JP3010393B2 - Method for producing acid chloride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing carboxylic acid chlorides useful as various surfactants such as detergents and fabric softeners, and as raw materials for medicines and agricultural chemicals. More specifically, the present invention relates to a method for producing a corresponding carboxylic acid chloride from an aliphatic carboxylic acid and thionyl chloride or phosgene in a high yield in a short time by using a copolymer of N-vinylacetamide and divinylbenzene as a catalyst. .

[0002]

2. Description of the Related Art As a conventional method for producing an aliphatic carboxylic acid chloride, there is known a method of reacting the carboxylic acid with a phosphorus chloride compound such as phosphorus trichloride or a chlorinating agent such as thionyl chloride or phosgene. ing. Among them, the method using phosphorus trichloride as a chlorinating agent has problems in separation and purification and environmental conservation since phosphorous acid is generated as a by-product. For this reason, various methods have been studied which utilize thionyl chloride and phosgene, which generate hydrogen chloride gas, which is extremely easy to recover, as a by-product as a raw material for the chlorination reaction of organic carboxylic acids. Many methods using various catalysts have been reported because of poor performance.

[0003] For example, there is a method of accelerating the reaction by adding pyridine. In this case, the coloration of the product is remarkable, and pyridine hydrochloride formed from pyridine and hydrogen chloride precipitates in the reaction system. Absent. Other catalysts for reacting aliphatic carboxylic acids with phosgene include quaternary ammonium salts, quaternary phosphonium salts, tertiary amines, tertiary phosphines, N, N-disubstituted formamides and tetraalkylthioureas. It is known. When reacting an aliphatic carboxylic acid with thionyl chloride or phosgene in the presence of these catalysts, each requires a long heating time of 14 to 15 hours, and due to the heat received for a long time,
The resulting carboxylic acid chloride is disadvantageous in that the coloring of the carboxylic acid chloride becomes remarkable and by-products are formed, with the result that the yield is reduced. In order to further separate the used catalyst, a distillation operation is necessary, and part of the material is deteriorated by heating at that time,
Further, there is a disadvantage that the yield is reduced. Accordingly, an object of the present invention is to provide a highly active catalyst capable of producing the corresponding carboxylic acid chloride from carboxylic acid chloride and thionyl chloride or phosgene in a short time with high yield and high purity, and to establish a production technique using the catalyst. Is to do.

[0004]

Means for Solving the Problems The present inventors have developed a cross-linked type obtained by cross-linking the main chain of a homopolymer or copolymer containing at least 3 mol% or more of a component having an N-vinylcarboxylic acid amide structure with a cross-linking agent. The present inventors have found that N-vinylcarboxylic acid amide is excellent as a catalyst for the reaction between an aliphatic carboxylic acid and thionyl chloride or phosgene and can achieve the above-mentioned objects, and thus completed the present invention. That is, the present invention relates to a method for producing a carboxylic acid chloride by reacting an aliphatic carboxylic acid with thionyl chloride or phosgene.

[0005]

Embedded image

(Wherein, R represents a hydrogen atom or a methyl group, X is a —COOY group (in the group, Y is a lower alkyl group), and a —CONNH group (in the group, Z is a lower alkyl group.) ), An aryl group, a cyano group, a 2-ketopyrrolidinyl group, a lower alkoxy group, a lower acyl group or a lower acyloxy group, and the molar ratio of m: n is 3 to 100:
97 to 0. )
The main chain structure of a homopolymer or copolymer having an average degree of polymerization of the main chain of 100 to 5000 is converted by a crosslinking agent having at least two or more acrylate structure, acrylamide structure or N-vinylcarboxylic acid amide structure in one molecule. Crosslinked N formed by crosslinking at a crosslinking density of 1/2 to 1/500
-A method for producing carboxylic acid chloride, comprising using a vinyl carboxylic acid amide resin.

