JP2012176932A - Method for preparation of salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparation of a salt used for an acid generator etc., in a resist composition.SOLUTION: The salt represented by formula (I) [wherein, Qand Qrepresent each a fluorine atom or a 1-6C perfluoroalkyl group, Y represents a 1-18C hydrocarbon group which may have a substituted group, and Zrepresents an organic cation] is prepared by reacting a compound represented by formula (II) (Q, Qand Y represent each the same in the above ), a salt represented by formula (III) [wherein Zrepresents an organic cation, and Xrepresents an anion] and water in the presence of an organic base.

Description

  The present invention relates to a method for producing a salt used as an acid generator or the like for a resist composition.

［式中、Ｑ^１及びＱ^２は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。Ｙは、置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表し、該脂肪族炭化水素基を構成するメチレン基は、酸素原子、スルホニル基又はカルボニル基に置き換わっていてもよい。Ｚ^＋は有機カチオンを表す。］
で示される塩（以下、塩（Ｉ）と記載することがある。）の製造方法としては、例えば、下式に示す製造方法が知られている（特許文献１）。

Formula (I)

[Wherein, Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. Y represents an optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the methylene group constituting the aliphatic hydrocarbon group is replaced with an oxygen atom, a sulfonyl group or a carbonyl group. May be. Z ⁺ represents an organic cation. ]
For example, a production method represented by the following formula is known as a method for producing a salt represented by formula (hereinafter, sometimes referred to as salt (I)) (Patent Document 1).

JP 2006-257078 A

  In the above-mentioned production methods known from the past, the target salt (I) is obtained as a mixture with an inorganic salt (NaCl in the case of the above formula), and only the salt (I) is obtained in a sufficiently satisfactory yield by separating them. It was difficult to get.

［式中、Ｑ^１及びＱ^２は、それぞれ独立に、フッ素原子又は炭素数１〜６のペルフルオロアルキル基を表す。Ｙは、置換基を有していてもよい炭素数１〜１８の脂肪族炭化水素基を表し、該脂肪族炭化水素基を構成するメチレン基は、酸素原子、スルホニル基又はカルボニル基に置き換わっていてもよい。］
で表される化合物と式（ＩＩＩ）

［式中、Ｚ^＋は有機カチオンを表し、Ｘ⁻はアニオンを表す。］
で表される塩と水とを反応させる式（Ｉ）

［式中、Ｑ^１、Ｑ^２、Ｙ及びＺ^＋は、それぞれ上記と同じ意味を表す。］
で表される塩の製造方法。
［２］式（ＩＩＩ）におけるＸ⁻が、ハロゲン化物イオン又はＲＳＯ_４ ⁻（式中、Ｒは炭素数１〜６のアルキル基を表す。）である［１］記載の製造方法。
［３］有機塩基が、トリアルキルアミンである［１］又は［２］記載の製造方法。 The present invention includes the following inventions.
[1] Formula (II) in the presence of an organic base

[Wherein, Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. Y represents an optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the methylene group constituting the aliphatic hydrocarbon group is replaced with an oxygen atom, a sulfonyl group or a carbonyl group. May be. ]
And a compound represented by formula (III)

[Wherein, Z ⁺ represents an organic cation, and X ⁻ represents an anion. ]
Wherein the salt represented by formula (I) is reacted with water

[Wherein, Q ¹ , Q ² , Y and Z ⁺ represent the same meaning as described above. ]
The manufacturing method of the salt represented by these.
[2] The production method according to [1], wherein X ⁻ in the formula (III) is a halide ion or RSO ₄ ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms).
[3] The production method according to [1] or [2], wherein the organic base is a trialkylamine.

  According to the production method of the present invention, the salt (I) containing no inorganic salt can be produced with a better yield than conventional.

  Hereinafter, the present invention will be described in detail.

In the above formula (I) and formula (II), Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. Examples of the C 1-6 perfluoroalkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, and a perfluoropentyl group. And perfluorohexyl group. Q ¹ and Q ² are preferably a trifluoromethyl group or a fluorine atom, and more preferably a fluorine atom.

  In the above formulas (I) and (II), Y represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent. Among the aliphatic hydrocarbon groups, a group containing an alkyl group having 1 to 6 carbon atoms or a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferable, and an alicyclic hydrocarbon having 3 to 12 carbon atoms. A group containing a group is more preferable, and a group containing an alkyl group having 1 to 6 carbon atoms and an alicyclic hydrocarbon group having 3 to 12 carbon atoms is more preferable.

Examples of the substituent that the aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by Y may have include, for example, a halogen atom (excluding a fluorine atom), a hydroxy group, and 1 to 12 carbon atoms. Alkoxy groups, C 6-18 aromatic hydrocarbon groups, C 7-21 aralkyl groups, C 2-4 acyl groups, glycidyloxy groups, or — (CH ₂ ) _j —O—CO—R. and a group represented by ^b1 (wherein R ^b1 represents a hydrocarbon group having 1 to 16 carbon atoms, j represents an integer of 0 to 4). The aromatic hydrocarbon group and aralkyl group here may further have a substituent such as an alkyl group, a halogen atom or a hydroxy group.

Among the alicyclic hydrocarbon groups contained in the aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by Y, examples of those having such a substituent include the following.

  The methylene group constituting the aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by Y may be replaced with an oxygen atom, a sulfonyl group or a carbonyl group. Examples of the group in which the methylene group constituting the alicyclic hydrocarbon group is replaced with an oxygen atom, a sulfonyl group or a carbonyl group include, for example, a cyclic ether group (one or two of the methylene groups constituting the alicyclic hydrocarbon group are A group in which an oxygen atom is substituted), a cyclic ketone group (a group in which one or two methylene groups constituting an alicyclic hydrocarbon group are replaced by a carbonyl group), a sultone ring group (which constitutes an alicyclic hydrocarbon group) Two adjacent methylene groups in the methylene group are groups in which an oxygen atom and a sulfonyl group are substituted, respectively. A group in which an oxygen atom and a carbonyl group are substituted, respectively).

