JP2009096767A - Method for producing sulfonyl halide derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method by which an alicyclic sulfonyl halide derivative can industrially advantageously be produced in good yield. <P>SOLUTION: The method for producing the sulfonyl halide derivative comprises reacting a diene compound represented by general formula (I) with a 2-haloethanesulfonyl halide in the presence of a base. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to the following general formula (III)

(Wherein R ¹ and R ⁴ each independently represents a hydrogen atom, an alkyl group or an alkoxy group, or an alkylene group which may contain an oxygen atom or a sulfur atom at any position by bonding to each other, —O -Or -S-, R ² and R ³ each independently represent a hydrogen atom, an alkyl group or an alkoxy group, and X ² represents a fluorine atom, a chlorine atom or a bromine atom. The present invention relates to a method for producing a sulfonyl halide derivative (hereinafter referred to as sulfonyl halide derivative (III)). The sulfonyl halide derivative (III) obtained by the present invention is useful as a raw material for paints, functional polymers, pharmaceuticals, agricultural chemicals and other fine chemicals.

  Conventionally, as a method for producing a sulfonyl halide derivative (III), a base is allowed to act on 2-haloethanesulfonyl halide to obtain a vinylsulfonyl halide as an intermediate (Patent Document 1, Non-Patent Documents 1, 2, and 3). A method of reacting the vinylsulfonyl halide and diene compound with Diels-Alder (see Patent Documents 2 and 3 and Non-Patent Document 4) is known.

JP 2006-515601 A U.S. Pat. No. 3,136,787 Special table 2003-525311 gazette Journal of the American Chemical Society, 1954, Vol. 76, pp. 1926 to 1929 (Journal of the American Chemical Society) Chemistry of Materials, 2003, Vol. 15, pp. 1512-1517. The Journal of Organic Chemistry, 1979, Vol. 44, No. 22, pp. 3847-3858, The Journal of Organic Chemistry. Journal of the American Chemical Society, 1951, 73, 3258-3260

  However, the yield obtained by the above method is not always satisfactory, and the yield is low particularly when a cyclic diene compound such as cyclopentadiene is used as the diene compound. In addition, among the above methods, when vinylsulfonyl chloride is used as an intermediate, it requires a very low temperature of −50 to −60 ° C. in the production method of vinylsulfonyl chloride, which is disadvantageous for industrial production. Since the vinyl sulfonyl chloride is easily self-polymerized, the stability during storage or in the reaction system is poor, which causes a decrease in the yield of the sulfonyl halide derivative (III). Therefore, none of these methods can be said to be a method capable of industrially advantageously producing the sulfonyl halide derivative (III).

  Therefore, an object of the present invention is to provide a method by which the sulfonyl halide derivative (III) can be produced industrially advantageously in good yield.

  As a result of intensive studies to solve the problems of the background art described above, the present inventors have made a self-polymerization by reacting 2-haloethanesulfonyl halide with a diene compound in the presence of a base. It has been found that the sulfonyl halide derivative (III) can be produced in a high yield under mild conditions that do not require cryogenic temperatures, because easy vinylsulfonyl halide is quickly consumed in the intended reaction and self-polymerization is suppressed.

  According to the present invention, the object is as follows:

(Wherein R ¹ , R ² , R ³ , and R ⁴ are as defined above) and a diene compound (hereinafter referred to as diene compound (I)), and the following general formula (II)

(Wherein, X ² is as defined above. X ¹ represents a fluorine atom, a chlorine atom, or a bromine atom) (hereinafter referred to as 2-haloethanesulfonyl halide (II). Is achieved by providing a method for producing a sulfonyl halide derivative (III) by reacting in the presence of a base.

  According to the present invention, a sulfonyl halide derivative (III) that is useful as a raw material for paints and functional polymers, a raw material for pharmaceuticals, agricultural chemicals, and other fine chemicals is produced in good yield and industrially advantageously. Can do.

