JP2002167340A - Production method of onium salt derivative and novel onium salt derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of onium salt derivatives which is capable of synthesizing in high yield the onium salt derivatives useful as an acid generator or the like used in a chemical amplification type resist, and also provide a novel onium salt derivatives. SOLUTION: Onium sulfonic acid derivatives or an onium phosphoric acid derivatives are obtained in high yield by reaction of sulfonic ester derivatives or phosphoric ester derivatives with an onium salt derivative having a halogenci anion or a carboxylate anion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an onium-type strong acid generator which generates a strong acid when irradiated with UV light, KrF excimer laser light, ArF excimer laser light, F ₂ excimer laser light, electron beam or X-ray. The present invention relates to a method for producing a useful onium salt derivative and a novel onium salt derivative.

[0002]

2. Description of the Related Art In recent years, the light source of an exposure apparatus used for photolithography has become shorter and shorter in fine processing as semiconductor devices have become more highly integrated. Recently, KrF excimer laser light (248.4 nm) has been studied. However, a resist material for using this KrF excimer laser beam as a light source is required to respond to exposure with high sensitivity.

As one of the methods for this purpose, it has been proposed to use a so-called chemically amplified resist material which increases the sensitivity by incorporating a compound having a property of generating an acid upon exposure (Polym. Eng.
Sci. , Vol. 23, 1012 (1983)).

[0004] Further, a compound capable of generating an acid upon exposure, which is used in the above-mentioned chemically amplified resist material (hereinafter, referred to as a compound).
Onium salts such as diazonium diallyl or alkyliodonium triallyl or alkylsulfonium salts have been reported as acid generators (US Pat. No. 4,491,628, US Pat. No. 4,603,101).
No., JP-B-2-27660, JP-A-62-114
No. 0).

As an acid generator, 6-dinitrobenzyl tosylate and the like have been reported (Fl Hou).
Liban et al., Advances in Response
tTechnology and Processin
g, SPIE, Vol. 920, 67, (1988)
etc).

[0006] Among such acid generators, onium salts such as iodonium or sulfonium, particularly onium salt derivatives having sulfonate as an anion, are widely used because of their good solution stability during storage.

A method of producing such an onium salt derivative by subjecting an onium salt derivative having an anion to a halogen ion to a salt exchange with sulfonic acid, a silver salt of sulfonic acid or an alkali metal salt is known (for example, ,
J. Polymer Sci. , Symposium
No. 56, p. 383 (1976) and J. Org. Rad. C
uring, vol. 4, p. 2 (1977)).

However, the exchange reaction with sulfonic acid or an alkali metal salt of sulfonic acid is an equilibrium reaction.
The problem that it is necessary to use 1.5 mole equivalent or more of sulfonic acid or an alkali metal salt of sulfonic acid with respect to an onium salt derivative having an anion as a halogen ion, or an onium salt having a selected sulfonate as an anion There is a problem that halide ions are mixed in the derivative.
Further, the method using a silver salt has a problem that the silver salt is expensive.

The sulfonic acids produced using such a sulfonium salt as an acid generator have a wide variety of substituents ranging from an aromatic group to an alkyl group. Therefore, an anion exchange method from a common intermediate is preferred. However, since all sulfonic acids are stronger acids than sulfuric acid, in a normal salt exchange, anions as a raw material necessarily remain due to an equilibrium relationship in the reaction, which adversely affects the resist.

Onium salt derivatives having sulfonates as anions have been used as heat or photoinitiators for various anionic polymerizable compounds such as epoxy, in addition to photoacid generators for chemically amplified resists. I have.

The present invention has been made in view of such circumstances, and a method for producing an onium salt derivative capable of synthesizing an onium salt derivative useful as an acid generator or the like used in a chemically amplified resist in a high yield. And a new onium salt derivative.

[0012]

The present inventors have made intensive efforts to solve the above-mentioned problems, and as a result, have found that an onium salt derivative having a halogen anion or a carboxylate anion can be added to a sulfonate ester derivative or a phosphorus ester derivative. The inventors have found that an onium sulfonic acid derivative or an onium phosphoric acid derivative can be obtained in high yield by reacting an acid ester derivative, and thus completed the present invention. In addition, the present inventors have found that a novel onium salt derivative having phosphate as an anion can be obtained, and that an onium salt derivative having sulfonate as an anion can be efficiently produced from the novel onium salt phosphate derivative. And completed the present invention.

When a sulfonate is allowed to react with an onium salt derivative having a halogen anion or a carboxylate anion in the presence of a predetermined compound such as an orthoacid ester, the same sulfonate is converted into an anion. It has been found that an onium salt derivative can be produced, and the present invention has been completed.

Further, after a sulfonic acid derivative such as dialkyl sulfate is reacted with an onium salt derivative having a halogen anion or a carbochelate anion, a sulfonate is further reacted to obtain a high yield of the onium sulfonic acid derivative. The present invention has been completed by finding that it can be obtained at a high rate.

According to the first aspect of the present invention, an onium salt derivative represented by the following general formula (1) to (4) is reacted with a compound represented by the following general formula (5) to (7). The method for producing an onium salt derivative is characterized by obtaining onium salt derivatives represented by the general formulas (8) to (19).

[0016]

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(R ₁ , R ₂ and R ₃ are each independently
Represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, an aralkyl group or a phenacyl group having 25 or less carbon atoms which may be substituted, and at least _one of R ₁ and R ₃ and R ₂ and R ₅ One together may represent a divalent organic group. R ₄ represents a divalent organic group having 20 or less carbon atoms. Q ^- is a halogen anion, or carbon atoms represent 10 following carbocyclylalkyl chelating anions. )

[0018]

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(R ₆ is an optionally substituted carbon number 2
5 or less represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, or an aralkyl group. R
₇ represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, or an aralkyl group having 10 or less carbon atoms which may be substituted. R ₈ and R ₉ each independently represent an alkyl group, a cycloalkyl group, a perfluoroalkyl group, or an aralkyl group having 10 or less carbon atoms which may be substituted. )

[0020]

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[0021]

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[0022]

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The second aspect of the present invention is characterized in that, in the first aspect, R ₇ of the sulfonic acid ester of the above general formula (5) is a lower alkyl sulfonate having a lower alkyl group having up to 5 carbon atoms. In the method for producing an onium salt derivative.

A third aspect of the present invention is the method for producing an onium salt derivative according to the first or second aspect, wherein the reaction is carried out while removing generated R ₇ Q outside the reaction system.

A fourth aspect of the present invention is the method for producing an onium salt derivative according to any one of the first to third aspects, wherein the reaction is carried out in a solvent.

A fifth aspect of the present invention is a compound represented by the following general formula (1):
By reacting an onium salt derivative represented by any one of (1) to (4), a compound represented by the following general formula (21) to (23), and a sulfonic acid derivative represented by the following general formula (24), A method for producing an onium salt derivative characterized by obtaining onium salt derivatives represented by the general formulas (25) to (28).