（式（Ｙ１）〜式（Ｙ５）中、＊は結合手を表す。） From the viewpoint of the performance of the salt (I) as an acid generator contained in a resist composition used for fine processing of a semiconductor using a lithography technique, an aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by Y above The alicyclic hydrocarbon group contained in the alicyclic hydrocarbon group represented by any of the following formula (Y1), formula (Y2), formula (Y3), formula (Y4) and formula (Y5) Group is preferred, and among these, an alicyclic hydrocarbon group represented by any one of formula (Y1), formula (Y2), formula (Y3) and formula (Y5) is more preferred, and formula (Y1) and formula The alicyclic hydrocarbon group represented by any one of (Y2) is more preferable. The hydrogen atom constituting these alicyclic hydrocarbon groups may be substituted with a substituent that the aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by Y may have a hydroxy group. It is preferably substituted with a group.

(In formula (Y1) to formula (Y5), * represents a bond)

  From the viewpoint of the performance of the salt (I) as an acid generator contained in a resist composition used for microfabrication of a semiconductor using a lithography technique, an aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by Y Is preferably a hydroxyadamantylmethyl group.

In the above formula (I) and formula (II), * —C (Q ¹ ) (Q ² ) —CO—O—Y [wherein Q ¹ , Q ² and Y represent the same meaning as above, * Represents a bond with SO ₂ F or SO ₃ ^— . Specific examples of the structure represented by formula (b1-1-1), formula (b1-1-2), formula (b1-1-3), formula (b1-1-4) ), Formula (b1-1-5), formula (b1-1-6), formula (b1-1-7), formula (b1-1-8) and formula (b1-1-9) [hereinafter, “ It represents like "formula (b1-1-1)-formula (b1-1-9)". The structure represented by] is mentioned. In the structure represented by any one of the formulas (b1-1-1) to (b1-1-9), L ^b1 is a single bond or an alkylene group having 1 to 6 carbon atoms, and is a single bond or a methylene group. Is preferred. R ^b2 and R ^b3 are each independently defined as a substituent that the aliphatic hydrocarbon group having 1 to 18 carbon atoms represented by Y may have, An alkyl group of 4 is preferable, and a methyl group is more preferable.

  Specific examples of the sulfonate anion (anion portion of the salt (I)) having a structure represented by any one of the formulas (b1-1-1) to (b1-1-9) include JP-A-2010-204646. Examples thereof include sulfonate anions described in Japanese Patent Publication.

As a structure represented by the above * -C (Q ¹ ) (Q ² ) —CO—O—Y (wherein Q ¹ , Q ² , Y and * each have the same meaning as above), Y Is a specific example in which is a group containing an alicyclic hydrocarbon group represented by the formula (Y1) or the formula (Y2). Examples of the structure in which Y is a group containing an unsubstituted alicyclic hydrocarbon group include structures represented by any of the following formulas (b1-s-1) to (b1-s-9). .

Examples of the structure in which Y is a group containing an alicyclic hydrocarbon group having a hydroxy group include those represented by any of the following formulas (b1-s-10) to (b1-s-18). It is done.

Examples of the structure in which Y is a group containing a cyclic ketone group include structures represented by any of the following formulas (b1-s-19) to (b1-s-29).

Examples of the structure in which Y is a group containing an aromatic hydrocarbon group include structures represented by any of the following formulas (b1-s-30) to (b1-s-35).

The structure in which Y is a group containing the lactone ring group or the sulfonic acid ring group is a structure represented by any of the following formulas (b1-s-36) to (b1-s-41). Can be mentioned.

Moreover, as a structure whose Y is an alkyl group, the structure represented by the following formula | equation (b1-s-42) is mentioned.

Examples of the compound represented by the above formula (II) (hereinafter sometimes referred to as compound (II)) include compounds having a structure in which * in each of the above structures is bonded to SO ₂ F.

  Compound (II) can be synthesized, for example, according to the method described in Inorganic Chemistry, 1991, 30 (25), 4821-6.

［式中、Ｑ^１、Ｑ^２及びＹは、それぞれ上記と同じ意味を表す。］ In addition, compound (II) can be obtained, for example, by subjecting a compound represented by the following formula (II-a) and a compound represented by the following formula (II-b) to an ester exchange reaction in a solvent in the presence of a base. Can be manufactured. Examples of the base include titanium isopropoxide. Examples of the solvent include chloroform and n-heptane. The reaction temperature is preferably in the range of 5 ° C. or higher and lower than the boiling point of the solvent, more preferably in the range of 20 ° C. or higher and lower than the boiling point of the solvent, and more preferably the reflux temperature condition of the solvent. One of the compounds represented by the formula (II-a), methyl fluorosulfonyl (difluoro) acetate (both Q ¹ and Q ² are fluorine atoms) is commercially available. Examples of the compound represented by the formula (II-b) include 3-hydroxymethyladamantan-1-ol and the like, and a commercially available product may be used, or it may be produced and used by any known method. .

[Wherein, Q ¹ , Q ² and Y each have the same meaning as described above. ]

［式中、Ｑ^１、Ｑ^２及びＹは、それぞれ上記と同じ意味を表す。］ Furthermore, the compound (II) is produced, for example, by subjecting a compound represented by the following formula (Ja) and a compound represented by the following formula (II-b) to a dehydration reaction in a solvent in the presence of an acid. You can also Examples of the acid include sulfuric acid. Examples of the solvent include dichloroethane and chloroform. The reaction temperature is preferably in the range of 5 ° C. or higher and lower than the boiling point of the solvent, more preferably in the range of 20 ° C. or higher and lower than the boiling point of the solvent, and more preferably the reflux temperature condition of the solvent. Fluorosulfonyl (difluoro) acetic acid (both Q ¹ and Q ² are fluorine atoms), which is one of the compounds represented by formula (Ja), is commercially available.

