JP2006316007A - Sulfonic acid halide compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an α,β-unsaturated ester-substituted sulfonic acid halide compound. <P>SOLUTION: The method for producing an α,β-unsaturated ester-substituted sulfonic acid halide compound expressed by general formula (IV) comprises the reaction of a sultone compound expressed by general formula (I) with an α,β-unsaturated carboxylic acid compound expressed by general formula (II) and the reaction of the obtained compound expressed by general formula (III) with a halogenating agent. In the formulas, n is 3 or 4; R<SB>1</SB>, R<SB>2</SB>and R<SB>3</SB>are each independently hydrogen atom or a substituted or unsubstituted alkyl or aryl group; M<SB>1</SB>and M<SB>2</SB>are each hydrogen atom or a cationic species; and X<SB>1</SB>is a halogen atom. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to α, β-unsaturated ester-substituted sulfonic acid halide compounds that are extremely important as raw materials and compound intermediates for dyes, agricultural chemicals, pharmaceuticals, electronic materials and the like, and a method for producing the same.

In recent years, polymers are frequently used in the field of electronic materials and the like, and α, β unsaturated ester compounds represented by acrylic esters are frequently used as raw materials. With the demand for higher functionality of materials, the development of derivatives having various functional substituents for acrylate derivatives is also desired, and linkages that link such functional substituents or functional substituents. As the group, sulfonic acid ester compounds and sulfonamide compounds are useful. As a precursor for synthesizing a sulfonic acid ester compound and a sulfonamide compound, a sulfonic acid chloride compound is most frequently used. From the above, it can be said that the α, β unsaturated ester-substituted sulfonic acid chloride compound is a very useful compound, but the synthesis method of such a compound has not been known so far. On the other hand, as a method for synthesizing α, β unsaturated ester-substituted sulfonic acid, for example, a reaction between a sultone compound and an α, β unsaturated carboxylic acid compound is known. In this example, a sulfonic acid-bonded dye is synthesized. There was no description about a sulfonic-acid chloride compound (for example, refer nonpatent literature 1). Accordingly, it has been desired to develop α, β unsaturated ester-substituted sulfonic acid halide compounds such as α, β unsaturated ester-substituted sulfonic acid chlorides and production methods thereof.
Helvetica Chimica Acta, 68, 1782, 1985

  An object of the present invention is to provide an α, β unsaturated ester-substituted sulfonic acid halide compound and an efficient production method thereof.

The present invention provides the following methods and compounds.
(1) A compound represented by the following general formula (III) by reacting a sultone compound represented by the following general formula (I) with an α, β unsaturated carboxylic acid compound represented by the following general formula (II): Of the α, β unsaturated ester-substituted sulfonic acid halide compound represented by the following general formula (IV), wherein the compound represented by the general formula (III) is reacted with a halogenating agent: Production method.

  In the formula, n represents 3 or 4.

In the formula, R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group. M ₁ represents a hydrogen atom or a cationic species.

In formula, n is synonymous with n in general formula (I). R _{1, R 2,} and _{R 3} are each synonymous with _R 1, _{R 2,} and _{R 3} in the general formula (II). M ₂ represents a hydrogen atom or a cationic species.

In formula, n is synonymous with n in general formula (I). R _{1, R 2,} and _{R 3} are each synonymous with _R 1, _{R 2,} and _{R 3} in the general formula (II). X ₁ represents a halogen atom.
(2) The α, β unsaturated ester-substituted sulfonic acid halide compound according to (1), wherein R ₁ , R ₂ , and R ₃ in the compound represented by the general formula (II) are hydrogen atoms Manufacturing method.
(3) A sulfonic acid halide compound represented by the following general formula (V).
General formula (V)

In the formula, n represents 3 or 4. X ₂ represents a halogen atom.

  According to the present invention, an α, β unsaturated ester-substituted sulfonic acid halide compound and a production method thereof can be provided. The sulfonic acid halide compound thus obtained is useful as a raw material for synthesizing pharmaceuticals, agricultural chemicals, electronic materials and other functional compounds.

  The method for producing an α, β unsaturated ester-substituted sulfonic acid halide compound represented by the general formula (IV) of the present invention comprises a sultone compound represented by the general formula (I) and an α represented by the general formula (II). , Β-unsaturated carboxylic acid compound is reacted to form a compound represented by the general formula (III), and the compound represented by the general formula (III) is reacted with a halogenating agent.

