CN101774908B - Method for producing m-chlorobenzoyl chloride - Google Patents
Method for producing m-chlorobenzoyl chloride Download PDFInfo
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- CN101774908B CN101774908B CN2010101099707A CN201010109970A CN101774908B CN 101774908 B CN101774908 B CN 101774908B CN 2010101099707 A CN2010101099707 A CN 2010101099707A CN 201010109970 A CN201010109970 A CN 201010109970A CN 101774908 B CN101774908 B CN 101774908B
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Abstract
The invention relates to a method for producing m-chlorobenzoyl chloride, in which m-nitrotoluene is used as raw material, pyridine, pyridinium salt, pyridine derivative containing halogen and fat groups on a ring, salt thereof and N, N-dimethylformamide and salt thereof are used as catalysts, and substitution reaction between the m-nitrotoluene and chlorine is carried out at ordinary pressure and the temperature of 120-220 DEG C to obtain more than 90 percent m-chlorobenzoyl chloride crude. The chloride is directly hydrolyzed to obtain m-chlorobenzoic acid which is then reacted with thionyl chloride and rectified to obtain high-purity m-chlorobenzoyl chloride. The invention directly takes the m-nitrotoluene as the raw material, the m-chlorobenzoyl chloride is obtained via chlorination by chlorine with the catalysts under UV-irradiation, and hydrolysis is further carried out to obtain the m-chlorobenzoic acid. Each step of reaction is carried out under a relatively mild technological condition. The invention has the advantages of low cost and high yield and product purity, by-product hydrochloric acid and dilute nitric acid can both be used. Three wastes are not generated, energy is saved, and environment is protected.
Description
Technical field
The invention belongs to medicine and the manufacture method of pesticide intermediate use chemical products, particularly a kind of method of producing the existing procucts m-chlorobenzoyl chloride in chemical feedstocks and chemical product manufacturing.
Background technology
M-chlorobenzoyl chloride is mainly used in the fields such as medicine, agricultural chemicals, dyestuff intermediate and biochemical industry and catalyzer, can synthesize the intermediate of he fixed and An Feitading of thunder chlorine etc., weedicide bifenox.In addition, the m-chlorobenzoyl chloride chlorine in ring also can be replaced the generation fluorochemicals by fluorine, is the important intermediate of a new generation's medicine, agricultural chemicals, dyestuff and Organic chemical products.Two of m-chlorobenzoyl chloride and m-chlorobenzoic acids can transform simply mutually.
Produce at present m-chlorobenzoyl chloride mainly from two kinds of raw materials: the first is take Benzoyl chloride as raw material, gets m-chlorobenzoyl chloride with chlorinated with chlorine.This technique is simple, and the three wastes are few, and cost is also lower, but because product purity is not high, can not satisfy the requirement that medicine and other fine chemical product are produced; The second is take m-chlorotoluene as raw material, by two kinds of explained hereafter m-chlorobenzoyl chlorides, and the one, m-chlorotoluene gets m-chlorobenzoic acid with atmospheric oxidation, then makes m-chlorobenzoyl chloride through sulfur oxychloride or phosgene reaction.Another technique is to make m-chlorobenzoyl chloride with m-chlorotoluene chlorination, hydrolysis.This two technique is simple, but raw materials cost is high because m-chlorotoluene is to reduce by meta-nitrotoluene to make meta-aminotoluene, then through the three wastes many and unmanageable diazotization, method for hydrolysis preparation and get.
Summary of the invention
The purpose of this invention is to provide a kind ofly directly take meta-nitrotoluene as raw material, make the method for m-chlorobenzoyl chloride through chlorinated with chlorine under catalyzer and UV-irradiation.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of producing m-chlorobenzoyl chloride, it is characterized in that: take meta-nitrotoluene as raw material, with the pyridine derivate that contains halogen, fat group on pyridine, pyridinium salt, ring and their salt, N, one or more of dinethylformamide and salt thereof are catalyzer, under UV-irradiation, temperature is controlled at 120～220 ℃ and carries out introduce chlorine gas to make reaction, gets the m-chlorobenzoyl chloride of content more than 90%; This muriate is again through direct rectifying or be hydrolyzed to get m-chlorobenzoic acid with usual method, then gets the high purity m-chlorobenzoyl chloride with sulfur oxychloride reaction, rectifying; In described method: the usage quantity of catalyzer is meta-nitrotoluene 0.1%～5% of the quality that feeds intake in mass; In introduce chlorine gas to make reaction, the chlorine intake is 105%～130% of theoretical amount, and chlorine passes into speed control and completed at 20～50 hours; The sulfur oxychloride usage quantity is 1.1～1.3 mol ratios of meta-nitrotoluene charging capacity in this production method.