[Wherein, Q ¹ , Q ² and Y each have the same meaning as described above. ]

In the above formulas (I) and (III), examples of the organic cation represented by Z ⁺ include organic oniums such as organic sulfonium cation, organic iodonium cation, organic ammonium cation, organic benzothiazolium cation, and organic phosphonium cation. And cations. From the viewpoint of the performance of the salt (I) as an acid generator contained in a resist composition used for microfabrication of a semiconductor using a lithography technique, among these, an organic sulfonium cation and an organic iodonium cation are preferable. A cation represented by any one of (b2-1) to formula (b2-4) is more preferable.

In formula (b2-1) to formula (b2-4),
R ^{b4 to} R ^b6 each independently represents an alkyl group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The alkyl group may be substituted with a hydroxy group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon group has a halogen atom or a carbon number. The aromatic hydrocarbon group may be substituted with 2 to 4 acyl groups or glycidyloxy groups, and the aromatic hydrocarbon group is a halogen atom, a hydroxy group, an alkyl group having 1 to 36 carbon atoms, or an alicyclic group having 3 to 36 carbon atoms. It may be substituted with a hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms. Two ^members selected from R ^b4 , R ^b5 and R ^b6 may be combined to form a ring containing a sulfur atom.

The ring which may be formed by combining two selected from R ^b4 , R ^b5 and R ^b6 is any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated. It may be a ring and may contain one or more sulfur atoms and / or one or more oxygen atoms as long as it contains one or more sulfur atoms. As the ring, a ring having 3 to 18 carbon atoms is preferable, and a ring having 4 to 13 carbon atoms is more preferable.

R ^b7 and R ^b8 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
m2 and n2 each independently represent an integer of 0 to 5. When m2 is 2 or more, the plurality of R ^b7 may be the same or different from each other. When n2 is 2 or more, the plurality of R ^b8 may be the same or different from each other.

R ^b9 and R ^b10 each independently represent an alkyl group having 1 to 36 carbon atoms or an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or R ^b9 and R ^b10 are bonded to each other, A 3-membered ring to a 12-membered ring (preferably a 3-membered ring to a 7-membered ring) are formed with the sulfur atom bonded thereto. The methylene group constituting the ring may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
R ^b11 represents a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ^b12 represents 1 carbon atom. Represents an alkyl group of ˜12, an alicyclic hydrocarbon group of 3 to 18 carbon atoms or an aromatic hydrocarbon group of 6 to 18 carbon atoms, or R ^b11 and R ^b12 are bonded to each other, A 4-membered ring to a 12-membered ring (preferably a 4-membered ring to a 7-membered ring) are formed with the carbon atom. The methylene group constituting the ring may be replaced with an oxygen atom, a sulfur atom or a carbonyl group.
Among R ^{b9 to} R ^b12 , the alkyl group preferably has 1 to 12 carbon atoms, and the alicyclic hydrocarbon group preferably has 3 to 36 carbon atoms, more preferably 4 to 12 carbon atoms. The aromatic hydrocarbon group is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or an alkylcarbonyloxy group having 2 to 13 carbon atoms. May be substituted.
Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, Examples thereof include a pentylcarbonyloxy group, a hexylcarbonyloxy group, an octylcarbonyloxy group, and a 2-ethylhexylcarbonyloxy group.

R ^{b13 to} R ^b18 each independently represent a hydroxy group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
L ^b11 represents a sulfur atom or an oxygen atom.
o2, p2, s2, and t2 each independently represents an integer of 0 to 5.
q2 and r2 each independently represents an integer of 0 to 4.
u2 represents 0 or 1.
When o2 is 2 or more, the plurality of R ^b13 may be the same or different. When p2 is 2 or more, the plurality of R ^b14 may be the same or different. When q2 is 2 or more, A plurality of R ^b15 may be the same or different. When r2 is 2 or more, a plurality of R ^b16 may be the same or different. When s2 is 2 or more, a plurality of R ^b17 are the same or different. And when t2 is 2 or more, the plurality of R ^b18 may be the same or different.

Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl or 2-ethylhexyl.
Preferred alicyclic hydrocarbon groups are cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclodecyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane- 1-yl group or isobornyl group.
Preferred aromatic hydrocarbon groups are phenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-cyclohexylphenyl, 4-methoxyphenyl, biphenylyl or naphthyl. It is.
Examples of the alkyl group substituted with an aromatic hydrocarbon group include aralkyl groups such as a benzyl group.
Examples of the ring formed by R ^b9 and R ^b10 bonded together and the sulfur atom to which they are bonded together include, for example, a thiolane-1-ium ring (tetrahydrothiophenium ring), a thian-1-ium ring, Examples include 1,4-oxathian-4-ium ring.
Examples of the ring formed by combining R ^b11 and R ^b12 together with the carbon atoms to which they are bonded include an oxocycloheptane ring, an oxocyclohexane ring, an oxonorbornane ring, and an oxoadamantane ring.

  Specific examples of the organic cation represented by the formulas (b2-1) to (b2-4) include those described in JP2010-204646A.

Among the above organic cations, the organic cation is represented by the above formula (b2-1) from the viewpoint of the performance of the salt (I) as an acid generator contained in a resist composition used for fine processing of a semiconductor using a lithography technique. The organic cation is preferably an organic cation represented by the following formula (b2-1-1) [hereinafter referred to as “cation (b2-1-1)”. ], More preferably a triphenylsulfonium cation (in formula (b2-1-1), v2 = w2 = x2 = 0) or a tolylsulfonium cation (in formula (b2-1-1), v2 = w2 = X2 = 1, and R ^b19 , R ^b20 and R ^b21 are all methyl groups).

