JP3266358B2 - Method for producing alkylsulfonate derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing an alkylsulfonate derivative.

[0002]

2. Description of the Related Art Conventionally, as a sensitizing dye 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. Compounds in which a sulfoalkyl group is bonded to a quaternary nitrogen atom of a nitrogen-containing heterocyclic ring constituting a mother nucleus of a cyanine dye are 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]

Embedded image

[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, and R ² and R ³ may combine to form a ring); 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 the alkylsulfonate derivative represented by
No. 5339).

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

[0007]

Embedded image

[Wherein A, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R
⁸ and X are as defined above], and a linear alkyl sulfonate activated by a halogen atom, a sulfonyloxy group, or the like, to react with the nitrogen-containing heterocyclic compound. A method in which a sulfoalkyl group is bonded to the nitrogen atom of the above.

This activated chain alkyl sulfonate has a high nucleophilicity of the compound to be sulfoalkylated,
If the sulfoalkylation reaction proceeds under relatively mild conditions, it is an advantageous sulfoalkylating reagent in terms of structural flexibility. However, when a nitrogen atom is quaternized by reacting the activated linear alkyl sulfonate with the nitrogen-containing heterocyclic compound represented by the general formula (1), the activated linear alkyl There is a problem that the side reaction in which the active site of the sulfonate is thermally eliminated is increased, and the intended alkylsulfonate compound cannot be obtained.

An aliphatic sultone is known as a sulfoalkylating reagent for a compound having active hydrogen (JP-A-1-187543). It is said that the aliphatic sultone reacts with the amine compound without a catalyst to introduce a sulfone group, and binds the aliphatic sultone to the nitrogen atom of the nitrogen-containing heterocyclic compound represented by the general formula (1). If possible, there should be few side reactions that occur when using structurally activated linear alkyl sulfonates. However, when the aliphatic sultone is allowed to act on 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 rates were very low. The reason is that an aliphatic sultone molecule is formed due to steric hindrance caused by a hydrogen atom or other substituent bonded to the 8-position carbon atom of the naphthalene nucleus of the nitrogen-containing heterocyclic compound represented by the general formula (1). Is considered to be prevented from approaching the nitrogen atom of the nitrogen-containing heterocyclic compound.

[0011]

SUMMARY OF THE INVENTION 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 salt. provide.

[0012]

According to the present invention, there is provided the following 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, and R ² and R ³ may combine to form a ring); Has 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, an alkylthio group which may have a substituent, Or an optionally substituted alkylsulfonyloxy group or an optionally substituted arylsulfonyloxy group, and R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ Has a hydrogen atom , an alkyl group, an aryl group,
Good alkoxy, aryloxy, haloalkyl
Group, alkylthio group, halogen atom, cyano group, carbo
Represents a xyl group, a sulfo group or a sulfonic acid group . And a nitrogen-containing heterocyclic compound represented by the following general formula (2):

[0014]

Embedded image Wherein Z represents an alkylene group which may have a substituent, and an aliphatic sultone represented by the following general formula (3):

[0015]

Embedded image Wherein 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 represented by the formula:

The preferred embodiments of the present invention are as follows.

(1) R ⁴ , R ⁵ ,
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,
Aryloxy group, haloalkyl group, alkylthio group,
The method for producing the above alkylsulfonate derivative, which represents 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 by an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 14 carbon atoms, or a sulfonate group. An alkoxy group having 1 to 25 carbon atoms, which may be
Aryloxy group, haloalkyl having 1 to 3 carbon atoms
A method for producing the above alkylsulfonate derivative, which represents a 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-
Or -CR ² R ³ - and is the production method of the alkyl sulfonate derivatives of the above.

(4) The 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) The method for producing an alkylsulfonate derivative as described above, wherein Z is a straight-chain alkylene group having 3 or 4 carbon atoms which has 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 alkylsulfonate derivative as described above, wherein the Lewis acid is a boron trifluoride etherate complex.