The alkyl group represented by R ¹ and R ⁴ may be any of a linear, branched, or cyclic alkyl group, and may have a substituent. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the substituent include lower alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. An alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group or a tert-butoxy group; an acyloxy group such as an acetyloxy group or a propionyloxy group;
The alkoxy group represented by R ¹ and R ⁴ may be any of a linear, branched, or cyclic alkoxy group, and may have a substituent. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a cyclopentyl group, and a cyclohexyl group. Examples of the substituent include lower alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. An alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group or a tert-butoxy group; an acyloxy group such as an acetyloxy group or a propionyloxy group;
In addition, the alkylene group that may contain an oxygen atom or a sulfur atom at any position represented by a combination of R ¹ and R ⁴ may be any of a linear, branched, or cyclic alkylene group. It may have a group. For example, —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, —C (CH _{3) 2 -, - CH 2} -O-CH 2 -, - CH 2 -O- (CH 2) 2 -, - CH 2 -O- (CH 2) 3 -, - CH 2 -O- (CH 2 ) ₄ −, —CH ₂ —O— (CH ₂ ) ₅ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₃ —, — _{(CH 2) 2 -O- (CH} 2) 4 -, - (CH 2) 3 -O- (CH 2) 3 -, - CH 2 -S-CH 2 -, - CH 2 -S- (CH 2 _{) 2 -, - CH 2 -S-} (CH 2) 3 -, - CH 2 -S- (CH 2) 4 -, - CH 2 -S- (CH 2) 5 -, - (CH 2) 2 - S- (CH _{) 2 -, - (CH 2} ) 2 -S- (CH 2) 3 -, - (CH 2) 2 -S- (CH 2) 4 -, - (CH 2) 3 -S- (CH 2) 3 -, Cyclohexane-1,2-diyl group, cyclopentane-1,2-diyl group, cyclopentane-1,3-diyl group and the like. Examples of the substituent include lower alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. An alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group or a tert-butoxy group; an acyloxy group such as an acetyloxy group or a propionyloxy group;

The alkyl group represented by R ² and R ³ may be any of a linear, branched, or cyclic alkyl group, and may have a substituent. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the substituent include lower alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. An alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group or a tert-butoxy group; an acyloxy group such as an acetyloxy group or a propionyloxy group;
The alkoxy group represented by R ² and R ³ may be any of a linear, branched, or cyclic alkoxy group, and may have a substituent. Examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a cyclopentyl group, and a cyclohexyl group. Examples of the substituent include lower alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. An alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group or a tert-butoxy group; an acyloxy group such as an acetyloxy group or a propionyloxy group;

  Specific examples of the diene compound (I) include, for example, 1,3-butadiene, isoprene, 2,4-hexadiene, cyclopentadiene, 2-acetyloxycyclopentadiene, 1,3-cyclohexadiene, 1-methoxy-1, Examples include 3-butadiene, 1-methoxy-1,3-cyclohexadiene, furan, and thiophene.

  Specifically, 2-haloethanesulfonyl halide (II) is 2-fluoroethanesulfonyl fluoride, 2-fluoroethanesulfonyl chloride, 2-fluoroethanesulfonyl bromide, 2-chloroethanesulfonyl fluoride, 2-chloroethanesulfonyl chloride, 2-chloroethanesulfonyl bromide, 2-bromoethanesulfonyl fluoride, 2-bromoethanesulfonyl chloride, and 2-bromoethanesulfonyl bromide. Among these, 2-chloroethanesulfonyl fluoride, 2-chloroethanesulfonyl bromide, Chloroethanesulfonyl chloride and 2-chloroethanesulfonyl bromide are preferred.

  The amount of the diene compound (I) used in the present invention is preferably in the range of 0.8 mol to 50 mol, and in the range of 0.9 mol to 20 mol, relative to 1 mol of 2-haloethanesulfonyl halide (II). Is more preferable, and the range of 1.0 mol to 10 mol is more preferable.

  Examples of the base used in the present invention include alkali metal hydrides such as sodium hydride and potassium hydride; alkaline earth metal hydrides such as magnesium hydride and calcium hydride; alkali metals such as sodium hydroxide and potassium hydroxide. Hydroxides; Alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; Sodium bicarbonate Alkaline metal metal oxides such as magnesium oxide and calcium oxide; tertiary amines such as triethylamine, tributylamine and diisopropylethylamine; pyridine, 2-picoline, 2,6- Lutidine, 2,4,6- Lysine, nitrogen-containing aromatic ring compounds such as quinoline.

