JPH11199540A - Production of 3-chloropropionyl chloride - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively obtain the subject chloropropionyl chloride that is useful as an intermediate for pharmaceutical and agrochemicals in high yield via a one-step process by reaction of acrylic acid with thionyl chloride in the presence of a basic organic compound. SOLUTION: (A) Acrylic acid and (B) thionyl chloride are reacted with each other in a basic organic compound as N,N-dimethylformamide. In a preferred embodiment, 1 mole of the component A is allowed to react with 1.0-1.2 mole of the component B in the component C in a 0.1-10 time molar amount based on the component A at 30-110 deg.C to give the objective compound. In a preferred embodiment, the whole amount of the component A is charged in the reactor, then the component B is dripped usually over a period of 0.5-24 hours. After completion of the dripping, the reaction mixture is preferably retained for 0.1-10 hours under agitation, until the reaction finishes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 3-chloropropionic chloride which is useful as an intermediate for medical and agricultural chemicals.

[0002]

2. Description of the Related Art As a method for producing 3-chloropropionic acid chloride, (1) a method of chlorinating 3-chloropropionic acid with a chlorinating agent such as phosphorus trichloride, thionyl chloride, phosgene, and (2) acrylic acid Alternatively, after adding hydrogen chloride to acrylonitrile, a chlorinating agent such as phosphorus trichloride, thionyl chloride, or phosgene is allowed to act to chlorinate, (3) phosgene is reacted with acrylic acid to perform 3-
There are known a method for producing chloropropionic acid chloride (U.S. Pat. No. 4,213,919), and a method (4) for reacting benzotrichloride with acrylic acid (JP-A-61-155351).

However, none of these methods can be said to be industrially satisfactory manufacturing methods and has some problems. For example, in the method (1) using 3-chloropropionic acid as a raw material, 3-chloropropionic acid is relatively expensive and cannot be said to be an economically advantageous method. On the other hand, (2) ~
The method (4) is advantageous in that acrylic acid or acrylonitrile as a raw material can be obtained at low cost.

The most common method among (2) to (4) is
The method of (2) is a two-stage reaction of an addition reaction of hydrogen chloride and a chlorination reaction, so that the process becomes complicated. Also,
Among the chlorinating agents, phosphorus compounds such as phosphorus trichloride have a problem that the post-treatment of the phosphorus compound after the reaction is troublesome, and phosgene has a problem that it is difficult to handle because it is extremely toxic.

[0005] The method (3) has the advantage that the desired 3-chloropropionic acid chloride can be produced in one step, but it is difficult to handle phosgene as described above.

In the method (4), the desired product can be produced in a single step in a high yield. However, since 3-chloropropionic chloride and an equivalent amount of benzoyl chloride are produced as by-products, it is necessary to separate them by means such as distillation. There is. However, since 3-chloropropionic acid chloride is easily converted to acrylic acid chloride by heating, distillation operation is difficult, and there is a problem in industrial production.

[0007]

The use of thionyl chloride as a chlorinating agent has a problem that an equivalent amount of hydrogen chloride and sulfur dioxide are produced as by-products, so that neutralization of these gases is necessary, but the reaction proceeds well. However, it is relatively inexpensive, has low toxicity among chlorinating agents, and is industrially excellent in that it is liquid and easy to handle.

[0008] Therefore, it would be industrially very advantageous if 3-chloropropionic acid chloride could be produced in one step by using thionyl chloride as a chlorinating agent using inexpensive acrylic acid as a raw material.

Although the target substance is different, an example in which acrylic acid is chlorinated with thionyl chloride is described in JP-A-5-331122. However, as shown in the examples of this publication, when acrylic acid is chlorinated with thionyl chloride, acrylic acid chloride in which acrylic acid is only chlorinated and 3-chloropropionic acid to which hydrogen chloride has been added are added. Chloride is produced at a molar ratio of about 65% and 35%, respectively. That is, the main product is acrylic acid chloride, and the yield of 3-chloropropionic acid chloride is low.

