JP3103203B2 - Method for selectively producing alicyclic polyacid halide diastereomer and novel alicyclic polyacid halide cyclopentane-1,2,4-tricarbonyl chloride obtained by this method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for the selective production of alicyclic polyacid halide diastereomers and to a novel alicyclic polyacid halide obtained by this production method. Among the cyclic polyacid halide diastereomers, the alicyclic polyacid halide diastereomers suitable for industrial production methods capable of producing the trans form very easily and with high purity and high yield To provide a novel alicyclic polyacid halide cyclopentane-1,2,4-tricarbonyl chloride, which is attracting attention as an industrial raw material for producing a selective membrane and a separation membrane such as a reverse osmosis membrane. is there. In this specification, the trans form is defined as an anti-state in the IUPAC notation, that is, when the dihedral angle of XCCY (X and Y are substituents) is +90 to + 150 °. + Anticlinal (+ ac), +15
+ Antiperiplanar (+ ap) from 0 to 180 ° and -90 to
-Anticlinal (-ac) at 150 °, -150 to 180 °
In the range of -antiperiplanar (-ap).

[0002]

BACKGROUND OF THE INVENTION Alicyclic polyacid halides are important as materials for producing polymers such as crosslinking agents and condensing agents. Of the alicyclic polyacid halide diastereomers, when only the trans form is selectively used, thermal properties such as the melting point and glass transition point of the formed polymer, physical properties such as strength, linear expansion coefficient, and residual It becomes easy to control the chemical properties such as the number of functional groups and the molecular weight distribution within a certain range.

[0003]

2. Description of the Related Art Among alicyclic polyacid halide diastereomers, as a method for selectively producing a trans form, conventionally, an alicyclic polyfunctional carboxylic acid is esterified with an esterifying agent such as diazomethane. This is separated into a cis form and a trans form using a silica gel column, and only the trans form of the obtained alicyclic polyfunctional carboxylic acid ester is hydrolyzed to return to the trans form of the alicyclic polyfunctional carboxylic acid. ,
This has been done by a method of halogenating this with a halogenating agent such as phosphorus pentachloride.

[0004]

However, in the above-mentioned conventional method, the reaction of an esterifying agent such as diazomethane hardly proceeds in a short time, and the alicyclic polyfunctional carboxylic acid ester is adsorbed on silica gel for a long time. Decomposition of the alicyclic polyfunctional carboxylic acid ester occurs, and even if the column carrier is changed to a carrier such as florisil, activated alumina, or basic alumina, the decomposition of the alicyclic polyfunctional carboxylic acid ester is inevitable, It was difficult to mass-produce with high yield, and was not suitable as an industrial production method. Furthermore, when the trans form of the alicyclic polyfunctional carboxylic acid ester is hydrolyzed, a by-product is generated, so that its purity is low. In view of such circumstances, among the alicyclic polyacid halide diastereomers in the industry, an industrial production method capable of selectively and very easily producing a trans form in high purity and high yield. Therefore, it has been desired to create a production method suitable for the above, and a novel alicyclic polyvalent acid halide useful as a polymer material, particularly for a separation membrane such as a reverse osmosis membrane.

[0005]

Means for Solving the Problems According to the present invention, a compound of an element capable of forming a covalent bond with a halogen, an oxygen and a halogen among the elements located in the third period of the periodic table in the alicyclic polyfunctional carboxylic acid. Wherein the trans-isomer is selectively halogenated by reacting the trans-isomer with a halogenating agent, and then the trans-isomer is separated from unreacted alicyclic polyfunctional carboxylic acid cis-form or acid anhydride. The present invention provides a method for selectively producing a cyclic polyacid halide diastereomer and a novel alicyclic polyacid halide cyclopentane-1α, 2β, 4β-tricarbonyl chloride obtained by the production method. Eliminate all conventional problems.