In formula (b2-1-1), R ^b19 , R ^b20 and R ^b21 each independently represent a halogen atom (preferably a fluorine atom), a hydroxy group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms or a carbon number. ^Represents an alkoxy group having 1 to 12, and two selected from R ^b19 , R ^b20 and R ^b21 together represent a single bond, —O— or a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms; A ring containing a sulfur atom may be formed.
As this C1-C18 aliphatic hydrocarbon group, a C1-C12 alkyl group or a C4-C18 alicyclic hydrocarbon group is preferable, and a C1-C12 alkyl group is more preferable. . Moreover, the hydrogen atom contained in this C1-C18 aliphatic hydrocarbon group is a halogen atom, a hydroxy group, a C1-C12 alkoxy group, a C6-C18 aromatic hydrocarbon group, carbon number. It may be substituted with 2 to 4 acyl groups or glycidyloxy groups.
v2, w2 and x2 each independently represent an integer of 0 to 5 (preferably 0 or 1).
When v2 is 2 or more, a plurality of R ^b19 may be the same or different from each other, and when w2 is 2 or more, a plurality of R ^b20 may be the same or different from each other. When x2 is 2 or more, a plurality of R ^b21 may be the same or different from each other.

Here, the specific example of the cation (b2-1-1) which is a suitable organic cation is shown.

The following are mentioned as a specific example of the cation in which the ring containing a sulfur atom was formed among cations (b2-1-1).

The following are mentioned as a specific example of the cation in which the ring containing a sulfur atom was formed among cations (b2-1).

Examples of the cation (b2-2) include the following.

Moreover, as an organic cation, the following organic cations are suitable among the organic cations represented by Formula (b2-3).

In the above formula (III), examples of the anion represented by X ⁻ include a halide ion or RSO ₄ ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms). Ions, bromide ions or CH ₃ SO ₄ ^— are preferred.

The salt represented by the above formula (III) (hereinafter sometimes referred to as salt (III)) is a combination of the above Z ⁺ and X ⁻ . Z ⁺ and X ⁻ can be arbitrarily combined, and can be appropriately selected depending on the reactivity, the type of the desired salt (I), and the like. Among these, triphenylsulfonium methyl sulfate, triphenylsulfonium chloride, and triphenylsulfonium bromide are preferable. A commercially available salt (III) may be used, and the salt (III) may be produced by any known method.

  The amount of salt (III) used is preferably in the range of 1.0 to 1.5 mol and more preferably in the range of 1.0 to 1.1 mol with respect to 1 mol of compound (II).

  As the water, industrial water, tap water, distilled water, ion-exchanged water and the like can be used. The amount used may be 1 mol or more with respect to 1 mol of compound (II), and a large excess amount may be used also as a solvent. The range of 1-10 mass parts is preferable with respect to 1 mass part of compound (II), and the range of 2-5 mass parts is more preferable.

［式（Ｎ−１）中、
Ｒ^N1、Ｒ^N2及びＲ^N3は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のヒドロキシアルキル基、炭素数１〜６のアルコキシアルキル基、炭素数３〜１２のシクロアルキル基、置換されてもよいフェニル基、置換されてもよい炭素数７〜１２のアラルキル基、置換されてもよいナフチル基又は置換されてもよい炭素数５〜１０のヘテロ芳香環基を表す。］ Examples of the organic base include compounds represented by the following formula (N-1).

[In the formula (N-1),
R ^N1 , R ^N2 and R ^N3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 1 to 6 carbon atoms, or 3 to 3 carbon atoms. 12 cycloalkyl groups, an optionally substituted phenyl group, an optionally substituted aralkyl group having 7 to 12 carbon atoms, an optionally substituted naphthyl group, or an optionally substituted heteroaromatic ring having 5 to 10 carbon atoms Represents a group. ]

Among these, trialkylamines such as trimethylamine and triethylamine, dialkylamines such as diethylamine, monoalkylamines such as monoethylamine, ammonia, and compounds represented by the following are preferable, and trialkylamines are more preferable.

  The amount of the organic base used is preferably in the range of 1 to 5 mol and more preferably in the range of 1.1 to 3 mol with respect to 1 mol of the salt (III).

  In the present invention, the reaction of compound (II), salt (III) and water is carried out in the presence of an organic base, but is preferably carried out in the presence of an organic solvent. Examples of the organic solvent include halogenated hydrocarbon solvents such as chloroform and dichloromethane, ester solvents such as ethyl acetate, and among them, halogenated hydrocarbon solvents are preferable. The amount of the organic base used is preferably in the range of 1 to 10 mol, more preferably in the range of 2 to 5 mol, with respect to 1 part by mass in total of the compound (II) and the salt (III).

  The reaction temperature is preferably in the range of 5 ° C. or higher and 100 ° C. or lower (if the boiling point of the organic solvent is lower than 100 ° C.), preferably 10 to 50 ° C. The range of 20-40 degreeC is more preferable, and the range of 20-40 degreeC is further more preferable. The reaction time can be appropriately determined by following the reaction end point, and is usually in the range of 1 minute to 24 hours.

  The production method of the present invention is carried out by mixing compound (II), salt (III), water and an organic base, if necessary in the presence of an organic solvent. Although the mixing order is not particularly limited, it is preferable to carry out by adding compound (II) to a mixture of salt (III), water and organic solvent.

  The mixture after completion of the reaction usually contains a salt (I). The salt (I) can be isolated by subjecting such a mixture to normal post-treatment such as liquid separation, concentration, crystallization (mixing with a poor solvent, cooling crystallization, etc.), filtration and the like. The isolated salt (I) may be further purified by a usual purification treatment such as washing and recrystallization.

