-exposure baked (PB) on a hot plate at 110°C to form a resist film with a thickness of 50 nm. The resulting resist film was irradiated with an electron beam using an EB lithography system (ELS-7500, manufactured by Elionix Co., Ltd.) in a 1:1 line-and-space setting with 50 nm spacing. After this irradiation, the resist film was heated at 110°C for 90 seconds and then immersed in a 2.38% by mass TMAH alkaline developer for 60 seconds to perform development. The resist film was then washed with ultrapure water for 30 seconds and dried to form a resist pattern.
[0729] (Resist Pattern Shape Evaluation) The cross-sectional shape of the obtained 50 nm L / S (1:1) resist pattern was observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd. Regarding the resist pattern shape after development, a pattern width at a position 10% above the pattern height from the surface of the silicon wafer relative to the half-width of the pattern cross section was evaluated as "A" if it was less than +10% of the half-width, and a pattern width at a position 10% above the half-width was evaluated as "C" if it was +10% or more of the half-width. (Resist Pattern Defects) Furthermore, regarding the resist pattern defects after development, the number of spherical foreign particles in a 1 μm long resist pattern was determined as an index. (Evaluation Criteria) S: Number of spherical foreign matter = 0 A: 0 < number of spherical foreign matter ≦ 5 C: 5 < number of spherical foreign matter (Electron Beam Litigation Sensitivity) The minimum amount of electron beam energy capable of lithography of a shape without pattern collapse was defined as "electron beam lithography sensitivity." Electron beam lithography sensitivity equivalent to or better than that of Comparative Example 1 was rated as "A," and sensitivity inferior to that of Comparative Example 1 was rated as "C."
[0730]
[0731] [Examples 8 to 11] EUV Exposure Sensitivity, Etching Defects (EUV Exposure Sensitivity) The compositions prepared in Examples 4 to 7 and 7A to 7C were spin-coated onto silicon wafers and then baked at 110°C for 60 seconds to form photoresist layers with a thickness of 100 nm. For the composition of Comparative Example 3, Compound 3-1 was used instead of Compound 1-3 in Example 4. Next, the composition was exposed to 1 mJ / cm using an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by LithoTech Japan Co., Ltd.). ２ to 1 mJ / cm ２ 80 mJ / cm ２After maskless shot exposure with the exposure dose increased to 1000 ppm, the wafer was baked (PEB) at 110°C for 90 seconds and developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, yielding a wafer with 80 shots of exposure on the wafer. For each of the resulting shot exposure areas, the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), profile data of the film thickness versus exposure dose was obtained, and the exposure dose at which the slope of the film thickness variation versus exposure dose was greatest was determined as the sensitivity value (mJ / cm). ２ ) and used as an index of the EUV sensitivity of the resist.
[0732] (Evaluation of Etching Defects) The composition used in the EUV exposure sensitivity measurement was applied to an 8-inch silicon wafer having a 100 nm-thick oxide film formed on the outermost surface, and baked at 110°C for 60 seconds to form a photoresist layer with a thickness of 100 nm. Next, using an extreme ultraviolet (EUV) exposure device "EUVES-7000" (product name, manufactured by Litho Tech Japan Co., Ltd.), the entire wafer was subjected to shot exposure at an exposure dose 10% less than the EUV sensitivity value obtained in the above-mentioned EUV sensitivity evaluation, and further baked at 110°C for 90 seconds (PEB) and developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, thereby obtaining a wafer that had been shot-exposed for 80 shots across the entire wafer.
[0733] (Etching Defects) The exposed wafers thus produced were subjected to etching using an etching device "Telius SCCM" (product name, manufactured by Tokyo Electron Ltd.). ４ Etching was performed using Ar / Ar gas until the oxide film was etched by 50 nm. The wafers produced by etching were subjected to defect evaluation using a defect inspection device "Surfscan SP5" (product name, manufactured by KLA Corporation), and the number of cone defects of 19 nm or more was determined as an index of etching defects. (Evaluation criteria) A: Number of cone defects ≦ 10 B: 10 < Number of cone defects ≦ 80 C: 80 < Number of cone defects ≦ 400 D: 400 < Number of cone defects
[0734] (Changes in Etching Defect Evaluation Over Time) The composition used in the etching defect evaluation was left at room temperature for 7 days, and then the etching defect evaluation was performed again. When the change in EUV sensitivity before and after leaving was less than 6%, it was evaluated as "G", and when it was 6% or more, it was evaluated as "N".
