Method for producing compounds, intermediates and compounds

Abstract

To provide a production method for producing a compound suitable as an acid generator for a resist composition at high yield.SOLUTION: A method for producing a compound includes the steps of: subjecting a compound represented by general formula (C-1) to a condensation reaction with a compound represented by general formula (C-2) to give a compound (B0p) represented by general formula (b0p); and subjecting the compound (B0p) to an ion exchange reaction with a compound represented by general formula (C-3) to give a compound (B0) represented by general formula (b0) (where X0 is I or the like, Rm is a hydroxy group or the like, and a and b each denote a hydroxy group or a carboxy group, L02 and Vb0 each denote a single bond or the like, R0 denotes H or the like, Mpm'+ denotes an organic ammonium cation or the like, L001 denotes an ester bond, X- denotes a counter anion, Mm+ denotes an organic cation).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a process for the preparation of compounds, intermediates and compounds. [Background technology]

[0002] In recent years, advances in lithography technology have led to rapid progress in miniaturization of patterns in the manufacture of semiconductor devices and liquid crystal display devices. A common method of miniaturization is to use shorter wavelengths (higher energy) exposure light sources.

[0003] Resist materials are required to have lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions. As a resist material that satisfies such requirements, a chemically amplified resist composition that contains a base component whose solubility in a developer changes due to the action of acid, and an acid generator component that generates acid upon exposure, has been used so far.

[0004] In forming a resist pattern, the behavior of the acid generated from an acid generator component upon exposure is considered to be one factor that greatly influences the lithography properties. A wide variety of acid generators have been proposed for use in chemically amplified resist compositions, including, for example, onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators. Onium salt acid generators mainly have an onium ion such as triphenylsulfonium in the cation moiety, and generally use an alkylsulfonate ion or a fluorinated alkylsulfonate ion in which some or all of the hydrogen atoms in the alkyl group are substituted with fluorine atoms in the anion moiety of the onium salt acid generator.

[0005] As lithography technology continues to advance and its application fields expand, a wide variety of acid generators have been developed to improve lithography properties. There is a demand for a production method that can produce the acid generators in high yield.

[0006] For example, Patent Document 1 discloses a method for producing a second ammonium salt compound produced by reacting a first ammonium salt compound with a nitrogen-containing compound having a lone electron pair, the first ammonium salt compound having a first ammonium cation that is primary, secondary or tertiary, and a conjugate acid of the nitrogen-containing compound having a larger acid dissociation constant (pKa) than the first ammonium cation, and a method for producing a compound comprising a step of salt-exchanging the ammonium salt compound produced by this production method with a sulfonium cation or an iodonium cation that is more hydrophobic than the conjugate acid of the nitrogen-containing compound. In addition, in the examples of Patent Document 1, a relatively hydrophilic -SO 2 A method for producing a compound having a --containing cyclic group is disclosed. It is disclosed that the method for producing this compound can provide an acid generator with few impurities in high yield. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2014-15433 A Summary of the Invention [Problem to be solved by the invention]

[0008] In order to further improve lithography properties, various studies have been conducted on the structure of the anion part of onium salt-based acid generators. For example, onium salt-based acid generators that contain a benzene ring having an iodine atom or a bromine atom in the anion part and have relatively high hydrophobicity have been developed. For onium salt-based acid generators in which the anion part has a specific structure, the yield is not sufficient when using conventional methods for producing compounds such as those described in Patent Document 1, and an optimal production method according to the desired structure is required.

[0009] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a compound that is useful as an acid generator for a resist composition, which can be obtained in high yield, an intermediate of the compound, and a compound used by the method for producing the compound. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention employs the following configuration. That is, a first aspect of the present invention is a method for producing a compound, comprising the steps of: subjecting a compound represented by the following general formula (C-1) and a compound represented by the following general formula (C-2) to a condensation reaction to obtain a compound (B0p) represented by the following general formula (b0-p); and subjecting the compound (B0p) and a compound represented by the following general formula (C-3) to an ion exchange reaction to obtain a compound (B0) represented by the following general formula (b0).

[0011] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. One of a and b is a hydroxy group, and the other is a carboxy group. z is an integer of 0 to 10. L 02 represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, -SO2 -, -N(R a )-C(=O)-, -N(R a )-, -C(R a )(R a )-N(R a )-, -C(R a )(N(R a )(R a ))-, or -C(=O)-N(R a )-. R a are each independently a hydrogen atom or an alkyl group. 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more. L 001 is an ester bond [-C(=O)-O-, -OC(=O)-]. X - is the counter anion. M m+ represents an organic cation having a valence of m, where m is an integer of 1 or more.

[0012] A second aspect of the present invention is an intermediate used in the production method of the compound of the first aspect of the present invention, which is represented by the following general formula (b0-p).

[0013] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. L 001 is an ester bond [-C(=O)-O-, -OC(=O)-]. z is an integer of 0 to 10. L 02 represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, -SO 2 -, -N(R a)-C(=O)-, -N(R a )-, -C(R a )(R a )-N(R a )-, -C(R a )(N(R a )(R a ))-, or -C(=O)-N(R a )-. R a are each independently a hydrogen atom or an alkyl group. 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more.

[0014] A third aspect of the present invention is a compound represented by the following general formula (b0-p-1).