  The amount of the base used in the present invention is preferably in the range of 0.8 mol to 5 mol with respect to 1 mol of 2-haloethanesulfonyl halide (II), and is 0 from the viewpoint of economy and ease of post-treatment. More preferably, it is in the range of 8 mol to 3 mol.

  The present invention can be carried out in the presence or absence of a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methoxyphenol, benzoquinone, tolquinone, 4-tert-butylcatechol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, and 2-tert-butyl-4. , 6-dimethylphenol, phenothiazine and the like. One type of polymerization inhibitor may be used, or two or more types may be used in combination. When using a polymerization inhibitor, the amount used is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less, based on the mass of the entire reaction mixture.

  The present invention can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as the reaction is not inhibited. For example, aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; halogens such as chlorobenzene and fluorobenzene Aromatic hydrocarbons; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diglyme, triglyme, tetraglyme; halogenation such as dichloromethane, chloroform, 1,2-dichloroethane Aliphatic hydrocarbons; acetonitrile and the like. These may be used singly or in combination of two or more. In the case of using a solvent, the amount used is preferably 100 parts by mass or less with respect to 1 part by mass of 2-haloethanesulfonyl halide (II) from the viewpoints of reaction rate, economy, environmental protection, and the like. The amount is more preferably no greater than 10 parts by mass, and even more preferably no greater than 10 parts by mass.

  The reaction temperature of the present invention varies depending on the type of diene compound (I), 2-haloethanesulfonyl halide (II) and base used, but is usually in the range of -30 ° C to 200 ° C. The reaction temperature is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, from the viewpoint of the reaction rate. Moreover, from a viewpoint of suppression of side reactions, such as superposition | polymerization, 100 degrees C or less is preferable and 50 degrees C or less is more preferable.

  Although there is no restriction | limiting in particular in the reaction pressure of this invention, It is simple and preferable to implement under a normal pressure.

  The reaction time of the present invention varies depending on the diene compound (I), 2-haloethanesulfonyl halide (II), base, and reaction temperature to be used, but is usually preferably in the range of 0.5 to 48 hours, and preferably 1 to A range of 24 hours is more preferred.

  The reaction operation method in the present invention is not particularly limited as long as the reaction is carried out in a state where the diene compound (I), 2-haloethanesulfonyl halide (II), and a base coexist in the reactor. For example, (1) a batch reactor in which 2-haloethanesulfonyl halide (II), diene compound (I), a base, a polymerization inhibitor, if necessary, and a solvent are optionally added and reacted, (2) batch A method in which a diene compound (I), a base, a polymerization inhibitor, if necessary, and a solvent are charged in a chemical reactor, and 2-haloethanesulfonyl halide (II) is added to the mixture at a predetermined temperature, (3 ) A method in which a batch reactor is charged with diene compound (I), 2-haloethanesulfonyl halide (II), a polymerization inhibitor as required, and optionally a solvent, and a base is added to this mixture at a predetermined temperature, (4) A batch reactor is charged with the diene compound (I), a polymerization inhibitor, if necessary, and a solvent as required, and this mixture is charged with 2-haloethanesulfonyl halide at a predetermined temperature. Although a method of adding id (II) with a base, respectively separately are mentioned, the preferred method of (3) and (4).

Isolation and purification of the sulfonyl halide derivative (III) from the reaction mixture obtained in the present invention can be carried out by methods generally used for isolation and purification of organic compounds. For example, after completion of the reaction, the sulfonyl halide derivative (III) can be isolated by filtering the reaction mixture and then concentrating the obtained filtrate. Then, if necessary, the sulfonyl halide derivative (III) with high purity can be obtained by purification by recrystallization, distillation, silica gel chromatography or the like. Moreover, a single isomer with high purity can be obtained by repeating purification.
Moreover, it can also be used for another reaction with a reaction mixture, and it can also isolate and refine | purify.