The salt (I) thus obtained is a combination of a sulfonate anion and an organic cation as represented by the formula (I). The sulfonate anion is, for example, an anion having a structure in which * in the structure represented by the formula (b1-s-1) to the formula (b1-s-42) is bonded to SO ₃ ^— , and the organic cation Is, for example, a cation represented by the above formula (b2-c-1) to formula (b2c-24), and these can be arbitrarily combined. The combinations of the sulfonate anion and the organic cation are shown in Tables 1 and 2. In Tables 1 and 2, * —C (Q ¹ ) (Q ² ) —CO—O—Y [wherein Q ¹ , Q ² and Y represent the same meaning as described above. ], A sulfonate anion containing a structure represented by the formula (b1-s-1) as a structure represented by the formula (b1-s-1) is represented according to the formula number, and the formula (b2 The organic cation represented by -c-1) is represented as "(b2-c-1)" or the like according to the formula number.

  From the viewpoint of the performance of the salt (I) as an acid generator contained in a resist composition used for fine processing of a semiconductor using a lithography technique, a more preferable salt (I) is specifically shown. Such a salt (I) is represented by the following formula (I-1), formula (I-2), formula (I-3), formula (I-4), formula (I-5), formula (I- 6), Formula (I-7), Formula (I-8), Formula (I-9), Formula (I-10), Formula (I-11), Formula (I-12), Formula (I-13) ), Formula (I-14), Formula (I-15), Formula (I-16), Formula (I-17), Formula (I-18), Formula (I-19), and Formula (I-20) It is represented by either. Among them, formula (I-2), formula (I-3), formula (I-6), formula (I-7), formula (I-11), formula (I-12), formula (I-13) And those represented by any one of formulas (I-14), (I-18), (I-19) and (I-20). In addition, as described above, since Y is preferably a group containing an alicyclic hydrocarbon group which may have a substituent, in this respect, formula (I-2), formula (I-3), What is represented by any one of (I-6), formula (I-7), (I-11), formula (I-18), formula (I-19) and formula (I-20) is more preferable. .

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
In Examples, Production Examples and Comparative Examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

  The quantification of the compound and salt was carried out using mass spectrometry (LC: Agilent model 1100, MASS: Agilent LC / MSD type or LC / MSD TOF type).

式（Ｈ−１）で表される化合物４０．００部とクロロホルム２４０部とを混合し、２３℃で３０分間攪拌した。得られた混合溶液に、式（ＩＩ−１）で表される化合物４６．３８部及びチタニウムイソプロポキシド１．２５部を添加し、更に６３℃で６時間還流しながらメタノールを留去した。得られた反応物にシリカゲル１２．５０部を添加攪拌後、ろ過した。得られたろ液を濃縮した後、濃縮物にｎ−ヘプタン３００部を添加した後、濃縮した。得られた濃縮物に、ｎ−ヘプタン１００部を添加し、２３℃で６時間撹拌後、濾過することにより、式（ＩＩ−２）で表される化合物６９．４７部を得た。 Production Example 1: Production of compound represented by formula (II-2)

40.00 parts of the compound represented by the formula (H-1) and 240 parts of chloroform were mixed and stirred at 23 ° C. for 30 minutes. To the obtained mixed solution, 46.38 parts of the compound represented by the formula (II-1) and 1.25 parts of titanium isopropoxide were added, and methanol was distilled off while refluxing at 63 ° C. for 6 hours. To the obtained reaction product, 12.50 parts of silica gel was added and stirred, followed by filtration. After concentrating the obtained filtrate, 300 parts of n-heptane was added to the concentrate, followed by concentration. To the obtained concentrate, 100 parts of n-heptane was added, stirred at 23 ° C. for 6 hours, and filtered to obtain 69.47 parts of a compound represented by the formula (II-2).

式（Ｊ−６）で表される化合物１５．００部、式（Ｈ−６）で表される化合物８．７９部、濃硫酸０．１０４部及びジクロロエタン１５０部を混合し、８５℃で６時間還流しながら脱水した。得られた反応物に、５％炭酸水素ナトリウム水溶液８６．９５部を添加攪拌後分液し、有機層を回収した。回収された有機層に、イオン交換水８６．９５部を添加攪拌後分液し、有機層を回収した。この水洗を４回行った。得られた有機層を濃縮することにより、式（ＩＩ−６）で表される化合物１５．１１部を得た。 Production Example 2: Production of compound represented by formula (II-6)

15.00 parts of the compound represented by the formula (J-6), 8.79 parts of the compound represented by the formula (H-6), 0.104 parts of concentrated sulfuric acid, and 150 parts of dichloroethane were mixed and mixed at 85 ° C. It dehydrated while refluxing for hours. To the obtained reaction product, 86.95 parts of 5% aqueous sodium hydrogen carbonate solution was added and stirred for liquid separation, and the organic layer was recovered. To the recovered organic layer, 86.95 parts of ion-exchanged water was added and stirred for liquid separation, and the organic layer was recovered. This washing with water was performed 4 times. The obtained organic layer was concentrated to obtain 15.11 parts of a compound represented by the formula (II-6).

