JP2004262846A - Method for producing 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a highly reactive 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride. <P>SOLUTION: The method comprises reacting chlorinating agent(s) with cyclohexane-1,2,4-tricarboxylic acid. In this method, the chlorinating agent is at least one selected from the group consisting of phosphorus trichloride, phosphorus pentachloride, phosphoryl chloride, phosgene, trichloromethyl chloroformate, thionyl chloride and benzotrichloride. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel method for producing 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride.
[0002]
[Prior art]
Conventionally, cyclohexane-1,2,4-tricarboxylic acid has been known as a resin raw material. However, since it has poor reactivity with diamines and diols, it takes a long time for the polycondensation reaction, and There are problems such as low molecular weight. For this reason, compounds that are more reactive when used industrially are strongly desired.
[0003]
4-Chloroformyl-cyclohexane-1,2-dicarboxylic anhydride is a novel compound not described in any literature, and no literature describing a method for producing the compound has been found so far.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for efficiently producing 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride having excellent reactivity.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, cyclohexane-1,2,4-tricarboxylic acid was treated with acetic anhydride to obtain 4-carboxy-1,2-dicarboxylic anhydride, Next, it has been found that 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride can be produced by reacting the obtained 4-carboxy-1,2-dicarboxylic anhydride with a chlorinating agent. However, a large amount of an anhydrous agent such as acetic anhydride is required in the acid anhydride conversion step of the above technique, which is economically disadvantageous and has problems such as complicated post-treatment after the reaction. .
[0006]
Therefore, as a result of further studies, the present inventors have found that by reacting cyclohexane-1,2,4-tricarboxylic acid with a chlorinating agent, an acid anhydride conversion step with acetic anhydride or the like becomes unnecessary, and in one step. It has been found that 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride can be obtained, and the present invention has been completed based on such findings.
[0007]
That is, the present invention provides the following method for producing 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride.
[0008]
[1] A process for producing 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride, comprising reacting cyclohexane-1,2,4-tricarboxylic anhydride with a chlorinating agent.
[0009]
[2] The method according to item 1, wherein the chlorinating agent is at least one selected from the group consisting of phosphorus trichloride, phosphorus pentachloride, phosphoryl chloride, phosgene, trichloromethyl chloroformate, thionyl chloride, and benzotrichloride. A method for producing chloroformyl-cyclohexane-1,2-dicarboxylic anhydride.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
The cyclohexane-1,2,4-tricarboxylic acid (hereinafter referred to as "cyclohexanetricarboxylic acid") according to the present invention can be prepared by a known method (for example, see JP-A-8-325201 and JP-A-8-325202). The compounds can be easily obtained by subjecting a benzene-1,2,4-tricarboxylic acid derivative to nuclear hydrogenation according to the described method or the like).
[0011]
The chlorinating agent used in the present invention is not particularly limited as long as it is a compound capable of converting an organic acid into an acid chloride, and specific examples thereof include phosphorus trichloride, phosphorus pentachloride, phosphoryl chloride, phosgene, and trichloromethyl. Examples include chloroformate, thionyl chloride, benzotrichloride and the like. As these chlorinating agents, ordinary commercial industrial products can be used, and they can be used alone or in combination of two or more.
[0012]
As the amount of the chlorinating agent to be used, 2 molar equivalents or more of the chlorinating agent is required based on 3 mols of the carboxyl group of cyclohexanetricarboxylic acid, and usually 2 to 40 molar equivalents, preferably 2 to 20 molar equivalents. Range.
[0013]
The reaction temperature varies depending on the chlorinating agent or solvent used, but is usually in the range of 10 ° C to the boiling point of the chlorinating agent or solvent used, and particularly preferably 40 to 100 ° C. If the reaction temperature is too low, the progress of the reaction is slow, and if it is too high, the amount of by-products increases.
[0014]
The reaction time varies depending on the chlorinating agent used and the reaction temperature, but may be appropriately determined, and is usually about 0.5 to 30 hours, preferably about 1 to 10 hours.
[0015]
Since the reaction of the present invention is performed in a homogeneous solution or suspension, it is preferable to perform the reaction using a solvent.However, when phosphorus trichloride, sulfolyl chloride, thionyl chloride or benzotrichloride is used as the chlorinating agent, Can be carried out without a solvent.