[0006]

The structure of the present invention will be described below in detail. First, a method for selectively producing an alicyclic polyacid halide diastereomer will be described. The alicyclic polyfunctional carboxylic acid used as a starting material in the present invention includes cyclopropanedicarboxylic acid, cyclopropanetricarboxylic acid, cyclobutanedicarboxylic acid, cyclobutanetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanedicarboxylic acid, and cyclopentanetricarboxylic acid , Cyclopentanetetracarboxylic acid, cyclopentanepentacarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, cyclohexanepentacarboxylic acid, cyclohexanehexacarboxylic acid, cycloheptanedicarboxylic acid, cycloheptanetricarboxylic acid, cycloheptanetetracarboxylic acid Acid, cycloheptanepentacarboxylic acid, cycloheptanehexacarboxylic acid, cycloheptaneheptacarboxylic acid Preferred examples include cyclooctanedicarboxylic acid, cyclooctanetricarboxylic acid, cyclooctanetetracarboxylic acid, cyclooctanepentacarboxylic acid, cyclooctanehexacarboxylic acid, cyclooctaneheptacarboxylic acid, and cyclooctaneoctacarboxylic acid. However, there is no particular limitation.

In the present invention, the compound of oxygen and halogen, which is an element capable of forming a covalent bond with halogen among the elements located in the third period of the periodic table, is used as a halogenating agent, and the alicyclic polyfunctional carboxylic acid described above is used. The acid is dissolved or dispersed in the halogenating agent and reacted. Here, Periodic Table 3
Examples of the elements located at the periodicity and capable of forming a covalent bond with halogen include silicon (Si), phosphorus (P), and sulfur (S). As a compound of such an element, oxygen and halogen, Examples of suitable halogenating agents include, but are not particularly limited to, thionyl halide, phosphoryl halide, sulfuryl halide and the like.
Among these halogenating agents, thionyl halides include thionyl chloride and thionyl bromide, and phosphoryl halides include phosphoryl chloride and phosphoryl bromide.Sulfuryl halides include sulfuryl chloride and sulfuryl bromide. Although each is illustrated as a preferred embodiment, there is no particular limitation. The addition amount of such a halogenating agent is more preferably 1 to 10 mol, preferably 1 to 3 mol, per 1 mol of carboxyl group of the alicyclic polyfunctional carboxylic acid as a starting material.

At the time of this reaction, a solvent which is compatible with the above-mentioned halogenating agent and which does not react with the halogenating agent may be added. Solvents which are compatible with the halogenating agent and do not react with the halogenating agent and which can be added to the reaction system of the present invention include, for example, alkanes, alkenes, alicyclic hydrocarbons, heterocyclic compounds, aromatic compounds Group hydrocarbons, organic halides, ethers, ketones, esters, sulfur compounds, nitrogen compounds and the like are preferred.

Specifically, the alkanes include 2-methylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-pentane, 2,2,3-trimethylpentane, n-hexane, heptane, n- Octane and isooctane are exemplified. Examples of the alkene include 1-pentene, 2-pentene, 1-hexene, 2-hexene, and 3-hexene.
Hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 2-octene and the like are exemplified. Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane and the like.

The heterocyclic compounds include furan, 2-methylfuran, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, trioxane, pyridine, thiophene, N-methyl-2-pyrrolidone, 1- Methyl-2-pyrrolidone and the like are exemplified.
Examples of the aromatic hydrocarbon include benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-xylene
-Diethylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene and the like. As organic halides, dichloromethane, chloroethane,
1,1-dichloroethane, 1,2-dichloroethane,
1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,
1,2,2-tetrachloroethane, chloroform, carbon tetrachloride, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, pentachloroethane, hexachloroethane, propyl chloride, isopropyl chloride, 1,2-dichloropropane, 1,2,3-trichloropropane, allyl chloride, butyl chloride, sec-butyl chloride, isobutyl chloride, te chloride
rt-butyl, 1-chloropentane, chlorobenzene, o
-Dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o-
Chlorotoluene, p-chlorotoluene, bromoform,
Ethyl bromide, 1,2-dibromoethane, 1,1,2,2
-Tetrabromoethane, propyl bromide, isopropyl bromide, bloomobenzene, o-bulmobenzene, fluorobenzene, benzotrifluoride, hexafluorobenzene, chlorobromomethane, trichlorofluoromethane,
1-bromo-2-chloroethane, 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,2,2
-Tetrachloro-1,2-difluoroethane and the like.