[0015] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. L 001 is an ester bond [-C(=O)-O-, -OC(=O)-]. z is an integer of 0 to 10. Vb 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more. Effect of the Invention

[0016] According to the present invention, a compound useful as an acid generator for a resist composition can be obtained in high yield. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] In this specification and claims, the term "aliphatic" is a relative concept to aromaticity and is defined as meaning a group, compound, etc. that does not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When describing "optionally having a substituent," it means replacing a hydrogen atom (-H) with a monovalent group or a methylene group (-CH 2 -) is replaced with a divalent group.

[0018] In the present specification and claims, some structures represented by chemical formulas may have asymmetric carbons, and may have enantiomers or diastereomers. In such cases, a single chemical formula represents all of the isomers. These isomers may be used alone or as a mixture.

[0019] (Method of producing the compound) The method for producing the compound of this embodiment includes a step of subjecting a compound represented by the following general formula (C-1) and a compound represented by the following general formula (C-2) to a condensation reaction to obtain a compound (B0p) represented by the following general formula (b0-p) (hereinafter also referred to as "Step A"), and a step of subjecting the compound (B0p) and a compound represented by the following general formula (C-3) to an ion exchange reaction to obtain a compound (B0) represented by the following general formula (b0) (hereinafter also referred to as "Step B").

[0020] The compound produced by the method for producing a compound according to the present embodiment is a compound useful as an acid generator for a resist composition. Specifically, the compound has an iodine atom in the anion portion that has a high absorption cross section for EUV and EB. Therefore, the sensitivity to EUV and EB can be improved compared to conventional acid generators that do not have an iodine atom. In addition, since the anion portion has an iodine atom, the solubility in a developer can be appropriately adjusted. Therefore, by adding this compound to a resist composition, it is possible to further improve lithography properties.

[0021] <Process A> Step A is a step of subjecting a compound represented by the following general formula (C-1) (hereinafter also referred to as "compound (C1)") and a compound represented by the following general formula (C-2) (hereinafter also referred to as "compound (C2)") to a condensation reaction to obtain a compound (B0p) represented by the following general formula (b0-p) (hereinafter also referred to as "compound (B0p)").

[0022] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. One of a and b is a hydroxy group, and the other is a carboxy group. z is an integer of 0 to 10. L 02 represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, -SO 2 -, -N(R a )-C(=O)-, -N(R a )-, -C(R a )(R a )-N(R a )-, -C(R a )(N(R a )(R a ))-, or -C(=O)-N(R a )-. R aare each independently a hydrogen atom or an alkyl group. 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more. L 001 is an ester bond [-C(=O)-O-, -OC(=O)-].

[0023] ≪Compound (C1)≫ The compound (C1) is a compound represented by the following general formula (C-1).

[0024] [ka] [In formula (C-1), X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. a is a hydroxy group or a carboxy group.

[0025] In the above general formula (C-1), X 0 is a bromine atom or an iodine atom, and is preferably an iodine atom.

[0026] In the above general formula (C-1), R m R is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. m The alkyl group in is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group. In the above general formula (C-1), R m Among the above, is preferably a hydroxy group or a fluorine atom.

[0027] In the above general formula (C-1), nb1 is an integer of 1 to 5, nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. nb1 is preferably an integer of 1 to 3. nb2 is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0028] In the above general formula (C-1), a is a hydroxy group or a carboxy group, and one of a and b described below is a hydroxy group and the other is a carboxy group.

[0029] Specific examples of the compound (C1) in the method for producing a compound of this embodiment are shown below.

[0030] [ka]

[0031] ≪Compound (C2)≫ The compound (C2) is a compound represented by the following general formula (C-2).

[0032] [ka] In formula (C-2), b is a hydroxy group or a carboxy group, and z is an integer of 0 to 10. 02 represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, -SO 2 -, -N(R a )-C(=O)-, -N(R a )-, -C(R a )(R a )-N(R a )-, -C(R a )(N(R a )(R a ))-, or -C(=O)-N(R a )-. R a are each independently a hydrogen atom or an alkyl group. 0 R is a single bond, an alkylene group, or a fluorinated alkylene group.0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more.

[0033] In the above general formula (C-2), b is a hydroxy group or a carboxy group, and one of the above-mentioned a and b is a hydroxy group and the other is a carboxy group.

[0034] In the above general formula (C-2), z is an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3.

[0035] In the above general formula (C-2), L 02 represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, -SO 2 -, -N(R a )-C(=O)-, -N(R a )-, -C(R a )(R a )-N(R a )-, -C(R a )(N(R a )(R a ))-, or -C(=O)-N(R a )-. R a are each independently a hydrogen atom or an alkyl group. L 02 The alkylene group in a Each of the alkyl groups preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0036] In the above general formula (C-2), L 02 Among the above, is preferably a single bond, -OCO-, or -COO-, more preferably a single bond or -COO-, and further preferably a single bond.

[0037] In the above general formula (C-2), Vb0 is an alkylene group, a fluorinated alkylene group, or a single bond. Vb 0 The alkylene group and the fluorinated alkylene group in Vb each preferably have 1 to 4 carbon atoms, and more preferably have 1 to 3 carbon atoms. 0 The fluorinated alkylene group in the formula (I) includes alkylene groups in which some or all of the hydrogen atoms are substituted with fluorine atoms. 0 is preferably an alkylene group having 1 to 4 carbon atoms, a fluorinated alkylene group having 1 to 4 carbon atoms, or a single bond, and more preferably a single bond or a group in which some of the hydrogen atoms of an alkylene group having 1 to 3 carbon atoms have been substituted with fluorine atoms.

[0038] In the above general formula (C-2), R 0 R is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. 0 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.

[0039] In the above general formula (C-2), Mp m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less, and m' is an integer of 1 or more.

