JPS59108736A - Preparation of acid chloride - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an intermediate for drugs, perfume, etc. without causing coloring with easy separation of a catalyst, by using a high polymer catalyst containing a specific functional group, reacting a sulfone group- or carboxyl group-containing compound with phosgene. CONSTITUTION:In the presence of a catalyst of high polymer having a functional group containing a hetero atom, a sulfone group-containing or carboxyl group- containing compound such as acrylic acid, lauric acid, stearic acid, etc. is reacted with preferably stoichiometric amount of phosgene based on 1 equivalent sulfone group or carboxyl group in the raw material compound at about 0- 150 deg.C, to give the desired compound. A high polymer containing one or more functional groups shown by the formula I (R1 is the same or different 1-4C alkyl; R2 is H, etc.), group shown by the formula II, formula III, etc., having >=500 polymerization degree, is used as the catalyst used in the above-mentioned reaction.

Description

[Detailed description of the invention] The present invention relates to a method for producing acid chloride.

More specifically, the present invention relates to a method for producing acid chloride using a new catalyst.

The "polymer catalyst" used in the present invention has a polymerization degree of 500.
It refers to the above-mentioned polymers with specific functional groups.

Acid chlorides are useful as intermediates for pharmaceuticals, agricultural chemicals, dyes, and the like. Numerous patents and documents have been reported as methods for producing acid chlorides, but examples include dimethylformamide, tetraalkylthiourea, quaternary ammonium salts,
A method for obtaining the corresponding carboxylic acid chloride by reacting a carboxylic acid with phosgene in the presence of a low-molecular compound catalyst such as a phosphonium salt or imitazole (for example, JP-A-41-2
7362, JP-A-44-27863, and JP-A-47-18021) are known.

However, when using the above-mentioned known catalysts, distillation is generally used to color the catalyst during the reaction due to decomposition and taring, or to separate the product acid chloride from the catalyst. There is a disadvantage that coloration occurs.

In view of these circumstances, the inventors 41 and others conducted intensive research to establish a method for producing acid chloride that overcomes the above-mentioned drawbacks, and as a result, they completed the method of the present invention.

That is, the present invention provides a method for producing acid chloride, which comprises reacting a compound having a sulfonic acid group or a carboxylic acid group with phosgene in the presence of a polymeric catalyst having a functional group containing a heteroatom. There is something to do.

Carrying out the method of the present invention (in this case, compounds having a sulfonic acid group or a carbonic acid group used as raw materials include acrylic acid, lauric acid, stearic acid, cyclohexanecarboxylic acid, benzoic acid, isophthalic acid, terephthalic acid,
Carboxylic acids such as acetic acid, propionic acid, butyric acid, methacrylic acid, crotonic acid, caprylic acid, oleic acid, chloroacetic acid, oxalic acid, succinic acid, adipic acid, phenylacetic acid, cinnamic acid, phthalic acid, naphthalene carboxylic acid, benzene Examples include sulfonic acids such as sulfonic acid, (0-, m-, P-)acetylaminobenzenesulfonic acid, L,2-ethanedisulfonic acid, naphthalene, and sulfonic acid.

In the method of the present invention, the polymer catalyst used as a catalyst is a polymer having a polymerization degree of 500 or more and having a functional group containing a l\tero atom such as nitrogen, phosphorus, or sulfur.

The use of this catalyst has the advantage of preventing coloration of the acid chloride product or facilitating separation of the acid chloride produced and the catalyst.

The polymeric catalyst having a functional group containing a hetero atom used in the method of the present invention is as follows: The alkyl group and R3 represent a phenyl group or an alkyl group having 1 to 10 carbon atoms.)
Preferably, S (wherein R1 is an alkyl group having 1 to 4 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 is a phenyl group or an alkyl group having 1 to 4 carbon atoms Polymers having one or more functional groups consisting of .) in their molecules are generally used.