Examples of ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, anisole, ethyl vinyl ether, butyl vinyl ether, phenetole, butyl phenyl ether, amyl phenyl ether, methoxy toluene, benzyl Ethyl ether, diphenyl ether, dibenzyl ether, veratrol,
Examples include propylene oxide. As ketones,
Acetone, methyl ethyl ketone, 2-pentanone, 3-
Pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonylacetone, methyl oxide, holon,
Examples include isophorone, cyclohexanone, methylcyclohexanone, acetophenone and the like. As esters, methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetal Sec-hexyl acetate, 2-ethylbutyl acetal, 2-ethylhexyl acetal, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, butyrate, isobutyrate, isovalerate , Stearic acid ester, benzoic acid ester, cinnamic acid ester, abietic acid ester, dioctyl adipate, γ-butyrolactone, oxalate ester, malonate ester, maleate ester, dibutyrate tartrate , Tributyl citrate, sabacic acid ester,
Phthalate, ethylene glycol ester, diethylene glycol monoacetate, monoacetin, diacetin, triacetin, monobutyrin, diethyl carbonate,
Examples include ethylene carbonate, propylene carbonate, borate esters, phosphate esters, lactate esters, methyl salicylate, methyl acetoacetate, ethyl acetoacetate, and ethyl cyanoacetate.

Examples of the sulfur compound include carbon disulfide, dimethyl sulfate, diethyl sulfate, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-
And propane sultone. Examples of the nitrogen compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, acetonitrile, propionitrile, succinyl nitrile, butyronitrile, isobutyronitrile, valeronitrile, benzonitrile, α-tolunitrile and the like. Is done. In addition to the above, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate and the like are exemplified. In the present invention, a single solvent or a mixed solvent of these substances can be used, but is not particularly limited to the above.

This halogenation reaction is carried out at a temperature of 0 to 120 ° C., preferably 20 to 80 ° C., and the purity and yield of the trans alicyclic polyacid halide diastereomer obtained are obtained. Is more desirable because it is possible to further improve The reason for limiting the halogenation temperature in this manner is that the reaction is not carried out at a temperature lower than 0 ° C., whereas the temperature is higher than 120 ° C., because the generation of by-products becomes excessive, which is not preferable. When the temperature is lower than 20 ° C., the reaction is performed, but the reaction takes a long time for a sufficient reaction, resulting in poor efficiency.On the other hand, when the temperature is higher than 80 ° C., among the alicyclic polyacid halogenated diastereomers formed by the reaction, This is because the trans form may be decomposed or a by-product may be generated. But,
In the present invention, the temperature is not necessarily limited to the above-mentioned temperature, and varies depending on various conditions at the time of the synthesis reaction. Although the reaction time varies depending on the temperature conditions,
The reaction is desirably performed at 0 to 70 ° C for 1 to 10 hours.

After the above-mentioned halogenation reaction, if an unreacted halogenating agent and a solvent compatible with the halogenating agent and not reacting with the halogenating agent are added, they are distilled off under reduced pressure, and the reaction product is removed. Concentrate. When the solvent which is compatible with the halogenating agent and does not react with the halogenating agent is distilled off under reduced pressure,
It is particularly desirable to concentrate by evaporating under reduced pressure under a temperature condition of 0 to 20 ° C. lower than the temperature at which the halogenation is performed, preferably 5 to 10 ° C., and among alicyclic polyacid halogenated diastereomers, It is possible to further improve the purity and yield of the trans isomer. For example, if the halogenation is carried out at 60 ° C., when a solvent which is compatible with the unreacted halogenating agent and which does not react with the halogenating agent is added, the solvent is distilled off under reduced pressure and the temperature for concentration is 50 to 55 ° C. Is desirable. As described above, the reason why the concentration temperature when the solvent that is compatible with the halogenating agent and does not react with the halogenating agent is added is set to be 0 to 20 ° C. lower than the temperature at which the halogenation was performed is that This is because if the concentration is performed at the same temperature as the temperature at which the concentration is performed, the concentration can hardly be performed. On the other hand, if the concentration is performed at a temperature lower than 20 ° C., the concentration cannot be performed efficiently. When the temperature is closer to the halogenation temperature than 5 ° C., concentration can be performed, but among the alicyclic polyacid halogenated diastereomers formed by the reaction, the generation of the trans form is not stable for each lot of the reaction, This is because the by-products may increase, while on the other hand, at a temperature lower than 10 ° C., it takes a long time to concentrate, and the efficiency is low. However, in the present invention, the temperature is not necessarily 5 to 10 ° C.
The temperature is not limited to a temperature lower by ° C., but may vary depending on various conditions at the time of concentration, and may be appropriately determined.