[0016]
The solvent that can be used is not particularly limited as long as it is a solvent inert to the reaction, and specifically, hexane, heptane, cyclohexane, benzene, toluene, xylene and other aliphatic and aromatic hydrocarbon solvents; chloroform, Halogenated hydrocarbon solvents such as methylene chloride, 1,2-dichloroethane and chlorobenzene; ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; Examples include aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, and organic bases such as pyridine and picoline. Further, these solvents can be mixed and used as a reaction solvent. Usually, the amount of the solvent is preferably 0.1 to 50 times, more preferably 0.5 to 20 times the weight of cyclohexanetricarboxylic acid.
[0017]
In addition, for the purpose of accelerating the reaction, an organic or inorganic catalyst can be appropriately added to the reaction solution depending on the chlorinating agent to be used.
[0018]
Examples of the organic catalyst include tertiary amines such as pyridine, triethylamine, tributylamine and 4-dimethylaminopyridine, N, N-disubstituted formamide, tetraalkylurea, tertiary phosphine, quaternary ammonium salts, and quaternary. Examples thereof include a phosphonium salt. The use amount of these catalysts is not particularly limited, but is 0.001 to 5 mol, preferably 0.01 to 3 mol, per 1 mol of cyclohexanetricarboxylic acid.
[0019]
Examples of the inorganic catalyst include metal halides or metal oxides such as magnesium, calcium, barium, aluminum, titanium, iron, copper, silver, tin, and zinc. Specific examples of such inorganic catalysts include magnesium chloride, copper chloride, stannic chloride, barium chloride, ferrous chloride, ferric chloride, ferrous oxide, and ferric oxide. The use amount of these catalysts is preferably in the range of 0.001 to 0.1 mol per 1 mol of cyclohexanetricarboxylic acid.
[0020]
The above reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. If necessary, the above inert gas can be dried with calcium chloride, silica gel or the like before use.
[0021]
The reaction of the present invention is usually performed under normal pressure, but can also be performed under pressure.
[0022]
After completion of the reaction, the solvent, excess chlorinating agent and / or by-products are removed from the reaction solution by decantation, distillation, filtration, centrifugation or the like, whereby 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride is obtained. Can be obtained with high purity and high yield. Further, if necessary, it can be purified by a conventional method such as distillation.
[0023]
The 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride obtained according to the present invention includes resin materials such as polyesterimide resin and polyamideimide resin, hardener materials such as epoxy resin and polyurethane resin, and raw materials for resist material. Are useful compounds.
[0024]
【Example】
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these ranges.
[0025]
Production Example 1
A 500 ml autoclave equipped with a magnetic stirrer was charged with 30 g of benzene-1,2,4-tricarboxylic anhydride and 70 g of methanol, and subjected to esterification at a temperature of 220 ° C. for 1 hour. To this solution was added 1 g of a catalyst in which 5% by weight of ruthenium was supported on activated carbon, and hydrogenation was performed at a hydrogen pressure of 12 MPa and a temperature of 120 ° C. The absorption of hydrogen was stopped after a reaction time of 2.5 hours, and the amount of hydrogen absorbed at that time was 99.1% of the theoretical amount of hydrogen absorbed. Next, the activated carbon-supported ruthenium catalyst in the reaction solution was filtered off, and the reaction product was measured with an ultraviolet spectrophotometer. As a result, no absorption of benzene nuclei was observed, and it was confirmed that the hydrogenation reaction was completed. As a result of gas chromatographic analysis, the purity of cyclohexane-1,2,4-tricarboxylic acid trimethyl ester was 97.2%.
[0026]
The obtained cyclohexane-1,2,4-tricarboxylic acid trimethyl ester was transferred to a four-necked flask equipped with a dropping tube, a distilling decanter, a thermometer and a stirrer, and heated to remove the solvent. Next, 30 g of sulfolane was added to dissolve cyclohexane-1,2,4-tricarboxylic acid trimethyl ester, 30 g of water and 7 g of sulfuric acid were added, and the mixture was heated to 130 ° C. to perform hydrolysis. Water was added dropwise at a rate of 10 g / h, the amount of methanol in the distilled water was analyzed, and the hydrolysis reaction was followed. Crystals are precipitated as the hydrolysis proceeds. Distillation of methanol was stopped in 3 hours, and it was confirmed that the hydrolysis reaction was completed. Next, after filtering off, the obtained crystal was washed three times with water and dried at a pressure of 4 kPa and a temperature of 80 ° C. to obtain 28.5 g of cyclohexane-1,2,4-tricarboxylic acid (yield: 84.4%). Was.