The repeating unit N represented by the above general formula
Specific examples of the monomer having a vinyl carboxylic acid amide structure and the copolymer component are shown below as typical examples. Component having an N-vinylcarboxylic acid amide structure: N-vinylformamide, N-vinylacetamide, and the like, and N-vinylacetamide is particularly preferable. Copolymer components: acrylic acid esters such as acrylic acid methyl ester, ethyl ester, propyl ester and butyl ester; acrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N Acrylamide such as N, N-diethylacrylamide, dimethylaminomethylacrylamide, dimethylaminoethylacrylamide, dimethylaminopropylacrylamide, dimethylaminobutylacrylamide, diethylaminomethylacrylamide, diethylaminoethylacrylamide, diethylaminopropylacrylamide, diethylaminoacrylbutyramide; styrene; Styrene derivatives such as methylstyrene; acrylonitrile; Pyrrolidone; Mechirubinirue -
Vinyl ethers such as ter, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether; vinyl ketones such as methyl vinyl ketone; vinyl carboxylate such as vinyl acetate and vinyl propionate.

Of these, methyl acrylate, ethyl acrylate, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-dimethylacrylamide
N-diethylacrylamide, acrylonitrile, N-
Preferred are vinylpyrrolidone, vinyl acetate and the like. In the case of a copolymer, N-
At least 3 components having a vinylcarboxylic acid amide structure
It must be contained in an amount of at least mol%, and below this does not result in a highly active catalyst which is a feature of the present invention.

As the crosslinking agent, a compound having at least two acrylate structures, acrylamide structures or N-vinylcarboxylic acid amide structures in one molecule is used. Representative examples are specifically illustrated below.
N, N'-methylenebisacrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meta)
Acrylate, N, N'-1,4-butylenebis (N-
Vinylacetamide), N, N'-1,6-hexylenebis (N-vinylacetamide), N, N'-1,10
-Decylene bis (N-vinylacetamide), N, N '
-3-oxa-1,5-pentylenebis (N-vinylacetamide), N, N'-3,6-dioxa-1,8-
Octylene bis (N-vinylacetamide), N, N '
-P-xylylenebis (N-vinylacetamide),
N, N'-diacetyl-N, N'-divinyl-1,4-
Bisaminomethylcyclohexane.

All of these crosslinking agents are compounds having good copolymerizability with N-vinylcarboxylic acid amide. In the case of a homopolymer of N-vinyl carboxylic acid amide, among these crosslinking agents, N, N'-1,4-butylenebis (N-
Vinylacetamide), N, N'-1,6-hexylenebis (N-vinylacetamide), N, N'-1,10
-Decylene bis (N-vinylacetamide), N, N '
-3-oxa-1,5-pentylenebis (N-vinylacetamide), N, N'-3,6-dioxa-1,8-
Octylene bis (N-vinylacetamide), N, N '
-P-xylylenebis (N-vinylacetamide),
N, N'-diacetyl-N, N'-divinyl-1,4-
Compounds having two N-vinylcarboxylic acid amide structures such as bisaminomethylcyclohexane are particularly preferably used. Further, in the case of a copolymer of N-vinylcarboxylic acid amide, it is preferable to use a combination of two kinds of the compound having two N-vinylcarboxylic acid amide structures and the compound having two acrylate ester structures or two acrylamide structures. .

The amount of the crosslinking agent used ranges from 0.2 to 50 mol%, preferably from 3 to 25 mol%, based on the total amount of the (co) polymerization component and the crosslinking agent. Incidentally, when the amount of the cross-linking agent used is less than 0.2 mol% based on the amounts of the (co) polymerization component and the cross-linking agent, the ratio of the non-cross-linked polymer chains increases, and the physical strength as a catalyst cannot be maintained. . On the other hand, when it is more than 50 mol%, the crosslink density of the obtained resin becomes too high, so that the catalytic activity is remarkably reduced. This is presumed to be due to the fact that the reaction rate depends on the diffusion control of the reaction substrate into the resin.

The (co) polymer resin used for the catalyst in the present invention can be synthesized using various known polymerization reactions.
Usually, it is desirable to use a method such as solution polymerization or reversed phase suspension polymerization. For example, a method in which N-vinylcarboxylic acid amide, a copolymer component, and a crosslinking agent are subjected to radical polymerization using a suitable radical initiator is convenient. In these production methods, a commonly used polymerization initiator, for example, azobisisobutyronitrile, which is an oil-soluble azo initiator, can be used.
In the case of the solution polymerization method, for example, N is added to an organic solvent such as benzene.
-The method is carried out by dissolving a vinyl carboxylic acid amide, a copolymer component and a crosslinking agent, adding a predetermined amount of an initiator under a nitrogen stream, and raising the temperature to a predetermined temperature. The polymerization initiation temperature is usually about 10 to 60 ° C, and the reaction time is about 1 to 50 hours. The amount of the initiator is based on the total amount of the monomers used.
The range is 0.001 to 5.0% by weight, preferably 0.01 to 1.0% by weight. In the method of the present invention, by using the resin prepared as described above as a catalyst, the intended object of obtaining a carboxylic acid chloride of excellent quality in a high yield in a short time is achieved. Further, this resin can be produced in good yield by using the above-mentioned crosslinking agent, and exhibits a highly active catalytic action.