  The sultone compound represented by the general formula (I) used in the present invention is one in which n represents 3 or 4, specifically, propane sultone (n = 3) or butane sultone (n = 4). is there.

Next, the compound represented by formula (II) used in the present invention will be described in detail.
In the general formula (II), R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group. The alkyl group represents a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, Examples include t-pentyl, cyclopropyl, cyclohexyl, 2-ethylhexyl, dodecyl and the like. The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, more preferably 6 to 25 carbon atoms, and examples thereof include phenyl, naphthyl, and anthryl. R ₁ , R ₂ and R ₃ are more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

Examples of the substituent that R ₁ , R ₂ and R ₃ may have include, for example, an alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably having 1 to 50 carbon atoms, Preferably it is a 1-18 alkyl group, for example, methyl, ethyl, isopropyl, t-butyl, t-pentyl, cyclopropyl, cyclohexyl, 2-ethylhexyl, dodecyl etc.), an alkenyl group (preferably having 2 carbon atoms). -50, more preferably 2-18 substituted or unsubstituted alkenyl groups such as vinyl, alkynyl groups (preferably 2-50 carbon atoms, more preferably 2-18 substituted or unsubstituted alkynyl groups, Ethynyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 50 carbon atoms, more preferably 3 to 18 carbon atoms, Cyclohexyl), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, more preferably 6 to 25 carbon atoms, such as phenyl, naphthyl, anthryl),

Halogen atom (for example, fluorine, chlorine, bromine, iodine), acylamino group (preferably an acylamino group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms such as acetylamino, butanoylamino, benzoylamino, trifluoro Acetylamino, picolinoylamino), an acyloxy group (preferably an acyloxy group having 1 to 50 carbon atoms, for example, acetoxy, tetradecanoyloxy, benzoyloxy), an acyl group (preferably 1 to 50 carbon atoms, more preferably 1-18 acyl groups, for example, formyl, acetyl, pivaloyl, tetradecanoyl, cyclohexylcarbonyl, benzoyl, trifluoroacetyl), aryloxycarbonyl groups (preferably having 7 to 50 carbon atoms, more preferably 7 to 25 carbon atoms). An aryloxycarbonyl group For example, a carbamoyl group (preferably a carbamoyl group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-diethylcarbamoyl, N- Mesylcarbamoyl), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms such as N, N-dimethylcarbamoyloxy), a carbonamido group (preferably having 1 to 50 carbon atoms). More preferably, it is a 1 to 18 carbonamido group, for example, formamide, N-methylacetamide, acetamide, N-methylformamide, benzamide), a sulfonamide group (preferably having 1 to 50 carbon atoms, more preferably 1 to 1 carbon atoms). 18 sulfonamide groups, for example methanesulfo An amide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), an alkoxy group (preferably an alkoxy group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms such as methoxy, propoxy, isopropoxy, octyloxy , T-octyloxy, dodecyloxy, 2- (2,4-di-t-pentylphenoxy) ethoxy), an aryloxy group (preferably an aryloxy group having 6 to 50 carbon atoms, more preferably 6 to 25 carbon atoms, For example, phenoxy, 4-methoxyphenoxy, naphthoxy), sulfamoyl group (preferably a sulfamoyl group having 0 to 50 carbon atoms, more preferably 0 to 25, for example, sulfamoyl, N-butylsulfamoyl, N, N-diethyl Sulfamoyl, N-methyl-N- (4-methoxyphenyl) Sulfamoyl),

