JPH06239845A - Production of alkylsulfonate derivative - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as a synthetic intermediate for cyanine-based dyes which are sensitizing dyes of photographic photosensitive materials in high yield by reacting a compound having a naphthalene nucleus with an aliphatic sultone in the presence of Lewis acid. CONSTITUTION:A nitrogen-containing heterocyclic compound of formula I (X us 0, S, NR<1>, Se, Te or CR<2>R<3>; R<1> to R<3> are H, lower alkyl, etc.; A is H, mercapto, arylthio, aralkyl, sulfo, halogen, etc.; R<4> to R<8> are H or substituent group) is made to react with an aliphatic sultone of formula II (Z is alkylene) in the presence of a Lewis acid (e.g. boron trifluoride ether complex) at 120-250 deg.C to provide the objective compound of formula III. The compound of the formula I and the compound of the formula II are used in a molar ratio of 1:l to 5. As the compound of formula III, 2-methylnaphtho[1,2-d]thiazolium-3- butanesulfonate is exemplified.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing an alkyl sulfonate derivative.

[0002]

2. Description of the Related Art Conventionally, as sensitizing dyes for photographic light-sensitive materials,
A compound having a sulfoalkyl group as a side chain of a mother nucleus of a cyanine dye is known. A compound in which a sulfoalkyl group is bonded to a quaternary nitrogen atom of a nitrogen-containing heterocycle that constitutes the mother nucleus of a cyanine dye is often used.

As a precursor for producing a cyanine dye having a sulfoalkyl group bonded to a quaternary nitrogen atom,
The following general formula (3):

[0004]

[Chemical 7]

[In the formula, X is --O--, --S--, --NR ¹
-, - Se -, - Te-, or -CR ² R ³ - (where, R ¹
, R ² and R ³ each independently represent a hydrogen atom or a lower alkyl group which may have a substituent, and R ² and R ³ may combine to form a ring), A Represents a hydrogen atom or an alkyl group, and R ⁴ ,
R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a substituent. ] It is known that an alkyl sulfonate derivative represented by the following formula can be used (JP-A-3-10).
5339 publication).

As a method for synthesizing the compound represented by the general formula (3), the following general formula (1):

[0007]

[Chemical 8]

[Wherein A, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R
⁸ and X are as described above], and a nitrogen-containing heterocyclic compound represented by the above formula is reacted with a chain alkyl sulfonate activated by a halogen atom or a sulfonyloxy group, A method of attaching a sulfoalkyl group to the nitrogen atom of is considered.

This activated chain alkyl sulfonate has a high nucleophilicity of the compound to be sulfoalkylated,
When the sulfoalkylation reaction proceeds under relatively mild conditions, it is an advantageous sulfoalkylation reagent in terms of structural freedom. However, when the activated chain alkyl sulfonate is reacted with the nitrogen-containing heterocyclic compound represented by the general formula (1) to quaternize the nitrogen atom, the activated chain alkyl There is a problem in that the number of side reactions in which the active site of the sulfonate is thermally eliminated increases, and the desired alkyl sulfonate compound cannot be obtained.

Aliphatic sultone is known as a sulfoalkylating reagent for a compound having active hydrogen (Japanese Patent Laid-Open No. 1-187543). It is said that the aliphatic sultone reacts with an amine compound without a catalyst to introduce a sulfone group, and the aliphatic sultone is bonded to the nitrogen atom of the nitrogen-containing heterocyclic compound represented by the above general formula (1). If possible, the side reaction that would occur when using the structurally activated chain alkyl sulfonate should hardly occur. However, even if the aliphatic sultone is allowed to react with the nitrogen-containing heterocyclic compound represented by the general formula (1) under heating, the compound represented by the general formula (3) is not produced at all, or even if it is produced, the compound is recovered. The rate was extremely low. The reason is that the aliphatic sultone molecule is sterically hindered by a hydrogen atom or another substituent bonded to the 8-position carbon atom of the naphthalene nucleus of the nitrogen-containing heterocyclic compound represented by the general formula (1). It is considered that this is because the access to the nitrogen atom of the nitrogen-containing heterocyclic compound is prevented.