[0027]

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(R ₁ , R ₂ and R ₃ are each independently
Represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, an aralkyl group or a phenacyl group having 25 or less carbon atoms which may be substituted, and at least _one of R ₁ and R ₃ and R ₂ and R ₅ One together may represent a divalent organic group. R ₄ represents a divalent organic group having 20 or less carbon atoms. Q ^- is a halogen anion, or carbon atoms represent 10 following carboxylate anions. )

[0029]

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(R ₁₀ is hydrogen, carbon atom 2 which may be substituted
5 or less represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, or an aralkyl group. R
₁₁ , R ₁₂ and R ₁₃ are each independently an alkyl group, a cycloalkyl group having 10 or less carbon atoms which may be substituted,
Represents a perfluoroalkyl group or an aralkyl group. )

[0031]

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(R ₁₅ is an optionally substituted carbon number 2
5 or less represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, or an aralkyl group. Y
Represents a hydrogen atom, an alkali metal, or ammonium. )

[0033]

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According to a sixth aspect of the present invention, in the fifth aspect, the compound of the general formulas (21) to (23) is added to the onium salt derivative of the general formulas (1) to (4) by 1 ~ 1
A method for producing an onium salt derivative characterized by using 0 times by mole.

According to a seventh aspect of the present invention, in the fifth or sixth aspect, the sulfonic acid derivative is represented by the general formula (1)
(4) The method for producing an onium salt derivative according to (4), wherein the onium salt derivative is used in a molar amount of 1 to 2 times that of the onium salt derivative.

The eighth aspect of the present invention is a method of the present invention, wherein the following general formula (1)
The onium salt derivative represented by any one of (1) to (4) is reacted with a sulfate represented by the following general formula (29), and the onium salt derivative obtained by this reaction is represented by the following general formula (24). A method for producing an onium salt derivative, characterized in that an onium salt derivative represented by any of the general formulas (25) to (28) is obtained by reacting with a sulfonic acid derivative.

[0037]

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(R ₁ , R ₂ and R ₃ are each independently
Represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, an aralkyl group or a phenacyl group having 25 or less carbon atoms which may be substituted, and at least _one of R ₁ and R ₃ and R ₂ and R ₅ One together may represent a divalent organic group. R ₄ represents a divalent organic group having 20 or less carbon atoms. Q ^- is a halogen anion, or carbon atoms represent 10 following carboxylate anions. )

[0039]

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(R ₁₆ and R _{17 each} represent an alkyl group, a cycloalkyl group, a perfluoroalkyl group, or an aralkyl group having 10 or less carbon atoms which may be substituted.)

[0041]

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(R ₁₅ is an optionally substituted carbon number 2
5 or less represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, or an aralkyl group. Y
Represents a hydrogen atom, an alkali metal, or ammonium. )

[0043]

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A ninth aspect of the present invention is the method for producing an onium salt derivative according to the eighth aspect, wherein the sulfate of the general formula (29) is dimethyl sulfate or diethyl sulfate.

A tenth aspect of the present invention is a compound represented by the following general formula (1)
2) Onium salt derivatives represented by general formulas (25) to (28) by reacting the onium salt derivatives represented by (15) with sulfonic acid derivatives represented by the following general formula (24) And a process for producing an onium salt derivative.

[0046]

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(R ₁ , R ₂ and R ₃ are each independently
Represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, an aralkyl group or a phenacyl group having 25 or less carbon atoms which may be substituted, and R ₁ and R ₃
And at least one of R ₂ and R ₅ may together represent a divalent organic group. R ₄ represents a divalent organic group having 20 or less carbon atoms. R ₈ and R ₉ each independently represent an alkyl group, a cycloalkyl group, a perfluoroalkyl group, or an aralkyl group having 10 or less carbon atoms which may be substituted. )

[0048]

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(R ₁₅ is an optionally substituted carbon atom 2
5 or less represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, or an aralkyl group. Y
Represents a hydrogen atom, an alkali metal, or ammonium. )

[0050]

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An eleventh aspect of the present invention is a compound represented by the following general formula (1)
(2) An onium salt derivative represented by (15).

[0052]

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(R ₁ , R ₂ and R ₃ are each independently
Represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, an aralkyl group or a phenacyl group having 25 or less carbon atoms which may be substituted, and R ₁ and R ₃
And at least one of R ₂ and R ₅ may together represent a divalent organic group. R ₄ represents a divalent organic group having 20 or less carbon atoms. R ₈ and R ₉ each independently represent an alkyl group, a cycloalkyl group, a perfluoroalkyl group, or an aralkyl group having 10 or less carbon atoms which may be substituted. )

In the present invention, the onium salt derivative represented by the above general formulas (1) to (4) is used as a raw material, and is reacted with a sulfonic acid ester, a phosphoric acid ester or a sulfuric acid ester to obtain a high yield. An onium salt sulfonic acid derivative or an onium salt phosphoric acid derivative is obtained.

Here, the general formulas (1) to
The onium salt derivative of (4) is iodonium salt and sulfonium salt having iodine and sulfur as central elements, but ammonium salt, phosphonium salt and the like may be used.

Here, R ₁ , R ₂ and R ₃ each independently represent an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, an aralkyl group, or an phenacyl group, R ₁
And R ₃ and at least one of R ₂ and R ₅ may together represent a divalent organic group, and specific examples thereof will be shown below.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an iso-amyl group and a sec-amyl group.
-Amyl group, 2-methylbutyl group, 2-methyl-2-butyl group, 1,1-dimethylbutyl group, 2-hexyl group,
A chain having 3 to 8 carbon atoms, such as a 1,1,1-trimethylbenzyl group, a 1,1-dimethylhexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; Or a cyclic alkyl group. Examples of the cycloalkyl group include a cycloalkyl group having 3 to 20 carbon atoms (eg, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a bicycloheptyl group, and the like). Examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorooctyl group, and the like.

The aromatic organic group is an organic group having a monocyclic or condensed-ring carbocyclic structure or a monocyclic or condensed-ring aromatic nucleus. Examples of the aromatic nucleus in the aromatic organic group include phenyl and biphenyl. Group, naphthyl group, anthryl group, phenanthryl group and the like. These aromatic nuclei may have a substituent at an appropriate position. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms (such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group), and an alkoxy group having 1 to 12 carbon atoms (such as a methoxy group, an ethoxy group, and a propoxy group). , A butoxy group, etc.), an acyl group having 2 to 11 carbon atoms (e.g., acetyl group, benzoyl group, etc.), an acyloxy group having 2 to 11 carbon atoms (e.g., acetyloxy group, benzoyloxy group, etc.), and having 7 to 20 carbon atoms. Examples include aralkyl groups (eg, benzyl group, diphenylmethyl group, phenylpropyl group, etc.), nitro groups, cyano groups, butoxycarbonyloxy groups, and halogen atoms (eg, fluorine, chlorine, bromine, and iodine atoms). These substituents are 2
There can be more than one type.

Specifically, phenyl, halogenated phenyl, hydroxyphenyl, alkoxyphenyl, aminophenyl, alkoxycarbonylphenyl, formylphenyl, thiophenyl, thioalkoxyphenyl, cyanophenyl, etc. Aryl group can be mentioned.

The aralkyl group includes, for example, those having 7 to 7 carbon atoms.
20 aralkyl groups (for example, benzyl group, naphthylmethyl group, anthranylmethyl group, diphenylmethyl group, etc.)
These aralkyl groups can have a substituent at an appropriate position of the aromatic nucleus, and examples of the substituent include the same substituents as those described for the aromatic organic group. it can.

More specifically, phenylbenzyl, halogenated benzyl, hydroxybenzyl, alkoxyphenylbenzyl, aminobenzyl, alkoxycarbonylbenzyl, formylphenyl, thiobenzyl, thioalkoxybenzyl, cyanobenzyl And the like.