An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 50 carbon atoms, more preferably 2 to 18 carbon atoms, such as cyclohexyloxycarbonyl, methoxycarbonyl, isopropoxycarbonyl, t-butoxycarbonyl), N-acylsulfamoyl group (Preferably an N-acylsulfamoyl group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms, such as N-tetradecanoylsulfamoyl, N-benzoylsulfamoyl), an alkylsulfonyl group (preferably An alkylsulfonyl group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms, such as methanesulfonyl, isopropylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl), arylsulfonyl group ( An arylsulfonyl group having 6 to 50 carbon atoms, more preferably 6 to 25 carbon atoms, such as benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl), an alkoxycarbonylamino group (preferably having 2 to 2 carbon atoms). 50, more preferably 2 to 18 alkoxycarbonylamino groups, for example, ethoxycarbonylamino, isopropyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino groups (preferably having 7 to 50 carbon atoms, more preferably 7 An aryloxycarbonylamino group having ˜25, for example, phenoxycarbonylamino, naphthoxycarbonylamino), an amino group (preferably an amino group having 0 to 50 carbon atoms, more preferably 0 to 18 carbon atoms, such as amino, Tilamino, diethylamino, diisopropylamino, anilino), cyano group, nitro group, carboxyl group, hydroxy group, sulfo group, mercapto group, alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms). For example, methanesulfinyl, octanesulphinyl), arylsulfinyl group (preferably an arylsulfinyl group having 6 to 50 carbon atoms, more preferably 6 to 25 carbon atoms such as benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl) An alkylthio group (preferably an alkylthio group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms such as methylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 50 carbon atoms, more preferably Or an arylthio group having 6 to 25, such as phenylthio or naphthylthio, or a ureido group (preferably a ureido group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms such as 3-methylureido or 3,3-dimethylureido. , 1,3-diphenylureido), a heterocyclic group (preferably a heterocyclic group having 2 to 50 carbon atoms, more preferably 2 to 25, and examples of the hetero atom include at least one of nitrogen, oxygen, sulfur and the like. Including 3- to 12-membered monocyclic or condensed rings such as 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2- Benzothiazolyl, 2-benzoxazolyl, 2-quinazolinon-3-yl, 1,1-dioxo-1,2,4-benzothiadia N-3-yl, etc.), a sulfamoylamino group (preferably a sulfamoylamino group having 0 to 50 carbon atoms, more preferably 0 to 18 carbon atoms, such as N-butylsulfamoylamino, N-phenylsulfuryl). Famoylamino), silyl group (preferably a silyl group having 3 to 50 carbon atoms, for example, trimethylsilyl, dimethyl-t-butylsilyl, triphenylsilyl), phosphonyl group (preferably 1 to 50 carbon atoms, more preferably 1 -18 phosphonyl groups such as phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), azo groups (preferably azo groups having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms such as phenylazo), imide groups (Preferably an imide group having 1 to 50 carbon atoms, more preferably 1 to 18 carbon atoms such as N-succinimide and N- Taruimido), and the like.
R ₁ , R ₂ and R ₃ may be the same or different, and may be bonded to each other to form a ring. The aforementioned substituents and rings may be further substituted with a substituent, and examples of the substituent include the groups mentioned as the substituents for R ₁ , R ₂ and R ₃ .

In the general formula (II), M ₁ represents a hydrogen atom or a cationic species. Examples of the cationic species include alkali metal ions (for example, sodium ions and potassium ions), alkaline earth metal ions (for example, magnesium ions and calcium ions), quaternary ammonium ions (for example, tetrabutylammonium ions and benzyltriethylammonium ions), and organic bases. Examples of organic bases include cations obtained by adding protons to amines (eg, ammonia, triethylamine), anilines (eg, diethylaniline), aromatic heterocycles (eg, pyridine, imidazole), guanidines (eg, tetramethyl). Guanidine), nitrogen-containing heterocycles (for example, 1,8-diazabicyclo [5,4,0] -7-undecene) and the like. Preferably, M ₁ is a hydrogen atom. Further, when M ₁ is an m-valent ion, in the general formula (II), 1 / m M ₁ is bonded.

Next, the compounds represented by formula (III) and formula (IV) will be described in detail. In general formula (III) and general formula (IV), n is synonymous with n in general formula (I). In the general formula (III), general formula _(IV), R 1, _{R 2} and _{R 3} are respectively the same meaning as _R 1, _{R 2} and _{R 3} in formula (II), and preferred ranges are also the same. In the general formula (III), M ₂ represents a hydrogen atom or a cationic species. Examples given as M ₁ in the general formula (II) can be mentioned as a cationic species. Further, when M ₂ is an m-valent ion, the general formula (III) indicates that 1 / m M ₂ is bonded. Preferably, M ₂ is a sodium ion or a potassium ion.

In the general formula (IV), X ₁ represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), and preferably a chlorine atom.