A specific object of the present invention is to provide a method for producing 3-chloropropionic acid chloride in one step with high yield by chlorinating acrylic acid with thionyl chloride.

[0011]

Means for Solving the Problems The inventors of the present invention intend to synthesize 3-chloropropionic acid chloride by effectively utilizing hydrogen chloride produced as a by-product when chlorinating acrylic acid as a raw material with thionyl chloride. As a result, the inventors have found that by reacting acrylic acid and thionyl chloride in the presence of a basic organic compound, 3-chloropropionyl chloride can be synthesized in one step in a high yield, and completed the present invention. Was.

Here, the present invention is a process for producing 3-chloropropionic chloride, which comprises reacting acrylic acid and thionyl chloride in the presence of a basic organic compound. The reaction formula of the method of the present invention is shown below.

[0013]

Embedded image

As can be seen from the above reaction formula, when thionyl chloride acts on acrylic acid, carboxylic acid groups are first chlorinated to form acrylic acid chloride, and hydrogen chloride and sulfur dioxide are produced as by-products. By-product hydrogen chloride is added to the double bond of acrylic acid chloride to produce the desired 3-chloropropionic acid chloride.

The addition of hydrogen chloride to the double bond results in 3-chloropropionic chloride having chlorine added at the 3-position and hydrogen added at the 2-position. Of the two types of acid gas produced as a by-product in the first reaction, hydrogen chloride is consumed in the reaction system, so sulfur dioxide is mainly released from the reaction system,
Neutralization is relatively easy.

Not all of the starting acrylic acid is subjected to the above two-stage reaction in the above order. Hydrogen chloride by-produced in the first reaction reacts with unreacted acrylic acid remaining in the reaction system, and hydrogen chloride is added to the double bond of acrylic acid, and then this addition product is chlorinated with thionyl chloride. There may also be some raw materials that go through the process of producing 3-chloropropionic chloride.

Without the presence of a basic organic compound, as shown in JP-A-5-331122, the probability of stopping the reaction at the first reaction increases, and acrylic acid chloride becomes a main product. On the other hand, when the reaction is carried out in the presence of a basic organic compound according to the present invention, the addition reaction of hydrogen chloride to acrylic acid chloride proceeds easily.
-Chloropropionic acid chloride can be obtained in good yield. When an inorganic base (eg, NaOH) is used as a basic compound, it reacts with hydrogen chloride by-produced in the first reaction to form a salt (eg, NaCl), so that the subsequent hydrogen chloride addition reaction does not proceed. .

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION As shown above, the reaction used in the present invention is a two-stage reaction. However, in practice, the above two-stage reaction proceeds only by reacting acrylic acid with thionyl chloride. The reaction operation is one stage. That is, when acrylic acid and thionyl chloride are reacted in the presence of a basic organic compound, the above-mentioned two-step reaction automatically proceeds.

The amount of thionyl chloride used is preferably 0.8 to 1.5 times the molar ratio of acrylic acid, more preferably
1.0 to 1.2 times. If the amount of thionyl chloride is too small, the conversion of acrylic acid decreases, and if it is too large, unreacted thionyl chloride remains, which is not economical.

The basic organic compound is not particularly limited as long as it is present in a reaction solution under predetermined reaction conditions. Illustrative compounds include propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine,
Dodecylamine (laurylamine), tridecylamine, tetradecylamine, pentadecylamine, cetylamine, stearylamine, 2-ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, 3-methoxypropylamine, 3-ethoxypropyl Aliphatic primary amines such as amine and ethanolamine;
Aliphatic secondary amines such as diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, distearylamine, di-2-ethylhexylamine; triethylamine, tripropylamine, tributylamine, triamylamine, triethylamine Octylamine, triethylhexylamine,
Aliphatic tertiary amines such as dimethyloctylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine; tetramethylethylenediamine, 3- (dibutylamino) propylamine, 3- (methylamino) propylamine, 3- ( Dimethylamino)
Diamines such as propylamine; alicyclic amines such as cyclopropylamine, cyclobutylamine, cyclopentylamine and cyclohexylamine; aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, toluidine, benzylamine, dibenzylamine; Aromatic amines such as diphenylamine, triphenylamine and naphthylamine; N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone,
Acid amides such as N-methyl-2-pyrrolidone and hydantoins; pyridines such as pyridine, picoline and lutidine; quinolines such as quinoline, isoquinoline, methylquinoline and dimethylquinoline; Examples include imidazoles and pyrrolidines. Among them, N, N-dimethylformamide is particularly preferred.