R ₄ may be a divalent organic group such as an arylene group, an alkylene group, a cycloalkylene group, an aralkylene group and the like. Specific examples include a phenylene group, a naphthylene group, an ethylene group and a propylene group. , Butylene group, hexylene group, cyclohexylene group,
Xylylene groups and the like can be mentioned.

When R ₁ and R ₃ and / or R ₂ and R _{5 in the} general formulas (3) and (4) are formed together, the divalent organic group is represented by the general formula (3) (4) forming an aliphatic or aromatic heterocyclic structure with the sulfur atom in (2)
Is a valence organic group. As such a divalent organic group,
For example, an organic group represented by the following formula can be exemplified.

[0064]

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Q ^- represents a halogen anion or a carboxylate anion having 10 or less carbon atoms.

Examples of the halogen anion include a fluorine ion, a chlorine ion, a bromine ion and an iodine ion.

The carboxylate anion is selected from the group represented by the following general formula (20).

[0068]

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Here, R ₁₉ represents hydrogen or an optionally substituted alkyl group having 10 or less carbon atoms, preferably an alkyl group having 5 or less carbon atoms.

The general formulas (5) to (7) which are reacted with the onium salt derivatives of the general formulas (1) to (4) are a sulfonic acid ester, a phosphoric acid ester and a sulfate ester.

Here, specific examples of R _{6 to} R ₉ will be shown.

R ₆ has an optionally substituted carbon number of 25
The following are an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, and an aralkyl group, and specific examples are shown below.

Examples of the alkyl group include an optionally substituted alkyl group having 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group).

Further, as the perfluoroalkyl group,
Examples thereof include a trifluoromethyl group, a nonafluorobutyl group, a perfluorooctyl group and the like.

The cycloalkyl group includes, for example, a cycloalkyl group having 3 to 15 carbon atoms (eg, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a bicycloheptyl group, a 7,7-dimethyl-2-oxopicyclo [2,2,1 ] Heptane-1-methyl group and the like).

Examples of the aromatic organic group include those having 6 to 6 carbon atoms.
25 aromatic organic groups (e.g., phenyl, tolyl, trimethylphenyl, isopropylphenyl, triisopropylphenyl, t-butylphenyl, fluorophenyl, bis (trifluoromethyl) phenyl, difluorophenyl, Trifluorophenyl group,
Trifluoromethylphenyl group, pentafluorophenyl group, naphthyl group, anthryl group, 9,10-dimethoxyanthryl group, phenanthryl group and the like).

The aralkyl group includes, for example, those having 7 to
20 aralkyl groups (for example, benzyl group, naphthylmethyl group, anthranylmethyl group, diphenylmethyl group, etc.)
Can be mentioned.

R ₇ , R ₈ and R _{9 each} represent an alkyl group, a cycloalkyl group, a perfluoroalkyl group or an aralkyl group having 10 or less carbon atoms which may be substituted.
An alkyl group having 5 or less carbon atoms is preferred.

The reaction of the present invention can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent. As the solvent to be used, for example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, di-t-butyl ether, acetonitrile, benzonitrile And the like, and preferred are ethers.

The reaction temperature of the present invention is not particularly limited, but is preferably 0 ° C. to 200 ° C.

The reaction of the present invention is a transesterification reaction in which R ₇ -Q such as an alkyl halide is formed, and it is preferable to remove this R ₇ -Q from the reaction system. Therefore, R ₇ −
The lower the boiling point of Q, the easier it is to remove. As a method for removing the R ₇ -Q produced in the reaction, for example, methods such as excluding the reaction system as a gas is reacted at temperatures above the boiling point of R ₇ -Q using high boiling point than R ₇ -Q solvent There is.

The onium salt derivatives represented by the general formulas (8) to (19) produced by the above-described method can be used as they are as an acid generator or the like. Can be used. In particular, the onium salt sulfonic acid derivatives represented by the general formulas (16) and (17) can be obtained from UV light, KrF excimer laser light, Ar
F excimer laser light, F ₂ excimer laser light,
It is useful as an onium-type strong acid generator that generates a strong acid upon irradiation with an electron beam or X-ray.

The onium salt phosphoric acid derivatives represented by the general formulas (12) to (15) are novel compounds. Such a compound is an onium salt having a phosphoric acid ester, which is a conjugate base of a weak acid, in the anion part, and can be used as an acid generator itself, but is easily sulfonated by strong salt exchange with a strong acid such as sulfonic acid. An onium salt derivative having a conjugate base of an acid as a counter ion can be obtained without impurities such as halogen.

When such an onium salt phosphoric acid derivative is produced by the above-mentioned method of the present invention, the above reaction conditions may be used, but particularly preferred reaction conditions will be described below.

The amount of the phosphoric acid ester used in synthesizing the onium salt phosphoric acid derivative is 1 to 3 equivalents, more preferably 1.2 to 2 equivalents, per 1 equivalent of the onium salt. When this phosphate ester is used as a solvent,
5 to 30 equivalents, more preferably 10 to 20 equivalents, is suitable for 1 equivalent of the onium salt.

The reaction solvent is 1 to 1 equivalent of the onium salt.
~ 20 liters (expressed as L), more preferably 5 ~
10 L is appropriate. As the reaction solvent, a phosphate ester represented by the general formula (6) is usually used. That is, the phosphoric ester represented by the general formula (6) is used as a reaction reagent and a reaction solvent. When using a solvent, the solvent used in the present invention is not particularly limited, and a hydrocarbon solvent, a chlorine solvent, an alcohol solvent, an ether solvent, a nitrile solvent, an ester solvent, or the like may be appropriately used. it can. Preferably, high boiling solvents such as 1,2 dichloroethane and dioxane are suitable.

The reaction temperature is usually from 40 to 200 ° C., preferably from 50 to 180 ° C. If the reaction temperature is too high, the yield will decrease due to side reactions, and if the reaction temperature is low, the reaction time will be long.

The reaction time is generally 1 minute to 40 hours, preferably 5 minutes to 20 hours. The onium salt is usually insoluble at the beginning of the reaction, but dissolves as the reaction proceeds. However, diphenyliodonium chloride is hardly soluble in a solvent. When a phosphoric acid ester is used after completion of the reaction, the onium salt crystallizes when the reaction product is cooled. Next, it is washed with a small amount of a solvent such as alcohol, ether and acetone and then dried. When it is used for a salt exchange reaction, it may be used as it is.

Onium phosphate is water-soluble in many cases, whereas onium sulfonate to be salt-exchanged is extracted into the organic layer. Can be manufactured. As described above, the method for producing onium phosphate utilizes the fact that the haloalkane generated by the nucleophilic substitution reaction of the trialkyl phosphate of the halide to the alkyl group is removed outside the system, and as a result, the anion conversion proceeds smoothly. Is extremely efficient.

Further, by using the onium salt phosphoric acid derivative as a raw material and reacting it with a sulfonate of the general formula (24), the amount of sulfonic acid used can be reduced and the onium salt sulfonic acid derivative can be obtained in high yield. Can be obtained.

In the method of the present invention, it is particularly preferable to use onium dialkyl phosphate as a raw material.
The exchange between these and sulfonic acid is based on the fact that the pKa of the alkyl phosphoric acid in the resulting aqueous solution is about 2 and the sulfonic acid is-
Since it is significantly different from 3 to -6, the equilibrium is almost completely transferred to the onium sulfonate.

In the method of the present invention, sulfonic acid is used in an amount of 1 to 2 moles, preferably 1.05 to 1.2 moles, per 1 mole of onium phosphate. The reaction solvent is
1 to 20 L, preferably 5 to 1 mol of onium salt
It is better to use 10L.