[0011]

A method for producing an alkylsulfonate derivative represented by the general formula (3) in high yield from a nitrogen-containing heterocyclic compound represented by the general formula (1) and an aliphatic sultone. provide.

[0012]

The present invention provides the following general formula (1):

[0013]

[Chemical 9] [In formula, X is -O-, -S-, -NR < ¹ >-, -Se.
—, —Te— or —CR ² R ³ — (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or a lower alkyl group optionally having a substituent, and R ² and R ^{2 3} may combine to form a ring), A is a hydrogen atom,
Mercapto group, arylthio group, aralkyl group, sulfo group, halogen atom, alkyl group optionally having substituent (s), alkylthio group optionally having substituent (s), alkoxy group optionally having substituent (s) Represents an optionally substituted alkylsulfonyloxy group or an optionally substituted arylsulfonyloxy group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom. Or represents a substituent. ] A nitrogen-containing heterocyclic compound represented by
The following general formula (2):

[0014]

[Chemical 10] [Wherein Z represents an alkylene group which may have a substituent] is reacted with an aliphatic sultone in the presence of a Lewis acid to give the following general formula (3):

[0015]

[Chemical 11] [In the formula, A, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X and Z
Is as described above]. The method for producing an alkylsulfonate derivative is characterized by producing an alkylsulfonate derivative represented by

The preferred embodiments of the present invention are as follows.

(1) R ⁴ , R ⁵ in the general formula (1),
At least one of R ⁶ , R ⁷ and R ⁸ is an alkyl group,
An aryl group, an alkoxy group which may have a substituent,
A method for producing the above alkylsulfonate derivative, which represents an aryloxy group, an alkylthio group, a halogen atom, a cyano group, a carboxyl group, a sulfo group or a sulfonic acid group.

(2) At least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is substituted with an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a sulfonate group. Optionally substituted alkoxy group having 1 to 25 carbon atoms,
A method for producing the above alkylsulfonate derivative, which represents an aryloxy group, an alkylthio group having 1 to 3 carbon atoms, a halogen atom, a cyano group, a carboxyl group, a sulfo group or a sulfonic acid group.

(3) X is --O--, --S--, --NR ^1-
Alternatively, the method for producing the above alkylsulfonate derivative which is —CR ² R ³ —.

(4) A method for producing the above alkylsulfonate derivative, wherein A is an alkyl group having 1 to 5 carbon atoms, a mercapto group, an arylthio group, an alkylthio group or a sulfo group.

(5) A method for producing the above alkylsulfonate derivative, wherein Z is a straight-chain alkylene group having 3 or 4 carbon atoms and having no substituent.

(6) Z is an alkyl group having 1 to 10 carbon atoms,
The method for producing the above alkylsulfonate derivative, which is a linear alkylene group having 3 or 4 carbon atoms and having a substituent selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms and a halogen atom.

(7) The method for producing an alkyl sulfonate derivative, wherein the Lewis acid is a boron trifluoride ether complex.