The amount of the basic organic compound used is preferably 0.01 to 20 times the molar ratio of acrylic acid. If the amount is less than this, chlorination proceeds, but addition of hydrogen chloride to the double bond does not sufficiently occur, and the production rate of acrylic acid chloride increases, which is not desirable. Too much does not adversely affect the reaction, but does not change the effect. A more preferred amount is 0.5 to 10 times the above molar ratio.

The reaction can be carried out using an inert solvent such as benzene, toluene, xylene, methylene chloride, chloroform and the like. However, since acrylic acid and thionyl chloride are both liquid at room temperature, The reaction can be carried out sufficiently without using a solvent. The reaction temperature is not particularly limited, but in the case of normal pressure, from normal temperature to reflux temperature, for example,
The reaction proceeds sufficiently at a temperature of about 30 to 110 ° C. The reaction is usually carried out conveniently at normal pressure, but there is no problem if the reaction is carried out under pressure. Since the addition reaction of hydrogen chloride to the double bond is preferably under pressure, if it can cope with the generated sulfur dioxide gas (for example, if it is possible to cope with high-pressure specifications or reaction equipment that can adjust pressure) Performing under pressure is advantageous for the progress of the reaction.

There is no particular restriction on the reaction system, but it is industrially preferable to carry out the method by dropping one of the reaction components, that is, either thionyl chloride or acrylic acid, in order to control the reaction. In this case, the order of charging is not particularly limited.However, in order to effectively utilize hydrogen chloride by-produced by chlorination by adding to the double bond, the entire amount of acrylic acid is charged from the beginning, and thionyl chloride is added dropwise. It is desirable to do. As described above, hydrogen chloride can be added to the double bond even if acrylic acid has not undergone the first reaction. In addition, there is no problem in the method of simultaneously dropping acrylic acid and thionyl chloride.

The dropping time is determined in accordance with the charged capacity, the reaction temperature, the heat removal ability, the ability to remove sulfur dioxide gas, and the like, and is usually about 0.5 to 24 hours. After completion of the dropwise addition, it is preferable to complete the reaction by maintaining the same temperature or the same temperature while stirring for 0.1 to 10 hours. Since the gas generated during the reaction is an acidic gas mainly containing sulfur dioxide as described above, it is collected by a method such as absorption in an aqueous solution of a suitable base (eg, aqueous ammonia, ammonium carbonate, sodium hydroxide). do it.

After completion of the reaction, it is possible to purify 3-chloropropionic acid chloride by means such as distillation. However, as described above, 3-chloropropionic acid chloride is not thermally stable. If it does not hinder the step, it is preferable to use it as it is.

[0026]

The present invention will be described below in detail with reference to examples. In the examples,% for the purity of the reaction solution is% by weight, and% for the yield is mol%.

Example 1 Acrylic acid (73.0) was placed in a 200 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (1.01 mol) and 7.2 g of N, N-dimethylformamide (0.10 mol
mol) and heated to 70 ° C. with stirring. Next, 125.0 g (1.05 mol) of thionyl chloride was added dropwise over 5 hours while maintaining the reaction temperature at 70 ° C., and the mixture was further stirred at the same temperature for 0.5 hour to obtain 133.7 g of a reaction solution.

The reaction mixture was analyzed by gas chromatography to find that acrylic acid 1.0%, acrylic acid chloride 6.9%,
The yield of 3-chloropropionic acid chloride was 79.9%, the yield of acrylic acid chloride was 10.1%, and the yield of 3-chloropropionic acid chloride was 83.0%.