Method according to described production m-chlorobenzoyl chloride is characterized in that: the usage quantity of described catalyzer is meta-nitrotoluene 0.5%～2% of the quality that feeds intake in mass; In described introduce chlorine gas to make reaction, the chlorine intake is 109%～113% of theoretical amount; Described chlorine passed into speed control at 38～40 hours;
Method according to described production m-chlorobenzoyl chloride is characterized in that: described sulfur oxychloride usage quantity is 1.15 mol ratios of meta-nitrotoluene charging capacity.
Method according to described production m-chlorobenzoyl chloride is characterized in that: add 400 gram meta-nitrotoluenes in 500 milliliters of there-necked flasks, and 3 gram catalyzer pyridines, 1 gram catalyst n, dinethylformamide is spent heating material to 180 under UV-irradiation; Remain under 180 degree and slowly led to chlorine 8 hours continuously in bottle, then continued logical chlorine 30 hours under 200 degree, totally applied chlorine 885 grams obtain muriate 496.3 grams, and through gas chromatographic analysis, m-chlorobenzoyl chloride content is 92.3%; Muriate is hydrolyzed in dimethylbenzene, crystallization treatment gets m-chlorobenzoic acid 386 grams; M-chlorobenzoic acid gets m-chlorobenzoyl chloride 408 grams with the sulfur oxychloride reactive distillation again, and content is 99.58%.
Method according to described production m-chlorobenzoyl chloride is characterized in that: add 111 gram meta-nitrotoluenes in 250 milliliters of there-necked flasks, 1 gram catalyzer pyridine is spent heating material to 180 under UV-irradiation; Remain under 180 degree and slowly led to chlorine 13 hours continuously in bottle, then continued logical chlorine 20 hours under 200 degree, totally applied chlorine 230 grams; Obtain muriate 136.5 grams, through gas chromatographic analysis, m-chlorobenzoyl chloride content is 91.5%.
Method according to described production m-chlorobenzoyl chloride is characterized in that: add 800 kilograms of meta-nitrotoluenes in 1000 liters of lass lining reactors, 6 kilograms of catalyzer pyridines are spent heating material to 150 under UV-irradiation; Remain on the lower slowly logical chlorine continuously of 150 degree 1 hour, then continued logical chlorine 10 hours under 180 degree, continued logical chlorine 30 hours under 200 degree, 1820 kilograms of totally applied chlorines; Obtain 1016 kilograms of muriates, through gas chromatographic analysis, m-chlorobenzoyl chloride content is 86.7%; Muriate gets 848.5 kilograms of m-chlorobenzoyl chlorides through hydrolysis, acyl chloride reaction and rectifying again, and content is 99.71%.
Method according to described production m-chlorobenzoyl chloride is characterized in that: add 800 kilograms of meta-nitrotoluenes in 1000 liters of lass lining reactors, 6 kilograms of catalyzer pyridines are spent heating material to 150 under UV-irradiation; Remain on the lower slowly logical chlorine continuously of 150 degree 1 hour, then continued logical chlorine 10 hours under 180 degree, continued logical chlorine 30 hours under 200 degree, 1796 kilograms of totally applied chlorines; Obtain 1030 kilograms of muriates, through gas chromatographic analysis, m-chlorobenzoyl chloride content is 82.09%.
Beneficial effect of the present invention:
The present invention makes m-chlorobenzoyl chloride through chlorinated with chlorine directly take meta-nitrotoluene as raw material under catalyzer and UV-irradiation, further be hydrolyzed to get m-chlorobenzoic acid.Characteristics are that cost is low, and yield and product purity are high, and by-product hydrochloric acid and rare nitric acid all can utilize.
Pleasant and the satisfied method that cleans the synthetic m-chlorobenzoyl chloride of production requirement of operating environment of the present invention.
Adopt the m-chlorobenzoyl chloride of explained hereafter of the present invention to possess skills reliably, Production Flow Chart is short, and easy-to-operate, raw material are based on our country and easily purchased, this operational path and traditional route have been compared decrease production cost, the ton manufacturing price can reduce approximately more than 20,000 yuan, and the mother liquor reusable edible that produces in production process produces without the three wastes, environmental protection, it is pioneering both at home and abroad that less investment instant effect, present technique belong to, and possesses the very strong market competitiveness.