[0735]
[0736] [Example 12] Acid-Purified Product of Compound 3-2 (Treatment 1: Acid Purification) 150 g of a solution (10% by mass) of Compound 3-2 dissolved in PGMEA was charged into a 1000 mL four-neck flask (bottom-opening type) and heated to 80 ° C. with stirring. Next, 37.5 g of an aqueous oxalic acid solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes. This resulted in separation into an oil phase and an aqueous phase, and the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was charged into the obtained oil phase, stirred for 5 minutes, and then allowed to stand for 30 minutes, and the aqueous phase was removed. After repeating this operation three times, the flask was heated to 80 ° C. while reducing the pressure inside to 200 hPa or less, and the residual water and PGMEA were concentrated and distilled off. Thereafter, 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 a reduced metal content.
[0737] (Treatment 2: Treatment without Using Acid) A PGMEA solution of Compound 3-2 with a concentration adjusted to 10% by mass was obtained in the same manner as in Example 12, except that ultrapure water was used instead of the aqueous oxalic acid solution.
[0738] The metal contents were measured by ICP-MS for a 10 mass% PGMEA solution of Compound 3-2 that had not been treated, a 10 mass% PGMEA solution of Compound 3-2 that had been treated with Treatment 1, and a 10 mass% PGMEA solution of Compound 3-2 that had been treated with Treatment 2. The measurement results are shown in the table below.
[0739]
[0740] (EUV Exposure Sensitivity, Etching Defects) EUV exposure sensitivity and etching defects were measured using purified Compound 3-2 in the same manner as in Example 8. The measurement results are shown in the following table.
[0741]
[0742] Example 13 Synthesis of aldehyde having benzene as a parent structure The compound was produced according to the following scheme: The reaction was carried out under a nitrogen stream.
[0743]
[0744] (Synthesis of Compound 1-1, Compound 1-1a, and Compound 1-1b) 150 g (1.2 mol) of 4-hydroxybenzaldehyde and 1 L of methanol (Kanto Chemical) were weighed into a 3 L three-neck flask equipped with a stirrer and a nitrogen flow. The flask was immersed in a water bath, the temperature of the water bath was set to 40°C, and the mixture was heated with stirring under a nitrogen stream, and 200 mL of water was added. When the internal temperature reached 34°C, 309.4 g (3.7 mol) of sodium bicarbonate (NaHCO ３ ) was added all at once.
[0745] When the internal temperature reached 38°C, 654.5 g (2.6 mol) of iodine (I ２ ) was added in portions while being careful not to foam, and the mixture was stirred at 40°C for 3 hours. After that, the flask was cooled with water, and an aqueous sodium sulfite solution (Na ２ SO ３ ) was added dropwise until the reaction mixture turned pale yellow.
[0746] 3 L of water was placed in a container equipped with a stirrer, and the reaction solution was poured into the container and stirred for 15 minutes. The precipitate was filtered and washed with 500 mL of water. The filtered product was placed in a container equipped with a stirrer, and 1 L of water was added, followed by stirring for 15 minutes. The precipitate was filtered and washed with 300 mL of water.
[0747] The filtered material was placed in a container equipped with a stirrer, 500 mL of methanol was added, and the mixture was stirred for 15 minutes. The precipitate was filtered and washed with 150 mL of methanol. The precipitate was separated using column chromatography (Kanto Chemical Co., Inc. spherical silica 60N) with a gradient of ethyl acetate:hexane as the developing solvent at a ratio of 1:9 to 9:1, yielding Compound 1-1, Compound 1-1a, and Compound 1-1b in a relative ratio of approximately 1:0.9:0.5. The molecular weights of each component of the mixture were measured by LC-MS, and were 374 for Compound 1-1, 248 for Compound 1-1a, and 494 for Compound 1-1b.
[0748] (Synthesis of Compounds 1-3a and 1-3b) Compound 1-3a was obtained from compound 1-1a via compound 1-2a, and compound 1-3b was obtained from compound 1-1b via compound 1-2b, in the same manner as in Example 1.