Example 2 Acrylic acid 7.2 was placed in a 50 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.10 mol) and 0.73 g of N, N-dimethylformamide (0.01
mol) and heated to 70 ° C. with stirring. Next, 12.5 g (0.11 mol) of thionyl chloride was added dropwise over 0.5 hours while maintaining the reaction temperature at 70 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 11.2 g of a reaction solution.

The reaction mixture was analyzed by gas chromatography to find that acrylic acid 0.6%, acrylic acid chloride 13.7%,
The yield of 3-chloropropionic acid chloride was 79.7%, the yield of acrylic acid chloride was 17.0%, and the yield of 3-chloropropionic acid chloride was 70.3%.

Example 3 Acrylic acid 7.2 was placed in a 50 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.10 mol) and N, N-dimethylformamide 0.07 g (0.001 g)
mol) and heated to 70 ° C. with stirring. Next, 12.5 g (0.11 mol) of thionyl chloride was added dropwise over 0.7 hours while maintaining the reaction temperature at 70 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 8.5 g of a reaction solution.

When the reaction mixture was analyzed by gas chromatography, acrylic acid 0.8%, acrylic acid chloride 36.0%,
3-chloropropionic acid chloride was 62.4%, acrylic acid chloride yield was 35.3%, and 3-chloropropionic acid chloride yield was 61.1%.

Example 4 Acrylic acid 7.2 was placed in a 50 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.10 mol) and 7.2 g of N, N-dimethylformamide (0.10 mol
mol) and heated to 70 ° C. with stirring. Next, 12.5 g (0.11 mol) of thionyl chloride was added dropwise over 1 hour while maintaining the reaction temperature at 70 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 23.2 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 0.1%, acrylic acid chloride 5.7%,
The yield of 3-chloropropionic acid chloride was 45.8%, the yield of acrylic acid chloride was 14.5%, and the yield of 3-chloropropionic acid chloride was 83.6%.

Example 5 Acrylic acid 14.4 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.20 mol) and N, N-dimethylformamide 1.46 g (0.02
mol) and heated to 30 ° C. with stirring. Next, 25.1 g (0.21 mol) of thionyl chloride was added dropwise over 2.7 hours while maintaining the reaction temperature at 30 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 29.4 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 1.1%, acrylic acid chloride 16.2%,
The yield was 62.7% of 3-chloropropionic acid chloride, the yield of acrylic acid chloride was 26.2%, and the yield of 3-chloropropionic acid chloride was 72.5%.

Example 6 Acrylic acid 14.4 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.20 mol) and N, N-dimethylformamide 1.46 g (0.02
mol) and heated to 50 ° C. with stirring. Next, 25.1 g (0.21 mol) of thionyl chloride was added dropwise over 2.2 hours while maintaining the reaction temperature at 50 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 27.1 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 0.7%, acrylic acid chloride 8.3%,
The yield of 3-chloropropionic acid chloride was 80.0%, the yield of acrylic acid chloride was 12.4%, and the yield of 3-chloropropionic acid chloride was 85.3%.

Example 7 Acrylic acid 14.4 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.20 mol) and N, N-dimethylformamide 1.46 g (0.02
mol) and heated to 90 ° C. with stirring. Next, 25.1 g (0.21 mol) of thionyl chloride was added dropwise over 1.7 hours while maintaining the reaction temperature at 90 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 24.4 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 1.1%, acrylic acid chloride 7.6%,
The yield was 75.1% of 3-chloropropionic acid chloride, the yield of acrylic acid chloride was 10.2%, and the yield of 3-chloropropionic acid chloride was 72.1%.

Example 8 Acrylic acid 14.4 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.20 mol) and N, N-dimethylformamide 1.46 g (0.02
mol) and heated to 110 ° C. with stirring. next,
25.1 g (0.21 mol) of thionyl chloride was added dropwise over 1 hour while maintaining the reaction temperature at 110 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 18.8 g of a reaction solution.