More preferably, N-methylformamide group, N-ethylformamide group, imidazolyl group, N, page ethyl dithiocarbamate group, diphenylphosphinyl group, triphthyl and hytronenylphosphonium chloride F group, N
, N-dimethylthiocarbamate group, and N,N-diyumimethylthiocarbamate group.

The polymer having a functional group containing a heteroatom of the present invention is a halogenated resin such as polyvinyl chloride, polyacrylic acid chloride, chloropolystyrene, chloromethylpolystyrene, etc., and a trialkyl and triphenylposphine nitrogen-containing heterocycle. Compounds, sodium dithiocarbamate, phosphorous acid), realkyl, etc. can be reacted, or aminated resins such as aminated polyvinyl chloride, aminomethyl polystyrene, etc. can be reacted with phenyl quinate, N, N'-dialkylthiourine, etc.
, NN-sylylthiocarno〈moyl chloride, polymerine and phosphoric acid or trialkyl phosphite, etc. are reacted, or with a hydroxylated resin such as polyvinyl alcohol, polyacrylic acid, hydroxymethyl polystyrene, etc.
Polymers obtained by reacting N,,N-dialkylthiocarbamoyl chloride, etc. are generally used.

Depending on the catalyst used, some of the polymer catalysts are solid under reaction conditions, while others are rubbery or liquid.

In the case of solid polymers, the particle size is usually about 0.5 to 2 rug.
The granular form of D or the powder form crushed in a mortar is used.

The amount of polymeric catalyst used is generally 0.01 mol or more per 1 mol of sulfonic acid group or carboxylic acid group, particularly preferably 0.00 mol or more.
An amount of resin containing 2-1 moles of functional groups is used.

In carrying out the method of the present invention, acid chloride is produced by bringing the aforementioned compound having a sulfonic acid group or carbonic acid group into contact with phosgene.

In carrying out the production of acid chlorides according to the process of the invention, pure phosgene or industrial phoscene can be used as the phoscene.

The amount of phoscene to be used in the production of acid chloride is at least the chemical metric, preferably from 1.1 to 1.25 moles, per equivalent of sulfonic acid group or carboxylic acid group in the raw material compound.

Unreacted phoscene can be recovered and reused.

1] - Although it can be carried out in the presence of a hydrocarbon solvent such as hexane, diethyl ether, tetrahydrofuran solvent, or other inert organic solvent, using acid chloride as a solvent eliminates the need for solvent separation after the reaction. preferable.

There are no separate installations required, and it is usually carried out at around normal pressure.

After the reaction, the acid chloride reaction crude product is degassed by passing an inert gas such as nitrogen through it to remove unreacted phosgene and by-product hydrochloric acid.

Next, the acid chloride in the reaction product after the descaling treatment is separated from the polymer catalyst and recovered by allowing the reaction product to heat or separating by distillation.

The acid OIJ obtained in this way is used as an intermediate raw material for medicines, agricultural chemicals, dyes, and fragrances either as it is or after being purified.

As described above, by the method of the present invention for producing acid chloride using a compound having a sulfonic acid group or a carboxylic acid group and phosgene, it is possible to obtain a colorless target product, and it is possible to obtain a colorless target product, and it is possible to obtain a colorless target product using a compound having a sulfonic acid group or a carboxylic acid group and phosgene. The tube exhibits various industrial advantages in that it does not cause taring of the catalyst and the reaction operations such as separation of the generated crude acid chloride and the catalyst are simple.

Hereinafter, the method of the present invention will be explained in more detail with reference to Examples, but the method of the present invention is not limited thereto.

202 parts by weight of triphthylphosne 9 was reacted in a -4-methylformamide solvent to obtain a resin having a quaternary phosphonium base (P content 7.15% by weight) (hereinafter this resin will be referred to as catalyst A).Next, After adding 166 parts by weight of isophthalic acid, 20 parts by weight of catalyst A and 406 parts by weight of isophthalic acid chloride into a reactor equipped with a thermometer, a stirrer, a waste inlet pipe and a reflux condenser, ], l 0°C At this temperature, 24BmfJi parts of Posge was blown into the reactor for 8 hours. After the reaction was completed, nitrogen gas was blown in at the same temperature for about 30 minutes to remove the phosgene remaining in the reaction system. After phosgene was removed, the reaction mixture 10 doors fig
Distillation at pressure in the boiling range of 125-130°C yielded a white isophthalic acid chloride 607 compound.