[0749]
[0750] (Synthesis of a mixture of compounds 1-2, 1-2a, 1-2b, and 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 mixture were measured by LC-MS, and were 306 for compound 1-2a, 308 for compound 1-3a, 610 for compound 1-2b, and 614 for compound 1-3b.
[0751] Examples 14 to 18 Evaluation of EUV exposure sensitivity and etching defects Compositions were prepared in the same manner as in Example 4, using the following compounds as compound B. The mass ratio of each compound contained in the composition is shown in the table. EUV exposure sensitivity and etching defects were evaluated in the same manner as in Example 8. However, etching defects were evaluated according to the following criteria. (Evaluation criteria) S: Number of cone defects ≦ 6 A': 6 < Number of cone defects ≦ 10 B: 10 < Number of cone defects ≦ 80 C: 80 < Number of cone defects ≦ 400 D: 400 < Number of cone defects
[0752]
[0753] (Synthesis Example BPL1Rc) Using a 100 L glass-lined reaction vessel connected to a reflux condenser, 700 g of 4-hydroxybenzaldehyde was added to 1600 mL of dehydrated tetrahydrofuran (THF) in an ice bath under nitrogen flow and stirred with a stirring blade until dissolved. Next, 80 g of PPTS (pyridinium-p-toluenesulfonate) was added over 30 minutes while stirring in the ice bath, and the mixture was stirred for an additional 60 minutes. 500 g of ethyl vinyl ether (1.2 equivalents relative to the functional group equivalents) was added dropwise to the stirred reaction solution over 60 minutes, and the mixture was stirred for an additional 60 minutes at 35°C. 7.2 L of purified water was then added in an ice bath, and the mixture was stirred for 60 minutes, after which the organic phase was recovered. 2 L of ethyl acetate and 5 L of purified water were added to the recovered organic phase, and the mixture was stirred. The organic phase was then recovered and concentrated under reduced pressure to obtain 840 g of a white solid, the target protected compound BPL1Pc. The yield was 75%. The production was confirmed by NMR and LC-MS. The molecular weight was 194.
[0754]
[0755] Using the obtained BPL1Pc as a raw material, BPL1c was obtained in the same manner as in the reduction step BPL1R. The production was confirmed by NMR and LC-MS. The molecular weight was 196.
[0756]
[0757] (Synthesis Example BPL3R) BPL3R was obtained in the same manner as in Synthesis Example BPL1 using 4-hydroxy-3-methoxybenzaldehyde as a raw material. The production was confirmed by NMR and LC-MS. The molecular weight was 212.
[0758]
[0759] (Synthesis Example BPL4R) BPL4R was obtained in the same manner as in Synthesis Example BPL1 using 4-hydroxy-3-ethoxybenzaldehyde as a raw material. The production was confirmed by NMR and LC-MS. The molecular weight was 226.
[0760]
[0761] (Synthesis Example DML1bR) DML1bR was obtained in the same manner as in Synthesis Example DML1, except that iodic acid was used instead of iodine. The production was confirmed by NMR and LC-MS. The molecular weight was 362.
[0762]
[0763] (Synthesis Example Na-0b) In Example L1, the [protecting group introduction step] was carried out using 6-hydroxy-2-naphthaldehyde instead of 4-hydroxy-3,5-diiodobenzaldehyde, followed by the [reduction step] to obtain compound Na-0b. The production was confirmed by NMR and LC-MS. The molecular weight was 232.
[0764]
[0765] (Synthesis Example Na-0c) Compound Na-0c was obtained by using compound 2-2 instead of compound 2-3 in the synthesis of compound 2-4 in Example 2. The production was confirmed by NMR and LC-MS. The molecular weight was 274.
[0766]
[0767] (Synthesis Example Na-2b) In Example L1, the [protecting group introduction step] was carried out using 2-hydroxy-1-naphthaldehyde instead of 4-hydroxy-3,5-diiodobenzaldehyde, followed by the [reduction step] to obtain compound Na-2b. The production was confirmed by NMR and LC-MS. The molecular weight was 232.
[0768]
[0769] (Synthesis Example DMNa2-1bR) DMNa2-1bR was obtained in the same manner as in Synthesis Example DMN2-1, except that iodic acid was used instead of iodine. The production was confirmed by NMR and LC-MS. The molecular weight was 463.