[0040] Metal cations Examples of the metal cation include an alkali metal ion, an alkaline earth metal ion, a rubidium ion, a strontium ion, and a yttrium ion. Among these, an alkali metal ion or an alkaline earth metal ion is preferable, an alkali metal ion is more preferable, a sodium ion or a lithium ion is further preferable, and a sodium ion is particularly preferable.

[0041] Organic ammonium cations with LogP of 4.8 or less The organic ammonium cation is not particularly limited as long as it has a LogP of 4.8 or less. The lower limit of the organic ammonium cation is not particularly limited, and is, for example, −1.0 or more.

[0042] "LogP value" refers to the octanol / water partition coefficient (P ow ) is a logarithmic value of the "LogP value". The "LogP value" is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds. In general, the partition coefficient is calculated without relying on experiments, and in the present invention, the partition coefficient refers to the value calculated by CAChe Work System Pro Version 6.1.12.33. As the LogP value increases on the positive side of 0, the hydrophobicity increases, and as the absolute value increases on the negative side, the water solubility increases (high polarity). The LogP value is negatively correlated with the water solubility of organic compounds, and is widely used as a parameter to estimate the hydrophilicity / hydrophobicity of organic compounds.

[0043] In the method for producing a compound according to the present embodiment, when the cation moiety of the compound (C2) is an organic ammonium cation and has a LogP of 4.8 or less, the reaction in step B described below proceeds smoothly and the yield is improved. In addition, the target compound can be obtained with fewer impurities.

[0044] Specific examples of the organic ammonium cation include a cation represented by the following general formula (ca-p-1) and a cation represented by the following general formula (ca-p-2).

[0045] [ka] [In the formula, R 1 ~R 4 are each independently a hydrocarbon group which may have a substituent, or a hydrogen atom. 1 ~R 4 At least one of R is a hydrocarbon group which may have a substituent. 11 is the R 11is a group that forms an aromatic ring together with the nitrogen atom to which R is bonded. 12 is an alkyl group or a halogen atom, and y is an integer of 0 to 5.

[0046] In the above general formula (ca-p-1), R 1 ~R 4 R each independently represents a hydrocarbon group which may have a substituent, or a hydrogen atom. 1 ~R 4 The hydrocarbon groups in each of the above are preferably hydrocarbon groups having 1 to 15 carbon atoms, and more preferably hydrocarbon groups having 1 to 10 carbon atoms. 1 ~R 4 The total number of carbon atoms in the hydrocarbon group is preferably 1-20, more preferably 3-18, and even more preferably 4-15.

[0047] The hydrocarbon group includes a linear or branched alkyl group, or a cyclic hydrocarbon group.

[0048] The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms.

[0049] The cyclic hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The cyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.

[0050] The cyclic aromatic hydrocarbon group is preferably a phenyl group.

[0051] R 1 ~R 4Examples of the substituent that the hydrocarbon group in the formula (I) may have include an alkyl group, an alkoxy group, a hydroxyl group, an oxo group (=O), and an amino group.

[0052] In the above general formula (ca-p-2), R 11 is the R 11 is a group that forms an aromatic ring together with the nitrogen atom to which it is bonded. The aromatic ring is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring, and even more preferably a 6-membered ring.

[0053] In the above general formula (ca-p-2), R 12 is an alkyl group, and the above R 1 ~R 4 The straight or branched alkyl group in the above formula (I) is the same as that in the above formula (I).

[0054] In the above general formula (ca-p-2), y is an integer of 0 to 5, preferably 1 or 0, and more preferably 0.

[0055] Specific examples of the cation moiety of compound (C2) and the LogP value calculated by CAChe Work System Pro Version 6.1.12.33 are shown below.

[0056] [ka]

[0057] [ka]

[0058] In the above general formula (C-2), Mp m ' + Among the above, from the viewpoint of producing the target compound with fewer impurities and in high yield, it is preferable that the above-mentioned organic ammonium cation has a LogP of 4.8 or less, and more preferable is a cation represented by the above general formula (ca-p-1) or (ca-p-2) having a LogP of 4.8 or less.

[0059] Specific examples of the compound (C2) in the method for producing a compound of this embodiment are shown below.

[0060] [ka]

[0061] [ka]

[0062] ≪Compound (B0p)≫ The compound (B0p) is a compound represented by the following general formula (b0-p) obtained by a condensation reaction of the above-mentioned compound (C1) and compound (C2).

[0063] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. 001 is an ester bond [-C(=O)-O-, -OC(=O)-]. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. z is an integer of 0 to 10. L 02 represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, -SO 2 -, -N(R a )-C(=O)-, -N(R a )-, -C(R a )(R a )-N(R a )-, -C(R a )(N(R a )(R a ))-, or -C(=O)-N(R a )-. R a are each independently a hydrogen atom or an alkyl group. 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more.

[0064] X in the above general formula (b0-p) 0 , R m , nb1 and nb2 are X in the above general formula (C-1). 0 , R m , nb1 and nb2, respectively.

[0065] In the above general formula (b0-p), z and L 02 , Vb 0 , R 0 , Mp m ' + and m' are the same as z, L in the above general formula (C-2). 02 , Vb 0 , R 0 , Mp m ' + and m', respectively.

[0066] L in the above general formula (b0-p) 001 is an ester bond [-C(=O)-O-, -OC(=O)-] formed by a condensation reaction between a in the above-mentioned compound (C1) and b in the compound (C2).

[0067] Specific examples of the compound (B0p) in the production method of the compound of this embodiment are shown below.