After concentrating the reaction product, the trans-isomer is extracted from the alicyclic polyacid halide diastereomer. For this extraction, a solvent in which the unreacted cis-form or acid anhydride of the alicyclic polyfunctional carboxylic acid is difficult to dissolve, and among the alicyclic polyacid halide diastereomers, the trans-isomer is easily dissolved. Is used. Examples of the solvent that hardly dissolves the unreacted alicyclic polyfunctional carboxylic acid cis form or acid anhydride include, for example, alkanes, alkenes, alicyclic hydrocarbons, heterocyclic compounds, aromatic hydrocarbons, organic halides, and ethers. , Ketones, esters, sulfur compounds, nitrogen compounds and the like.

Specifically, alkanes include 2-methylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-pentane, 2,2,3-trimethylpentane, n-hexane, heptane, n-pentane Octane, isooctane and the like are exemplified. Alkenes include 1-pentene, 2-pentene, 1-hexene, 2-hexene,
-Hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 2-octene and the like are exemplified. Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane and the like.

Examples of the heterocyclic compound include furan, 2-methylfuran, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, trioxane, pyridine, thiophene, N-methyl-2-pyrrolidone, 1- Methyl-2-pyrrolidone and the like are exemplified.
Examples of the aromatic hydrocarbon include benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-xylene
-Diethylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene and the like. As organic halides, dichloromethane, chloroethane,
1,1-dichloroethane, 1,2-dichloroethane,
1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,
1,2,2-tetrachloroethane, chloroform, carbon tetrachloride, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, pentachloroethane, hexachloroethane, propyl chloride, isopropyl chloride, 1,2-dichloropropane, 1,2,3-trichloropropane, allyl chloride, butyl chloride, sec-butyl chloride, isobutyl chloride, te chloride
rt-butyl, 1-chloropentane, chlorobenzene, o
-Dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o-
Chlorotoluene, p-chlorotoluene, bromoform,
Ethyl bromide, 1,2-dibromoethane, 1,1,2,2
-Tetrabromoethane, propyl bromide, isopropyl bromide, bloomobenzene, o-bulmobenzene, fluorobenzene, benzotrifluoride, hexafluorobenzene, chlorobromomethane, trichlorofluoromethane,
1-bromo-2-chloroethane, 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,2,2
-Tetrachloro-1,2-difluoroethane and the like.

Examples of ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, anisole, ethyl vinyl ether, butyl vinyl ether, phenetole, butyl phenyl ether, amyl phenyl ether, methoxy toluene, benzyl Ethyl ether, diphenyl ether, dibenzyl ether, veratrol,
Examples include propylene oxide. As ketones,
Acetone, methyl ethyl ketone, 2-pentanone, 3-
Pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonylacetone, methyl oxide, holon,
Examples include isophorone, cyclohexanone, methylcyclohexanone, acetophenone and the like. As esters, methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetal Sec-hexyl acetate, 2-ethylbutyl acetal, 2-ethylhexyl acetal, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, butyrate, isobutyrate, isovalerate , Stearic acid ester, benzoic acid ester, cinnamic acid ester, abietic acid ester, dioctyl adipate, γ-butyrolactone, oxalate ester, malonate ester, maleate ester, dibutyrate tartrate , Tributyl citrate, sabacic acid ester,
Phthalate, ethylene glycol ester, diethylene glycol monoacetate, monoacetin, diacetin, triacetin, monobutyrin, diethyl carbonate,
Examples include ethylene carbonate, propylene carbonate, borate esters, phosphate esters, lactate esters, methyl salicylate, methyl acetoacetate, ethyl acetoacetate, and ethyl cyanoacetate.