The present invention also provides the above general formula (1): [wherein, X is -O-, -S-, -NR ^1- , -Se-,-.
Te- or -CR ² R ^3- (provided that R ¹ , R ² and R ³
Each independently represent a hydrogen atom or a lower alkyl group which may have a substituent, R ² and R ³ may combine to form a ring), and A represents a hydrogen atom or a mercapto group. , An arylthio group, an aralkyl group, a sulfo group, a halogen atom, an alkyl group which may have a substituent, an alkylthio group which may have a substituent, an alkoxy group which may have a substituent, a substituent Represents an alkylsulfonyloxy group which may have a group or an arylsulfonyloxy group which may have a substituent, and R ⁴ and R
⁵ , R ⁵ and R ⁶ , at least one combination of R ⁶ and R ^7, and R ⁷ and R ⁸ are linked to each other and together with the divalent hydrocarbon group of the naphthalene ring, an aromatic ring or cyclo Forming an alkene ring, and R
^{Among 4} , R ⁵ , R ⁶ , R ⁷ and R ⁸ , those not forming a ring may represent a substituent. ] The nitrogen-containing heterocyclic compound represented by the following general formula (2):
[Wherein Z represents an alkylene group which may have a substituent] is reacted with an aliphatic sultone in the presence of a Lewis acid to give the compound represented by the general formula (5): [wherein ,
A, the ^{R 4, R 5, R 6} , R 7, R 8, X and Z are production method of alkylsulfonate derivatives and generating an alkyl sulfonate derivative represented by are as described above] There is also.

The preferred embodiments of the present invention described above are as follows.

(1) R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R
⁷ and at least one combination of R ⁷ and R ⁸ are linked to each other to form a benzene ring or a cyclohexene ring together with the divalent hydrocarbon group of the naphthalene ring to which they are bonded. Process for producing alkyl sulfonate derivative.

(2) X is --O--, --S--, --NR ^1-
Alternatively, the method for producing the above alkylsulfonate derivative which is —CR ² R ³ —.

(3) A method for producing the above alkylsulfonate derivative, wherein A is an alkyl group having 1 to 5 carbon atoms, a mercapto group, an arylthio group, an alkylthio group or a sulfo group.

(4) The process for producing an alkylsulfonate derivative as described above, wherein Z is a straight-chain alkylene group having 3 or 4 carbon atoms having no substituent.

(5) Z is an alkyl group having 1 to 10 carbon atoms,
The method for producing the above alkylsulfonate derivative, which is a linear alkylene group having 3 or 4 carbon atoms and having a substituent selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms and a halogen atom.

(7) The method for producing an alkyl sulfonate derivative described above, wherein the Lewis acid is a boron trifluoride ether complex.

The nitrogen-containing heterocyclic compound which is one of the starting materials of the present invention is a compound represented by the above general formula (1).
In the general formula (1), X is -O-, -S-, -S.
e-, -NR ¹ -or -CR ² R ^3- (provided that R ² and R ³ are as described above), and -S
-, - O -, - NR 1 - or -CR ² R ³ - is preferably, in particular -S -, - O-or -NR ¹ - is preferably. Further, R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, for example, methyl,
It is preferably ethyl, propyl, butyl and the like, particularly preferably hydrogen atom, methyl or ethyl.
The substituent which R ¹ , R ² and R ³ may have is a halogen atom (eg, chlorine atom), an alkoxy group having 1 to 4 carbon atoms, an amino group (eg, methylamino group) or a hydroxy group. Preferably there is. R ² and R ³ may combine to form a ring containing oxygen or nitrogen (preferably a 6-membered ring) together with the carbon atom of the pyrrole ring (eg,
Pentamethylene oxide ring, N-methyl-piperazine ring).

Further, A is generally a hydrogen atom, an alkyl group, an aralkyl group, a mercapto group, an arylthio group, an alkylthio group which may have a substituent or a sulfo group. Alkylthio group is sulfonic acid group, 1 to 1 carbon atoms
It may be substituted with an alkoxy group having 6 or an alkoxyalkoxyalkoxy group having 1 to 6 carbon atoms. A is
Hydrogen atom, an alkylthio group having 1 to 4 carbon atoms, a benzyl group, an alkylthio group having 1 to 4 carbon atoms having the above-mentioned substituent, a phenylthio group or an alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl Preferably)
Is preferred, and a hydrogen atom or methyl is particularly preferred.