式（ＩＩ−６）で表される化合物５．００部とテトラヒドロフラン５０部とを混合し、２３℃で３０分間攪拌した後、−４０℃に冷却した。得られた混合物に、１Ｍ−水素化ホウ素のテトラヒドロフラン溶液１５．３２ｍｌを４０分かけて滴下した後、−４０℃で２４時間攪拌した。その後、０℃まで昇温した後、イオン交換水５０部及びクロロホルム１５０部を添加攪拌後、分液し、有機層を回収した。回収された有機層に、イオン交換水１５０部を添加攪拌後分液し、有機層を回収した。この水洗を２回行った。得られた有機層を濃縮することにより、式（ＩＩ−１９）で表される化合物３．８０部を得た。 Production Example 3: Production of compound represented by formula (II-19)

5.00 parts of the compound represented by the formula (II-6) and 50 parts of tetrahydrofuran were mixed, stirred at 23 ° C. for 30 minutes, and then cooled to −40 ° C. To the obtained mixture, 15.32 ml of 1M-borohydride tetrahydrofuran solution was added dropwise over 40 minutes, followed by stirring at −40 ° C. for 24 hours. Then, after heating up to 0 degreeC, 50 parts of ion-exchange water and 150 parts of chloroform were added and stirred, and it liquid-separated and collect | recovered the organic layers. To the recovered organic layer, 150 parts of ion-exchanged water was added and stirred for separation, and the organic layer was recovered. This washing with water was performed twice. The obtained organic layer was concentrated to obtain 3.80 parts of a compound represented by the formula (II-19).

式（ＩＩＩ−１）で表される塩２０．００部、クロロホルム１００部、イオン交換水６０部及びトリエチルアミン１３．５１部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、製造例１で得た式（ＩＩ−２）で表される化合物２２．５２部をクロロホルム７８．０４部に溶解した溶液を３０分かけて滴下し、更に２３℃で１時間撹拌した後、分液して有機層を回収した。回収された有機層にイオン交換水６０部を添加攪拌後分液し、有機層を回収した。この水洗を４回行った。得られた有機層を濃縮した後、濃縮物にアセトニトリル１００部を添加した後、濃縮した。得られた濃縮物に、アセトニトリル２７．３２部及びｔｅｒｔ−ブチルメチルエーテル２５７．５２部を添加し、撹拌後、濾過することにより、式（Ｉ−２）で表される塩２６．４８部（式（ＩＩ−１）で表される化合物に対する収率７６．１％、式（ＩＩＩ−１）で表される塩に対する収率８２．３％）を得た。 Example 1: Production of a salt represented by the formula (I-2)

20.00 parts of the salt represented by the formula (III-1), 100 parts of chloroform, 60 parts of ion-exchanged water and 13.51 parts of triethylamine were mixed and stirred at 23 ° C. for 30 minutes. A solution obtained by dissolving 22.52 parts of the compound represented by the formula (II-2) obtained in Production Example 1 in 78.04 parts of chloroform was added dropwise to the obtained mixed solution over 30 minutes, and further at 23 ° C. After stirring for 1 hour, the organic layer was recovered by liquid separation. To the recovered organic layer, 60 parts of ion-exchanged water was added and stirred for separation, and the organic layer was recovered. This washing with water was performed 4 times. After concentrating the obtained organic layer, 100 parts of acetonitrile was added to the concentrate, followed by concentration. To the obtained concentrate, 27.32 parts of acetonitrile and 257.52 parts of tert-butyl methyl ether were added, and after stirring, filtered, 26.48 parts of the salt represented by the formula (I-2) ( The yield of the compound represented by the formula (II-1) was 76.1%, and the yield of the salt represented by the formula (III-1) was 82.3%.

式（ＩＩＩ−２）で表される塩２０．００部、クロロホルム１００部、イオン交換水６０部及びトリエチルアミン１２．１５部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、製造例１で得た式（ＩＩ−２）で表される化合物２０．２５部をクロロホルム７０．１５部に溶解した溶液を３０分かけて滴下し、更に２３℃で１時間撹拌した後、分液して有機層を回収した。回収された有機層にイオン交換水６０部を添加攪拌後分液し、有機層を回収した。この水洗を４回行った。得られた有機層を濃縮した後、濃縮物にアセトニトリル１００部を添加した後、濃縮した。得られた濃縮物に、アセトニトリル２６．４０部及びｔｅｒｔ−ブチルメチルエーテル２５３．８３部を添加し、撹拌後、濾過することにより、式（Ｉ−３）で表される塩２８．９１部（式（ＩＩ−１）で表される化合物に対する収率７５．８％、式（ＩＩＩ−２）で表される塩に対する収率８１．９％）を得た。 Example 2: Production of salt represented by formula (I-3)

20.00 parts of the salt represented by the formula (III-2), 100 parts of chloroform, 60 parts of ion-exchanged water and 12.15 parts of triethylamine were mixed and stirred at 23 ° C. for 30 minutes. A solution obtained by dissolving 20.25 parts of the compound represented by the formula (II-2) obtained in Production Example 1 in 70.15 parts of chloroform was added dropwise to the obtained mixed solution over 30 minutes, and further at 23 ° C. After stirring for 1 hour, the organic layer was recovered by liquid separation. To the recovered organic layer, 60 parts of ion-exchanged water was added and stirred for separation, and the organic layer was recovered. This washing with water was performed 4 times. After concentrating the obtained organic layer, 100 parts of acetonitrile was added to the concentrate, followed by concentration. To the obtained concentrate, 26.40 parts of acetonitrile and 253.83 parts of tert-butyl methyl ether were added, and after stirring, filtered, 28.91 parts of the salt represented by the formula (I-3) ( A yield of 75.8% based on the compound represented by the formula (II-1) and a yield of 81.9% based on the salt represented by the formula (III-2) were obtained.

