JPH08311055A - Production of carboxyalkylthiosuccinic anhydride - Google Patents

Abstract

PURPOSE: To produce the subject compound little colored and having high purity in high yield by reacting a mercaptoalkyl carboxylic acid with maleic anhydride by using a polar solvent and a basic ion-exchange resin as a catalyst. CONSTITUTION: (A) Mercaptoalkyl carboxylic acid of the formula HOOCRSH (R is a 2-4C divalent hydrocarbon) is made to react with (B) maleic anhydride of formula I by using (C) a polar solvent (e.g. acetone, dioxane, etc.) having a solubility parameter of >=9.0 and capable of dissolving a raw material and a reaction product in the presence of (D) a basic ion-exchange resin (preferably, a resin having a tertiary amine as an ion-exchanging group) as a catalyst to obtain (E) a carboxyalkylthiosuccinic anhydride of formula II. Further, it is preferable to carry out the reaction at a molar ratio of the component A and the component B, the component A/the component B= 0.8-1.2 by using the component C of 0.5-10 times the total amount of the component A and the component B in weight, and the component D of 0.05-10wt.% of the total amount at a reaction temperature of 30-120 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing carboxyalkylthiosuccinic anhydride. For more information,
A polycarboxylic acid intermediate useful as a chelating agent, a water treatment agent, a builder for detergents, and the like, and a carboxyalkylthiosuccinic anhydride useful as an industrial intermediate have little coloration, high purity, and high yield. It relates to a manufacturing method obtained at a rate.

[0002]

2. Description of the Related Art It has been conventionally known to use a basic catalyst such as pyridine or triethylamine in a solvent when reacting various mercapto compounds with maleic anhydride. {Journal of Organic Chemistry Vol. 27, 3
Also, US Pat. No. 3,909,493 discloses that a salt of dimethylbenzylamine is used as a reaction catalyst.

[0003]

When the basic catalyst of amines such as pyridine and triethylamine is used,
Further, when a salt of dimethylbenzylamine is used, the reaction product is colored in blackish brown or brown, which requires many purification steps, resulting in a problem that the yield is reduced.

[0004]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that (1) a polar solvent is used (2)
It has been found that when the reaction is carried out using a basic ion exchange resin as a catalyst, there is little coloring, the number of purification steps is small, and the yield is high, and the present invention has been completed. That is, an object of the present invention is to provide the following manufacturing method. The following formula [1]

[0005]

Embedded image

In the production of carboxyalkylthiosuccinic anhydride represented by the formula (wherein R is a divalent hydrocarbon group having 2 to 4 carbon atoms), (1) Formula (2) HOOC-R -SH [2] (wherein R is a divalent hydrocarbon group having 2 to 4 carbon atoms) and (B) formula [3].

[0007]

[Chemical 4]

A method for producing a carboxyalkylthiosuccinic anhydride of the formula [1], characterized in that (2) a polar solvent is used and (3) a basic ion exchange resin is used as a catalyst. . Further, in producing the carboxyalkylthiosuccinic anhydride represented by the formula [1], (1) (A) the mercaptoalkylcarboxylic acid represented by the formula [2] and (B) the maleic anhydride represented by the formula [3]. The total amount of the compounds of formula [2] and formula [3] is (2) a polar solvent having a solubility parameter of 9.0 or more at a reaction molar ratio of formula [2] / formula [3] of 0.8 to 1.2. For 0.5 to 1
0 to 10 times by weight (3) 0.05 to 10% by weight based on the total amount of the compounds of formula [2] and formula [3] using a basic ion exchange resin as a catalyst (4) at a reaction temperature of 30 to 120 ° C A method for producing carboxyalkylthiosuccinic anhydride characterized by reacting.

R in the formulas [1] and [2] of the present invention is a divalent hydrocarbon group having 2 to 4 carbon atoms, specifically, ethylene group, propylene group, butylene group, isopropylene group. , And an isobutylene group.

The formula [2] used in the present invention is specifically as follows.
3-mercaptopropionic acid, 2-methyl-3-mercaptopropionic acid, 4-mercaptobutyric acid, 5-
Examples thereof include mercaptopentanoic acid. Preferred are 3-mercaptopropionic acid, 2-methyl-3-mercaptopropionic acid, and 4-mercaptobutyric acid.

The reaction molar ratio is such that the reaction molar ratio of the formula [2] / the formula [3] is 0.8 to 1.2. If the molar ratio is less than 0.8, unreacted maleic anhydride is increased. However, it is difficult to remove and purify, and it is not preferable. When the amount is more than 1.2, the amount of mercaptoalkylcarboxylic acid increases, and it is difficult to remove and purify.

The polar solvent used in the present invention is limited to those having a solubility parameter value of 9.0 or more and capable of dissolving raw materials and products. That is, mercaptoalkylcarboxylic acid, unsaturated dicarboxylic acid anhydride is dissolved,
And it is limited to those that dissolve the reaction product. Specific examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diethyl ketone; cyclic ethers such as dioxane; dimethylformamide, dimethyl sulfoxide, and the like. When the value of the solubility parameter is less than 9.0, the solubility is lowered, which is not preferable.

The amount of the solvent used is 0.5 to 10 times by weight the total amount of the compounds of the formulas [2] and [3]. Preferably, 2 to 5 times by weight is used. When the amount of the solvent used is less than 0.5 times by weight, the viscosity of the reaction system becomes high, which is not preferable, and when it is more than 10 times by weight, the production efficiency is deteriorated.
It takes time to remove the solvent, which is not preferable.