At least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is generally an alkyl group, an aryl group,
Represents an alkoxy group which may have a substituent, an aryloxy group, a haloalkyl group, an alkylthio group, a halogen atom, a cyano group, a carboxyl group, a sulfo group or a sulfonic acid group, and an alkyl group having 1 to 3 carbon atoms. ,
Aryl group having 6 to 14 carbon atoms (eg, phenyl, naphthyl, anthranyl), alkoxy group having 1 to 25 carbon atoms which may be substituted with a sulfonate group, aryloxy group (eg, phenoxy), carbon number It is preferably a haloalkyl group having 1 to 3 carbon atoms, an alkylthio group having 1 to 3 carbon atoms, a halogen atom, a cyano group, a carboxyl group, a sulfo group or a sulfonic acid group. In particular, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 25 carbon atoms which may be substituted with a sulfonate group, a phenoxy group, an alkylthio group having 1 to 3 carbon atoms, a halogen atom, a cyano group, It represents a carboxyl group, a sulfo group or a sulfonic acid group.

Further, the compound represented by the above-mentioned general formula (1) of the present invention, which is another embodiment of the above-mentioned compound, is X:
Although A and A have the same definitions as above, they are compounds having a condensed ring. That is, R ⁴ and R ⁵ , R ⁵ and R ⁶ , R
^At least one combination of ⁶ and R ⁷ and R ⁷ and R ⁸ is linked to each other to form an aromatic ring or a cycloalkene ring together with the divalent hydrocarbon group of the naphthalene ring to which they are bonded. However, the rest was not performed in the formation of the inner ring of ^{R 4, R 5, R 6} , R 7 and R ^8, may represent a substituent. The aromatic ring is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. The aromatic ring is preferably formed by R ⁴ and R ^5, or R ⁵ and R ⁶ , and further R ⁵ and R ⁶
Is preferably formed by The cycloalkene ring is preferably a cyclohexene ring. The cycloalkene ring is preferably formed by R ⁶ and R ⁷ . The aromatic ring or cycloalkene ring may further have a substituent.

The nitrogen-containing heterocyclic compound represented by the general formula (1) is the general formula (3) produced by the present invention.
Since the known alkyl sulfonate derivative represented by is mainly used as an intermediate for a cyanine dye, the nitrogen-containing heterocyclic compound is selected according to the structure of the alkyl sulfonate derivative required as an intermediate. do it.

Preferred specific examples of the nitrogen-containing heterocyclic compound represented by the general formula (1) are compounds capable of synthesizing an alkylsulfonate derivative represented by the following general formula (3), for example, naphthyl. 2-methylnaphtho [1,2-d], which may have a substituent on the group.
Examples thereof include thiazole, 2-methylnaphtho [1,2-d] oxazole and 2-methylnaphtho [1,2-d] selenazole.

Aliphatic sultone which is another raw material of the present invention is a compound represented by the above general formula (2). In the general formula (2), Z is a linear alkylene group having no substituents and having 3 or 4 carbon atoms (for example, a propylene group,
Butylene group), and an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, butyl), 1 to 1 carbon atoms.
3 or 4 carbon atoms having a substituent selected from the group consisting of 3 alkoxy groups (eg methoxy, ethoxy, propoxy) and halogen atoms (eg fluorine, chlorine).
It is preferably a straight-chain alkylene group (for example, propylene group, butylene group).

Preferred specific examples of the aliphatic sultone are 1,3-propane sultone and 1-methyl-1,3.
-Propane sultone, 1,4-butane sultone, 2-methyl-1,4-butane sultone and the like can be mentioned.

The Lewis acid used in the present invention may be any known Lewis acid. The Lewis acid is a boron trifluoride ether complex, zinc chloride, zinc chloride, since the yield of the alkylsulfonate derivative is high and the post-treatment of the reaction mixture is easy.
Aluminum chloride, stannic chloride, ferric chloride and the like are preferable, and boron trifluoride ether complex is particularly preferable.

Typical examples of the alkyl sulfonate derivative represented by the above general formula (3) include the compounds shown below.