The yield based on the raw material, isophthalic acid, was 7%.

Examples 2 to 14 Catalyst B: Quaternary phosphonium base obtained by reacting 197 parts by weight of chloromethylated polystyrene and 2c; s parts by weight of triphenylphosphine in a dimethylformamide solvent (P content: 26.32% by weight) resin with

Catalyst C: Obtained by reacting 197 parts by weight of chloromethino-X styrene with 1055 parts by weight of a 40% by weight aqueous solution of 7-methylamine in a toluene solvent, and then formylating it with 621 parts by weight of phenyl formate in a diethyl ether solvent. A resin having a tertiary amide group (N content: 2.45% by weight).

Catalyst D; tertiary amide group-containing (N content 675% by weight)
@Fat.

Catalyst E: having a tertiary amide group (N content 297% by weight) resin.

Catalyst F: An amide type resin obtained by reacting 63 parts by weight of polyvinyl chloride resin with 85 parts by weight of 2-pyrrolidone (N content: 6.09% by weight).

Catalyst G: A resin having an imidazolyl group (N content, Clt, 74% by weight) obtained by reacting 197 parts by weight of chloromethylated polystyrene with 87 parts by weight of imidazole.

Catalyst H: 197 parts by weight of chloromethylated polystyrene was mixed with N,N-
A dithiocar obtained by reacting with 382 parts of sodium N,N-diethyldithiocarbamate in a dimethylformamide solvent (having S content of 10, 5
8% by weight) resin.

Catalyst ①: Contains a dithiocarbamate group obtained by reacting 63 parts by weight of granulated polyhinyl chloride with 382 ilk of N,N-sodium diethyldithiocarbamate in an N,N-dimethylpolamide solvent (S content: 12. 93% by weight) resin.

To the catalyst, 105 parts by weight of 4% cross-linked polystyrene was mixed with 12 parts by weight of acetyl chloride in a carbon disulfide solvent in the presence of anhydrous aluminum chloride.
The carboxypolystyrene obtained by reacting with 1213 parts by weight of an aqueous sulfur-IJ sodium hypochlorite solution was reduced with lithium aluminum hydride in an ether solvent to obtain hydroxydimethylisipolystyrene. This is N,N-diethylthiocarbamoyl chloride 1
A resin having thiocarbamate groups (S content 5.70% by weight) obtained by reacting with 52 parts by weight.

For the catalyst; obtained by reacting 63 parts by weight of polyhinyl chloride resin with 103 parts by weight of diethylenetriamine in an aqueous solvent (N content 14 parts by weight).
70% by weight) aminated resin.

Catalyst L: having a thiourea group (S
Content 8. oo weight 9%) resin.

Catalyst 1; Contains a phosphate group obtained by reacting 197 parts by weight of chloromethylated polystyrene with 498 parts by weight of triethyl phosphite in a toluene solvent (P content: 9.48% by weight)
resin.

Catalyst N: Strongly basic anion exchange resin Duolite A-101D
(Duolite A-101D) (trade name manufactured by Diamond Jamrock Co., Ltd.) 212 parts by weight was chlorinated in the presence of Abbisisobutyronitrile, and then aminated with 103 parts by weight of diethyl and lentriamine. A resin having phosphoric acid groups (P content: 6.69% by weight) obtained by reacting 281 parts by weight of an aqueous formalin solution with 498 parts by weight of phosphorous acid in the presence of % hydrochloric acid.

Catalyst O: Contains a phosphate group obtained by reacting 129 parts by weight of the catalyst with 281 parts by weight of formalin aqueous solution and 498 parts by weight of triethyl phosphite in the presence of 86% hydrochloric acid (P content 8.87% by weight) )resin.