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] The condensation reaction in step A may be carried out in the presence of a condensing agent and a base catalyst (additive). Specific examples of the condensing agent include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide (DIC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, carbonyldiimidazole (CDI), and the like. Specific examples of the base catalyst include tertiary amines such as trimethylamine, triethylamine, and tributylamine; aromatic amines such as pyridine, pyrrolidinopyridine, and 4-(dimethylamino)pyridine (DMAP); diazabicyclononene (DBN); and diazabicycloundecene (DBU).

[0073] The condensation reaction in step A may be carried out in the presence of an acid catalyst. Specific examples of the acid catalyst include diphosphorus pentoxide and methanesulfonic acid.

[0074] The reaction time in step A is, for example, preferably from 5 minutes to 24 hours, more preferably from 10 to 120 minutes, and even more preferably from 10 to 60 minutes. The reaction temperature in step A is preferably from 0 to 50°C, more preferably from 10 to 30°C.

[0075] Examples of the reaction solvent in step A include dichloromethane, dichloroethane, chloroform, diethyl ether, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, dimethylsulfoxide, and the like.

[0076] After the condensation reaction is completed, the compound in the reaction solution may be isolated and purified. For the isolation and purification, a conventionally known method can be used, and for example, a suitable combination of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. can be used.

[0077] <Process B> Step B is a step of subjecting the above-mentioned compound (B0p) and a compound represented by the following general formula (C-3) to an ion exchange reaction to obtain a compound (B0) represented by the following general formula (b0).

[0078] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. L 001 is an ester bond [-C(=O)-O-, -OC(=O)-]. z is an integer of 0 to 10. L 02 represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, -SO 2 -, -N(R a )-C(=O)-, -N(R a )-, -C(R a )(R a )-N(R a )-, -C(R a )(N(R a )(R a ))-, or -C(=O)-N(R a )-. R a are each independently a hydrogen atom or an alkyl group. 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more. X -is the counter anion. M m+ represents an organic cation having a valence of m, where m is an integer of 1 or more.

[0079] ≪Compound (C3)≫ The compound (C3) is a compound represented by the following general formula (C-3).

[0080] [ka] [In the formula, X - is the counter anion. M m+ represents an organic cation having a valence of m, where m is an integer of 1 or more.

[0081] In the above general formula (C-3), X - is the counter anion. X - Examples of the ions include ions that can become acids with lower acidity than the compound (B0p), specifically, halogen ions such as bromide ion and chloride ion, BF 4 - , AsF 6 - , SbF 6 - , P.F. 6 - , ClO 4 - etc.

[0082] In the above general formula (C-3), M m+ represents an organic cation having a valence of m, where m is an integer of 1 or more. m+ is preferably a sulfonium cation or an iodonium cation.

[0083] Preferred cationic moieties ((M m+ ) 1 / m ) include organic cations represented by the following general formulas (ca-1) to (ca-5), respectively.

[0084] [ka] [In the formula, R 201 ~R207 , and R 211 ~R 212 R each independently represents an aryl group, an alkyl group, or an alkenyl group which may have a substituent. 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 may be bonded to each other to form a ring together with the sulfur atom in the formula. 208 ~R 209 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an SO 2 -containing cyclic group. 201 represents -C(=O)- or -C(=O)-O-. 201 each independently represents an arylene group, an alkylene group, or an alkenylene group; x is 1 or 2. W 201 represents a (x+1)-valent linking group.

[0085] In the above general formulas (ca-1) to (ca-5), R 201 ~R 207 , and R 211 ~R 212 The aryl group in the formula (I) may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 201 ~R 207 , and R 211 ~R 212 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 201 ~R 207 , and R 211 ~R 212 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 201 ~R 207 , and R 210 ~R 212Examples of the substituent that may be possessed by the group include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0086] [ka] [In the formula, R' 201 are each independently a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

[0087] Optionally substituted cyclic groups: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

[0088] R' 201 The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. R' 201 Specific examples of the aromatic ring of the aromatic hydrocarbon group in the above formula include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. R' 201Specific examples of the aromatic hydrocarbon group in the above include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), and a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.). The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0089] R' 201 The cyclic aliphatic hydrocarbon group in the formula (I) is an aliphatic hydrocarbon group containing a ring in the structure. Examples of aliphatic hydrocarbon groups that contain a ring in their structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.

[0090] Among them, R' 201The cyclic aliphatic hydrocarbon group in is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.

[0091] The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, specifically, a methylene group [-CH 2 -], ethylene group [-(CH 2 ) 2 -], trimethylene group [-(CH 2 ) 3 -], tetramethylene group [-(CH 2 ) 4 -], pentamethylene group [-(CH 2 ) 5 -] etc. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, specifically, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -C(CH 2 CH 3 ) 2 -, etc. alkylmethylene groups; -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, -CH(CH 2CH 3 )CH 2 -, -C(CH 2 CH 3 ) 2 -CH 2 -, etc. alkyl ethylene groups; -CH(CH 3 )CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, etc.; -CH(CH 3 )CH 2 CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH 2 The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0092] Also, R' 201 The cyclic hydrocarbon group in may contain a heteroatom, such as a heterocycle. Specifically, lactone-containing cyclic groups represented by the following general formulae (a2-r-1) to (a2-r-7), -SO represented by the following general formulae (a5-r-1) to (a5-r-4), 2 -containing cyclic groups, and other heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16), respectively.