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

[0055]

[Chemical 25]

[0056]

[Chemical formula 26]

[0057]

[Chemical 27]

[0058]

[Chemical 28]

[0059]

[Chemical 29]

[0060]

[Chemical 30]

[0061]

[Chemical 31]

[0062]

[Chemical 32]

The method of the present invention can be carried out by heating the mixture of the above-mentioned nitrogen-containing heterocyclic compound, aliphatic sultone and Lewis acid to a predetermined reaction temperature to cause a reaction. The reaction operation method is not particularly limited,
A method is preferred in which a mixture of the above-mentioned nitrogen-containing heterocyclic compound and an aliphatic sultone is heated to a reaction temperature, and then a Lewis acid is added to this mixture with stirring, preferably gradually.

In the method of the present invention, the amount ratio of the nitrogen-containing heterocyclic compound to the aliphatic sultone is generally in the molar ratio of nitrogen-containing heterocyclic compound: aliphatic sultone = 1: 1 to 5, particularly 1: 1. A molar ratio of 5 to 2 is preferred. The amount of the Lewis acid used varies depending on the types of the nitrogen-containing heterocyclic compound, the aliphatic sultone and the Lewis acid, but is generally 1: 1 to 3 mol ratio, particularly 1: 1 to the nitrogen-containing heterocyclic compound. A molar ratio of 1.5 is preferred.

The reaction temperature is generally 120 to 250 ° C, preferably 160 to 190 ° C. If the reaction temperature is lower than the above range, the yield of the alkyl sulfonate derivative decreases, and if the reaction temperature is higher than the above range,
There is almost no further increase in the yield of the alkyl sulfonate derivative, the raw materials and products may be decomposed, and heat energy may be lost.

In the above reaction, it is not necessary to use another inert solvent. Of course, if necessary, an inert solvent that does not participate in the above reaction (for example, sulfolane) may be added. The reaction pressure is such that the reaction mixture can be maintained in a liquid state at the above reaction temperature. The above reaction generally depends on the reaction raw material, reaction temperature, etc.
Almost the highest yield is reached in 0 minutes to 3 hours.

In the above reaction, the aliphatic sultone may be hydrolyzed without reacting with the nitrogen-containing heterocyclic compound to produce an acid. In this case, in order to neutralize the acid, the reaction mixture is added with Basic substances that do not react with alkyl sulfonate derivatives (eg sodium acetate, 2,6
-Lutidine etc.) is preferably added.

After completion of the reaction, the alkyl sulfonate derivative is separated from the product mixture by a conventional method and purified as necessary to obtain the alkyl sulfonate derivative. As a method for separating and purifying the alkylsulfonate derivative,
It is possible to employ a method in which the reaction product mixture is poured into a poor solvent such as ethyl acetate, filtered after crystallization and recrystallized from an alcoholic solvent such as methanol, ethanol or propanol.

By the method of the present invention, an alkyl sulfonate derivative can be obtained in a yield of 40% or more (generally 50% or more) based on the nitrogen-containing heterocyclic compound.

[0070]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1] Synthesis of 2-methylnaphtho [1,2-d] thiazolium 3-butanesulfonate [compound of the above (C-1)]

In a round-bottomed flask equipped with a stirrer and a reflux condenser, 14 g (0.07 mol) of 2-methylnaphtho [1,2-d] thiazole and 1,4-butanesaltone 1 were added.
4 g (0.10 mol) was added, the flask was immersed in an oil bath, and the contents were heated to 160 ° C. While stirring the contents of the flask, add 14 m of boron trifluoride ether complex.
1 (0.11 mol) was gradually added (in about 10 minutes), and the contents of the flask were maintained at 160 ° C. to carry out the reaction for 1 hour.

After completion of the reaction, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
Drying at 1 ° C. for 1 hour gave 12.0 g (51% yield as the title compound) of white crystals.

The white crystals were confirmed to be the title compound by NMR and FAB mass spectra.