式（ＩＩＩ−１８）で表される塩２０．００部、クロロホルム１００部、イオン交換水６０部及びトリエチルアミン１０．０３部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、製造例１で得た式（ＩＩ−２）で表される化合物１６．７２部をクロロホルム６６．８８部に溶解した溶液を３０分かけて滴下し、更に２３℃で１時間撹拌した後、分液して有機層を回収した。回収された有機層にイオン交換水５０部を添加攪拌後分液し、有機層を回収した。この水洗を５回行った。得られた有機層を濃縮した後、濃縮物にアセトニトリル１００部を添加した後、濃縮した。得られた濃縮物に、酢酸エチル３０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル３０部を加えて攪拌し、上澄液を除去した。得られた残渣をクロロホルムに溶解し、濃縮することにより、式（Ｉ−１８）で表される塩２３．８４部（式（ＩＩ−１）で表される化合物に対する収率７６．０％、式（ＩＩＩ−１８）で表される塩に対する収率８２．１％）を得た。 Example 3: Production of salt represented by formula (I-18)

20.00 parts of the salt represented by the formula (III-18), 100 parts of chloroform, 60 parts of ion-exchanged water and 10.03 parts of triethylamine were mixed and stirred at 23 ° C. for 30 minutes. A solution obtained by dissolving 16.72 parts of the compound represented by the formula (II-2) obtained in Production Example 1 in 66.88 parts of chloroform was dropped into the obtained mixed solution over 30 minutes, and further at 23 ° C. After stirring for 1 hour, the organic layer was recovered by liquid separation. To the recovered organic layer, 50 parts of ion-exchanged water was added and stirred for liquid separation, and the organic layer was recovered. This water washing was performed 5 times. After concentrating the obtained organic layer, 100 parts of acetonitrile was added to the concentrate, followed by concentration. 30 parts of ethyl acetate was added to the resulting concentrate and stirred, and the supernatant was removed. To the obtained residue, 30 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to give 23.84 parts of a salt represented by the formula (I-18) (yield: 76.0% based on the compound represented by the formula (II-1), A yield of 82.1% based on the salt represented by the formula (III-18) was obtained.

式（ＩＩＩ−１）で表される塩２０．００部、クロロホルム１００部、イオン交換水６０部及びトリエチルアミン１３．５１部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、製造例１で得た式（ＩＩ−６）で表される化合物２０．５０部をクロロホルム７１．７６部に溶解した溶液を３０分かけて滴下し、更に２３℃で１時間撹拌した後、分液して有機層を回収した。回収された有機層にイオン交換水５０部を添加攪拌後分液し、有機層を回収した。この水洗を４回行った。得られた有機層を濃縮した後、濃縮物にアセトニトリル１００部を添加した後、濃縮した。得られた濃縮物に、酢酸エチル３０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル３０部を加えて攪拌し、上澄液を除去した。得られた残渣をクロロホルムに溶解し、濃縮することにより、式（Ｉ−６）で表される塩２５．８９部（式（Ｊ−６）で表される化合物に対する収率７２．３％、式（ＩＩＩ−１）で表される塩に対する収率８２．６％）を得た。 Example 4: Production of a salt represented by the formula (I-6)

20.00 parts of the salt represented by the formula (III-1), 100 parts of chloroform, 60 parts of ion-exchanged water and 13.51 parts of triethylamine were mixed and stirred at 23 ° C. for 30 minutes. A solution obtained by dissolving 20.50 parts of the compound represented by the formula (II-6) obtained in Production Example 1 in 71.76 parts of chloroform was added dropwise to the obtained mixed solution over 30 minutes, and further at 23 ° C. After stirring for 1 hour, the organic layer was recovered by liquid separation. To the recovered organic layer, 50 parts of ion-exchanged water was added and stirred for liquid separation, and the organic layer was recovered. This washing with water was performed 4 times. After concentrating the obtained organic layer, 100 parts of acetonitrile was added to the concentrate, followed by concentration. 30 parts of ethyl acetate was added to the resulting concentrate and stirred, and the supernatant was removed. To the obtained residue, 30 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to give 25.89 parts of the salt represented by the formula (I-6) (yield 72.3% based on the compound represented by the formula (J-6), A yield of 82.6% based on the salt represented by the formula (III-1) was obtained.

式（ＩＩＩ−１）で表される塩２０．００部、クロロホルム１００部、イオン交換水６０部及びトリエチルアミン１３．５１部を混合し、２３℃で３０分間攪拌した。得られた混合溶液に、製造例１で得た式（ＩＩ−６）で表される化合物２０．６３部をクロロホルム７２．１９部に溶解した溶液を３０分かけて滴下し、更に２３℃で１時間撹拌した後、分液して有機層を回収した。回収された有機層にイオン交換水５０部を添加攪拌後分液し、有機層を回収した。この水洗を４回行った。得られた有機層を濃縮した後、濃縮物にアセトニトリル１００部を添加した後、濃縮した。得られた濃縮物に、酢酸エチル３０部を加えて攪拌し、上澄液を除去した。得られた残渣にｔｅｒｔ−ブチルメチルエーテル３０部を加えて攪拌し、上澄液を除去した。得られた残渣をクロロホルムに溶解し、濃縮することにより、式（Ｉ−１９）で表される塩２５．２１部（式（ＩＩ−６）で表される化合物に対する収率６０．５％、式（ＩＩＩ−１）で表される塩に対する収率８０．２％）を得た。 Example 5: Production of salt represented by formula (I-19)

20.00 parts of the salt represented by the formula (III-1), 100 parts of chloroform, 60 parts of ion-exchanged water and 13.51 parts of triethylamine were mixed and stirred at 23 ° C. for 30 minutes. A solution obtained by dissolving 20.63 parts of the compound represented by the formula (II-6) obtained in Production Example 1 in 72.19 parts of chloroform was added dropwise to the obtained mixed solution over 30 minutes, and further at 23 ° C. After stirring for 1 hour, the organic layer was recovered by liquid separation. To the recovered organic layer, 50 parts of ion-exchanged water was added and stirred for liquid separation, and the organic layer was recovered. This washing with water was performed 4 times. After concentrating the obtained organic layer, 100 parts of acetonitrile was added to the concentrate, followed by concentration. 30 parts of ethyl acetate was added to the resulting concentrate and stirred, and the supernatant was removed. To the obtained residue, 30 parts of tert-butyl methyl ether was added and stirred, and the supernatant was removed. The obtained residue was dissolved in chloroform and concentrated to give 25.21 parts of the salt represented by the formula (I-19) (yield 60.5% based on the compound represented by the formula (II-6), A yield of 80.2% based on the salt represented by the formula (III-1) was obtained.