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] R' 201 Examples of the substituent in the cyclic group include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. As the halogen atom as a substituent, a fluorine atom is preferred. Examples of halogenated alkyl groups as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms. The carbonyl group as a substituent is a methylene group (-CH 2 -) is a group that substitutes

[0097] A chain alkyl group which may have a substituent: R' 201 The chain alkyl group may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and most preferably has 1 to 10 carbon atoms. The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 15 carbon atoms, and most preferably has 3 to 10 carbon atoms. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.

[0098] An optionally substituted chain alkenyl group: R' 201 The chain alkenyl group may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.

[0099] R' 201 Examples of the substituent in the chain alkyl or alkenyl group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, the above R' 201 and the like.

[0100] R' 201 In addition to the above, the optionally substituted cyclic group, the optionally substituted chain alkyl group, or the optionally substituted chain alkenyl group may be an acid-dissociable group represented by the following formula (a1-r-2):

[0101] [ka] [In the formula, Ra' 4 ~Ra' 6 are each a hydrocarbon group, and Ra' 5 , Ra' 6 may be bonded to each other to form a ring.

[0102] Ra' 4 ~Ra'6 Examples of the hydrocarbon group include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group.

[0103] Among them, R' 201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane; a lactone-containing cyclic group represented by each of the general formulae (a2-r-1) to (a2-r-7) above; -SO represented by each of the general formulae (a5-r-1) to (a5-r-4) above; 2 -containing cyclic groups and the like are preferred.

[0104] In the above general formulas (ca-1) to (ca-5), R 201 ~R 203 , R 206 ~R 207 , R 211 ~R 212 When they are bonded to each other to form a ring together with the sulfur atom in the formula, they are not included in the heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, as well as in the carbonyl groups, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )-(applicable R N is an alkyl group having 1 to 5 carbon atoms.) The ring formed is preferably a 3- to 10-membered ring, including the sulfur atom, and particularly preferably a 5- to 7-membered ring, in which a ring containing a sulfur atom in the ring skeleton in the formula is a 3- to 10-membered ring, inclusive of the sulfur atom. Specific examples of the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.

[0105] R 208 ~R 209each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they are alkyl groups they may be bonded to each other to form a ring.

[0106] R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an SO 2 -containing cyclic group. R 210 The aryl group in the formula (I) may be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred. R 210 The alkyl group in is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. R 210 The alkenyl group in the formula (I) preferably has 2 to 10 carbon atoms. R 210 In the formula (I), optionally substituted SO 2 Examples of the --containing cyclic group include "-SO 2 -containing polycyclic group" is preferred, and a group represented by the above general formula (a5-r-1) is more preferred.

[0107] Y 201 each independently represents an arylene group, an alkylene group, or an alkenylene group. Y 201 The arylene group in the formula (I) is an unsubstituted arylene group having 6 to 20 carbon atoms. Y 201 The alkylene group and alkenylene group in the above formula include unsubstituted alkylene groups and alkenylene groups having 6 to 20 carbon atoms.

[0108] In the above formula (ca-4), x is 1 or 2. W 201 is a (x+1)-valent linking group, that is, a divalent or trivalent linking group. W 201 The divalent linking group in W may be, for example, a divalent hydrocarbon group which may have a substituent.201 The divalent linking group in may be linear, branched, or cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of an arylene group is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and the phenylene group is particularly preferred. W 201 The trivalent linking group in 201 and a group in which one hydrogen atom has been removed from the divalent linking group represented by the formula: W 201 As the trivalent linking group in the formula (I), a group in which two carbonyl groups are bonded to an arylene group is preferable.

[0109] Specific examples of suitable cations represented by the above formula (ca-1) include cations represented by the following chemical formulas (ca-1-1) to (ca-1-72), respectively.

[0110] [ka]

[0111] [ka]

[0112] [ka] [In the formula, g1, g2, and g3 each represent a repeating number, where g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20.]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka] [In the formula, R” 201 is a hydrogen atom or a substituent, and the substituent is the above-mentioned R 201 ~R 207 , and R 210 ~R 212 The substituents are the same as those exemplified as the substituents that may be possessed by the

[0117] Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, and the like.

[0118] Specific examples of suitable cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0119] [ka]

[0120] Specific examples of suitable cations represented by the formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0121] [ka]

[0122] Specific examples of suitable cations represented by the formula (ca-5) include cations represented by the following general formulas (ca-5-1) to (ca-5-3).

[0123] [ka]

[0124] Among the above, the cationic part ((M m+ ) 1 / m ) is preferably a cation represented by general formula (ca-1) or (ca-2).

[0125] ≪Compound (B0)≫ The compound (B0) is a compound represented by the following general formula (b0) obtained by subjecting the above-mentioned compound (B0p) and compound (C3) to an ion exchange reaction.

[0126] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. L 001 is an ester bond [-C(=O)-O-, -OC(=O)-]. z is an integer of 0 to 10. L 02 represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, -SO 2 -, -N(R a )-C(=O)-, -N(R a )-, -C(R a )(R a )-N(R a )-, -C(R a )(N(R a )(R a ))-, or -C(=O)-N(R a )-. R a are each independently a hydrogen atom or an alkyl group. 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m+ represents an organic cation having a valence of m, where m is an integer of 1 or more.

[0127] The anion moiety of compound (B0) is the same as the anion moiety of compound (B0p) described above. The cationic moiety of compound (B0) is the same as the cationic moiety of compound (C3) described above.

[0128] Specific examples of the compound (B0) in the method for producing a compound of this embodiment are shown below.

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] The reaction time in step B is, for example, preferably from 0.5 minutes to 24 hours, more preferably from 5 minutes to 12 hours, and further preferably from 10 to 60 minutes. The reaction temperature in step B is preferably from 0 to 50°C, more preferably from 10 to 30°C.