As the reaction solvent, generally, a halogen-based solvent (methylene chloride, chloroform) is used, but any solvent can be used as long as it forms two layers with water and can dissolve the onium salt as a solute. May be used.

The reaction temperature may generally be room temperature, and the exchange reaction is carried out instantaneously, so that the reaction time is not particularly limited.

After completion of the reaction, water and alkaline water (for example,
If an aqueous solution of an amine such as ammonia is added to make the solution alkaline, the exchange reaction proceeds quickly and excess acid can be expelled to the aqueous layer. The desired product can be obtained by removing the aqueous layer, washing the organic layer several times with water until the pH becomes neutral, drying, removing the solvent, and purifying by recrystallization or the like.

In the process of the present invention, the acid strength of the phosphate is extremely weaker than that of ordinary sulfonic acid, and although it is often water-soluble, the salt-exchanged onium sulfonate is extracted into the organic layer. Therefore, it can be almost selectively produced as a sulfonate in combination with the equilibrium based on the acid strength.

In the present invention, the onium salt derivatives represented by the general formulas (1) to (4) are combined with the onium salt derivatives represented by the general formulas (21) to (2)
By reacting the compound represented by 3) with a sulfonic acid salt of the general formula (24), an onium sulfonic acid salt can be obtained in one step with a high yield.

Here, the compounds represented by the general formulas (21) to (23) are orthocarboxylic acid esters, phosphoric acid esters, and sulfuric acid esters. R _{10 in the} general formula (21) can be hydrogen or a substituent similar to R ₆ described above. Further, R _{11 to} R ₁₃ in the general formulas (21) to (23) can be the same substituents as R ₇ and R ₈ described above.

On the other hand, R ₁₅ of the sulfonate represented by the general formula (24) is an alkyl group, a cycloalkyl group, a perfluoroalkyl group or an aromatic organic group, which may have 25 or less carbon atoms. Represents an aralkyl group. Specific examples are shown below.

Examples of the alkyl group include an optionally substituted alkyl group having 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group).

Further, as the perfluoroalkyl group,
Examples thereof include a trifluoromethyl group, a nonalurobutyl group, a perfluorooctyl group, and the like, and a perfluoroalkyl group is particularly preferable.

Examples of the cycloalkyl group include a cycloalkyl group having 3 to 15 carbon atoms (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, bicycloheptyl group, 7,7-dimethyl-2-oxobicyclo).
[2,2,1] heptane-1-methyl group etc.).

As the aromatic organic group, for example, those having 6 carbon atoms
To 25 aromatic organic groups (for example, phenyl group, tolyl group, trifluoromethylphenyl group, pentafluorophenyl group, naphthyl group, anthryl group, 9,10-dimethoxyanthryl group, phenanthryl group and the like). it can. Examples of the aralkyl group include, for example, those having 7 carbon atoms.
To 20 aralkyl groups (for example, benzyl group, naphthylmethyl group, anthranylmethyl group, diphenylmethyl group and the like).

In the general formula (24), Y is a hydrogen atom,
Represents an alkali metal such as lithium, sodium, potassium and / or ammonium. Here, ammonium is represented by the following general formula (21).

[0105]

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(R _{20 to} R ₂₃ represent hydrogen, an alkyl group, an aralkyl group, or an aryl group.)

In the reaction using such a compound and a sulfonate, these compounds are decomposed by the acid-catalyzed action of sulfonic acid to generate a cation, which reacts with an anion such as a halide. Then, it is considered that the reaction proceeds smoothly by generating an alkyl halide or the like to remove anions such as a halide and replacing the sulfonic acid with a salt instead.

In the method of the present invention, the compound such as the ortho acid ester is used in an amount of 1 to 10 times, preferably 1.2 to 5 times the molar amount of the onium salt derivative.

The sulfonate is used in an amount of 1 to 2 moles, preferably 1.05 to 1.2 moles, per mole of the onium salt derivative.
Use molar times.

As the solvent used in this reaction, a chlorine-based solvent, an alcohol-based solvent, an ether-based solvent, a nitrile-based solvent, an ester-based solvent, a carboxylic acid-based solvent and the like can be appropriately used. Chloroform is preferred.

This reaction usually proceeds at room temperature, but the reaction can be accelerated by heating.
It is usually within 100 ° C, preferably 40 to 60 ° C.

The reaction time depends on the reaction temperature. To reduce the concentration of anions such as halides to 50 ppm or less, the reaction is carried out at room temperature.
It requires 2-4 hours at 40 ° C.

After completion of the reaction, aqueous ammonia is added to make the mixture alkaline, and the desired product is extracted from the solvent used. The solution is dried and then recrystallized after evaporation of the solvent.

The onium sulfonate produced by the method of the present invention described above can be said to be useful as an acid generator for a chemically amplified resist because the content of a halide harmful to the resist process can be suppressed to a very low level.

Further, in the present invention, the compounds represented by the general formulas (1) to
The onium salt derivative of (4) is reacted with a sulfuric ester of the general formula (29), and further reacted with a sulfonic ester of the general formula (24) to easily and economically produce high-purity sulfonic acid. An onium salt derivative having a conjugate base as a counter ion is obtained.

The substituents R ₁₆ and R ₁₇ in the general formula (29) are
It is the same as R ₇ and R _{8 in} the general formula (7), but is preferably an alkyl group having 5 or less carbon atoms, and most preferably
It is a methyl group or an ethyl group.

The method of the present invention comprises an onium salt derivative represented by the general formulas (1) to (4) as raw materials (hereinafter described as an onium salt derivative having a halogen as an anion):
The method includes a first step of reacting with a sulfuric acid ester such as dialkyl sulfate (hereinafter, referred to as an alkyl ester). The above step provides an onium salt derivative having a monoalkyl sulfate ion as a counter ion.

In this step, the onium salt derivative having a halogen ion is reacted with dialkyl sulfate to obtain
It is presumed that an onium salt derivative having a monoalkyl sulfate ion as a counter ion and an alkyl halide are formed.
Therefore, halide ions can be removed from the reaction system by removing the generated alkyl halide out of the reaction system. As the dialkyl sulfate, a lower dialkyl sulfate, particularly, dimethyl sulfate and / or diethyl sulfate is preferable. By using the lower dialkyl sulfate, the generated alkyl halide or the like can be easily removed as a gas outside the reaction system.

The above first step can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent. As the solvent to be used, for example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, diethyl ether, diisopropyl ether, methyl-t-butyl ether, di-t
Ethers such as -butyl ether; and nitriles such as acetonitrile and benzonitrile. The reaction temperature is not particularly limited, but is preferably 30 ° C to 12 ° C.
0 ° C, particularly preferably 40 ° C to 100 ° C.

When reacting an onium salt derivative having a halogen ion as an anion with a dialkyl sulfate, the molar ratio of the onium salt derivative having a halogen ion as an anion to the dialkyl sulfate is not particularly limited. 1.0: 1.0 to 2.0. 1.0:
If the molar ratio of dialkyl sulfate is lower than 1.0, halide ions remain after the reaction, which is not preferable. The molar ratio of dialkyl sulfuric acid may be 2.0 or more. However, if it is large, unreacted dialkyl sulfuric acid remains after the reaction, which is not preferable.