Examples of the sulfur compound include carbon disulfide, dimethyl sulfate, diethyl sulfate, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-
And propane sultone. Examples of the nitrogen compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, acetonitrile, propionitrile, succinyl nitrile, butyronitrile, isobutyronitrile, valeronitrile, benzonitrile, α-tolunitrile and the like. Is done. In addition to the above, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate and the like are exemplified. In the present invention, a single solvent or a mixed solvent of these substances can be used, but is not particularly limited to the above. As described above, in the present invention, the trans isomer among the alicyclic polyacid halide diastereomers is selectively produced from the alicyclic polyfunctional carboxylic acid.

Next, the novel alicyclic polyacid halide cyclopentanetricarbonyl chloride obtained by the above-mentioned production method will be described. This acid chloride alicyclic polyacid halide cyclopentanetricarbonyl chloride has (1α, 2β, 4
β) is cyclopentane- (1α, 2β, 4β) -tricarbonyl chloride represented by the general formula (2).

Embedded image

This cyclopentane- (1α, 2β, 4
β) -Tricarbonyl chloride is a liquid substance at room temperature (25 ° C.). Such cyclopentanetricarbonyl chloride can be easily obtained by the above-described method for selectively producing an alicyclic polyacid halide diastereomer according to the present invention.

First, cyclopentane-1,2,4-tricarboxylic acid represented by the general formula (3) is used as an alicyclic polyfunctional carboxylic acid as a starting material, and halogenation is performed with a halogenating agent.

Embedded image

As the halogenating agent, among the elements located in the third period of the periodic table, a compound of an element capable of forming a covalent bond with halogen, and a compound of oxygen and halogen can be used without limitation. , Phosphoryl halide, sulfuryl halide and the like are used as preferred embodiments. Using such a halogenating agent, a temperature of 50
After reacting at ~ 80 ° C for 1 to 10 hours, the reaction solution is distilled off under reduced pressure after the completion of the reaction and concentrated, using a solvent which does not easily dissolve the above-mentioned unreacted alicyclic polyfunctional carboxylic acid cis-form or acid anhydride. By extraction, the cyclopentane- (1α, 2β, 4β) -tricarbonyl chloride according to the present invention is obtained.

Such cyclopentane- (1α, 2
(β, 4β) -Tricarbonyl chloride is a substance of great interest as a material for reverse osmosis membranes.

[0025]

EXAMPLES The method for selectively producing an alicyclic polyacid halide diastereomer according to the present invention will be described more clearly with reference to the following examples.

Example 1 10 g (51 mmol) of cyclopentane-1,2,4-tricarboxylic acid whose two isomers are known from gas chromatography of a methylated product (see FIG. 1) 36 g (305 mmol) of thionyl chloride was added to 55
Stirring was performed at 60 ° C. The reaction product was concentrated with an evaporator, and 300 ml of n-hexane was added. After stirring well, the mixture was allowed to stand for several minutes, and then the supernatant was poured into another container and collected. 2,4-Tricarbonyl chloride was obtained. The obtained cyclopentane
-1,2,4-tricarbonyl chloride has an absorption wave number (cm ^-1 ) of an infrared absorption spectrum of 2930 (W), 1790 (s), 1450
(m), 1010 (m) (see FIG. 2) and the proton magnetic resonance spectrum ( ¹ HNMR) (400 MHz) of this product.
z, DMSO) are 2.40 to 2.75 (4H, m), 3.40 to 3.90 (3H,
m) (see FIG. 3 and FIG. 4), so that cyclopentane- (1α, 2β, 4β)-in which the position of 1,2 is trans
It was found that tricarbonyl chloride was selectively obtained. The product weighed 5.2 g and the yield was
41%. Further, the product was methyl esterified, and the purity by gas chromatography was 97%.