[NMR] δ: 2.15 (q, 2H) 2.40 (m, 2H) 2.95 (t, 2H) 3.30 (s, 3H) 5.70 (t, 2H) 7. 8 to 8.9 (m, 6H)

[FAB mass spectrum] m / e: 336

Comparative Example 1 The same procedure as in Example 1 was repeated except that the reaction temperature was 220 ° C. and the heating time was 6 hours without using the boron trifluoride ether complex.
-Methylnaphtho [1,2-d] thiazole and 1,4-
The butanesultone mixture was heated and worked up. However, the target compound, 2-methylnaphtho [1,2
Only trace amounts of -d] thiazolium 3-butane sulfonate were obtained.

Example 2 Synthesis of 2-methyl-6-methoxynaphtho [1,2-d] thiazolium 3-butanesulfonate [compound of (C-6) above]

A round bottom flask equipped with a stirrer and a reflux condenser was charged with 2-methyl-6-methoxynaphtho [1,2-
d] 16 g (0.07 mol) of thiazole and 14 g (0.10 mol) of 1,4-butane sultone were added, the flask was immersed in an oil bath and the contents were heated to 160 ° C. While stirring the flask contents, 14 ml (0.11 mol) of boron trifluoride ether complex was gradually added to the flask contents (taking about 10 minutes), and the flask contents were maintained at 160 ° C. for 1 hour. The reaction was carried out.

After the reaction was completed, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
After drying at ℃ for 1 hour, the title compound as white crystals 1
Obtained 4.2 g.

Example 3 2-Methylnaphtho [1,2-d] oxazolium 3-
Synthesis of butane sulfonate [compound of (C-13) above]

In a round-bottomed flask equipped with a stirrer and a reflux condenser, 12.8 g (0.07 mol) of 2-methylnaphtho [1,2-d] oxazole and 14 g (0.10 mol) of 1,4-butanesultone. The flask was placed in an oil bath and the contents were heated to 160 ° C. While stirring the flask contents, 14 ml (0.11 mol) of boron trifluoride ether complex was gradually added to the flask contents (taking about 10 minutes), and the flask contents were maintained at 160 ° C. for 1 hour. The reaction was carried out.

After completion of the reaction, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
After drying at ℃ for 1 hour, the title compound as white crystals 1
5.6 g (yield 70%) was obtained.

Example 4 2-Methylphenanthro [1,2-d] thiazolium
3-Butane sulfonate [Compound of the above (C-21)]
Synthesis of

In a round-bottomed flask equipped with a stirrer and a reflux condenser, 17.4 g (0.07 mol) of 2-methylphenanthro [1,2-d] thiazole and 14 g (0. 10 mol), the flask was immersed in an oil bath and the contents were heated to 160 ° C. While stirring the flask contents, 14 ml (0.11 mol) of boron trifluoride ether complex was gradually added to the flask contents (in about 10 minutes), and the flask contents were maintained at 160 ° C.
A time reaction was performed.

After completion of the reaction, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
After drying at ℃ for 1 hour, the title compound as white crystals 1
8.2 g (yield 70%) was obtained.

Example 5 2-Methyl-5-phenoxynaphtho [1,2-d] thiazolium 3-butanesulfonate [(C-23) above]
Of compounds]

A 2-methyl-5-phenoxynaphtho [1,2] was added to a round bottom flask equipped with a stirrer and a reflux condenser.
-D] thiazole 20.4 g (0.07 mol) and 1,
14 g (0.10 mol) of 4-butane sultone was added and the flask was immersed in an oil bath to heat the contents to 160 ° C. While stirring the contents of the flask, 28 ml (0.22 mol) of boron trifluoride ether complex was gradually added (taking about 10 minutes) to the contents of the flask to make 160
The reaction was carried out for 1 hour while maintaining the temperature at ℃.

After the reaction was completed, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
After drying at ℃ for 1 hour, the title compound as white crystals 1
5.0 g (yield 50%) was obtained.