The onium salt derivative having the conjugate base of the monoalkyl sulfate obtained in the first step as a counter ion is reacted with sulfonic acid and / or an alkali metal salt of sulfonic acid and / or an ammonium salt of sulfonic acid. By the second step, an onium salt derivative having a target conjugate base of sulfonic acid as a counter ion can be obtained. The sulfonic acid and its salt used in the second step are represented by the general formula (24).

In the second step of the present invention, when the onium salt derivative having a conjugate base of a monoalkyl sulfate as a counter ion is reacted with sulfonic acid and / or a salt thereof, the conjugate base of the monoalkyl sulfate is reacted with the counter ion. The molar ratio between the onium salt derivative and the sulfonic acid and / or salt thereof is not particularly limited, but is preferably 1.0: 1.0 to 1.5. Although this ratio may be less than 1.0, it is not preferable because the yield of an onium salt having a target conjugate base of a sulfonic acid as a counter ion decreases. Although it may be 1.5 or more, it is not economical to use sulfonic acid and / or a salt thereof in a large excess.

The reaction of the second step of the present invention can be carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent. As the solvent to be used, for example, water, dichloromethane, chloroform, carbon tetrachloride,
Examples thereof include halogenated hydrocarbons such as chlorobenzene, ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether and di-t-butyl ether, and nitriles such as acetonitrile and benzonitrile, and preferably water. Further, a mixed solvent of the above organic solvent and water is also preferable. The reaction temperature in the second step is not particularly limited.

[0124]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by way of examples, but it goes without saying that the content of the present invention is not limited by these examples. Each compound is NM
Identified by R, IR, UV and MASS.

Example 1 Synthesis of bis (p-tert-butylphenyl) iodonium p-toluenesulfonate 428.8 g (1.0 mol) of bis (p-tert-butylphenyl) iodonium chloride and p-toluenesulfonic acid 223.5 g (1.2 mol) of methyl was suspended in 500 ml of t-butyl methyl ether.
Heat to 5 ° C to 58 ° C and reflux with stirring for 5 hours. After cooling the reaction solution, a white solid was separated by filtration. The white solid was washed with t-butyl methyl ether and dried under vacuum to obtain 513.7 g (yield 91%) of bis (p-tert-butylphenyl) iodonium p-toluenesulfonate.

The chlorine ion content of the obtained white solid was determined by silver nitrate titration to be 8 ppm.

(Example 2) Synthesis of bis (p-tert-butylphenyl) iodonium p-toluenesulfonate Instead of methyl p-toluenesulfonate in Example 1, 257.1 g of isopropyl p-toluenesulfonate
(1.2 mol), except that bis-p-toluenesulfonate (p-ter
479.9 g (85% yield) of (t-butylphenyl) iodonium was obtained. The chloride ion content was 38 ppm.

Example 3 Synthesis of triphenylsulfonium p-toluenesulfonate 390.3 g of triphenylsulfonium iodide (1.0 m
ol) and 223.5 g of methyl p-toluenesulfonate
(1.2 mol) was added with 500 ml of acetonitrile,
The mixture was heated to 82 ° C to 85 ° C and refluxed for 5 hours while stirring. After cooling the reaction solution, acetonitrile was distilled off under reduced pressure. The remaining pale yellow solid was washed with methylene chloride and dried under vacuum to obtain 369.4 g (yield: 85%) of triphenylsulfonium p-toluenesulfonate.

The iodine ion content of the obtained white solid was determined by silver nitrate titration to be 83 ppm.

Example 4 Synthesis of bis (p-tert-butylphenyl) iodonium 9,10-dimethoxyanthracene-2-sulfonate 6.4 g (15 mmol) of bis (p-tert-butylphenyl) iodonium chloride and methyl -9,10-
6.48 g of dimethoxyanthracene-2-sulfonic acid
(19.5 mmol) was added with 90 ml of acetonitrile, heated to 82 to 85 ° C., and refluxed for 20 hours with stirring. After cooling the reaction solution, the precipitated solid was separated by filtration. The solid was washed with ethyl acetate and dried under vacuum to obtain 8.32 g (yield 78%) of bis (p-tert-butylphenyl) iodonium 9,10-dimethoxyanthracene-2-sulfonate. The chloride ion content of the obtained solid was determined by silver nitrate titration.
It was 10 ppm.

Example 5 Synthesis of bis (p-tert-butylphenyl) camphorsulfonate 17.06 g (39.79 mmol) of bis (p-tert-butylphenyl) iodonium chloride and 10.78 g of methyl camphorsulfonic acid ( 43.76mmo
To 1), 50 ml of ethyl acetate was added, heated to 77 ° C. to 80 ° C., and refluxed for 24 hours with stirring. After cooling the reaction solution, the solid was filtered off. The solid was recrystallized from acetone and dried under vacuum to obtain 20.63 g (yield 83
%) Bis (p-tert-butylphenyl) iodonium camphorsulfonate was obtained.

The chloride ion content of the obtained solid was determined by silver nitrate titration and found to be 20 ppm.

Example 6 Synthesis of bis (p-tert-butylphenyl) iodonium p-toluenesulfonate
467 mg (1.0 mmol) of acetate and 204 mg (1.1 mmol) of methyl p-toluenesulfonate are suspended in 5 ml of t-butyl methyl ether, and this suspension is heated to 55 ° C. to 58 ° C., and stirred. Reflux for hours. After cooling the reaction solution, a white solid was separated by filtration. The white solid was washed with t-butyl methyl ether and dried under vacuum to obtain 521 mg (yield 91%) of bis (p-tert-butylphenyl) iodonium p-toluenesulfonate.

Example 7 Synthesis of bis (p-tert-butylphenyl) iodonium p-toluenesulfonate Instead of methyl p-toluenesulfonate in Example 6, 257.1 m of isopropyl p-toluenesulfonate
g (1.2 mmol) by the same operation as in Example 6, except that bis-p-toluenesulfonic acid (pt
492 mg (85% yield) of tert-butylphenyl) iodonium were obtained.

Example 8 Synthesis of triphenylsulfonium p-toluenesulfonate 336 mg of triphenylsulfonium propionate
(1.0 mmol) and methyl p-toluenesulfonate 2
Acetonitrile (5 ml) was added to 04 mg (1.1 mmol), and the mixture was refluxed for 5 hours while stirring. After cooling the reaction solution, acetonitrile was distilled off under reduced pressure. The remaining pale yellow solid was washed with methylene chloride and dried under vacuum to obtain 492 mg (yield: 85%) of triphenylsulfonium p-toluenesulfonate.

(Example 9) Synthesis of camphorsulfonic acid bis (p-tert-butylphenyl) iodonium salt Bis (p-tert-butylphenyl) iodonium salt
50 ml of ethyl acetate was added to 467 mg (1 mmol) of acetate and 259 mg (1.05 mmol) of methyl camphorsulfonic acid, and the mixture was refluxed for 24 hours with stirring. After cooling the reaction solution, the solid was filtered off. The solid was recrystallized from acetone and dried in vacuum to obtain 518 m
g (83% yield) of bis (p-t) camphorsulfonic acid
(tert-butylphenyl) iodonium was obtained.

Example 10 Synthesis of bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate 467 mg (1 mmol) of bis (p-tert-butylphenyl) iodonium acetate and methyl trifluoromethanesulfonate 170mg (1.05mmo
5 ml of tert-butyl methyl ether was added to 1),
The reaction was carried out with stirring at room temperature for 4 hours. The purified solid was filtered off and dried under vacuum to obtain 412 mg (yield 76%) of bis (p-p-trifluoromethanesulfonic acid).
(tert-Butylphenyl) iodonium was obtained.