Catalyst P: 105 parts by weight of polystyrene L/N in the presence of anhydrous ferric chloride,
Lithium polystyrene was obtained by reacting with 87 parts by weight of bromine in a carbon tetrachloride solvent and then with 64 parts by weight of a 1.6 M n-butyllithium hexane solution in a tetrahydrofuran solvent. This was reacted with 300 parts by weight of chlordiphenylphosphine in a tetrahydrofuran solvent, and further oxidized with 371 parts by weight of 40% peracetic acid in a methylene chloride solvent.
0.42% by weight) resin.

The results shown in Table 1 were obtained.

Comparative Example Dimethylformamide 20 was used instead of catalyst A in Example 1.
The reaction was carried out in exactly the same manner except that part by weight was used as a catalyst. Approximately 6 hours and 20 minutes after the start of the reaction, the color of the reaction mixture suddenly turned black and tar formation occurred. After phosgene removal, the reaction mixture was heated to 75 to 89 m Hg pressure.
Dimethylformamide was removed by distillation in the boiling range of 76 °C, followed by 106-109 °C at 2 mm Hg pressure.
Distillation in the boiling range of 595 parts by weight of yellow isophthalic acid chloride was obtained. The yield based on the raw material isophthalic acid was 93%.

Example 15 197 parts by weight of non-crosslinked chloromethylated polynarene was added to N
, with 382 parts by weight of sodium N,N-diethylthiocarbamate in N-dimethylformamide solvent,
having a dithiocarbamate group (S-containing jl11.78
Weight%) Soluble resin (hereinafter, this resin is referred to as catalyst Q)
) was obtained. Next, 15 parts by weight of catalyst Q was blown into the reactor for 8 hours, residual phoscene was removed, and chlorobenzene was recovered by distillation. After this lm
Distillation in the boiling range of 105 DEG-107 DEG C. at Hg pressure gave 193 parts by weight of white isophthalic acid chloride. The yield was 95% based on the raw material isophthalic acid.

Examples 16 to 23 When various sulfonic acids or carboxylic acids were reacted with phosgene under the conditions shown in Table 2 using Catalyst A used in Example 1, the results shown in Table 2 were obtained. It was done.

Procedural amendment (voluntary) d Commissioner of the Japan Patent Office Kazuo Wakasugi L' - 14 indications 1982 Patent Application No. 218816 2 Name of the invention Method for producing acid chloride Address 81T Address name, 5-15 Kitahama, Higashi-ku, Osaka City Name (209) Sumitomo Chemical Co., Ltd. Representative: Takeshi Kamigata 4; Agent: Sumitomo 1b Gakko Kogyo Co., Ltd., 5-15 Kitahama, Higashi-ku, Osaka City; Claims column of the specification subject to amendment; Column for detailed description of the invention.

6. Contents of amendment (1) Correct the scope of claims by filling in the attached sheet.

(2) “υ N-ethylformamide group, imitazolyl” (in the formula,
R1 is the same or different alkyl groups having 1 to 10 carbon atoms, 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which is the same or different from each other, and 3 is a phenyl group or the same or different from each other. represents an alkyl group having 1 to 10 carbon atoms. ) Preferably, (wherein 1 is the same or mutually different alkyl group having 1 to 4 carbon atoms, R2 is a hydrogen atom or the same or mutually different alkyl group having 1 to 4 carbon atoms, and R8 is phenyl Polymers having one or more functional groups in the molecule are generally used. More preferably, N-methylformamide group, N-ethylformamide group, imidazolyl group.''

(3) “N,N-diethyldithiocarbamate group,” in the first to last lines of page 8 of the specification.
・・・・・・(omitted)・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・Polyvinyl alcohol, polyacrylic acid, hydroxymethylbo'' means l'-N, N-diethyldithiocarbamate group, Schiff . Examples thereof include monomers having functional groups such as enylphosphinyl group, tributyl and triphenylphosphonium chloride groups, N,N-dimethylthiocar 1<mate group, N,N-diethylthiocarbamate group, and the like.