(Example 2) 10 g of cyclopentane-1,2,3,4-tetracarboxylic acid in which it is known from gas chromatography of a methylated product (see FIG. 5) that four kinds of isomers are present. 34.5 g (332 mmol) of thionyl chloride was added to (41 mmol), and the mixture was stirred at 75 to 80 ° C. The reaction product was concentrated with an evaporator, 300 ml of heptane was added, and the mixture was stirred well and allowed to stand for several minutes. Thereafter, the supernatant was poured into another container and collected, and the solution was concentrated to obtain cyclopentane-1,2,
3,4-Tetracarbonyl chloride was obtained. The obtained cyclopentane-1,2,3,4-tetracarbonyl chloride has an absorption wave number (cm ^-1 ) of an infrared absorption spectrum of 2900 (W).
, 1790 (s), 1450 (W), 1260 (m), and 1010 (m) (see FIG. 6) and a proton magnetic resonance spectrum ( ¹ HNMR) (400 MHz, D
(MSO) were 2.95 to 3.05 (2H, m) and 3.20 to 3.25 (2H, m) (see FIGS. 7 and 8).
Cyclopentane- (1α, 2
(β, 3α, 4β) -tetracarbonyl chloride was found to be selectively obtained. The weight of this product was 5.6 g, and the yield was 43%. Further, the product was methyl esterified, and the purity by gas chromatography was 94%.

(Comparative Example) 10 g (50 mmol) of cyclopentane-1,2,4-tricarboxylic acid and 63 g (304 mmol) of phosphorus pentachloride as in Example 1 were suspended in 400 ml of n-heptane.
Stirring was performed at 60 ° C. After reacting at this temperature for 9 hours, it was cooled. The reaction product was filtered, concentrated in an evaporator, added with 300 ml of n-hexane, stirred well, and the supernatant was poured into another container and collected. This solution was concentrated to obtain cyclopentane-1,2,4-tricarbonyl chloride. The weight of this product was 8.3 g, and the yield was 65%. The obtained cyclopentane-1,2,4-tricarbonyl chloride has an absorption wave number (cm ^-1 ) in an infrared absorption spectrum.
Were 2930 (W), 1790 (s), 1450 (m), and 1010 (m) (see FIG. 9) and a proton magnetic resonance spectrum ( ¹ HN).
MR) (400MHz, DMSO), 1.80 ~ 3.00 (4H, m), 3.
25 to 4.00 (3H, m) (see Fig. 10 and Fig. 11)
Cyclopentane- (1α, 2) where the position of 1,2 is trans
It was found that a mixture of β, 4β) -tricarbonyl chloride and cyclopentane- (1β, 2β, 4β) -tricarbonyl chloride in which the 1,2 position is cis was obtained.

[0029]

As described in detail above, the present invention relates to a method of forming an alicyclic polyfunctional carboxylic acid with an element capable of forming a covalent bond with a halogen, oxygen and halogen among the elements located in the third period of the periodic table. The trans isomer is selectively halogenated by reacting the compound as a halogenating agent, and then the trans isomer is separated from unreacted alicyclic polyfunctional carboxylic acid cis form or acid anhydride. Because it is a method for the selective production of alicyclic polyacid halide diastereomers,
An industrially useful alicyclic polyvalent that can control physical and chemical properties such as thermal properties, strength, and linear expansion coefficient within a certain range as a polymer production material such as a crosslinking agent and a condensing agent. The trans-isomer of the acid halide diastereomer has an excellent effect that it can be produced very easily and with high purity and high yield. Furthermore, the novel alicyclic polyacid halide cyclopentane-1α, 2β, 4β-tricarbonyl chloride obtained by the above method has an excellent effect to be a very useful substance as a material for a reverse osmosis membrane.