[Example 6] Synthesis of 2-methyl-6-sulfonaphtho [1,2-d] thiazolium 3-butanesulfonate [compound of (C-26) above]

In a round bottom flask equipped with a stirrer and reflux condenser, 2-methyl-6-sulfonaphtho [1,2-
d] 21.1 g (0.07 mol) of thiazole and 1,4
14 g (0.10 mol) of butane sultone were placed, the flask was immersed in an oil bath and the contents were heated to 160 ° C.
While stirring the contents of the flask, gradually add 14 ml (0.11 mol) of a boron trifluoride ether complex (about 1 mol).
The reaction was carried out for 1 hour, maintaining the flask contents at 160 ° C.

After the reaction was completed, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
After drying at ℃ for 1 hour, the title compound as white crystals 1
9.3 g (yield 63%) was obtained.

Example 7 2-Methylnaphtho [1,2-d] selenazolium 3-
Synthesis of butane sulfonate [compound of (C-15) above]

In a round-bottomed flask equipped with a stirrer and a reflux condenser, 17.2 g (0.07 mol) of 2-methylnaphtho [1,2-d] selenazole and 14 g (0.10 mol) of 1,4-butane sultone. The flask was placed in an oil bath and the contents were heated to 160 ° C. While stirring the flask contents, 14 ml (0.11 mol) of boron trifluoride ether complex was gradually added to the flask contents (taking about 10 minutes), and the flask contents were maintained at 160 ° C. for 1 hour. The reaction was carried out.

After completion of the reaction, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
After drying at ℃ for 1 hour, the title compound as white crystals 1
4.7 g (yield 55%) was obtained.

Example 8 Synthesis of 1,2-dimethylnaphtho [1,2-d] imidazolium 3-butanesulfonate [compound of (C-37) above]

In a round bottom flask equipped with a stirrer and a reflux condenser, 13.7 g (0.07 mol) of 1,2-dimethylnaphtho [1,2-d] imidazole and 14 g (0. 10 mol), the flask was immersed in an oil bath and the contents were heated to 160 ° C. While stirring the contents of the flask, 28 ml (0.22 mol) of boron trifluoride ether complex was gradually added (taking about 10 minutes) thereto, and the contents of the flask were maintained at 160 ° C. for 1 hour. The reaction was carried out.

After the completion of the reaction, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
After drying at 0 ° C. for 1 hour, the title compound was obtained as white crystals.
73 g (yield 42%) was obtained.

Example 9 2-Methylanthro [1,2-d] thiazolium 3-
Synthesis of butane sulfonate [compound of (C-58) above]

In a round-bottomed flask equipped with a stirrer and a reflux condenser, 17.4 g (0.07 mol) of 2-methylanthro [1,2-d] thiazole and 14 g (0.10 mol) of 1,4-butanesaltone were added. The flask was placed in an oil bath and the contents were heated to 160 ° C. While stirring the flask contents, 14 ml (0.11 mol) of boron trifluoride ether complex was gradually added to the flask contents (taking about 10 minutes), and the flask contents were maintained at 160 ° C. for 1 hour. The reaction was carried out.

After completion of the reaction, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
After drying at ℃ for 1 hour, the title compound as white crystals 1
5.6 g (60% yield) was obtained.

Example 10 2-Methylthionaphtho [1,2-d] thiazolium 3
-Synthesis of butane sulfonate [compound of (C-60) above]

In a round-bottomed flask equipped with a stirrer and a reflux condenser, 16.2 g (0.07 mol) of 2-methylthionaphtho [1,2-d] thiazole and 14 g (0.10 mol of 1,4-butanesaltone) were added. ) Was put, the flask was immersed in an oil bath, and the contents were heated to 160 ° C. While stirring the flask contents, 14 ml (0.11 mol) of boron trifluoride ether complex was gradually added to the flask contents (taking about 10 minutes), and the flask contents were maintained at 160 ° C. for 1 hour. The reaction was carried out.