The polymer having a functional group containing a heteroatom of the present invention is
By reacting halogenated resins such as polyvinyl chloride, polyacrylic acid chloride, chloropolystyrene, and chloromethylpolystyrene with trialkyl and triphenylphosphine, nitrogen-containing heterocyclic compounds, sodium dithiocarbamate, trialkyl phosphite, etc. , aminated polyhinyl chloride, aminomethyl polystyrene and other aminated resins, phenyl formate, N, N'-dialkylthiourea, N.

It is corrected to "react N-dialkylthiocarbemoyl chloride, formalin, and phosphoric acid or trialkyl phosphite, etc.," or "polyvinyl alfur, polyacrylic acid, hydroxymethyl phosphide."

(4) On page 17, line 6 of the specification, the phrase "chlorinated with chlorine" is corrected to "chlorinated with chlorine."

(5) Meiji PJI, page 21, lines 4-5 says "N,N-diethylthiocarbamate 1helium") -N,
N-diethyldithiocarbamate thorium” is corrected.

(1) A method for producing an acid chloride, which comprises reacting a compound having a sulfonic acid group or a carboxylic acid group with phosgene in the presence of a polymeric catalyst having a functional group containing a hetero atom.

(2) The basic molecular catalyst having a functional group containing a heteroatom is
R2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which is the same or different from each other; 2. The method for producing acid chloride according to claim 1, wherein the sieve molecule is a sieve molecule having one or more functional groups consisting of ) in its molecule.

(3) A polymer catalyst having a functional group containing a heteroatom is η1 (wherein R1 is the same or different alkyl group having 1 to 4 carbon atoms, R2 is a hydrogen atom or the same or different from each other) is a polymer having one or more functional groups in its molecule, consisting of an alkyl group having 1 to 4 carbon atoms and a moiety representing a phenyl group or an alkyl group having 1 to 4 carbon atoms, which is the same or different from each other. The method for producing acid talolide according to claim 1 or 2, characterized in that:

(4) The amount of the polymer catalyst having a functional group containing a heteroatom is such that the amount of the resin containing the functional group is about 0.01 mol or more per 1 mol of sulfonic acid group or carboxylic acid group. A method for producing acid chloride according to claim 1, 2 or 3.

(5) Claims 1.2 and 8. characterized in that the reaction temperature is 70 to 110°C. Or the method for producing acid chloride according to item 4.

(6) Claim 1.2 characterized in that an acid chloride corresponding to an acid compound having a sulfonic acid group or a carboxylic acid group is used as the reaction solvent. B. The method for producing acid chloride according to item 4 or 5.

Claims (1)

[Scope of Claims] ++) A method for producing an acid chloride, which comprises reacting a compound having a sulfonic acid group or a carboxylic acid group with phosgene in the presence of a polymeric catalyst having a functional group containing a petro atom. (2) A polymer catalyst having a functional group containing a heteroatom is 1 (wherein, R1 is an alkyl group having 1 to 10 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R3 is phenyl or an alkyl group having 1 to 10 carbon atoms) in its molecule. . (3) A polymeric catalyst having a functional group containing a heteroatom, or an alkyl group having 1 to 4 carbon atoms, -n-,) in its molecule, the polymer is a polymer having one or more functional groups in its molecule. Method for producing acid chloride. (4) The amount of the polymer catalyst having a kanno group containing a hetero atom is such that the amount of the resin containing a functional group is about 0.01 mol or more per 1 mol of sulfonic acid group or carboxylic acid group. A method for producing acid chloride according to claim 32 or 3. (5) The method for producing acid chloride according to claim 1.2, 8 or 4, wherein the reaction temperature is 70 to 110°C. (6) Production of acid chloride according to claim 1.2, 3.4 or 5, characterized in that an acid chloride equivalent to an acid compound having a sulfonic acid group or a carboxylic acid group is used as the reaction solvent. Method.