Further, the present invention provides a compound of the general formula (1): wherein 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 optionally substituted lower alkyl group, R ² and R ³ may be linked to form a ring), A is a hydrogen atom,
Mercapto group, arylthio group, aralkyl group, sulfo group, halogen atom, alkyl group which may have a substituent, alkylthio group which may have a substituent, alkoxy group which may have a substituent represents an optionally having an alkyl sulfonyloxy group or a substituent substituted aryl sulfonyloxy group, R ⁴
And R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ^7, and R ⁷ and R ⁸ are linked to each other to form an aromatic ring together with a divalent hydrocarbon group of a naphthalene ring bonded to each other. Or R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ which have not formed a ring are a hydrogen atom, an alkyl group, an aryl
Group, alkoxy group which may have a substituent, aryl
Oxy, haloalkyl, alkylthio, halogen
Atom, cyano group, carboxyl group, sulfo group or sulfo
Represents an acid group . A nitrogen-containing heterocyclic compound represented by the general formula (2): wherein Z represents an alkylene group which may have a substituent; there is reacted under the above general formula (3): ^{wherein, a, R 4, R 5} , R 6, R 7, R 8, X and Z
Is as described above.] There is also a method for producing an alkylsulfonate derivative characterized by producing an alkylsulfonate derivative represented by the following formula:

The preferred embodiments of the present invention 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 is linked to each other to form a benzene ring or a cyclohexene ring together with a divalent hydrocarbon group of a naphthalene ring to which each is bonded. A method for producing an alkylsulfonate derivative.

(2) X is -O-, -S-, -NR ^1-
Or -CR ² R ³ - and is the production method of the alkyl sulfonate derivatives of the above.

(3) The 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 method for producing an alkylsulfonate derivative as described above, wherein Z is a straight-chain alkylene group having 3 or 4 carbon atoms which has 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 alkylsulfonate derivative as described above, wherein the Lewis acid is a boron trifluoride etherate complex.

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

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. The alkylthio group is a sulfonic acid group and has 1 to 1 carbon atoms.
It may be substituted with 6 alkoxy groups or an alkoxyalkoxyalkoxy group having 1 to 6 carbon atoms. A is
A hydrogen atom, an alkylthio group having 1 to 4 carbon atoms, a benzyl group, an alkylthio group having 1 to 4 carbon atoms, a phenylthio group or an alkyl group having 1 to 5 carbon atoms having the above substituent (for example, methyl, ethyl Preferably
And particularly preferably a hydrogen atom or methyl.

In addition, 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 optionally substituted alkoxy group, 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 further has an alkyl group having 1 to 3 carbon atoms. ,
An aryl group having 6 to 14 carbon atoms (eg, phenyl, naphthyl, anthranyl), an alkoxy group having 1 to 25 carbon atoms which may be substituted with a sulfonate group, an aryloxy group (eg, phenoxy), a carbon atom number It is preferable to represent 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, in the compound of the present invention represented by the above general formula (1), a compound of another embodiment different from the above compound is represented by X
And A have the same definition as above, but are compounds having a condensed ring. That is, R ⁴ and R ⁵ , R ⁵ and R ⁶ , R
^At least one combination of R ⁶ and R ⁷ and R ⁷ and R ⁸ are linked to each other to form an aromatic ring or a cycloalkene ring together with a divalent hydrocarbon group of a naphthalene ring to which they are bonded. However, the remainder of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ which did not form an inner ring is a hydrogen atom,
An alkyl group, an aryl group, an optionally substituted
Alkoxy group, aryloxy group, haloalkyl group,
Kirthio group, halogen atom, cyano group, carboxyl
Group, sulfo group or sulfonic acid group . As the aromatic ring, a benzene ring and a naphthalene ring are preferable, and a benzene ring is more preferable. Further, the aromatic ring is represented by R ⁴
And R ⁵ or R ⁵ and R ^{6, and} more preferably R ⁵ and R ⁶ . The cycloalkene ring is preferably a cyclohexene ring. Further, the cycloalkene ring is represented by R ⁶ and R
Preferably, it is formed by ⁷ . The aromatic ring or cycloalkene ring may further have a substituent.

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

Preferred specific examples of the nitrogen-containing heterocyclic compound represented by the above 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 in the group
Thiazole, 2-methylnaphtho [1,2-d] oxazole, 2-methylnaphtho [1,2-d] selenazole and the like can be mentioned.

The aliphatic sultone as 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 straight-chain alkylene group having 3 or 4 carbon atoms which has no substituent (for example, propylene group,
Butylene group), and an alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, propyl, butyl),
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).
Is preferably a linear alkylene group (for example, a propylene group and a butylene group).

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

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

Representative compounds of the alkylsulfonate derivative represented by the above general formula (3) include the following compounds.