[0770]
[0771] (Synthesis Example DMN2-3cP) Using iodic acid instead of iodine, DMN2-3c was obtained in the same manner as in Synthesis Example DMN2-3. Subsequently, using DMN2-3c instead of DMN2-3, the compound DMN2-3cP was obtained in the same manner as DMN2-3P. The production was confirmed by NMR and LC-MS. The molecular weight was 547.
[0772]
[0773] (Synthesis Example Ad-A-2b) Ad-A-2b was obtained in the same manner as in the synthesis of Ad-A-2, except that 1,3,5-adamantanetriol was used instead of 1-iodoadamantane-3,5-diol. The production was confirmed by NMR and LC-MS. The molecular weight was 414.
[0774]
[0775] (Synthesis Example Ad-A-2c) Ad-A-2c was obtained in the same manner as in the synthesis of Ad-2-3, except that 1,3,5-adamantanetriol was used instead of Ad2-2. The production was confirmed by NMR and LC-MS. The molecular weight was 540.
[0776]
[0777] (Synthesis Example Ad-A-2d) Ad-A-2d was obtained in the same manner as in the synthesis of Ad-2-4, except that 1,3,5-adamantanetriol was used instead of Ad2-2. The production was confirmed by NMR and LC-MS. The molecular weight was 484.
[0778]
[0779] (Synthesis Example Ad-2-3b) Ad-2-3b was obtained in the same manner as in the synthesis of Ad-A-2, except that 1,3,5,7-adamantanetetraol was used instead of Ad-A-1. The production was confirmed by NMR and LC-MS. The molecular weight was 506.
[0780]
[0781] (Synthesis Example DMA1bP) DMA1b was obtained in the same manner as in the synthesis of DMA1a, except that iodic acid was used instead of hydrogen iodide. The production was confirmed by NMR and LC-MS. The molecular weight was 350. Next, a mixture of DMA1bP and DMA1bP2 was obtained in the same manner as in the synthesis of DMA1aP, except that DMA1b was used instead of DMA1a. This mixture was purified and separated by column chromatography to obtain DMA1bP and DMA1bP2. The production was confirmed by NMR and LC-MS. The molecular weights of DMA1bP and DMA1bP2 were 656 and 194, respectively.
[0782]
[0783] From the above results, the compound of this embodiment has industrial applicability, for example, being able to provide a composition for lithography that has high sensitivity and few defects in EUV exposure while maintaining a good pattern shape.
[0784] Example 19-1 Evaluation was carried out in the same manner as in Examples 4 and 8, except that compound B shown in the table below was used instead of compound 1-3 shown in Example 14, and the evaluation conditions were changed to a post-exposure bake temperature of 100°C for 120 seconds. As a result, as shown in the table below, favorable evaluation results were confirmed for both the resist pattern and EUV exposure sensitivity, similar to those of Examples 4 and 8.
[0785]
[0786] Example 19-2 Evaluation was carried out in the same manner as in Examples 4 and 8, except that compound B1 shown in the table below was used instead of compound 1-3 shown in Example 14, and the evaluation conditions were changed to a post-exposure bake temperature of 100°C for 120 seconds. As a result, as shown in the table below, favorable evaluation results were confirmed for both the resist pattern and EUV exposure sensitivity, similar to those of Examples 4 and 8.
[0787]
[0788] Example 19-3 Evaluation was carried out in the same manner as in Examples 4 and 8, except that compound B1 shown in the table below was used instead of compound 1-3 shown in Example 14, and the evaluation conditions were changed to a post-exposure bake temperature of 100°C for 120 seconds. As a result, as shown in the table below, good evaluation results were confirmed for both the resist pattern and EUV exposure sensitivity, similar to those of Examples 4 and 8.
[0789]
[0790]
[0791] Example 20-1 Evaluation of EUV sensitivity and etching defects was carried out in the same manner as in Examples 14 to 18, except that Compound B1 and Compound B2 shown in the table below were used in place of Compound 1-3 and Compound 1-3a in the ratios shown below.
[0792]
[0793]
[0794] Example 20-2 Evaluation of EUV sensitivity and etching defects was carried out in the same manner as in Examples 14 to 18, except that Compound B1 and Compound B2 shown in the table below were used in place of Compound 1-3 and Compound 1-3a in the ratios shown below.