  The Diels-Alder reaction between vinylsulfonyl chloride and a cyclic diene compound is difficult and the yield is low. According to the present invention, the sulfonyl halide derivative (III) can be obtained in a short period of time under mild conditions and in good yield.

  The sulfonyl halide derivative (III) obtained by the present invention can be used as a raw material for paints, functional polymers, pharmaceuticals, agricultural chemicals and other fine chemicals, whether it is a mixture of isomers or a single isomer. It can be preferably used.

  The sulfonyl halide derivative (III) obtained by the present invention can give a sulfonamide derivative in a high yield by reacting with a primary amine or a secondary amine, and the sulfonic acid in a high yield by reacting with an alcohol. An ester derivative can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited at all by these Examples.

<Example 1>
Synthesis of 5-norbornene-2-sulfonyl chloride A 4-liter flask with an internal volume of 1 liter equipped with a thermometer was charged with 0.35 g of phenothiazine, 480 g of tetrahydrofuran, and 72.9 g (1.10 mol) of cyclopentadiene and stirred. While cooling to 0-5 ° C. Next, 172.3 g (1.00 mol) of 2-chloroethanesulfonyl chloride and 122.1 g (1.20 mol) of 2-chloroethanesulfonyl chloride were respectively weighed into separate dropping funnels, and simultaneously dropped at an internal temperature of 0 to 5 ° C. over 3 hours. It was. After completion of the dropwise addition, the reaction mixture was stirred at 0 to 5 ° C. for 3 hours, and then the deposited salt was filtered to obtain 746.5 g of a 5-norbornene-2-sulfonyl chloride tetrahydrofuran solution (net 158.0 g; 82%). When this solution was distilled, 135.9 g (distillation yield 86%) of 5-norbornene-2-sulfonyl chloride was obtained at a boiling point of 102.0 to 103.0 ° C./0.5 mmHg.

<Example 2>
Synthesis of a mixture of 3-methyl-3-cyclohexene-1-sulfonyl chloride and 4-methyl-3-cyclohexene-1-sulfonyl chloride A phenothiazine 0. 18 g, 240 g of tetrahydrofuran and 37.5 g (0.55 mol) of isoprene were charged and cooled to 0 to 5 ° C. with stirring. Next, 86.2 g (0.50 mol) of 2-chloroethanesulfonyl chloride and 61.1 g (0.60 mol) of 2-chloroethanesulfonyl chloride were respectively weighed into separate dropping funnels, and simultaneously dropped at an internal temperature of 0 to 5 ° C. over 3 hours. It was. After completion of the dropwise addition, the reaction mixture was stirred at 0 to 5 ° C. for 5 hours, and then the deposited salt was filtered to obtain 375.5 g of 4-methyl-3-cyclohexene-1-sulfonyl chloride tetrahydrofuran solution (net 87). .6 g; yield 90%). When the solution was distilled, a mixture of 3-methyl-3-cyclohexene-1-sulfonyl chloride and 4-methyl-3-cyclohexene-1-sulfonyl chloride at a boiling point of 87.0-88.0 ° C./0.8 mmHg 82. 7 g (distillation yield 85%) was obtained.

<Comparative Example 1>
Synthesis of 5-norbornene-2-sulfonyl chloride A three-necked flask with an internal volume of 200 ml equipped with a stirrer and thermometer was charged with 50 g of tetrahydrofuran and 16.3 g (0.10 mol) of 2-chloroethanesulfonyl chloride. Cooled to ~ 5 ° C. Subsequently, 12.2 g (0.12 mol) of triethylamine was added dropwise over 2 hours while maintaining the internal temperature at 0 to 5 ° C. After completion of the dropwise addition, the reaction mixture was stirred for 2 hours while maintaining at 0 to 5 ° C. At this time, all 2-chloroethanesulfonyl chloride was consumed, and it was confirmed by GC analysis of the reaction mixture that vinylsulfonyl chloride was formed. To this reaction mixture, 7.28 g (0.11 mol) of cyclopentadiene was added and stirred at an internal temperature of 0 to 5 ° C. for 20 hours. After confirming the completion of the reaction, the deposited salt was filtered to obtain 86.8 g of 5-norbornene-2-sulfonyl chloride tetrahydrofuran solution (net 7.32 g; yield 38%).