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

The method of the present invention can be carried out by heating a 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 aliphatic sultone is heated to a reaction temperature, and then a Lewis acid is added to the mixture with stirring, preferably gradually.

In the method of the present invention, the ratio of the nitrogen-containing heterocyclic compound to the aliphatic saltone used is generally a molar ratio of nitrogen-containing heterocyclic compound: aliphatic saltone = 1: 1 to 5, particularly 1: 1. The molar ratio is preferably 5 to 2. The amount of the Lewis acid used depends on the types of the nitrogen-containing heterocyclic compound, aliphatic sultone and Lewis acid, but is generally in a molar ratio of 1: 1 to 3 with respect to the nitrogen-containing heterocyclic compound, especially 1: 1 to 1: 1. Preferably, the molar ratio is 1.5.

The reaction temperature is generally from 120 to 250 ° C., preferably from 160 to 190 ° C. When the reaction temperature is lower than the above range, the yield of the alkylsulfonate derivative decreases, and when the reaction temperature is higher than the above range,
The yield of the alkylsulfonate derivative is hardly further increased, and the raw materials and products may be decomposed, resulting in a loss of heat energy.

In the above reaction, it is not necessary to use another inert solvent. Of course, if necessary, an inert solvent (eg, sulfolane) that does not participate in the above reaction may be added. The reaction pressure is such that the reaction mixture can be kept liquid at the above reaction temperature. The above reaction varies depending on the reaction raw material, reaction temperature, and the like.
Nearly 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 contains Basic substances that do not react with the alkylsulfonate derivative (for example, sodium acetate, 2,6
-Lutidine).

After completion of the reaction, the alkylsulfonate derivative is separated from the product mixture by a conventional method, and if necessary, purified to obtain the alkylsulfonate derivative. As a method for separating and purifying the alkylsulfonate derivative,
A method in which the reaction product mixture is poured into a poor solvent, for example, ethyl acetate, filtered after crystallization, and recrystallized from an alcoholic solvent, for example, methanol, ethanol, propanol, or the like, can be employed.

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

[0070]

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 (C-1)]

A round bottom flask equipped with a stirrer and a reflux condenser was charged with 14 g (0.07 mol) of 2-methylnaphtho [1,2-d] thiazole and 1,4-butanesultone 1
4 g (0.10 mol) was charged, the flask was immersed in an oil bath, and the content was heated to 160 ° C. While stirring the contents of the flask, add 14 m of boron trifluoride etherate
1 (0.11 mol) was added slowly (taking about 10 minutes), and the reaction was carried out for 1 hour while maintaining the contents of the flask at 160 ° C.

After the completion of the reaction, the reaction product mixture was cooled to room temperature, 280 ml of ethyl acetate was added to the flask, and the mixture was stirred, whereby white crystals were precipitated. The crystals are filtered off and 50
Drying at 1 ° C. for 1 hour gave 12.0 g (yield 51% as the title compound) of white crystals.

This white crystal was confirmed to be the title compound by NMR and FAB mass spectrum.

[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 procedure of Example 1 was repeated, except that the reaction temperature was set to 220 ° C. and the heating time was set to 6 hours without using the boron trifluoride etherate.
-Methylnaphtho [1,2-d] thiazole and 1,4-
The mixture of butanesultone was heated and worked up. However, the target compound, 2-methylnaphtho [1,2
-D] Only trace amounts of thiazolium 3-butanesulfonate were obtained.

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

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

After completion of the reaction, the reaction product mixture was cooled to room temperature, 280 ml of ethyl acetate was added to the flask, and the mixture was stirred, whereby white crystals were precipitated. The crystals are filtered off and 50
After drying at ℃ for 1 hour, the title compound was obtained as white crystals.
4.2 g were obtained.

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

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

After the completion of the reaction, the reaction product mixture was cooled to room temperature, 280 ml of ethyl acetate was added to the flask, and the mixture was stirred, whereby white crystals were precipitated. The crystals are filtered off and 50
After drying at ℃ for 1 hour, the title compound was obtained as white crystals.
5.6 g (70% yield) was obtained.

Example 4 2-Methylphenanthro [1,2-d] thiazolium
3-butanesulfonate [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 of 1,4-butanesultone (0.1 g) were added. 10 mol), the flask was immersed in an oil bath, and the content was heated to 160 ° C. While stirring the contents of the flask, 14 ml (0.11 mol) of boron trifluoride etherate was gradually added thereto (in about 10 minutes), and the contents of the flask were maintained at 160 ° C. for 1 hour.
A time reaction was performed.