It is to be noted that N is preferable as a catalyst raw material of the present invention.
-Vinylacetamide is, for example, N- (α) synthesized from acetaldehyde, acetamide and alcohol.
(Alkoxyethyl) acetamide can be easily synthesized by thermal decomposition (see JP-A-50-76015). Alternatively, it can be synthesized by thermal decomposition of ethylidene bisacetamide synthesized from acetaldehyde and acetamide (J. Am. Chem. Soc., 98,
5996 (1976)). On the other hand, a compound having two N-vinylcarboxylic acid amide structures can be easily synthesized with good yield using, for example, N-vinylcarboxylic acid amide and diol as raw materials (Japanese Patent Application No. 3-116193).

The carboxylic acid to be chlorinated in the present invention is a saturated or unsaturated fatty acid. In particular,
Higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid; aliphatic monocarboxylic acids such as acetic acid, trimethylacetic acid and butyric acid; halogen-substituted aliphatic monocarboxylic acids such as chloroacetic acid and dichloroacetic acid;
Examples thereof include aliphatic dicarboxylic acids such as adipic acid and sebacic acid. In the method of the present invention, the amount of the catalyst to be added is 0.01 to 5.0% by weight, preferably 0.05 to 2.0% by weight, based on the starting aliphatic carboxylic acid. The amount of thionyl chloride or phosgene used is preferably from 1.05 to 5.0 moles per mole of the starting aliphatic carboxylic acid, but is preferably from 1.5 to 5.0 moles.
3.0 moles is good. In the method of the present invention, the reaction can be carried out at a lower temperature in a shorter time than in a method using a conventional catalyst system. The reaction temperature varies depending on the type of the starting aliphatic carboxylic acid, but is generally 0 to 150 ° C, preferably 20 to 150 ° C, and more preferably 30 to 100 ° C. The reaction time also depends on the type of aliphatic carboxylic acid and the reaction temperature, but is usually 30 minutes to 10 hours, preferably 1 to 5 hours.
It is about an hour. The pressure at which the reaction is carried out is not critical for the process according to the invention, as in the case of the known conventional processes,
It is usually carried out under normal pressure for reasons of equipment simplification. However, when the reaction under normal pressure is difficult due to the low boiling point of the aliphatic carboxylic acid as the raw material, it is necessary to carry out the reaction under pressure using a pressure-resistant reactor.

The process of the present invention can be carried out without a solvent or in the presence of a solvent which is inert under the reaction conditions.
The use of a solvent reduces the space / time yield as a function of the amount of solvent, but is preferred to moderate the reaction and keep the reaction mixture at a given temperature. As the solvent, pentane, hexane, heptane, octane, cyclohexane,
Hydrocarbons such as methylcyclohexane, benzene, toluene, xylene and ethylbenzene, methylene chloride, chloroform, dichloroethane, tetrachloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, dichlorobenzene, chloroxylene, dichloroxylene Examples thereof include aliphatic and aromatic halogen compounds such as methyl acetate, esters such as ethyl acetate, nitriles such as acetonitrile, dimethyl sulfoxide and the like, and mixtures thereof.