[0795]
[0796]
[0797] Example 20-3 Evaluation of EUV sensitivity and etching defects was carried out in the same manner as in Examples 14 to 18, except that Compound B1 and Compound B2 shown in the table below were used in place of Compound 1-3 and Compound 1-3a in the ratios shown below.
[0798]
[0799]
[0800] Example 21 Compounds subjected to treatment 1 or treatment 2 were obtained in the same manner as in Example 12, except that the compounds shown in the table below were used instead of compound 3-2, and the EUV sensitivity and etching defects were evaluated. As a result, as in Example 12, good results were confirmed for EUV sensitivity and etching defects for all compounds.
[0801]
[0802]
[0803] [Example 22] The following composition was prepared according to the method of Example 4. (Values: parts by mass)
[0804]
[0805] The composition was subjected to an aging test under the following conditions, and the state of the solution after the test was evaluated by absorbance using a spectrophotometer. Specifically, the spectrum in the visible light region of the sample after the aging test was measured to determine the "aver...
Claims
1. The following formula (1): (Wherein, RG is a group containing at least one cyclic structure, I is an iodine atom, R １ are the same or different monovalent functional groups having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, n is an integer of 1 to 5, and m is an integer of 1 to 5.
2. The RG group is a group derived from benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring, or a polycyclic alicyclic ring, which may have a substituent; １ R is selected from the group consisting of a hydroxyl group and an ether group having a protecting group. ｆ and a hydrocarbon group R having 0 to 30 carbon atoms which may have a substituent. ｇ The compound according to claim 1, which is one selected from the group consisting of:
3. The above R ｆ is selected from the group consisting of one or more hydroxyl groups and ether groups having a protecting group which is removable by an acid, an alkali, or heat; ｆ 3. The compound of claim 2, wherein:
4. The compound according to claim 1, wherein RG is a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, or adamantane, which may have a substituent.
5. The compound according to claim 4, wherein RG is a group derived from benzene, naphthalene, or adamantane which may have a substituent.
6. R １ -OR ２ , -COOR ３ , -CH ２ -OR ４ or —CHO, where R ２ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an aryl group having 1 to 30 carbon atoms; R ３ is a hydrogen atom, an optionally substituted alkyl group having 1 to 29 carbon atoms, or an optionally substituted aryl group having 1 to 29 carbon atoms; R ４ The compound according to claim 1, wherein is a hydrogen atom, an optionally substituted alkyl group having 1 to 29 carbon atoms, or an optionally substituted aryl group having 1 to 29 carbon atoms.
7. R １ The compound of claim 1 , wherein 8. The compound according to claim 1, represented by any one of the following formulas: (Wherein, Z is I, R １ or a linking group for forming a dimer, １ is defined the same as in formula (1), A is a group having a protecting group, R is a non-functional organic group, and R １ , A and R are bonded to possible positions, r1 to r4 are integers from 0 to 5, and the sum of r1 to r4 in one benzene is equal to or less than the valence of the benzene. (In the formula, I, A, R １ is defined as above, R″ is a hydrogen atom or R １ s1 is an organic group other than 1 to 7, s2 and s3 are integers from 0 to 7, and s4 is an integer from 1 to 7. However, the sum of s1 to s4 is equal to or less than the valence of naphthalene, and at least one of s2 and s3 is selected to be 1 or more. (In the formula, I, R １ , R″ is defined 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, provided that the sum of t1 to t3 is equal to or less than the valence of adamantane.) 9. The compound according to claim 8, which is represented by any one of the following formulas: (In the formula, I, Z, R, R １ , A is defined the same as in formula (Bz). (In the formula, I, R １ A and R" are defined the same as in formula (N); x and y are 0 or 1, provided that at least one of them is 1; s4' represents the number of R"s that can be bonded to the 1-, 7- and 8-positions of naphthalene, and is an integer of 1 to 3. (In the formula, I, R １ , R″ is defined as in formula (Ad), one of D is I, and the other of D is R １ It is.) 10. The compound according to claim 9, represented by any one of the following formulas: (In the formula, I, Z, R, R １ , A is defined the same as in formula (Bz). (In the formula, I, R １ , R″, A, x, y, and s4′ are defined the same as in formula (n). (In the formula, I, R １ , R″ is defined the same as in formula (Ad).