  The production method of the present invention comprises reacting a sultone compound represented by the general formula (I) with an α, β unsaturated carboxylic acid compound represented by the general formula (II) and a compound represented by the general formula (III) And a second step of producing a sulfonic acid halide compound represented by the general formula (IV) by reacting the compound represented by the general formula (III) with a halogenating agent.

  In the first step, it is preferable to use a base together with the sultone compound represented by the general formula (I) and the α, β unsaturated carboxylic acid compound represented by the general formula (II). Examples of the base that can be used in the present invention include hydroxide compounds (for example, sodium hydroxide, potassium hydroxide, tetrabutylammonium hydroxide), carbonate compounds (for example, sodium carbonate, potassium carbonate, tetrabutylammonium carbonate), amines (Eg, ammonia, triethylamine), anilines (eg, diethylaniline), aromatic heterocycles (eg, pyridine, imidazole), guanidines (eg, tetramethylguanidine), bicarbonate compounds (eg, sodium bicarbonate), nitrogen-containing hetero Rings (eg 1,8-diazabicyclo [5,4,0] -7-undecene), acetic acid compounds (eg sodium acetate, potassium acetate), metal salts of organic compounds (eg sodium methoxide, potassium t-butoxide) Etc.

  These bases may be used alone or in combination of two or more. The amount of the base used is 0.1 to 100 mol, preferably 0.5 to 10 mol, more preferably 1 to 5 mol, per mol of the compound represented by the general formula (II).

  The reaction in the first step and the second step of the present invention is preferably performed using a solvent. Specific examples of the solvent that can be used include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, and ethyl acetate. Butyl acetate, toluene, chlorobenzene, nitrobenzene, hexane, heptane, dimethylacetamide, dimethylformamide, sulfolane, tetrahydrofuran, dioxane, acetonitrile, dimethyl sulfoxide, methanol, ethanol, isopropanol, water, etc. You may use, and may mix and use 2 or more types. The solvent is 0.5 to 1000 parts by mass, preferably 1 to 50 parts by mass per 1 part by mass of the compound represented by the general formula (II) or 1 part by mass of the compound represented by the general formula (III). used.

  In the first step and the second step, the reaction temperature is preferably -78 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is usually several hours when the reaction temperature is around room temperature, but when the reaction is carried out at a lower temperature, the type of compound represented by the general formula (II), or the solvent used Depending on the type, it may take several days.

  In the present invention, after the first step, the compound represented by the general formula (III) may be isolated and then reacted with the halogenating agent, or the reaction product may be directly used as the halogenating agent without isolation. Although it may react, it is preferable to react with a halogenating agent after isolation.

In the present invention, the halogenating agent used in the second step is not particularly limited, and examples thereof include a chlorinating agent, a brominating agent, and an iodinating agent, and a chlorinating agent is preferable. Phosphorus oxychloride, phosphorus pentachloride, and phosphorus trichloride are preferable, and thionyl chloride and phosphorus oxychloride are more preferable. The amount of the halogenating agent used is 0.1 to 100 mol, preferably 0.5 to 10 mol, more preferably 1 to 5 mol, per mol of the compound represented by the general formula (III). .
In the halogenation step, it is also preferable to add an additive that accelerates the reaction. Examples of the additive include bases such as pyridine and aniline, amides such as dimethylformamide and dimethylacetamide, and quaternary ammonium such as tetrabutylammonium chloride. Examples include salt.

  The compound represented by the general formula (III), which is an intermediate product of the method of the present invention, and the compound represented by the general formula (IV), which is the final product, are obtained by methods such as recrystallization, distillation, column chromatography, etc. May be purified alone or in combination.

  Next, specific examples of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto.

  Next, specific examples of the compound represented by the general formula (III) are shown below, but the present invention is not limited thereto.

  Next, specific examples of the compound represented by the general formula (IV) are shown below, but the present invention is not limited thereto.

Another embodiment of the present invention is a sulfonic acid halide compound represented by the general formula (V). In the general formula (V), X ₂ represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), preferably a chlorine atom. These compounds can be produced by the production method described above. Examples of the sulfonic acid halide compound represented by the general formula (V) include the chloride compounds of the exemplified compounds (IV) -1 and (IV) -2 described above.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to these.