The process of the present invention can be performed in a discontinuous or continuous manner. In the case of a discontinuous type, after charging a predetermined amount of the raw material carboxylic acid and the catalyst into a reactor equipped with a stirrer, the temperature is raised while sufficiently stirring to a predetermined temperature. Next, thionyl chloride or phosgene is supplied into the reactor to react. The catalyst used in the present invention is a copolymer having a crosslinked structure and does not dissolve in any solvent. Therefore, the used catalyst can be easily collected by filtration or the like and reused. On the other hand, in the case of the continuous type, the catalyst is charged into a flow type reactor, and a mixture of the starting carboxylic acid and thionyl chloride or phosgene is passed through the reactor at a predetermined temperature. In any case, the end point of the reaction can be confirmed by analyzing the amount of the unreacted carboxylic acid in the reaction solution to be lower than the predetermined amount. The details of the reason why the catalyst according to the present invention exhibits high activity are not clear, but the fact that the hydrogen atom on the nitrogen of the monosubstituted carboxylic acid amide structure in the side chain of the resin has a large effect on the catalytic activity, more appropriately It is considered that the swellable polymer three-dimensional network plays a favorable role in the progress of the reaction.

[0017]

According to the present invention, a carboxylic acid chloride useful as a raw material for various surfactants (eg, detergents, fabric softeners), medicines or agricultural chemicals, etc. is prepared by crosslinking carboxylic acid with thionyl chloride or phosgene. And a high purity can be obtained in a short time with high yield using a small amount of a catalyst composed of N-vinylcarboxylic acid amide resin.

[0018]

The present invention will be described in more detail with reference to Examples of preparation of the catalyst used in the present invention (Examples 1 to 13), Examples of the method of the present invention using the catalyst (Examples 14 to 30) and Comparative Examples. However, the present invention is not limited by the following examples. Example 1 7.65 g (90 mmol) of N-vinylacetamide, N,
2.24 g (10 mmol) of N'-1,4-butylenebis (N-vinylacetamide) was dissolved in 10 ml of benzene, and 8.2 mg (0.05 mmol) of azobisisobutyronitrile, a radical polymerization initiator, was added. Polymerization was carried out at 60 ° C. for 48 hours. The gel obtained by the polymerization reaction was washed with methylene chloride using a Soxhlet extractor, and then dried. The yield was 9.69 g, and the yield based on the charged monomer was 97%. This is designated as catalyst A.

Example 2 In Example 1, 4.26 g of N-vinylacetamide (5
0 mmol) and 11.2 g (50 mmol) of N, N'-1,4-butylenebis (N-vinylacetamide).
14.84 g of a resin was obtained in the same manner as above except that it was used. This is designated as catalyst B.

Example 3 In Example 1, 5.96 g of N-vinylacetamide (7
0 mmol) and 6.72 g (30 mmol) of N, N'-1,4-butylenebis (N-vinylacetamide).
Except for using the above, 12.4 g of a resin was obtained. This is designated as catalyst C.

Example 4 In Example 1, 8.42 g of N-vinylacetamide (9
9 mmol) and 0.22 g (1 mmol) of vinylbenzene.
8.21 g of resin was obtained in the same manner except that l) was used. This is designated as catalyst D.

Example 5 In Example 1, N-vinylacetamide was used instead of N-vinylacetamide.
8.29 g of a resin was obtained in the same manner except that 6.40 g (90 mmol) of vinylformamide was used. This is designated as catalyst E.

Example 6 In Example 1, N, N'-1,4-butylenebis (N
-Vinylacetamide) in the same manner except that 2.40 g (10 mmol) of N, N'-3-oxa-1,5-pentylenebis (N-vinylacetamide) was used instead of
9.65 g of resin was obtained. This is designated as catalyst F.

Example 7 In Example 1, N, N'-1,4-butylenebis (N
-Vinylacetamide) in the same manner except that 2.78 g (10 mmol) of N, N'-diacetyl-N, N'-divinyl-bisaminomethylcyclohexane was used.
10.12 g of resin were obtained. This is designated as catalyst G.

Example 8 3.83 g (45 mmol) of N-vinylacetamide, 3.87 g (45 mmol) of methyl acrylate, N, N'-1,
1.12 g of 4-butylenebis (N-vinylacetamide)
(5 mmol) and 0.79 g (5 mmol) of N, N'-methylenebisacrylamide were dissolved in 10 ml of benzene, and 8.2 mg (0.05 mmol) of azobisisobutyronitrile, a radical polymerization initiator, was added. For 48 hours. The gel obtained by the polymerization reaction was washed with methylene chloride using a Soxhlet extractor, and then dried. The yield was 9.23 g. This is designated as catalyst H.