Though existing about m-chlorobenzoyl chloride production method patent, but owing to pursuing higher transformation efficiency, or product yield, often need add a certain amount of organic solvent and promotor, both made like this, still have ortho para and many chlorine substituent of higher amount to generate in the reaction mixture that generates, the present invention uses the pyridine derivate that contains halogen, fat group on pyridine, pyridinium salt, ring and their salt, N, two or more of dinethylformamide and salt thereof are as composite catalyst, and normal pressure and solvent-free lower reaction generate at higher temperature.This production method advantage is that cost is low, and yield and product purity are high, and by-product hydrochloric acid and rare nitric acid all can utilize.Produce energy-conserving and environment-protective without the three wastes.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments:
The present invention as shown in Figure 1, the present invention mainly adopts following route sintetics:
Take meta-nitrotoluene as raw material, under catalyzer existence and UV-irradiation, temperature is controlled at 120～220 ℃ of introduce chlorine gas to make reaction and can gets the m-chlorobenzoyl chloride of content more than 90% under normal pressure.Muriate is through direct rectifying or be hydrolyzed to get m-chlorobenzoic acid with usual method, then gets the high purity m-chlorobenzoyl chloride with sulfur oxychloride reaction, rectifying.Wherein catalyzer is pyridine derivate and their salt, DMF (DMF) and the salt thereof that contains halogen, fat group on pyridine, pyridinium salt, ring.Catalyzer can one or more use simultaneously.
Take meta-nitrotoluene, chlorine, sulfur oxychloride, catalyzer as the synthetic m-chlorobenzoyl chloride of main raw material, the conditions such as consumption of temperature of reaction, reaction times, proportioning raw materials, catalyzer of having studied respectively are on the impact of building-up reactions, determined optimum process condition. the sulfur oxychloride usage quantity is 1.1～1.3 mol ratios of meta-nitrotoluene charging capacity in this production method, optimum quantum of utilization 1.15 mol ratios; The catalyzer usage quantity is 0.1%～5% of meta-nitrotoluene charging capacity quality, optimum quantum of utilization 0.5%～2%; The chlorine intake is 105%～130% of theoretical amount (calculated amount), and best intake is 109%～113% of theoretical amount, and chlorine passes into speed control and completed at 20～50 hours, and Best Times 38～40 hours, introduce chlorine gas to make reaction are controlled at 120～220 ℃.
In technical recipe of the present invention:
In processing condition of the present invention:
Specific embodiment:
Embodiment 1
Add 400 gram meta-nitrotoluenes in 500 milliliters of there-necked flasks, 3 gram catalyzer pyridines, 1 gram catalyst n, dinethylformamide (DMF) is spent heating material to 180 under UV-irradiation.Remain under 180 degree and slowly led to chlorine 8 hours continuously in bottle, then continued logical chlorine 30 hours under 200 degree, totally applied chlorine 885 grams.Obtain muriate 496.3 grams, through gas chromatographic analysis, m-chlorobenzoyl chloride content is 92.3%.Muriate is hydrolyzed in dimethylbenzene, crystallization treatment gets m-chlorobenzoic acid 386 grams.M-chlorobenzoic acid gets m-chlorobenzoyl chloride 408 grams with the sulfur oxychloride reactive distillation again, and content is 99.58%.
Embodiment 2
Add 111 gram meta-nitrotoluenes in 250 milliliters of there-necked flasks, 1 gram catalyzer pyridine is spent heating material to 180 under UV-irradiation.Remain under 180 degree and slowly led to chlorine 13 hours continuously in bottle, then continued logical chlorine 20 hours under 200 degree, totally applied chlorine 230 grams.Obtain muriate 136.5 grams, through gas chromatographic analysis, m-chlorobenzoyl chloride content is 91.5%.
Embodiment 3
Add 800 kilograms of meta-nitrotoluenes in 1000 liters of lass lining reactors, 6 kilograms of catalyzer pyridines are spent heating material to 150 under UV-irradiation.Remain on the lower slowly logical chlorine continuously of 150 degree 1 hour, then continued logical chlorine 10 hours under 180 degree, continued logical chlorine 30 hours under 200 degree, 1820 kilograms of totally applied chlorines.Obtain 1016 kilograms of muriates, through gas chromatographic analysis, m-chlorobenzoyl chloride content is 86.7%.Muriate gets 848.5 kilograms of m-chlorobenzoyl chlorides through hydrolysis, acyl chloride reaction and rectifying again, and content is 99.71%.
Embodiment 4
Add 800 kilograms of meta-nitrotoluenes in 1000 liters of lass lining reactors, 6 kilograms of catalyzer pyridines are spent heating material to 150 under UV-irradiation.Remain on the lower slowly logical chlorine continuously of 150 degree 1 hour, then continued logical chlorine 10 hours under 180 degree, continued logical chlorine 30 hours under 200 degree, 1796 kilograms of totally applied chlorines.Obtain 1030 kilograms of muriates, through gas chromatographic analysis, m-chlorobenzoyl chloride content is 82.09%.