[0134] The reaction solvent in step B is preferably, for example, a mixed solvent of an organic solvent and water. Examples of the organic solvent include ketone solvents such as cyclohexanone, methyl ethyl ketone, and diethyl ketone; ether solvents such as diethyl ether, t-butyl methyl ether, and diisopropyl ether; halogen solvents such as tetrahydrofuran, 1,3-dioxolane, dichloromethane, and 1,2-dichloroethane; ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate, propionitrile, and mixed solvents thereof.

[0135] After the salt exchange reaction is completed, the compound in the reaction solution may be isolated and purified. For the isolation and purification, a conventionally known method can be used, and for example, a suitable combination of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. can be used. The structure of the compound obtained as above is 1 H-nuclear magnetic resonance (NMR) spectroscopy, 13 C-NMR spectroscopy, 19 Identification can be achieved by common organic analysis methods such as F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), elemental analysis, and X-ray crystal diffraction.

[0136] The raw materials used in each step may be commercially available or may be synthesized.

[0137] The method for producing the compound of the present embodiment described above employs a condensation reaction in step A, and therefore can improve the yield of compound (B0p) compared to conventional production methods (e.g., an SN2 reaction using a carboxylate anion and an alkyl halide). In addition, in step B, a metal cation or an organic ammonium cation having a LogP of 4.8 or less, which is a relatively hydrophilic cation, is used as the cation moiety of compound (C3) to be reacted with compound (B0p). This makes it possible for the ion exchange reaction in step B to proceed smoothly, thereby improving the yield of compound (B0). Therefore, according to the method for producing the compound of the present embodiment, a compound useful as an acid generator for a resist composition can be obtained in high yield. Furthermore, when an organic ammonium cation having a LogP of 4.8 or less is used as the cation moiety of compound (C3) to be reacted with compound (B0p), a compound useful as an acid generator for a resist composition can be obtained in high yield with fewer impurities (e.g., isomers, metals).

[0138] (Intermediate) The intermediate of this embodiment is an intermediate used in the method for producing the above-mentioned compound, and is an intermediate represented by the following general formula (b0-p).

[0139] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. L 001 is an ester bond [-C(=O)-O-, -OC(=O)-]. z is an integer of 0 to 10. L 02 represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, -SO 2 -, -N(R a )-C(=O)-, -N(R a )-, -C(R a )(R a )-N(R a )-, -C(R a )(N(R a )(R a ))-, or -C(=O)-N(R a )-. R a are each independently a hydrogen atom or an alkyl group. 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more.

[0140] The intermediate of this embodiment is the same as the above-mentioned compound (B0p). The intermediate of the present embodiment is a compound produced during the process for producing the compound described above. By producing compound (B0) via the intermediate of the present embodiment, the yield of compound (B0) can be improved.

[0141] (compound) The compound of this embodiment is a compound represented by the following general formula (b0-p-1).

[0142] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. L 001 is an ester bond [-C(=O)-O-, -OC(=O)-]. z is an integer of 0 to 10. Vb 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more.

[0143] The compound of this embodiment is the L 02 A preferred embodiment of the compound of this embodiment is a compound in which L of the above-mentioned compound (B0p) is a single bond. 02 This is the same as the compound (B0p) described above, except that is limited to being a single bond. The compound of the present embodiment is a compound produced during the process for producing the compound described above. By producing compound (B0) via the compound of the present embodiment, the yield of compound (B0) can be further improved.

[0144] The compound of the present embodiment can be produced by a condensation reaction of a compound represented by the following general formula (C-1) and a compound represented by the following general formula (C'-2). The method for producing the compound of this embodiment is the same as step A described above.

[0145] [ka] [In the formula, X 0 is a bromine atom or an iodine atom. m is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, and nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. One of a and b is a hydroxy group, and the other is a carboxy group. L 001 is an ester bond [-C(=O)-O-, -OC(=O)-]. z is an integer of 0 to 10. Vb 0 R is a single bond, an alkylene group, or a fluorinated alkylene group. 0 is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. m ' + is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more. EXAMPLES

[0146] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0147] In this example, the compound represented by chemical formula (C-1-1) is referred to as "compound (C-1-1)", and compounds represented by other chemical formulas are similarly referred to.

[0148] The compounds (C-1-1) to (C-1-14), (C-2-1) to (C-2-11), (X-1) to (X-3), and (C-3-1) to (C-3-6) used as raw materials are shown below. The combinations of raw materials, the intermediates obtained (compound (B0p), etc.), and the final products (compound (B0), etc.) are shown in Tables 1 to 4. In addition, for the compounds (C-2-1) to (C-2-11) and the compound (X-1), the LogP value of the cationic moiety is also shown.

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] [ka]

[0153] [ka]

[0154] <Step A: Step of obtaining compound (B0p)> Example 1 In a 100 mL recovery flask, add 2.00 g of compound (C-1-1), 1.06 g of D-1, 0.1 g of E-1, 2.51 g of compound (C-2-1), and CH 2 Cl 2 The mixture was stirred at room temperature. After confirming the disappearance of the raw materials, the solid matter was removed by filtration under reduced pressure. The filtrate was transferred to a separatory funnel and washed with water three times, and the organic layer was concentrated under reduced pressure. The concentrated residue was dissolved in 10 g of ethyl acetate by heating and cooled, and 30 g of tBuOMe was added to precipitate the solid matter. The solid matter was collected by filtration under reduced pressure and dried under reduced pressure to obtain 3.97 g of compound (B0p-1).