<Comparative example 2>
Synthesis of a mixture of 3-methyl-3-cyclohexene-1-sulfonyl chloride and 4-methyl-3-cyclohexene-1-sulfonyl chloride A three-necked flask having an internal volume of 200 ml equipped with a stirrer and a thermometer was charged with 50 g of tetrahydrofuran, -16.3 g (0.10 mol) of chloroethanesulfonyl chloride was charged and cooled to 0 to 5 ° C while stirring. Subsequently, 12.2 g (0.12 mol) of triethylamine was added dropwise over 2 hours while maintaining the internal temperature at 0 to 5 ° C. After completion of the dropwise addition, the reaction mixture was stirred for 2 hours while maintaining at 0 to 5 ° C. At this time, all 2-chloroethanesulfonyl chloride was consumed, and it was confirmed by GC analysis of the reaction mixture that vinylsulfonyl chloride was formed. 7.49 g (0.11 mol) of isoprene was added to this reaction mixture, and the mixture was stirred at an internal temperature of 0 to 5 ° C. for 20 hours. After confirming the completion of the reaction, the deposited salt was filtered to obtain 87.5 g of a tetrahydrofuran solution of a mixture of 3-methyl-3-cyclohexene-1-sulfonyl chloride and 4-methyl-3-cyclohexene-1-sulfonyl chloride ( Net 12.1 g; yield 62%).

Claims (5)

The following general formula (I)

(Wherein R ¹ and R ⁴ each independently represents a hydrogen atom, an alkyl group or an alkoxy group, or an alkylene group which may contain an oxygen atom or a sulfur atom at any position by bonding to each other, —O -Represents-or -S-, and R ² and R ³ each independently represents a hydrogen atom, an alkyl group or an alkoxy group.
A diene compound represented by the following general formula (II)

(In formula, X < ¹ >, X < ² > represents a fluorine atom, a chlorine atom, or a bromine atom each independently.)
A 2-haloethanesulfonyl halide represented by the following general formula (III) is reacted in the presence of a base:

(Wherein R ¹ , R ² , R ³ , R ⁴ and X ² are as defined above.)
The manufacturing method of the sulfonyl halide derivative represented by these. The following general formula (I)

(Wherein R ¹ and R ⁴ each independently represents a hydrogen atom, an alkyl group or an alkoxy group, or an alkylene group which may contain an oxygen atom or a sulfur atom at any position by bonding to each other, —O -Represents-or -S-, and R ² and R ³ each independently represents a hydrogen atom, an alkyl group or an alkoxy group.
A diene compound represented by the following general formula (II)

(In formula, X < ¹ >, X < ² > represents a fluorine atom, a chlorine atom, or a bromine atom each independently.)
A base is added to the 2-haloethanesulfonyl halide represented by the following general formula (III):

(Wherein R ¹ , R ² , R ³ , R ⁴ and X ² are as defined above.)
The manufacturing method of the sulfonyl halide derivative represented by these. The following general formula (I)

(Wherein R ¹ and R ⁴ each independently represents a hydrogen atom, an alkyl group or an alkoxy group, or an alkylene group which may contain an oxygen atom or a sulfur atom at any position by bonding to each other, —O -Represents-or -S-, and R ² and R ³ each independently represents a hydrogen atom, an alkyl group or an alkoxy group.
In the diene compound represented by the following general formula (II)

(In formula, X < ¹ >, X < ² > represents a fluorine atom, a chlorine atom, or a bromine atom each independently.)
A 2-haloethanesulfonyl halide represented by the following general formula (III):

(Wherein R ¹ , R ² , R ³ , R ⁴ and X ² are as defined above.)
The manufacturing method of the sulfonyl halide derivative represented by these. The method for producing a sulfonyl halide derivative according to claim 1, wherein R ¹ and R ⁴ are combined to form —CH ₂ —. The method for producing a sulfonyl halide derivative according to claim 1, wherein R ¹ and R ⁴ are bonded to form —CH ₂ —, and X ¹ and X ² are chlorine atoms.