Example 9 7.75 g of a resin was obtained in the same manner as in Example 8, except that 2.39 g (45 mmol) of acrylonitrile was used instead of methyl acrylate. This is designated as Catalyst I.

Example 10 9.19 g of a resin was obtained in the same manner as in Example 8, except that 3.83 g (45 mmol) of N-methylacrylamide was used instead of methyl acrylate. This is designated as catalyst J.

Example 11 The procedure of Example 8 was repeated, except that 3.87 g (45 mmol) of vinyl acetate was used instead of methyl acrylate.
20 g of resin were obtained. This is designated as catalyst K.

Example 12 In Example 8, 0.85 g of ethylene glycol diacrylate was used in place of N, N'-methylenebisacrylamide.
g (5 mmol), except that 9.25 g of a resin was obtained. This is designated as catalyst L.

Example 13 0.43 g (5 mmol) of N-vinylacetamide, 4.51 g (85 mmol) of acrylonitrile, N, N'-1,4
-Butylenebis (N-vinylacetamide) 0.22 g (1
mmol) and 1.39 g (9 mmol) of N, N'-methylenebisacrylamide were dissolved in 10 ml of benzene, and 8.2 mg (0.05 mmol) of azobisisobutyronitrile, a radical polymerization initiator, was added. Polymerization was carried out for 48 hours. The gel obtained by the polymerization reaction was washed with methylene chloride using a Soxhlet extractor, and then dried. The yield was 6.22 g.
This is designated as catalyst M.

Example 14 800 mg (4 mmol) of lauric acid, 944 mg (8 mmol) of thionyl chloride, 20 m of methylene chloride were placed in a glass reactor equipped with a stirrer, thermometer and reflux condenser.
1, 14 mg of catalyst A was added, and heated to 35 ° C. with stirring. Sulfur dioxide and hydrogen chloride were generated, and after 2 hours, lauric chloride was obtained almost quantitatively.

Examples 15 to 25 The reaction was carried out in the same manner as in Example 14 except that Catalysts B to L were used instead of Catalyst A. In each case, lauric chloride was obtained almost quantitatively.

Example 26 A reaction was carried out in the same manner as in Example 14 except that Catalyst M was used instead of Catalyst A. 8 lauric chloride
Obtained in 11 mg (93% yield).

Example 27 After completion of the reaction in Example 14, the catalyst was filtered off and recovered, and the reaction was carried out in the same manner as in Example 1 except that the catalyst was used in place of the catalyst A. Obtained quantitatively.

Example 28 A reaction was carried out in the same manner as in Example 14 except that 360 ml (16 mmol) of phosgene was used instead of thionyl chloride. Hydrogen chloride and carbon dioxide were generated, and lauric chloride was obtained almost quantitatively.

Example 29 A reaction was carried out in the same manner as in Example 14 except that 3.5 mg of Catalyst A was used. Lauric chloride is 828
mg (95% yield).

Example 30 A reaction was carried out in the same manner as in Example 14 except that 28 mg of Catalyst A was used. Lauric chloride was obtained almost quantitatively.

Comparative Example 1 A reaction was carried out in the same manner as in Example 14 except that no catalyst A was used. 61 mg (7% yield) of lauric chloride was obtained.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 53/38 B01J 31/06 C07C 51/60 C07B 61/00 300

Claims (1)

(57) [Claims] 1. A method for producing a carboxylic acid chloride by reacting a carboxylic acid with thionyl chloride or phosgene. (Wherein, R represents a hydrogen atom or a methyl group, and X represents-
COOY group (wherein Y is a lower alkyl group),-
CONZZ group (wherein Z is a lower alkyl group),
Represents an aryl group, a cyano group, a 2-ketopyrrolidinyl group, a lower alkoxy group, a lower acyl group or a lower acyloxy group, and the molar ratio of m: n is 3 to 100: 97 to 0. ), Wherein the main chain structure of a homopolymer or copolymer having an average degree of polymerization of the main chain of 100 to 5000 is represented by an acrylate ester structure in one molecule;
Crosslinking density of 1 with a crosslinking agent having at least two acrylamide structures or N-vinylcarboxylic acid amide structures
A method for producing a carboxylic acid chloride, comprising using a crosslinked N-vinylcarboxylic acid amide resin obtained by crosslinking at a rate of 1/2 to 1/500.