Example 1
Compound (IV) -1 was produced according to the following scheme.

  A mechanical stirrer was placed in a 200 ml three-necked flask, and 6.9 ml (0.10 mol) of acrylic acid ((II) -1) and 100 ml of toluene were added, and potassium t-butoxide (t -BuOK) 11.2 g (0.10 mol) was added little by little, and after the addition, the mixture was stirred at room temperature for 20 minutes. To this solution, 10.1 g (0.083 mol) of propane sultone ((I) -1) was added and stirred at 90 ° C. for 1 hour. After cooling to room temperature, the resulting salt was filtered and washed with toluene to obtain crude crystals of compound (III) -1. Yield 19.0 g (Yield 98.9%)

A 500 ml three-necked flask was charged with 12.1 g (0.052 mol) of compound (III) -1, 25 ml of dimethylformamide, and 100 ml of acetonitrile, and 4.6 ml (0.063 mol) of thionyl chloride (SOCl ₂ ) was added thereto. The solution was added dropwise and stirred at 35 ° C. for 1.5 hours. The mixture was poured into ice water, extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated on a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 5.3 g of the desired compound (IV) -1 as a transparent oil. (Yield 47.9%)
¹ H-NMR (400 MHz, in CDCl ₃ ): 6.44 (d; 1H), 6.13 (dd; 1H), 5.90 (d; 1H), 4.35 (t; 2H), 3. 81 (t; 2H), 2.49 to 2.40 (m; 2H)

Example 2
Compound (IV) -2 was produced according to the following scheme.

  A mechanical stirrer was placed in a 500 ml three-necked flask, 13.8 ml (0.20 mol) of acrylic acid ((II) -1) and 200 ml of toluene were added, and potassium t-butoxide (t- (BuOK) 22.4 g (0.20 mol) was added little by little, and after the addition, the mixture was stirred at room temperature for 20 minutes. To this solution, 27.2 g (0.20 mol) of butanesultone ((I) -2) was added and stirred at 100 ° C. for 3 hours. After cooling to 70 ° C., the resulting salt was filtered and washed with toluene and hexane to obtain crude crystals of compound (III) -2. Yield 44.1 g (Yield 89.6%)

In a 300 ml three-necked flask, 24.6 g (0.10 mol) of compound (III) -2, 20 ml of dimethylformamide and 100 ml of acetonitrile were placed, and 8.8 ml (0.12 mol) of thionyl chloride (SOCl ₂ ) was added thereto. The solution was added dropwise and stirred at 40 ° C. for 2 hours. The mixture was poured into ice water, extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated on a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 19.7 g of the desired compound (IV) -2 as a transparent oil. (Yield 86.8%)
¹ H-NMR (400 MHz, in CDCl ₃ ): 6.42 (d; 1H), 6.13 (dd; 1H), 5.87 (d; 1H), 4.23 (t; 2H), 3. 73 (t; 2H), 2.25 to 2.08 (m; 2H), 1.96 to 1.85 (m; 2H)

Claims (3)

A sultone compound represented by the following general formula (I) and an α, β unsaturated carboxylic acid compound represented by the following general formula (II) are reacted to form a compound represented by the following general formula (III). A process for producing an α, β unsaturated ester-substituted sulfonic acid halide compound represented by the following general formula (IV), wherein the compound represented by the general formula (III) is reacted with a halogenating agent.

In the formula, n represents 3 or 4.

In the formula, R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group. M ₁ represents a hydrogen atom or a cationic species.

In formula, n is synonymous with n in general formula (I). R _{1, R 2,} and _{R 3} are each synonymous with _R 1, _{R 2,} and _{R 3} in the general formula (II). M ₂ represents a hydrogen atom or a cationic species.

In formula, n is synonymous with n in general formula (I). R _{1, R 2,} and _{R 3} are each synonymous with _R 1, _{R 2,} and _{R 3} in the general formula (II). X ₁ represents a halogen atom. The method for producing an α, β unsaturated ester-substituted sulfonic acid halide compound according to claim 1, wherein R ₁ , R ₂ , and R ₃ in the compound represented by the general formula (II) are hydrogen atoms. . A sulfonic acid halide compound represented by the following general formula (V).

In the formula, n represents 3 or 4. X ₂ represents a halogen atom.