(Example 11) Production of diphenyliodonium trifluoromethanesulfonate 1.67 kg of diphenyliodonium chloride was slurried in 5.3 L of acetonitrile, and 0.80 kg of dimethyl sulfuric acid was gradually added with stirring at room temperature.
After the reaction solution was refluxed for 1 hour to carry out the reaction, acetonitrile as a reaction solvent was removed by distillation under reduced pressure. The obtained white solid was dissolved in 12 L of distilled water, and 0.95 kg of trifluoromethanesulfonic acid was gradually added dropwise, followed by stirring at room temperature for 1 hour. Filtration yielded 2.4 kg of a white solid. Since this product contained some acid, it was further recrystallized with 5 L of distilled water. After filtration and drying, a white solid of diphenyliodonium trifluoromethanesulfonate 1.9 was obtained.
kg (84% yield).

The onium salt obtained as described above was analyzed by ion chromatography for residual chloride ion and methyl sulfate ion.
It was confirmed that:

Example 12 Production of triphenylsulfonium trifluoromethanesulfonate 620 g of triphenylsulfonium iodide was stirred in 3 L of acetonitrile at room temperature to form a slurry, and 105 g of dimethyl sulfuric acid was gradually added. After confirming the dissolution of the solid, acetonitrile as a reaction solvent was distilled under reduced pressure. After dissolving the obtained solid in distilled water, 288 g of trifluoromethanesulfonic acid was added dropwise. After stirring for 1 hour, the obtained oil was extracted with dichloromethane, and the organic layer was washed with distilled water. Dichloromethane as a solvent was distilled under reduced pressure to obtain a highly viscous oil. By adding ether to this oil phase, white triphenylsulfonium trifluoromethanesulfonate 440 is obtained.
g (67% yield).

The onium salt obtained as described above was analyzed by ion chromatography for residual iodide ion and methyl sulfate ion.
It was confirmed that:

Example 13 Preparation of Triphenylsulfonium Perfluorobutanesulfonate 270 g of triphenylsulfonium iodide was stirred into 2.1 L of acetonitrile at room temperature to form a slurry, and 105 g of dimethyl sulfuric acid was gradually added. After confirming the dissolution of the solid, acetonitrile as a reaction solvent was distilled under reduced pressure. Potassium nonaflate 274 is added to the obtained solid.
g was added and dissolved in 2 L of distilled water. After stirring for 1 hour, the obtained oil was extracted with dichloromethane, and the organic layer was washed with distilled water. Dichloromethane as a solvent was distilled under reduced pressure to obtain a highly viscous oil. By adding ether to this oil phase, 425 g (yield 83%) of white triphenylsulfonium nonaflate was obtained.

The onium salt obtained as described above was analyzed by ion chromatography for residual iodide ion and methyl sulfate ion.
It was confirmed that:

Example 14 Preparation of triphenylsulfonium camphorsulfonate 40 g of triphenylsulfonium iodide was stirred in 200 ml of acetonitrile at room temperature to form a slurry, and 15 g of dimethyl sulfuric acid was gradually added. After confirming dissolution of the solid, 49 g of camphorsulfonic acid was added and the mixture was stirred for 12 hours. An oil obtained by distilling acetonitrile as a solvent under reduced pressure was dissolved in dichloromethane, and the organic layer was washed with distilled water. Dichloromethane as a solvent was distilled under reduced pressure to obtain a highly viscous oil. By adding ether to this oil phase, 9 g of white triphenylsulfonium camphorsulfonate (18% yield) was obtained.

The onium salt obtained as described above is treated with an iodide ion remaining by ion chromatography.
As a result of analyzing methyl sulfate ion, it was confirmed that both were 1 ppm or less.

(Example 15) Production of triphenylsulfonium methyl sulfate 3.9 g of triphenylsulfonium iodide was stirred in 10 ml of acetonitrile at room temperature to form a slurry, and 1.5 g of dimethyl sulfate was gradually added. After confirming the dissolution of the solid, acetonitrile as a reaction solvent was distilled under reduced pressure. Ether was gradually added to the obtained viscous solid to obtain 3.2 g (yield: 85%) of a white precipitate.

The white precipitate was subjected to 1H-NMR and C13-
As a result of analysis by NMR, it was confirmed that the substance was triphenylsulfonium methyl sulfate.

(Example 16) Diphenyliodonium
Synthesis of Tosylate (1) 315 mg of diphenyliodonium chloride (1 mm
ol), 296 mg (2 mmol) of ethyl orthoformate and 207 mg of dry toluenesulfonic acid (1.
2 mmol) is dissolved in 5 ml of dry methylene chloride and stirred under reflux for 5 hours. The reaction solution is made alkaline by adding 10 ml of 1% aqueous ammonia and then extracted twice with methylene chloride. After drying, the solvent was distilled off, and the resulting solid was washed with ether to obtain 229 mg (yield: 75%) of the desired compound as white crystals.

When the anion in the compound was measured by ion chromatography, the chloride content was 50 ppm or less.

Example 17 Diphenyliodonium
Synthesis of Tosylate (2) 315 mg of diphenyliodonium chloride (1 mm
ol), 2 mg (2 mmol) of methyl orthocarbonate and 207 mg of dry toluenesulfonic acid (1.2 m
mol) is dissolved in 5 ml of dry methylene chloride and stirred at room temperature for 2 hours. The reaction solution was made alkaline by adding 10 ml of 1% aqueous ammonia and then extracted twice with methylene chloride. After drying, the solvent was distilled off, and the resulting solid was washed with ether to obtain 280 mg (yield: 92%) of the desired compound as white crystals.

When the anion in the compound was measured by ion chromatography, the chloride content was 14 ppm or less.

(Example 18) Synthesis of triphenylsulfonium camphorsulfonate 390 mg of triphenylsulfonium iodide
(1 mmol) and 486 mg of ethyl orthoacetate (3 mm
ol) and 278 mg of camphorsulfonic acid (1.2 mg).
(mmol) is dissolved in 10 ml of dry methylene chloride and stirred at room temperature for 12 hours. The reaction solution was made alkaline by adding 10 ml of 1% aqueous ammonia and then extracted three times with methylene chloride. After drying, the solvent was distilled off, and the resulting semi-solid was washed with ether to give 410 mg (yield 82%) of the desired compound as white crystals.

When the anion in the compound was measured by ion chromatography, the chloride content was 10 ppm or less.

Example 19 Synthesis of di-tert-butylphenyliodonium triflate 443 mg (1 mmol) of di-tert-butylphenyliodonium chloride, 211 mg (1.5 mmol) of ethyl orthopropionate and 165 mg of trifluoromethanesulfonic acid (1.1 mmol) was dissolved in 10 ml of dry methylene chloride and stirred at room temperature for 2 hours.
The reaction solution was made alkaline by adding 10 ml of 1% aqueous ammonia and then extracted twice with methylene chloride. After drying, the solvent was distilled off, and the resulting solid was washed with ether to obtain 491 mg (yield: 91%) of the desired compound as white crystals.

When the anion in the compound was measured by ion chromatography, the chloride content was 10 ppm or less.

Example 20 Synthesis of di-tert-butylphenyliodonium pentafluorobenzenesulfonate 443 mg (1 mmol) of di-tert-butylphenyliodonium chloride and 342 m of ethyl orthoacetate
g (2 mmol) and 298 mg (1.2 mmol) of pentafluorobenzenesulfonic acid in chloroform 5m
and stirred under reflux for 2 hours. After the solvent was distilled off, the resulting solid was washed with ether to obtain 436 mg (yield: 68%) of the desired compound as white crystals.