[0027]
Example 1
In a 500 ml four-necked flask equipped with a dropping funnel, a condenser, a thermometer and a stirrer, 32.43 g (0.15 mol) of cyclohexane-1,2,4-tricarboxylic acid and 350 ml of 1,2-dichloroethane were charged and stirred. While maintaining the temperature at 60 ° C., 20.60 g (0.15 mol) of phosphorus trichloride was added dropwise over 2 hours. After completion of the dropwise addition, stirring was continued for another 2 hours. After completion of the reaction, the mixture was allowed to cool and stand still, and the by-product phosphorous acid as a lower layer was separated and removed, and the obtained reaction crude product was distilled under reduced pressure to obtain 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride. 30.25 g (yield 93.1%) was obtained.
[0028]
Example 2
6.49 g (0.03 mol) of cyclohexane-1,2,4-tricarboxylic acid, 16.66 g (0.08 mol) of phosphorus pentachloride and chlorinated in a 100 ml four-necked flask equipped with a condenser, a thermometer and a stirrer. 80 ml of benzene was charged and reacted at 50 ° C. for 5 hours while stirring. After completion of the reaction, chlorobenzene and phosphoryl chloride by-produced were distilled off under reduced pressure to obtain 6.35 g (yield 97.6%) of 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride.
[0029]
Example 3
6.49 g (0.03 mol) of cyclohexane-1,2,4-tricarboxylic acid and 50 g (0.42 mol) of thionyl chloride were charged into a 100 ml four-necked flask equipped with a condenser, a thermometer and a stirrer, and stirred. While refluxing for 2 hours. After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure to obtain 6.38 g (yield 98.1%) of 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride.
[0030]
Example 4
6.49 g (0.03 mol) of cyclohexane-1,2,4-tricarboxylic acid and 80 ml of tetrahydrofuran were charged into a 100 ml four-necked flask equipped with a gas inlet, a condenser, a thermometer and a stirrer, and stirred with stirring. While maintaining the temperature at ° C., phosgene diluted with dry nitrogen was blown in at a flow rate of 200 ml / hour for 12 hours (phosgene: 0.30 mol). After the completion of the reaction, dry nitrogen was blown while cooling to remove unreacted phosgene and hydrogen chloride. Thereafter, tetrahydrofuran was distilled off under reduced pressure to obtain 6.36 g (yield 97.8%) of 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride.
[0031]
Example 5
6.49 g (0.03 mol) of cyclohexane-1,2,4-tricarboxylic acid and 80 ml of chloroform were charged into a 100 ml four-necked flask equipped with a dropping funnel, a condenser, a thermometer and a stirrer, and stirred at 60 ° C. With the temperature maintained at, 19.78 g (0.10 mol) of trichloromethyl chloroformate was added dropwise over 10 hours. After completion of the dropwise addition, stirring was continued for another 2 hours. After completion of the reaction, chloroform was distilled off under reduced pressure to obtain 6.31 g (yield 97.0%) of 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride.
[0032]
Example 6
In a 500 ml four-necked flask equipped with a dropping funnel, a cooling tube, a thermometer and a stirrer, 78.19 g (0.40 mol) of benzotrichloride, 0.068 g (0.0003 mol) of stannic chloride and 100 ml of diethylene glycol dimethyl ether The mixture was charged, and while maintaining the temperature at 100 ° C. while stirring, 300 ml of a diethylene glycol dimethyl ether solution in which 32.43 g (0.15 mol) of cyclohexane-1,2,4-tricarboxylic acid was dissolved was added dropwise over 6 hours. After completion of the dropwise addition, stirring was continued for another 2 hours. After completion of the reaction, 30.10 g (yield 92.6%) of 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride was obtained by distillation under reduced pressure.
[0033]
【The invention's effect】
According to the present invention, a useful 5-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride having excellent reactivity as a resin raw material, a resin modifier, a resin curing agent intermediate and the like can be efficiently produced at a high yield. , Can be manufactured with high purity.

Claims (2)

A method for producing 4-chloroformyl-cyclohexane-1,2-dicarboxylic anhydride, comprising reacting cyclohexane-1,2,4-tricarboxylic acid with a chlorinating agent. The 4-chloro according to claim 1, wherein the chlorinating agent is at least one selected from the group consisting of phosphorus trichloride, phosphorus pentachloride, phosphoryl chloride, phosgene, trichloromethyl chloroformate, thionyl chloride, and benzotrichloride. A method for producing formyl-cyclohexane-1,2-dicarboxylic anhydride.