11. The above R １ is a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group, and A is -O-R ａ -O-R ｂ In the case of A' represented by (R ａ R is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear, branched or cyclic alkyl group having 1 to 3 carbon atoms, or is a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom, and contains one or more A'.
12. The compound according to claim 5, wherein RG is a group derived from benzene which may have a substituent.
13. RG is a group containing benzene, and R １ If there are multiple R １ does not include a combination of an alkoxy group (excluding those having a protecting group) and an aldehyde group, a combination of the alkoxy group and a hydroxyl group, or a combination of a hydroxyl group and an aldehyde group, RG is a group containing naphthalene, and R １ If there are multiple R １ The compound according to claim 1 , wherein:
14. The compound according to claim 12, represented by the following formula (Bz4): (In the formula, I, R, A and Z are defined as in formula (Bz). １’ are monovalent functional groups, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding hydroxyl groups; r1', r2', and r4' are integers of 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.
15. The compound according to claim 14, represented by the following formula (Bz4-1): (Wherein, I, R, Z and R １’ 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 equal to or less than the valence of benzene.
16. The compound according to claim 15, represented by the following formula (Bz4-2): (In the formula, I is defined the same as in formula (Bz4), r4' is an integer of 0 to 4, and r5' is an integer of 0 to 4.) 17. The compound according to claim 15, represented by any one of the following formulas:
18. The compound according to claim 12, represented by any one of the following formulas: (Wherein, I, R, Z, A and R １ is defined the same as in formula (Bz), A′ is a group having a protecting group, —O—R ａ -O-R ｂ , -O-CO-OR ｂ or -O-R ａ -C-O-R ｂ It is expressed as follows. ａ R is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.
19. The compound according to claim 12, represented by any one of the following formulas: (In the formula, I, R １ A is defined as in formula (Bz), A′ is a group having a protecting group, —O—R ａ -O-R ｂ , -O-CO-OR ｂ or -O-R ａ -C-O-R ｂ It is expressed as follows. ａ R is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom. Z' is I, R １ , or a hydrogen atom.) 20. The compound according to claim 5, wherein RG is a group derived from naphthalene which may have a substituent.
21. The compound according to claim 20, represented by any one of the following formulas: (In the formula, I, R １ , R″, A, x, y, and s4′ are defined the same as in formula (n).
22. The compound according to claim 21, represented by any one of the following formulas: (In the formula, I, R １ R″ is defined as in formula (n), A′ is a group having a protecting group, —O—R ａ -O-R ｂ , -O-CO-OR ｂ or -O-R ａ -C-O-R ｂ It is expressed as follows. ａ R is a linear or branched alkyl group having 1 to 3 carbon atoms. ｂ is a monovalent linear, branched, or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.
23. The above R １ The compound of claim 22 , wherein is a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group.
24. The compound according to claim 21, represented by any one of the following formulas: (In the formula, I, R １ , A, A', x, y are defined the same as in formula (n).
25. The compound according to claim 5, wherein RG is a group derived from an optionally substituted adamantane.
26. The compound according to claim 25, represented by any one of the following formulas: (In the formula, I, R １ , R″ is defined the same as in formula (Ad).
27. The above R １ is a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group.
28. The compound of claim 27, represented by any one of the following formulas: (In the formula, I, R １ is defined the same as in formula (Ad).
29. A composition comprising the compound of claim 1.
30. The composition of claim 29 for use in lithography.
31. The composition according to claim 30, comprising two or more compounds represented by formula (1).
32. The composition according to claim 29, further comprising a compound represented by the following formula (DM0-1) or the following formula (BP0-1), or a combination thereof: (wherein, RG, I, R １ is defined the same as in formula (1), Q is a group resulting from a group bonding between molecules or a single bond, n' is an integer of 0 to 5 and not more than n, m' is an integer of 1 to 5 and not more than m, and b is an integer of 1 to 4.