When the anion in the compound was measured by ion chromatography, the chloride content was 5 ppm or less.

(Example 21) Synthesis of triphenylsulfonium-4-trifluoromethylbenzenesulfonate 343 mg of triphenylsulfonium bromide (1
mmol) and 296 mg (2 mmol) of ethyl orthoformate
l) and 4-trifluoromethylbenzenesulfonic acid 2
71 mg (1.2 mmol) is dissolved in 10 ml of methylene chloride and stirred at room temperature for 6 hours. The reaction solution was made alkaline by adding 10 ml of 1% aqueous ammonia and then extracted three times with methylene chloride. After drying, the solvent was distilled off, and the resulting solid was washed in ether and stirred to obtain 375 mg (yield: 76%) of the desired compound as white crystals.

When the anion in the compound was measured by ion chromatography, the chloride content was 5 ppm or less.

(Example 22) Diphenyliodonium
Synthesis of triflate Diphenyliodonium dimethyl phosphate 31
5 mg (1 mmol) and trifluoromethanesulfonic acid 1
58 mg (1.01 mmol) of methylene chloride 10 ml
And stirred. The methylene chloride solution was distilled off half of the solvent, added with 50 ml of ether, and stirred to precipitate 109 mg of white crystals (yield: 72%) as a desired compound.

(Example 23) Synthesis of triphenylsulfonium-toluenesulfonate Diphenyliodonium-dimethylphosphate 31
5 mg (1 mmol) and p-toluenesulfonic acid 189
mg (1.1 mmol) was dissolved in methylene chloride (10 ml) and stirred. 10 ml of 1% aqueous ammonia was added, and after confirming that the solution was alkaline, the mixture was vigorously stirred. After standing still, the aqueous layer was taken out and washed with water until the aqueous layer showed neutrality.
The methylene chloride solution is dried to remove the solvent and washed with stirring with ether.
(Yield 84%) was precipitated.

(Example 24) Diphenyliodonium
Synthesis of camphorsulfonate diphenyliodonium dimethyl phosphate 31
5 mg (1 mmol) and 254 m of camphorsulfonic acid
g (1.1 mmol) was dissolved in 10 ml of methylene chloride and stirred. 10 ml of 1% aqueous ammonia was added, and after confirming that the solution was alkaline, the mixture was vigorously stirred. After standing still, the aqueous layer was taken out and washed with water until the aqueous layer showed neutrality.
The methylene chloride solution is dried, the solvent is distilled off, and the mixture is washed with stirring with ether.
(Yield 91%) was precipitated.

Example 25 Synthesis of di-tert-butylphenyliodonium / perfluorobenzenesulfonate 546 mg (1 mmol) of di-tert-butylphenyliodonium / diethylphosphate and 267 mg (1.1 mmol) of perfluorobenzenesulfonic acid were used. Dissolve in 10 ml of methylene chloride and add 1% aqueous ammonia
0 ml was added, and it was confirmed that the solution was alkaline, followed by vigorous stirring. After standing still, the aqueous layer was taken out and washed with water until the aqueous layer showed neutrality. The methylene chloride solution was dried, the solvent was distilled off, and the mixture was washed by stirring with ether. As a result, 435 mg (yield: 68%) of white crystals was precipitated as a desired compound.

Example 26 Synthesis of di-tert-butylphenyliodonium perfluorobutanesulfonate 546 mg (1 mmol) of di-tert-butylphenyliodonium diethylphosphate and 354 mg (1.1 mm) of sodium perfluorobutanesulfonate
ol) in 10 ml of water and 10 ml of methylene chloride
Extract three times. After the solvent was distilled off, the precipitated white solid was washed with ether and recrystallized from methylene chloride-ether, whereby 561 mg (81% yield) of white crystals were precipitated.

Example 27 Synthesis of diphenyliodonium dimethylphosphonate 315 mg of diphenyliodonium chloride (1 mm
ol) and 1 g of trimethylphosphoric acid were heated and stirred at 170 ° C. for 10 minutes. After the reaction product was once dissolved, the solid produced by cooling was washed with ether to obtain 250 mg (yield: 81.6%) of the desired compound as white crystals. When the anion in the compound was measured by ion chromatography, the chloride content was 10 ppm or less.

Example 28 Synthesis of triphenylsulfonium dimethylphosphonate 390 mg of triphenylsulfonium iodide
(1 mmol) and 1 g of trimethylphosphoric acid in 13
The mixture was stirred and heated at 0 ° C. for 3 hours. Thereafter, the homogeneous solution was cooled and the resulting solid was washed with IPA to obtain 280 mg (yield: 72.2%) of the desired compound as white crystals. When the anion in the compound was measured by ion chromatography, the iodide content was found to be 50 p.
pm or less.

Example 29 Synthesis of di-tert-butylphenyliodonium dimethyl phosphate (1) A solution of 443 mg (1 mmol) of di-tert-butylphenyliodonium chloride and 2 g of trimethylphosphoric acid was heated at (110 ° C.) for 1 hour. Stir and heat. The resulting solid was washed with ether to give 420 mg (yield: 78.7%) of the desired compound as white crystals. (The raw material iodoform chloride can be removed by acetone washing.)

(Example 30) Synthesis of di-tert-butylphenyliodonium dimethyl phosphate (2) 443 mg (1 mmol) of di-tert-butylphenyliodonium chloride and 0.5 g of trimethylphosphoric acid
Was dissolved in 5 ml of chloroform and stirred under reflux for 12 hours. After the solvent was distilled off, the resulting solid was washed with ether to obtain 400 mg (yield: 75.2%) of the desired compound as white crystals.

(Example 31) Synthesis of di-tert-butylphenyliodonium diethyl phosphate A solution of 443 mg (1 mmol) of di-tert-butylphenyliodonium chloride and 3 g of triethylphosphoric acid was stirred and heated at 110 to 120 ° C. for 1 hour. . The resulting solid was washed with ether to give 432 mg (yield: 69.2%) of the desired compound as white crystals.

Example 32 Hereinafter, an example of obtaining an onium salt derivative having a conjugate base of sulfonic acid as a counter ion from di-tert-butylphenyliodonium dimethyl phosphate will be described.

533 mg (1 mmol) of di-tert-butylphenyliodonium dimethyl phosphate
And 140 mg of p-toluenesulfonic acid (1.1 mmol
1) was dissolved in 10 ml of methylene chloride, and 10 ml of 1% aqueous ammonia was added to make the solution alkaline. After stirring for 10 minutes, the methylene chloride layer was extracted. The extract was washed with water, dried and evaporated, and the resulting crude crystals were recrystallized from ether-methylene chloride to obtain 410 mg (yield: 77.2%) of the compound to be obtained as white crystals of di-tert-butylphenyliodonium dimethyl. The sulfonate was obtained.