After the completion of the reaction, the reaction product mixture was cooled to room temperature, 280 ml of ethyl acetate was added to the flask, and the mixture was stirred, whereby white crystals were deposited. The crystals are filtered off and 50
After drying at ℃ for 1 hour, the title compound was obtained as white crystals.
8.2 g (yield 70%) was obtained.

Example 5 2-Methyl-5-phenoxynaphtho [1,2-d] thiazolium 3-butanesulfonate [(C-23)
Of the compound of

In a round bottom flask equipped with a stirrer and a reflux condenser, 2-methyl-5-phenoxynaphtho [1,2
-D] thiazole 20.4 g (0.07 mol) and 1,1
14 g (0.10 mol) of 4-butanesultone was charged, the flask was immersed in an oil bath, and the content was heated to 160 ° C. While stirring the contents of the flask, 28 ml (0.22 mol) of boron trifluoride etherate was gradually added thereto (in about 10 minutes), and the contents of the flask were added to 160 ml.
The reaction was carried out for 1 hour while maintaining the temperature.

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

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

In a round bottom flask equipped with a stirrer and a reflux condenser, 2-methyl-6-sulfonaphtho [1,2-
d] thiazole 21.1 g (0.07 mol) and 1,4
14 g (0.10 mol) of butane sultone was charged, the flask was immersed in an oil bath and the contents were heated to 160 ° C.
While stirring the contents of the flask, 14 ml (0.11 mol) of boron trifluoride etherate was gradually added thereto (about 1 ml).
(Required 0 minutes) and the reaction was carried out for 1 hour while maintaining the contents of the flask at 160 ° C.

After completion of the reaction, the reaction product mixture was cooled to room temperature, 280 ml of ethyl acetate was added to the flask, and the mixture was stirred, whereby white crystals were precipitated. The crystals are filtered off and 50
After drying at ℃ for 1 hour, the title compound was obtained as white crystals.
9.3 g (63% yield) were obtained.

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

A round bottom flask equipped with a stirrer and a reflux condenser was charged with 17.2 g (0.07 mol) of 2-methylnaphtho [1,2-d] selenazole and 14 g (0.10 mol) of 1,4-butanesultone. , And the flask was immersed in an oil bath and the contents were heated to 160 ° C. While stirring the contents of the flask, 14 ml (0.11 mol) of boron trifluoride etherate was gradually added thereto (taking about 10 minutes), and the contents of the flask were maintained at 160 ° C. for 1 hour. The reaction was performed.

After the completion of the reaction, the reaction product mixture was cooled to room temperature, 280 ml of ethyl acetate was added to the flask, and the mixture was stirred, whereby white crystals were precipitated. The crystals are filtered off and 50
After drying at ℃ for 1 hour, the title compound was obtained as white crystals.
4.7 g (55% yield) were obtained.

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

A round bottom flask equipped with a stirrer and a reflux condenser was charged with 13.7 g (0.07 mol) of 1,2-dimethylnaphtho [1,2-d] imidazole and 14 g of 1,4-butanesultone (0.1 g). 10 mol), the flask was immersed in an oil bath, and the content was heated to 160 ° C. While stirring the contents of the flask, 28 ml (0.22 mol) of boron trifluoride etherate was gradually added thereto (taking about 10 minutes), and the contents of the flask were maintained at 160 ° C. for 1 hour. The reaction was performed.

After the completion of the reaction, the reaction product mixture was cooled to room temperature, 280 ml of ethyl acetate was added to the flask, and the mixture was stirred, whereby white crystals were precipitated. The crystals are filtered off and 50
8. Dry at ℃ for 1 hour to give the title compound as white crystals.
73 g (yield 42%) was obtained.

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

A round bottom flask equipped with a stirrer and a reflux condenser was charged with 17.4 g (0.07 mol) of 2-methylanthro [1,2-d] thiazole and 14 g (0.10 mol) of 1,4-butanesultone. , And the flask was immersed in an oil bath and the contents were heated to 160 ° C. While stirring the contents of the flask, 14 ml (0.11 mol) of boron trifluoride etherate was gradually added thereto (taking about 10 minutes), and the contents of the flask were maintained at 160 ° C. for 1 hour. The reaction was performed.