式（ＩＩ−１）で表される化合物１００部とイオン交換水１５０部との混合物に、氷浴下、３０％水酸化ナトリウム水溶液２３０部を滴下した。得られた混合物を１００℃で３時間還流し、冷却後、これを濃塩酸８８部で中和した。得られた溶液を濃縮することにより式（Ｈ−２）で表される塩１６４．４部（無機塩（ＮａＣｌ）含有、純度６２．７％）を得た。得られた式（Ｈ−２）で表される塩１．９部（純度６２．７％）とＮ，Ｎ−ジメチルホルムアミド９．５部との混合物に、１，１’−カルボニルジイミダゾール１．０部を添加し、２時間撹拌して式（Ｈ−２）で表される塩を含む溶液を調製した。
一方、式（Ｈ−１）で表される化合物１．１部とＮ，Ｎ−ジメチルホルムアミド５．５部との混合物に、水素化ナトリウム０．２部を添加し、２時間撹拌した。得られた溶液に、前記の式（Ｈ−２）で表される塩を含む溶液を添加した。得られた溶液を１５時間撹拌し、式（Ｈ−３）で表される塩を含む溶液を得た。 Comparative Example 1: Production of salt represented by formula (I-2)

To a mixture of 100 parts of the compound represented by formula (II-1) and 150 parts of ion-exchanged water, 230 parts of a 30% aqueous sodium hydroxide solution was added dropwise in an ice bath. The resulting mixture was refluxed at 100 ° C. for 3 hours, cooled, and neutralized with 88 parts of concentrated hydrochloric acid. The obtained solution was concentrated to obtain 164.4 parts of a salt represented by the formula (H-2) (containing inorganic salt (NaCl), purity 62.7%). 1,1′-carbonyldiimidazole 1 was added to a mixture of 1.9 parts of the salt represented by the formula (H-2) (purity 62.7%) and 9.5 parts of N, N-dimethylformamide. 0.0 part was added and it stirred for 2 hours, and prepared the solution containing the salt represented by Formula (H-2).
On the other hand, 0.2 part of sodium hydride was added to a mixture of 1.1 parts of the compound represented by the formula (H-1) and 5.5 parts of N, N-dimethylformamide, and stirred for 2 hours. A solution containing the salt represented by the formula (H-2) was added to the obtained solution. The obtained solution was stirred for 15 hours to obtain a solution containing a salt represented by the formula (H-3).

上記で得た式（Ｈ−３）で表される塩含む溶液に、クロロホルム１７．２部及び式（ＩＩＩ−１）で表される塩を含む水溶液（１４．８％）２．９部を添加した。１５時間撹拌した後、分液して有機層を回収した。次いで、残った水層をクロロホルム６．５部で抽出することにより有機層を回収した。さらに残った水層に、前記の抽出操作を繰り返して行い、さらに有機層を回収した。前記の各有機層を合せた後、イオン交換水で洗浄し、その後、得られた有機層を濃縮した。濃縮物にｔｅｒｔ−ブチルメチルエーテル５．０部を添加し、撹拌後、濾過することにより白色固体として式（Ｉ−２）で表される塩０．２部（式（ＩＩ−１）で表される化合物に対する収率５．５％、式（Ｈ−２）で表される化合物に対する収率５．５％、式（ＩＩＩ−１）で表される塩に対する収率２３％）を得た。

In the solution containing the salt represented by the formula (H-3) obtained above, 17.2 parts of chloroform and 2.9 parts of an aqueous solution (14.8%) containing the salt represented by the formula (III-1) were added. Added. After stirring for 15 hours, the organic layer was recovered by liquid separation. Subsequently, the remaining aqueous layer was extracted with 6.5 parts of chloroform to recover the organic layer. Further, the above extraction operation was repeated on the remaining aqueous layer, and the organic layer was further recovered. The organic layers were combined, washed with ion-exchanged water, and then the obtained organic layer was concentrated. To the concentrate, 5.0 parts of tert-butyl methyl ether was added, stirred, and then filtered to obtain 0.2 parts of a salt represented by the formula (I-2) as a white solid (represented by the formula (II-1)). Yield of 5.5% with respect to the compound represented by formula (H-2), and yield of 23% with respect to the salt represented by formula (III-1). .

  According to the production method of the present invention, a target salt can be produced without using an alkali metal and with a higher yield than when an alkali metal is used. The salt obtained by the production method of the present invention can be used, for example, as an acid generator contained in a resist composition used for fine processing of a semiconductor using a lithography technique.

Claims (3)

In the presence of an organic base, the formula (II)

[Wherein, Q ¹ and Q ² each independently represent a fluorine atom or a C 1-6 perfluoroalkyl group. Y represents an optionally substituted aliphatic hydrocarbon group having 1 to 18 carbon atoms, and the methylene group constituting the aliphatic hydrocarbon group is replaced with an oxygen atom, a sulfonyl group or a carbonyl group. May be. ]
And a compound represented by formula (III)

[Wherein, Z ⁺ represents an organic cation, and X ⁻ represents an anion. ]
Wherein the salt represented by formula (I) is reacted with water

[Wherein, Q ¹ , Q ² , Y and Z ⁺ represent the same meaning as described above. ]
The manufacturing method of the salt represented by these. The production method according to claim 1, wherein X ⁻ in formula (III) is a halide ion or RSO ₄ ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms). The production method according to claim 1 or 2, wherein the organic base is a trialkylamine.