[0172]

As described above, according to the present invention,
It is possible to provide a method for producing an onium salt derivative capable of synthesizing an onium salt derivative useful as an acid generator or the like used in a chemically amplified resist in a high yield, and a novel onium salt derivative.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 309/30 C07C 309/30 309/43 309/43 381/12 381/12 C07F 9/11 C07F 9 / 11 G03F 7/004 503 G03F 7/004 503A (31) Priority claim number Japanese Patent Application No. 2000-284186 (P2000-284186) (32) Priority date September 19, 2000 (September 19, 2000) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 2000-286306 (P2000-286306) (32) Priority date September 21, 2000 (September 21, 2000) (33) Priority claim Country Japan (JP) F-term (reference) 2H025 AB16 BE07 4H006 AA01 AA02 AB40 AB76 AB81 AC90 BC31 BD20 BD70 4H050 AA01 AA02 AB40 AB76 AB81 AC90 BC31 BD20 BD70

Claims (11)

[Claims] 1. An onium salt derivative represented by the following general formulas (1) to (4) and a compound represented by the following general formulas (5) to (7) are reacted to form the following general formula (8) ) ~
A method for producing an onium salt derivative, which comprises obtaining the onium salt derivative represented by (19). Embedded image (R ₁ , R ₂ , and R ₃ each independently represent an optionally substituted alkyl group, cycloalkyl group, perfluoroalkyl group, aromatic organic group, aralkyl group, or phenacyl group having 25 or less carbon atoms. , R ₁ and R ₃ and R ₂ and R ₅ may be taken together to represent a divalent organic group, and R ₄ represents a divalent organic group having 20 or less carbon atoms. ^-. which is a halogen anion, or carbon atoms represent 10 following carbocyclylalkyl chelating anions) ## STR2 ## (R ₆ represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, an aromatic organic group, or an aralkyl group having 25 or less carbon atoms which may be substituted. R ₇ represents a carbon atom which may be substituted. Represents an alkyl group, a cycloalkyl group, a perfluoroalkyl group, or an aralkyl group of 10 or less, and R ₈ and R ₉ each independently represent an alkyl group or a cycloalkyl group having 10 or less carbon atoms which may be substituted. , A perfluoroalkyl group or an aralkyl group.) Embedded image Embedded image 2. The method for producing an onium salt derivative according to claim 1, wherein R ₇ of the sulfonic ester of the general formula (5) is a lower alkyl sulfonate which is a lower alkyl group having up to 5 carbon atoms. . 3. The method according to claim 1, wherein R _{7 is formed.}
A method for producing an onium salt derivative, wherein the reaction is carried out while removing Q out of the reaction system. 4. The method for producing an onium salt derivative according to claim 1, wherein the reaction is carried out in a solvent. 5. An ozone represented by the following general formulas (1) to (4):
Represented by the following general formulas (21) to (23)
And a sulfo represented by the following general formula (24)
By reacting with an acid derivative, the compound represented by the general formula (25)
To obtain an onium salt derivative represented by any one of (28) to (28).
A method for producing an onium salt derivative. Embedded image(R₁, R_Two, And R_ThreeAre each independently substituted
Alkyl group and cycloalkyl having good carbon number of 25 or less
Group, perfluoroalkyl group, aromatic organic group, aralkyl
A phenyl group or a phenacyl group;₁And R_ThreeAnd R_TwoAnd R_Fiveof
At least one of them together represents a divalent organic group
Good. R_FourRepresents a divalent organic group having 20 or less carbon atoms.
Q^-Is a halogen anion, or a carbon having 10 or less carbon atoms.
Represents a boxylate anion. )(R_TenIs hydrogen, an optionally substituted carbon atom having 25 or less carbon atoms,
Alkyl group, cycloalkyl group, perfluoroalkyl
Group, aromatic organic group, and aralkyl group. R₁₁, R ₁₂Passing
And R₁₃Are each independently an optionally substituted carbon number of 1
0 or less, alkyl group, cycloalkyl group, perfluoro
Represents a loalkyl group or an aralkyl group. )(R_FifteenIs a group having 25 or less carbon atoms which may be substituted
Alkyl group, cycloalkyl group, perfluoroalkyl
Group, aromatic organic group, and aralkyl group. Y is a hydrogen source
Represents an alkali, an alkali metal, and ammonium. ) 6. The method according to claim 5, wherein the general formula (21)
A method for producing an onium salt derivative, characterized in that the compound of formulas (1) to (23) is used in an amount of 1 to 10 times the mol of the onium salt derivative of formulas (1) to (4). 7. The onium salt derivative according to claim 5, wherein the sulfonic acid derivative is used in an amount of 1 to 2 times the mol of the onium salt derivative of the general formulas (1) to (4). Production method. 8. An onium salt derivative obtained by reacting an onium salt derivative represented by the following general formula (1) to (4) with a sulfate ester represented by the following general formula (29) And a sulfonic acid derivative represented by the following general formula (24) to react with the general formulas (25) to (28).
A method for producing an onium salt derivative, characterized by obtaining an onium salt derivative represented by the formula: Embedded image (R ₁ , R ₂ , and R ₃ each independently represent an optionally substituted alkyl group, cycloalkyl group, perfluoroalkyl group, aromatic organic group, aralkyl group, or phenacyl group having 25 or less carbon atoms. , R ₁ and R _{3 or} at least one of R ₂ and R ₅ may together represent a divalent organic group, and R ₄ represents a divalent organic group having 20 or less carbon atoms.
Q ^- is a halogen anion, or carbon atoms represent 10 following carboxylate anions. ) (R ₁₆ and R _{17 each} represent an alkyl group, a cycloalkyl group, a perfluoroalkyl group, or an aralkyl group having 10 or less carbon atoms which may be substituted.) (R ₁₅ represents an optionally substituted alkyl group, cycloalkyl group, perfluoroalkyl group, aromatic organic group, or aralkyl group having 25 or less carbon atoms. Y represents a hydrogen atom, an alkali metal, or ammonium. (Chemical Formula 13) 9. The method according to claim 8, wherein the general formula (29)
The method for producing an onium salt derivative, wherein the sulfate of the above is dimethyl sulfate or diethyl sulfate. 10. An onium salt derivative represented by the following general formulas (12) to (15) and a sulfonic acid derivative represented by the following general formula (24) are reacted to form a compound represented by the following general formulas (25) to (25). 28. A method for producing an onium salt derivative, which comprises obtaining the onium salt derivative represented by 28). Embedded image (R ₁ , R ₂ , and R ₃ each independently represent an optionally substituted alkyl group, cycloalkyl group, perfluoroalkyl group, aromatic organic group, aralkyl group, or phenacyl group having 25 or less carbon atoms. However, at least one of R ₁ and R ₃ and / or R ₂ and R ₅ may together represent a divalent organic group, and R ₄ represents a divalent organic group having 20 or less carbon atoms. R ₈ and R ₉ each independently represent an alkyl group, a cycloalkyl group having 10 or less carbon atoms which may be substituted;
Represents a perfluoroalkyl group or an aralkyl group. ) (R ₁₅ represents an optionally substituted alkyl group, cycloalkyl group, perfluoroalkyl group, aromatic organic group, or aralkyl group having 25 or less carbon atoms. Y represents a hydrogen atom, an alkali metal, or ammonium. ). 11. An onium salt derivative represented by the following general formulas (12) to (15). Embedded image (R ₁ , R ₂ , and R ₃ each independently represent an optionally substituted alkyl group, cycloalkyl group, perfluoroalkyl group, aromatic organic group, aralkyl group, or phenacyl group having 25 or less carbon atoms. However, at least one of R ₁ and R ₃ and / or R ₂ and R ₅ may together represent a divalent organic group, and R ₄ represents a divalent organic group having 20 or less carbon atoms. R ₈ and R ₉ each independently represent an alkyl group, a cycloalkyl group having 10 or less carbon atoms which may be substituted;
Represents a perfluoroalkyl group or an aralkyl group. )