After the reaction was completed, the reaction product mixture was cooled to room temperature, and 280 ml of ethyl acetate was added to the flask and stirred to precipitate white crystals. The crystals are filtered off and
After drying at ℃ for 1 hour, the title compound as white crystals 1
0.8 g (yield 58%) was obtained.

Comparative Example 2 The same procedure as in Example 3 was repeated except that the reaction temperature was 220 ° C. and the heating time was 6 hours without using the boron trifluoride ether complex.
-Methylnaphtho [1,2-d] oxazole and 1,4
-The butanesultone mixture was heated and worked up. However, the target compound, 2-methylnaphtho [1,2
-D] Oxazolium 3-butane sulfonate is 3.
Only 3 g (15% yield) was obtained.

[0106]

The method for producing an alkylsulfonate derivative of the present invention comprises preparing an alkylsulfonate derivative represented by the general formula (3) from a nitrogen-containing heterocyclic compound represented by the general formula (1) and an aliphatic sultone. In addition, it has a remarkably excellent effect that it can be manufactured in a high yield.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 293/12 471/10 101 7019-4C 491/107 7019-4C

Claims (3)

[Claims] 1. The following general formula (1): [In formula, X is -O-, -S-, -NR < ¹ >-, -Se.
—, —Te— or —CR ² R ³ — (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or a lower alkyl group optionally having a substituent, and R ² and R ^{2 3} may combine to form a ring), A is a hydrogen atom, a mercapto group, an arylthio group, an aralkyl group, a sulfo group, a halogen atom, an alkyl group which may have a substituent, a substituent An alkylthio group which may have, an alkoxy group which may have a substituent, an alkylsulfonyloxy group which may have a substituent or an arylsulfonyloxy group which may have a substituent And R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are
Represents a hydrogen atom or a substituent. ] A nitrogen-containing heterocyclic compound represented by the following general formula (2): [Wherein Z represents an alkylene group which may have a substituent] is reacted with an aliphatic sultone in the presence of a Lewis acid to give the following general formula (3): ] [In the formula, A, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X and Z
Is as described above], and a method for producing an alkylsulfonate derivative, which comprises producing an alkylsulfonate derivative represented by 2. R ⁴ , R ⁵ and R in the above general formula (1)
^At least one of ⁶ , R ⁷ and R ⁸ is an alkyl group, an aryl group, an alkoxy group which may have a substituent, an aryloxy group, an alkylthio group, a halogen atom, a cyano group, a carboxyl group, a sulfo group or a sulfone. The method for producing an alkylsulfonate derivative according to claim 1, which represents an acid group. 3. The following general formula (4): [In formula, X is -O-, -S-, -NR < ¹ >-, -Se.
—, —Te— or —CR ² R ³ — (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or a lower alkyl group optionally having a substituent, and R ² and R ^{2 3} may combine to form a ring), A is a hydrogen atom, a mercapto group, an arylthio group, an aralkyl group, a sulfo group, a halogen atom, an alkyl group which may have a substituent, a substituent An alkylthio group which may have, an alkoxy group which may have a substituent, an alkylsulfonyloxy group which may have a substituent or an arylsulfonyloxy group which may have a substituent Wherein at least one combination of R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ^7, and R ⁷ and R ⁸ is linked to each other and is a divalent hydrocarbon group of a naphthalene ring. With aromatic ring or cycloalkene A ring, and one of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ which has not been subjected to ring formation may represent a substituent. ] A nitrogen-containing heterocyclic compound represented by the following general formula (2): [Wherein Z represents an alkylene group which may have a substituent] is reacted with an aliphatic sultone in the presence of a Lewis acid to give the following general formula (5): ] [In the formula, A, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X and Z
Is as described above], and a method for producing an alkylsulfonate derivative, which comprises producing an alkylsulfonate derivative represented by