[0155] [ka]

[0156] (Examples 2 to 30, 32 to 39) Compounds (B0p-2) to (B0p-19) and (B0p-21) to (B0p-26) were obtained in the same manner as in the process for obtaining compound (B0p-1) in Example 1, except that the raw materials used were changed to the compounds shown in Tables 1 to 3.

[0157] (Example 31) In a 100 mL eggplant flask, 1.80 g of diphosphorus pentoxide, 15 g of chloroform, and 0.47 g of diethyl ether were placed and stirred at room temperature for 1 hour. 3.00 g of compound (C-1-14) and 2.6 g of compound (C-2-7) were placed and stirred at room temperature for 24 hours. After confirming the disappearance of the raw materials, the mixture was transferred to a separatory funnel and washed with water four times, and then the organic layer was concentrated under reduced pressure. The concentrated residue was dissolved in 10 g of ethyl acetate by heating and cooled, and 30 g of tBuOMe was added to precipitate the solid matter. The solid matter was collected by filtration under reduced pressure and dried under reduced pressure to obtain 4.58 g of compound (B0p-20).

[0158] [ka]

[0159] Comparative Example 1 In a 100 mL recovery flask, add 22.00 g of compound (C-1-12), 0.53 g of D-1, 0.05 g of E-1, 0.50 g of compound (X-2), and CH 2 Cl 2 The mixture was stirred at room temperature. After confirming the disappearance of the raw materials, the solid matter was removed by filtration under reduced pressure. The filtrate was transferred to a separatory funnel and washed with water three times, and the organic layer was concentrated under reduced pressure. The concentrated residue was dissolved in ethyl acetate by heating and cooled, and 30 g of tBuOMe was added to precipitate the solid matter. The solid matter was collected by filtration under reduced pressure and dried under reduced pressure to obtain 1.96 g of compound (b1-pre). Next, 1.96 g of compound (b1-pre), 0.44 g of sodium hydrogen sulfite, 0.53 g of sodium sulfite, and 10 g of water were added to a 100 mL three-neck flask, and the mixture was heated under reflux for 40 hours. 2 Cl 2 The organic layer was concentrated to obtain 1.28 g of compound (B0p-26).

[0160] [ka]

[0161] Comparative Example 2 In a 100 mL recovery flask, 22.00 g of compound (C-1-12), 0.60 g of sodium iodide, 0.55 g of potassium carbonate, 1.50 g of compound (X-3), and 10.0 g of dimethylformamide were placed, and the mixture was heated and stirred at an internal temperature of 90° C. for 24 hours. After confirming that the raw materials had disappeared, the mixture was transferred to a separating funnel and added to CH 2 Cl 2 The organic layer was concentrated under reduced pressure. The concentrated residue was dissolved in ethyl acetate by heating and cooled, and 30 g of tBuOMe was added to precipitate the solid matter. The solid matter was filtered off under reduced pressure and dried under reduced pressure to obtain 1.85 g of compound (B0p-26).

[0162] [ka]

[0163] Comparative Example 3 Compound (B1p-1) was obtained in the same manner as in the process for obtaining compound (B0p-1) in Example 1, except that compound (C-1-1) was changed to compound (C-1-12) and compound (C-2-1) was changed to the above compound (X-1).

[0164] The obtained compounds (B0p-1) to (B0p-26) and (B1p-1) are shown below. In this example, the compound represented by chemical formula (b0-p-1) is referred to as "compound (B0p-1)", and compounds represented by other chemical formulas are similarly referred to.

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] <Step B: Step of obtaining compound (B0)> Example 1 In a 100 mL separatory funnel, 3.97 g of compound (B0p-1), 2.19 g of compound (C-3-1), and CH 2 Cl 2 25 g of ethyl acetate and 25 g of water were added and the layers were separated. The aqueous layer was removed, and the organic layer was washed with hydrochloric acid and then with water, and then concentrated under reduced pressure. The concentrated residue was separated into CH 2 Cl 2 The mixture was dissolved in 5 g of tBuOMe and stirred. 15 g of tBuOMe was added to the solution to precipitate crystals. The solid content was filtered off under reduced pressure and dried under reduced pressure to obtain 4.41 g of compound (B0-1).

[0171] [ka]

[0172] (Examples 2 to 36, Comparative Examples 1 to 3) Compounds (B0-2) to (B0-31) shown below were obtained in the same manner as in the production method of compound (B0-1) of Example 1 above, except that the combination of compound (B0p-1) and salt-exchange compound (C-3-1) in the production of compound (B0-1) of Example 1 was changed to the above-mentioned compounds (B0p-1) to (B0p-26) and the above-mentioned salt-exchange compounds (C-3-1) to (C-3-6), respectively.

[0173] The obtained compounds (B0-1) to (B0-31) are shown below. In this example, the compound represented by chemical formula (b0-1) is referred to as "compound (B01)", and the compounds represented by other chemical formulas are similarly referred to.