[Brief description of the drawings]

FIG. 1 shows gas chromatography of a methylated starting material cyclopentane-1,2,4-tricarboxylic acid in one embodiment of the method for selectively producing an alicyclic polyacid halide diastereomer of the present invention. It is a chart figure.

FIG. 2 is an infrared absorption spectrum of cyclopentane- (1α, 2β, 4β) -tricarbonyl chloride.

FIG. 3 is a proton magnetic resonance spectrum of cyclopentane- (1α, 2β, 4β) -tricarbonyl chloride.

FIG. 4 is a partially enlarged spectrum diagram of the one shown in FIG. 3;

FIG. 5 is a chart showing gas chromatography of a methylated cyclopentane-1,2,3,4-tetracarboxylic acid.

FIG. 6: Cyclopentane- (1α, 2β, 3α, 4β)-
FIG. 3 is an infrared absorption spectrum of tetracarbonyl chloride.

FIG. 7: Cyclopentane- (1α, 2β, 3α, 4β)-
FIG. 3 is a proton magnetic resonance spectrum of tetracarbonyl chloride.

FIG. 8 is a partially enlarged spectrum diagram of the one shown in FIG. 7;

FIG. 9 shows cyclopentane- (1α, 2β, 4β) -tricarbonyl chloride and cyclopentane- (1β, 2β,
FIG. 3 is an infrared absorption spectrum diagram showing a mixture of 4β) -tricarbonyl chloride.

FIG. 10 shows cyclopentane- (1α, 2β, 4β) -tricarbonyl chloride and cyclopentane- (1β, 2β,
FIG. 4 is a proton magnetic resonance spectrum diagram showing a mixture of 4β) -tricarbonyl chloride.

FIG. 11 is a partially enlarged spectrum diagram of the one shown in FIG. 10;

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Yasuo Kihara 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nippon Denko Corporation (72) Inventor Masatoshi Maeda 1-1-1-2 Shimohozumi, Ibaraki-shi, Osaka No. Japan TEPCO (72) Inventor Yutaka Nakazono 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Japan Nippon Electric Works (72) Inventor Katsuhide Kojima 1-1-2, Shimohozumi, Ibaraki-shi, Osaka (1) 1-2, Shimohozumi, Ibaraki-shi, Osaka Prefecture, Japan 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Japan (72) Inventor, Kenji Matsumoto 1-1-2, Shimohozumi, Ibaraki-shi, Osaka, Japan (Japanese) JP-A-6-205952 (JP, A) JP-A-5-201918 (JP, A) JP-A-58-110538 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C07C 51/60 C07C 61/15 C07C 61/04 C07C 61/08 C07B 39/00 C07B 61/00 300

Claims (5)

(57) [Claims] 1. The alicyclic polyfunctional carboxylic acid is added to the Periodic Table 3
A trans-isomer is selectively halogenated by reacting a compound of oxygen and halogen with an element capable of forming a covalent bond with halogen among the elements located in the periodicity, and then reacting with an unreacted alicyclic compound A method for selectively producing an alicyclic polyacid halide diastereomer, comprising separating the trans form from a polyfunctional carboxylic acid cis form, an acid anhydride or the like. 2. The alicyclic polyacid halogen according to claim 1, wherein the halogenating agent is at least one selected from thionyl halide, phosphoryl halide, and sulfuryl halide. Process for the selective production of diastereomers. 3. The alicyclic polyfunctional carboxylic acid has 3 carbon atoms.
The method for selectively producing an alicyclic polyacid halide diastereomer according to any one of claims 1 to 2, wherein the diastereomer is a monocyclic ring. 4. The method according to claim 2, wherein the halogen of the thionyl halide, phosphoryl halide and sulfuryl halide is chlorine or bromine. Production method. 5. A novel alicyclic polyacid halide cyclopentane represented by the general formula 1 wherein the first, second and fourth positions of the trans form are (1α, 2β, 4β). 1
α, 2β, 4β-tricarbonyl chloride. Embedded image