Embodiment recited above is described the preferred embodiment of the present invention; be not that design of the present invention and protection domain are limited; under the prerequisite that does not break away from design concept of the present invention; various modification and improvement that in this area, common engineering technical personnel make technical scheme of the present invention all should fall into protection scope of the present invention.
The present invention is to be the method for the synthetic m-chlorobenzoyl chloride of raw material by meta-nitrotoluene.With the pyridine derivate that contains halogen, fat group on pyridine, pyridinium salt, ring and their salt, N, dinethylformamide and salt thereof are catalyzer, at normal pressure and 120～220 ℃ of temperature, meta-nitrotoluene and chlorine generation substitution reaction can get the m-chlorobenzoyl chloride crude product of content more than 90%.Muriate gets m-chlorobenzoic acid through direct hydrolysis again, then gets the high purity m-chlorobenzoyl chloride with sulfur oxychloride reaction, rectifying.Each step reaction is all carried out under relatively mild processing condition.
This operational path and traditional route have been compared decrease production cost, a ton manufacturing price can reduce approximately more than 20,000 yuan, and production process safety is easy to operate, and the mother liquor reusable edible that produces in production process produces without the three wastes, possesses the very strong market competitiveness.
Claims (3)
1. method of producing m-chlorobenzoyl chloride is characterized in that: add 400 gram meta-nitrotoluenes in 500 milliliters of there-necked flasks, 3 gram catalyzer pyridines, 1 gram catalyst n, dinethylformamide, under UV-irradiation with heating material to 180 ℃; Remain under 180 ℃ and slowly led to chlorine 8 hours continuously in bottle, then continued logical chlorine 30 hours under 200 ℃, totally applied chlorine 885 grams obtain muriate 496.3 grams, and through gas chromatographic analysis, m-chlorobenzoyl chloride content is 92.3%; Muriate is hydrolyzed in dimethylbenzene, crystallization treatment gets m-chlorobenzoic acid 386 grams; M-chlorobenzoic acid gets m-chlorobenzoyl chloride 408 grams with the sulfur oxychloride reactive distillation again, and content is 99.58%.
2. method of producing m-chlorobenzoyl chloride is characterized in that: add 111 gram meta-nitrotoluenes in 250 milliliters of there-necked flasks, 1 gram catalyzer pyridine, under UV-irradiation with heating material to 180 ℃; Remain under 180 ℃ and slowly led to chlorine 13 hours continuously in bottle, then continued logical chlorine 20 hours under 200 ℃, totally applied chlorine 230 grams; Obtain muriate 136.5 grams, through gas chromatographic analysis, m-chlorobenzoyl chloride content is 91.5%.
3. method of producing m-chlorobenzoyl chloride is characterized in that: add 800 kilograms of meta-nitrotoluenes in 1000 liters of lass lining reactors, 6 kilograms of catalyzer pyridines, under UV-irradiation with heating material to 150 ℃; Remain under 150 ℃ and slowly led to chlorine 1 hour continuously, then continued logical chlorine 10 hours under 180 ℃, continued logical chlorine 30 hours under 200 ℃, 1820 kilograms of totally applied chlorines; Obtain 1016 kilograms of muriates, through gas chromatographic analysis, m-chlorobenzoyl chloride content is 86.7%; Muriate gets 848.5 kilograms of m-chlorobenzoyl chlorides through hydrolysis, acyl chloride reaction and rectifying again, and content is 99.71%.
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| CN105353064B (en) * | 2015-12-14 | 2017-03-22 | 山东凯盛新材料股份有限公司 | Gas chromatography detection method for capryloyl chloride |
| CN107311859A (en) * | 2017-08-07 | 2017-11-03 | 江苏万隆化学有限公司 | A kind of efficient chlorobenzoyl chloride chlorination coproduction m-chlorobenzoyl chloride and 2, the method for 5 dichlorobenzoyl chlorides |
| CN109851489A (en) * | 2019-01-22 | 2019-06-07 | 江苏佳麦化工有限公司 | A kind of synthetic method of m-chlorobenzoyl chloride |
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Non-Patent Citations (2)
| Title |
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| JP特开平11-255680A 1999.09.21 |
| 贾学顺等.1-芳酰基3-(4-苯磺酰胺嘧啶)硫脲类化合物的合成.《有机化学》.1993,第13卷(第2期),250-252. * |
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