The basic ion-exchange resin of the catalyst used in the present invention is a weakly basic ion-exchange resin having a basic skeleton of a copolymer of styrene and divinylbenzene or a copolymer of divinylbenzene and methacrylate. It is a resin. Among them, those having a tertiary amino group as an ion exchange group are particularly preferable. As a specific commercially available product, a product name of DIAION WA3 manufactured by Mitsubishi Chemical Corporation
0, WA10, WA11 and ROHM AND
Examples include Amberlyst IRA94S and Amberlite IRA-93ZU manufactured by Haas.

The amount of the basic ion exchange resin used as the catalyst is
0.05 based on the total amount of the compounds of formula [2] and formula [3]
It is -10% by weight, preferably 0.1-2% by weight. If it is less than 0.05% by weight, the reaction rate becomes slow, which is not preferable, and if it is more than 10% by weight, the handling operation of a large amount of ion exchange resin and the operation of filtering are unfavorable.

The reaction temperature for reacting the compound of formula [2] with the compound of formula [3] is 30 to 120 ° C., more preferably 60 to 120 ° C.
90 ° C. If the temperature is lower than 30 ° C., the reaction takes a long time, and if the temperature is higher than 120 ° C., a side reaction occurs and the yield is lowered, which is not preferable.

The reaction may be carried out by charging the whole amount in a reaction vessel and stirring it, or by fixing the ion exchange resin in a column type reaction tube and circulating the reaction solution therein.

As the purification method after the reaction of the present invention, the ion-exchange resin is removed by filtration or the like, and then an aromatic solvent in which the product is insoluble is mixed with the filtrate to form crystals, or the reaction is carried out. You may use the method of crystallizing and purifying using the solvent used for.

[0019]

According to the production method of the present invention, a highly pure product having a good hue can be obtained in a high yield.

[0020]

The present invention will be described below in detail with reference to examples.

Example 1 196 g of maleic anhydride, 212 g of 3-mercaptopropionic acid, 800 g of methyl ethyl ketone and an ion exchange resin were placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube. 1 g of "DIAION WA30" was taken, the temperature was raised to 80 ° C. while introducing nitrogen gas, and the mixture was stirred for 3 hours. Then, it was cooled, and the ion exchange resin was filtered off from the reaction solution. The filtrate was heated to 100 ° C. and 400 g of methyl ethyl ketone as a solvent was distilled off. Then, while stirring, 200 g of toluene heated to 90 ° C. was added dropwise to this reaction solution little by little, and then cooled to 20 ° C. The generated pale yellow crystals were separated by filtration and dried to obtain 350.8 g of crystals. The purity determined from the liquid chromatogram was 98.4%.

<Measurement conditions for liquid chromatogram> Model: TRIROTAR TU manufactured by Hitachi Spectroscopy
-100 developing solvent; 0.03 wt% perchloric acid aqueous solution packed column; SHODEX C-811 column length; 40 cm sample amount; 1 μl outflow amount; 1.0 ml / min column temperature; 60 ° C. detector; UV210 nm raw material, The charged amount, reaction conditions and products are shown in Table 1, respectively.

[0023]

[Table 1]

The abbreviations used in the table are as follows. Catalyst; W30; Diaion WA30 (trade name of Mitsubishi Chemical Co., Ltd.) W10; Diaion WA10 (trade name of Mitsubishi Chemical Co., Ltd.) I93; Amberlite IRA-93ZU (trade name of Rohm and Haas Company) I94; Amberlyst IRA94S (trade name, manufactured by Rohm and Haas Co.) solvent; MEK; methyl ethyl ketone DOX; dioxane

Examples 2-5 In Example 1, 3-mercaptopropionic acid 212
Instead of g or ion exchange resin "Diaion W
Instead of 1 g of A30 ", a reaction was carried out in the same manner as in Example 1 by using the raw materials and reaction conditions shown in Table 1. The results are shown in Table 1.

Comparative Examples 1 to 3 Ion exchange resin "DIAION WA30" 1 of Example 1
Triethylamine or triethylenediamine was used as a catalyst instead of g, and the same reaction was carried out under the starting materials and reaction conditions shown in Table 1. The results are shown in Table 2.

[0027]

[Table 2]

The abbreviations used in the table are as follows. Catalyst; TEA; Triethylamine TDA; Triethylenediamine Solvent; TOL; Toluene DOX; Dioxane From the results of Tables 1 and 2 above, Examples 1 to 5 have better hues and higher purity and yield than Comparative Examples 1 to 3. It turns out that is even better.

Claims (2)

[Claims] 1. The following formula [1]: (However, R is a divalent hydrocarbon group having 2 to 4 carbon atoms.) In the production of carboxyalkylthiosuccinic anhydride, (1) (A) formula [2] HOOC-R-SH [ 2] (wherein, R is a divalent hydrocarbon group having 2 to 4 carbon atoms) and a mercaptoalkylcarboxylic acid (B) represented by the formula [3] And (2) a polar solvent and (3) a basic ion-exchange resin as a catalyst. A method for producing carboxyalkylthiosuccinic anhydride of the formula [1]. 2. When producing a carboxyalkylthiosuccinic anhydride represented by the above formula [1], (1) (A) a mercaptoalkylcarboxylic acid of the above formula [2] and (B) a mercaptoalkylcarboxylic acid of the above formula [3] Maleic anhydride is used in a reaction molar ratio of the formula [2] / the formula [3] of 0.8 to 1.2, and (2) a polar solvent having a solubility parameter of 9.0 or more is used in the formula [2] and the formula [3]. 0.5 to 1 relative to the total amount of compounds
0 to 10 times by weight (3) 0.05 to 10% by weight based on the total amount of the compounds of formula [2] and formula [3] using a basic ion exchange resin as a catalyst (4) at a reaction temperature of 30 to 120 ° C The method for producing carboxyalkylthiosuccinic anhydride according to claim 1, which comprises reacting.