When the reaction mixture was analyzed by gas chromatography, acrylic acid 0.6%, acrylic acid chloride 9.2%,
3-chloropropionic acid chloride was 72.8%, acrylic acid chloride yield was 9.6%, and 3-chloropropionic acid chloride yield was 54.0%.

Comparative Example 1 Acrylic acid 7.2 was placed in a 50 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.10 mol) and heated to 25 ° C. with stirring.
Next, 12.5 g (0.11 mol) of thionyl chloride was added dropwise over 0.5 hours while maintaining the reaction temperature at 25 ° C., and the mixture was further stirred at the same temperature for 7 hours to obtain 9.6 g of a reaction solution.

The reaction mixture was analyzed by gas chromatography to find that acrylic acid 5.5%, acrylic acid chloride 70.9%,
3-chloropropionic acid chloride was 22.3%, acrylic acid chloride yield was 75.2%, and 3-chloropropionic acid chloride yield was 16.8%.

Comparative Example 2 Acrylic acid 7.2 was placed in a 50 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.10 mol) and heated to 50 ° C. with stirring.
Next, 12.5 g (0.11 mol) of thionyl chloride was added dropwise over 1 hour while maintaining the reaction temperature at 50 ° C., and the mixture was further stirred at the same temperature for 1.5 hours to obtain 9.8 g of a reaction solution.

The reaction solution was analyzed by gas chromatography to find that 1.7% of acrylic acid, 54.6% of acrylic acid chloride,
3-chloropropionic acid chloride was 40.4%, acrylic acid chloride yield was 58.9%, and 3-chloropropionic acid chloride yield was 31.0%.

Comparative Example 3 Acrylic acid 14.4 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.20 mol) and heated to 90 ° C. with stirring.
Next, 25.1 g (0.21 mol) of thionyl chloride was added dropwise over 2.2 hours while maintaining the reaction temperature at 90 ° C, and the mixture was further stirred at the same temperature for 1 hour to obtain 20.9 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 2.1%, acrylic acid chloride 40.0%,
3-Chloropropionic acid chloride was 47.2%, acrylic acid chloride yield was 46.3%, and 3-chloropropionic acid chloride yield was 38.9%.

The reaction conditions and test results of Examples 1 to 8 and Comparative Examples 1 to 3 are summarized in Table 1.

[0050]

[Table 1]

As shown in Comparative Examples 1 to 3, when acrylic acid and thionyl chloride were reacted in the absence of a basic organic compound, the main product was acrylic acid chloride.
The yield of chloropropionic chloride was as low as 40% or less. On the other hand, when the same reaction is carried out in the presence of a basic organic compound according to the present invention, the amount of the basic organic compound used is as small as 0.01 mol times relative to acrylic acid, and even in Example 3, 3-chloropropionic acid chloride was used. A yield of 60% or more was obtained, and a high yield of about 85% could be obtained depending on the conditions.

Example 9 Acrylic acid 14.4 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
g (0.20 mol) and 1.58 g (0.02 mol) of pyridine were added and heated to 70 ° C. with stirring. Next, 25.1 g of thionyl chloride
(0.21 mol) was added dropwise over 2.3 hours while maintaining the reaction temperature at 70 ° C., and the mixture was further stirred at the same temperature for 2 hours to obtain 26.8 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 2.5%, acrylic acid chloride 8.7%,
3-Chloropropionic acid chloride was 66.1%, acrylic acid chloride yield was 12.9%, and 3-chloropropionic acid chloride yield was 69.9%.

Example 10 Acrylic acid 1 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
Put 4.4 g (0.20 mol) and 1.86 g (0.02 mol) of aniline,
Heat to 70 ° C. with stirring. Next, thionyl chloride 2
5.1 g (0.21 mol) was added dropwise over 2.3 hours while maintaining the reaction temperature at 70 ° C., and the mixture was further stirred at the same temperature for 1 hour.
3.1 g were obtained.

When the reaction solution was analyzed by gas chromatography, acrylic acid 2.0%, acrylic acid chloride 5.9%,
3-chloropropionic acid chloride was 68.9%, acrylic acid chloride yield was 7.5%, and 3-chloropropionic acid chloride yield was 62.6%.