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] The compound (C-2-11) used as the raw material for the above-mentioned compound (B0p-14) was synthesized by the following method. In a 100 mL recovery flask, add 2.00 g of butanoic acid, 4-[(tetrahydro-2H-pyran-2-yl)oxy]-, 1.2 g of compound D-1, 0.2 g of compound E-1, 2.5 g of compound (C-2-4), and CH 2 Cl 2 The mixture was stirred at room temperature. After confirming that the raw materials had disappeared, the solids were removed by filtration under reduced pressure. The filtrate was transferred to a separatory funnel and washed with water three times, and the organic layer was concentrated under reduced pressure. The concentrated residue was dissolved in 10 g of ethyl acetate by heating and cooled, and 30 g of tBuOMe was added to precipitate the solids. The solids were collected by filtration under reduced pressure and dried under reduced pressure to obtain 3.97 g of an intermediate. This intermediate was placed in a 100 mL eggplant flask, and 1.0 g of TsOH and 10 g of dichloromethane were added and stirred at room temperature. After confirming the disappearance of the raw materials, 10 g of 5% aqueous sodium bicarbonate solution was added to stop the reaction, and the mixture was transferred to a separatory funnel. The aqueous layer was removed, and the organic layer was concentrated after washing with water three times. The concentrated residue was dissolved in 10 g of ethyl acetate by heating and cooled, and 30 g of tBuOMe was added to precipitate the solid matter. The solid matter was collected by filtration under reduced pressure and dried under reduced pressure to obtain 3.80 g of compound (C-2-11).

[0179] [ka]

[0180] Tables 1 to 4 show the raw materials, intermediates (compound (B0p), etc.) and final compounds (compound (B0), etc.) used in the production methods of the above-mentioned compounds.

[0181] [Table 1]

[0182] [Table 2]

[0183] [Table 3]

[0184] [Table 4]

[0185] In Tables 1 to 4, the abbreviations have the following meanings. C-1-1 to C-1-14: The above-mentioned compounds (C-1-1) to (C-1-14) C-2-1 to C-2-11: The above-mentioned compounds (C-2-1) to (C-2-11) X-1 to X-3: The above-mentioned compounds (X-1) to (X-3) C-3-1 to C-3-6: The above-mentioned compounds (C-3-1) to (C-3-6)

[0186] D-1 to D-7: Compounds D-1 to D-7 represented by the following chemical formulas D-1 to D-7, respectively. E-1 to E-3: Compounds E-1 to E-3 represented by the following chemical formulas E-1 to E-3, respectively.

[0187] [ka]

[0188] [ka]

[0189] The yield in the production method of each compound (yield in step A, yield in step B, total yield (yield in step A x yield in step B)), and the amount of isomers and residual Na determined by the measurement methods described below are shown in Tables 5 to 8. It should be noted that the manufacturing method of the comparative example does not have step A or step B, but for convenience, the step corresponding to step A in the example will be referred to as step A, and the step corresponding to step B in the example will be referred to as step B.

[0190] [Measurement of isomer amounts] The amount of impurities (amount of isomers) of the compounds obtained by the manufacturing method of each example was quantified by LC-MS. "nd" means that it was below the detection limit.

[0191] [Measurement of remaining sodium] For the compounds obtained by the production methods of the respective examples, the amount of residual Na was quantified by ICP-MS.

[0192] [Table 5]

[0193] [Table 6]

[0194] [Table 7]

[0195] [Table 8]

[0196] As shown in Tables 5 to 8, it was confirmed that the methods for producing the compounds of Examples 1 to 39 were capable of producing the target compounds in higher yields than the methods for producing the compounds of Comparative Examples 1 to 3. Among the Examples, the methods for producing the compounds of Examples 1 to 37 used an organic ammonium salt as compound (C2), and therefore the residual Na content could be further reduced.

[0197] The method for producing the compound of Comparative Example 1 used compound (X-2) instead of compound (C2), and after the condensation reaction of compound (C1-1-12) with compound (X-2), the terminals were sulfonated. As a result, a large amount of isomers were produced, and the yield in step A was low. In the production method of the compound of Comparative Example 2, the yield in step A was low because the compound (X-3) having a chlorine atom at the end was used instead of the compound (C2). In the production method of the compound of Comparative Example 3, the compound (X-1), which has a high LogP value of the cationic moiety (LogP value: 7.81) and is relatively hydrophobic, was used instead of the compound (C2), and therefore the salt exchange reaction did not proceed sufficiently, resulting in a low yield in step B.

Claims

[Claim 1] A step of subjecting a compound represented by the following general formula (C-1) and a compound represented by the following general formula (C-2) to a condensation reaction to obtain a compound (B0p) represented by the following general formula (b0-p): a step of subjecting the compound (B0p) and a compound represented by the following general formula (C-3) to an ion exchange reaction to obtain a compound (B0) represented by the following general formula (b0); A method for producing a compound having the formula: 【Chemistry 1】 [In the formula, X ０ is a bromine atom or an iodine atom. ｍ is a hydroxy group, an alkyl group, a fluorine atom, or a chlorine atom. nb1 is an integer of 1 to 5, nb2 is an integer of 0 to 4, and 1≦nb1+nb2≦5. One of a and b is a hydroxyl group, and the other is a carboxyl group. z is an integer of 0 to 10. L ０２ represents a single bond, an alkylene group, -O-, -CO-, -OCO-, -COO-, or -SO ２ -, -N(R ａ )-C(=O)-,-N(R ａ ) -, -C(R ａ ) (R ａ )-N(R ａ ) -, -C(R ａ ) (N (R ａ ) (R ａ ))-, or -C(=O)-N(R ａ )-. ａ Each of Vb is independently a hydrogen atom or an alkyl group. ０ is a single bond, an alkylene group, or a fluorinated alkylene group. ０ is a hydrogen atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorine atom. ｍ ' ＋ is a metal cation or an organic ammonium cation having a LogP of 4.8 or less. m' is an integer of 1 or more. ００１ is an ester bond [-C(=O)-O-, -O-C(=O)-]. － is the counter anion. ｍ＋ represents an m-valent organic cation, where m is an integer of 1 or more.

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