After completion of the reaction, the reaction product mixture was cooled to room temperature, 280 ml of ethyl acetate was added to the flask, and the mixture was stirred, whereby white crystals were precipitated. The crystals are filtered off and 50
After drying at ℃ for 1 hour, the title compound was obtained as white crystals.
5.6 g (60% yield) was obtained.

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

A round bottom flask equipped with a stirrer and a reflux condenser was charged with 16.2 g (0.07 mol) of 2-methylthionaphtho [1,2-d] thiazole and 14 g (0.10 mol) of 1,4-butanesultone. ) Was added, the flask was immersed in an oil bath, and the content was heated to 160 ° C. While stirring the contents of the flask, 14 ml (0.11 mol) of boron trifluoride etherate was gradually added thereto (taking about 10 minutes), and the contents of the flask were maintained at 160 ° C. for 1 hour. The reaction was performed.

After the completion of the reaction, the reaction product mixture was cooled to room temperature, 280 ml of ethyl acetate was added to the flask, and the mixture was stirred, whereby white crystals were precipitated. The crystals are filtered off and 50
After drying at ℃ for 1 hour, the title compound was obtained as white crystals.
0.8 g (58% yield) was obtained.

Comparative Example 2 The procedure of Example 3 was repeated, except that the reaction temperature was set to 220 ° C. and the heating time was set to 6 hours without using the boron trifluoride etherate complex.
-Methylnaphtho [1,2-d] oxazole and 1,4
-Heating of the mixture of butanesultone and post-treatment. However, the target compound, 2-methylnaphtho [1,2
-D] oxazolium 3-butanesulfonate is 3.
Only 3 g (yield 15%) was obtained.

[0106]

The process for producing an alkylsulfonate derivative of the present invention comprises the steps of converting 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. And a remarkably excellent effect that it can be produced in a high yield.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07D 293/12 C07D 293/12 471/10 471/10 491/107 491/107 (58) Investigated field (Int.Cl. ⁷ , DB name) C07D 277/84 C07D 209/60 C07D 235/02 C07D 263/60 C07D 293/10 C07D 293/12 C07D 471/10 C07D 491/107 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. The following general formula (1): [Wherein 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 optionally substituted lower alkyl group, R ² and R ³ represents and may form a ring) connecting, 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, An alkylthio group which may have a substituent, 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 represent
Having a hydrogen atom , an alkyl group, an aryl group,
Alkoxy, aryloxy, haloalkyl
Group, alkylthio group, halogen atom, cyano group,
It represents a boxyl group, a sulfo group or a sulfonic acid group . And a nitrogen-containing heterocyclic compound represented by the following general formula (2): [Wherein Z represents an alkylene group which may have a substituent] with an aliphatic sultone represented by the following formula (3): ] Wherein A, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X and Z
Method for producing an alkyl sulfonate derivative which is characterized in Rukoto to produce an alkyl sulfonate derivative represented by are as defined above]. 2. R ⁴ , R ⁵ , R in the above general formula (1)
⁶ , at least one of R ⁷ and R ⁸ is an alkyl group, an aryl group, an optionally substituted alkoxy group, an aryloxy group, a haloalkyl group, an alkylthio group, a halogen atom, a cyano group, a carboxyl group, a sulfo group, The method for producing an alkylsulfonate derivative according to claim 1, which represents a sulfonic acid group or a sulfonic acid group. 3. The following general formula (1) : [Wherein 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 optionally substituted lower alkyl group, R ² and R ³ represents and may form a ring) connecting, 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, An alkylthio group which may have a substituent, 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. A combination of at least one of R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ^7, and R ⁷ and R ⁸ is connected to each other and bonded to each other to form a divalent hydrocarbon group of a naphthalene ring. Together with an aromatic ring or cycloalkene R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ , which form a ring and do not form a ring, include a hydrogen atom, an alkyl group, an aryl
Group, alkoxy group which may have a substituent, aryl
Loxy, haloalkyl, alkylthio, halogen
Atom, cyano group, carboxyl group, sulfo group or sulfo group
Represents a phonic acid group . And a nitrogen-containing heterocyclic compound represented by the following general formula (2): [In the formula, Z represents an alkylene group which may have a substituent] with an aliphatic sultone represented by the following formula (3) : ] Wherein A, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , X and Z
Method for producing an alkyl sulfonate derivative which is characterized in Rukoto to produce an alkyl sulfonate derivative represented by are as defined above].