33. The composition according to claim 32, wherein the compound represented by formula (DM0-1) is a compound represented by the following formula (DM1a), (Dn1), or (Da1), and the compound represented by formula (BP0-1) is a compound represented by the following formula (BP1a), (Bn1), or (Ba1). (Wherein, Z is I, R １ or a linking group for forming a dimer, １ is defined the same as in formula (1), A is a group having a protecting group, R is a non-functional organic group, and R １ , A and R are bonded to possible positions, r1 to r4 are integers from 0 to 5, and the sum of r1 to r4 in one benzene is equal to or less than the valence of the benzene. (In the formula, I, R １ A is defined as in formula (DM1a), R″ is a hydrogen atom or R １ an organic group other than I, R １ , A, and R" are bonded to available positions, Q is defined the same as in formula (DM0-1), s1 is an integer from 1 to 7, s2 and s3 are an integer from 0 to 7, and s4 is an integer from 1 to 7, provided that the sum of s1 to s4 is equal to or less than the valence of naphthalene, and either s2 or s3 is selected to be 1 or greater, and nd is an integer from 1 to 4.) (In the formula, I, R １ is defined the same as in formula (Dn1), R″ is a hydrogen atom or R １ R is an organic group other than ｄ is a single bond or -O- (ether bond), t1 is an integer from 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 13. However, the sum of t1 to t3 is equal to or less than the valence of adamantane. (In the formula, I, Z, R, R １ , A is defined 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, r4 is defined the same as in formula (DM1a). (In the formula, I, R １ , R″, and A are defined the same as in formulas (Dn1) and (Da1), s2 to s4 are defined the same as in formula (Dn1), and s1b is an integer from 0 to 6 that satisfies s1b≦(s1-1). Here, s1 is defined the same as in formula (Dn1). (In the formula, I, R １ , R″ is defined the same as in formulas (Dn1) and (Da1), t2 and t3 are defined the same as in formula (Da1), and t1b is an integer of 0 to 9 satisfying t1b≦(t1-1), where t1 is defined the same as in formula (Da1).
34. The composition according to claim 32, comprising a compound represented by formula (DM0-1).
35. The composition according to claim 34, wherein the compounds represented by formula (1) and formula (DM0-1) satisfy the following relationship: 0.1 ≧ [amount (mol) of compound of formula (DM0-1)] ÷ [amount (mol) of compound of formula (1)] ≧ 0.000001 36. The composition according to claim 32, comprising a compound represented by formula (BP0-1).
37. The composition according to claim 36, wherein the compound represented by formula (BP0-1) is a compound represented by formula (BP1a) and Z is not I, a compound represented by formula (Bn1), or a compound represented by formula (Ba1).
38. The composition according to claim 32, wherein the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relation: 0.1 ≧ ([total amount (mol) of the compound of formula (DM0-1) and formula (BP0-1)]) ÷ [amount (mol) of the compound of formula (1)] ≧ 0.000001 39. The composition according to claim 33, wherein the compound represented by formula (DM0-1) is a compound represented by the following formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb), and the compound represented by formula (BP0-1) is a compound represented by the following formula (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt). (In the formula, Z, R, R １ , A, r1, r2, r3, and r4a are defined the same as in formula (BP1a). (In the formula, Z, I, R １ , A, R, r1 to r4 are defined the same as in formula (DM1a). (In the formula, Z, R １ , A, R, r1 to r4 are defined the same as in formula (DM1a). (In the formula, R １ , R″, A, s2 to s4 are defined the same as in formula (Bn1). (In the formula, I, R １ , A, R″, Q, s1 to s4 are defined the same as in formula (Dn1). (In the formula, R １ , A, R″, Q, s2 to s4 are defined the same as in formula (Dn1). (In the formula, R １ , R″, t2, and t3 are defined the same as in formula (Ba1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1). (In the formula, R １ , R”, R ｄ , t2 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1). (In the formula, I, R １ , R”, R ｄ , t1 to t3 are defined the same as in formula (Da1).
40. The composition according to claim 30, wherein RG in the formula (1) is a group derived from benzene which may have a substituent.
41. The composition according to claim 30, wherein RG in the formula (1) is a group derived from naphthalene which may have a substituent.
42. The composition according to claim 30, wherein RG in formula (1) is a group derived from an optionally substituted adamantane.
43. The composition according to claim 29, which exhibits a sensitizing effect when exposed to radiation.
44. The composition of claim 29, having a metal impurity content of less than 1 ppm.
45. A method for exerting a sensitizing effect upon irradiation of a lithographic composition, using the compound according to claim 1.