Example 11 Acrylic acid 1 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
4.4 g (0.20 mol) and 2.02 g (0.02 mol) of triethylamine
And heated to 70 ° C. with stirring. Next, 25.1 g (0.21 mol) of thionyl chloride was added while maintaining the reaction temperature at 70 ° C.
The mixture was added dropwise over 8 hours, and further stirred at the same temperature for 1 hour to obtain 27.4 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 1.5%, acrylic acid chloride 9.9%,
The yield was 33.3% of 3-chloropropionic acid chloride, the yield of acrylic acid chloride was 15.0%, and the yield of 3-chloropropionic acid chloride was 46.8%.

Example 12 Acrylic acid 1 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
4.4 g (0.20 mol) and 7.07 g (0.02 mo
l) was added and heated to 50 ° C. with stirring. Next, 25.1 g (0.21 mol) of thionyl chloride was added dropwise over 2 hours while maintaining the reaction temperature at 50 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 33.0 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 0.6%, acrylic acid chloride 18.5%,
3-chloropropionic acid chloride was 48.1%, acrylic acid chloride yield was 33.8%, and 3-chloropropionic acid chloride yield was 62.4%.

Example 13 Acrylic acid 1 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
4.4 g (0.20 mol) and di-2-methylhexylamine 4.83
g (0.02 mol) and heated to 50 ° C. with stirring.
Next, 25.1 g (0.21 mol) of thionyl chloride was added dropwise over 2.2 hours while maintaining the reaction temperature at 50 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 29.9 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 0.5%, acrylic acid chloride 12.2%,
3-chloropropionic acid chloride was 49.4%, acrylic acid chloride yield was 20.1%, and 3-chloropropionic acid chloride yield was 58.1%.

Example 14 Acrylic acid 1 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
4.4 g (0.20 mol) and dilauryl monomethylamine 7.34 g
(0.02 mol) and heated to 50 ° C. with stirring. Next, 25.1 g (0.21 mol) of thionyl chloride was added dropwise over 2.3 hours while maintaining the reaction temperature at 50 ° C., and the mixture was further stirred at the same temperature for 1 hour to obtain 34.2 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 0.9%, acrylic acid chloride 15.8%,
The yield was 32.3% of 3-chloropropionic acid chloride, the yield of acrylic acid chloride was 29.8%, and the yield of 3-chloropropionic acid chloride was 57.0%.

Example 15 Acrylic acid 1 was placed in a 100 ml glass flask equipped with a stirrer, thermometer and reflux condenser.
4.4 g (0.20 mol) and 1.70 g (0.02 mol) of 2-pyrrolidone were added and heated to 50 ° C. with stirring. Next, 25.1 g (0.21 mol) of thionyl chloride was added at 1.5 ° C while maintaining the reaction temperature at 50 ° C.
The mixture was added dropwise over a period of time, and further stirred at the same temperature for 1 hour to obtain 25.3 g of a reaction solution.

When the reaction solution was analyzed by gas chromatography, acrylic acid 0.6%, acrylic acid chloride 12.9%,
The yield of 3-chloropropionic acid chloride was 77.6%, the yield of acrylic acid chloride was 18.1%, and the yield of 3-chloropropionic acid chloride was 77.4%.

The reaction conditions and results of Examples 9 to 15 are summarized in Table 2.

[0067]

[Table 2]

As can be seen from Table 2, the desired 3-chloropropionic acid chloride could be obtained in high yield even when the type of the basic organic compound to be present in the reaction system was changed to various compounds. .

[0069]

According to the present invention, an inexpensive raw material called acrylic acid is used, and this is reacted with thionyl chloride, which is easy to handle as a chlorinating agent. Propionic acid chloride can be produced in high yield. Therefore, the present invention is an advantageous production method suitable for industrial production of 3-chloropropionic acid chloride.

Claims (1)

[Claims] 1. A process for producing 3-chloropropionic acid chloride, which comprises reacting acrylic acid and thionyl chloride in the presence of a basic organic compound.