46. The method of claim 45, wherein two or more of said compounds are used.
47. The compound containing the RG group is provided with an iodine atom or an R １ A method for producing the compound according to claim 1, comprising the step of introducing a group.
48. A method for producing a compound represented by formula (1), wherein the compound represented by formula (1) is represented by formula (Bz): (In the formula, I, Z, R １ , A, R, and r1 to r4 are defined as in formula (DM1a). 1) preparing a compound represented by formula (MB); (In the formula, I, R １ , R, r1, and r2 are defined the same as in formula (Bz), and R １ 1) a step of iodinating the compound, 2) a step of introducing a protecting group into the compound, and 3) a step of reducing the compound.
49. The method for producing the compound according to claim 48, wherein the step of introducing a protecting group comprises a step of introducing a protecting group to the hydroxy group of formula (MB) using an inorganic base.
50. A method for producing a compound represented by formula (1), wherein the compound represented by formula (1) is represented by formula (Bz): (In the formula, I, Z, R １ , A, R, and r1 to r4 are defined the same as in formula (DM1a). 1) preparing a compound represented by formula (Bz4); (In the formula, I, R, A, and Z are defined as in formula (Bz), １’ are the same or different functional groups having 0 to 30 carbon atoms, excluding a monovalent hydroxyl group, containing no polymerizable unsaturated bond, and r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene. 2) a step of performing an iodination step of iodinizing the compound once or twice or more times.
51. A method for producing a compound represented by formula (1), wherein the compound represented by formula (1) is represented by formula (Bz): (In the formula, I, Z, R １ , A, R, and r1 to r4 are defined the same as in formula (DM1a). 1) preparing a compound represented by formula (Bz5); (In the formula, I, Z, R １ 1) a step of esterifying a carboxylic acid of a compound represented by formula (Bz5), and 2) a step of reducing the obtained ester group to convert it into a hydroxymethyl group.
52. A method for producing a compound represented by formula (1), wherein the compound represented by formula (1) is represented by formula (N): (In the formula, I, R １ , A, and R″ are defined the same as in formulas (Dn1) and (Bn1), where I, R １ , R″, and A are bonded to any available position, s1 is an integer of 1 to 7, s2 and s3 are an integer of 0 to 7, and s4 is an integer of 1 to 7, provided that the sum of s1 to s4 is equal to or less than the valence of naphthalene, and either s2 or s3 is selected to be 1 or greater. 1) preparing a compound represented by formula (MN); (In the formula, R １ 1) a step of iodinating the compound; 2) a step of introducing a protecting group into the compound; and 3) a step of reducing the compound.
53. A method for producing a compound represented by formula (1), wherein the compound represented by formula (1) is represented by formula (Ad): (In the formula, I, R １ , R″ are defined the same as in formula (Da1); I, R １ 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, provided that the sum of t1 to t3 is equal to or less than the valence of adamantane. 1) preparing a compound represented by formula (MA); (In the formula, R １ 10. The method for producing the compound according to claim 1, comprising the steps of: (a) forming a compound represented by the formula (A) with a fluorine atom; and (b) forming a compound represented by the formula (A).
54. A method for producing the compound according to claim 53, wherein the iodination step comprises a step of carrying out iodination in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent.
55. The method for producing the compound according to claim 53, wherein the iodination step includes a step of concentrating the reaction solution while distilling off water during the reaction.
56. The method for producing the compound according to claim 53, wherein the iodination step comprises a step of charging a substrate and an iodinating agent and then leaving the mixture to stand for 1 hour to 48 hours.
57. A method for producing the compound according to claim 1, comprising one or more steps selected from the following: 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. 1) preparing a compound represented by formula (Ad-A-3-0); 2) an oxidation step of oxidizing a compound represented by formula (Ad-A-3-0); 3) a step of esterifying a carboxylic acid of the obtained compound; 4) a step of hydrolyzing an ester group of the obtained compound to convert it to a carboxylic acid; and 5) an iodination step of iodinating the compound according to claim 57.
59. The method of any one of claims 47 to 58, further comprising a step of treatment with an adsorbent.
60. The compound according to claim 1, represented by the following formula (Ad-A-3):
61. The compound according to claim 1, represented by the following formula (Ad-A-4):