CN108409558A - A method of preparing oxalyl chloride - Google Patents
A method of preparing oxalyl chloride Download PDFInfo
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- CN108409558A CN108409558A CN201810323388.7A CN201810323388A CN108409558A CN 108409558 A CN108409558 A CN 108409558A CN 201810323388 A CN201810323388 A CN 201810323388A CN 108409558 A CN108409558 A CN 108409558A
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- oxalyl chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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Abstract
The present invention relates to a kind of method preparing oxalyl chloride, preparation method includes：S1, in reaction bulb, 250ml solvents, 90 110g oxalic acid, 2 5g catalyst are added, 30 40min are mixed and form solution A；S2, solution A are warming up to 50 60 DEG C under stiring, and bis- (trichloromethyl) carbonic esters of a certain amount of by-product suppressor, 200 210g are added dropwise and 300ml solvents are mixed to form solution B；S3, solution B side border ring steam the crude product in system until kettle temperature reaches 110 DEG C, and for the gas generated in reaction process with water multistage absorption, the aqueous solution of formation is salt soda acid, is sodium chloride after neutralization.The method provided by the invention for preparing oxalyl chloride, raw material is easy to get, post-processing is simple, safe operation, using organic amine as catalyst, thiourea derivative is as by-product suppressor, allow chlorination reaction is controllable, efficiency of pcr product is high, by-product is few, and the water in reaction process absorbs exhaust gas and forms hydrochloric acid, or Nacl is formed after neutralizing, it not will produce secondary pollution.
Description
Technical field
The invention belongs to organic chemistry fileds, are related to a kind of method preparing oxalyl chloride.
Background technology
Oxalyl chloride is the intermediate or reagent of the organic syntheses such as a kind of pesticide, medicine and coating, can be used for closing on pesticide
At sulfonylureas element, herbicide Bensulfuron-methyl, plant growth regulator etc.；It can pharmaceutically be used for synthesizing cephalo Pu or cefuroxime
Ester；It can be used for preparing methacryl isocyanates etc. in terms of coating；It is commonly used to prepare other acyl chlorides on laboratory or factory,
Its purposes is very extensive.
Traditional synthetic method using cheap oxalic acid as raw material, used chlorinating agent often use thionyl chloride (Chem.Med,
Chem, 2011,6 (10), 1892-1899；Chlorine/phosphorus oxychloride (JP2007326837)；Phosphorus pentachloride (Organic＆
Biomolecular Chemistry.2006.4 (3) .358-564) or phosphorus pentachloride/phosphorus oxychloride (US.S.R.1810328)
Deng.The major drawbacks of above-mentioned technique are to prepare the mixing for generating a large amount of spent acid in reaction process or generating after neutralizing
Salt, environmental issue are very prominent.
Invention content
It is a large amount of to solve generation after generating a large amount of spent acid in existing method synthesis oxalyl chloride technical process or neutralize
Salt-mixture, the problems such as causing serious environmental pollution.
Replacing above-mentioned traditional chlorinating agent with bis- (trichloromethyl) carbonic esters the present invention provides a kind of, in catalyst and
Be transformed oxalic acid under by-product suppressor effect the method for oxalyl chloride.This method raw material is easy to get, and post-processing is simple, operation peace
Entirely, the water in reaction process, which absorbs after exhaust gas forms hydrochloric acid, or neutralization, forms Nacl, to more environment-friendly.
The technical proposal for solving the technical problem of the invention is：
A method of oxalyl chloride being prepared, steps are as follows for the method：
S1, in reaction bulb, 250ml solvents, 90-110g oxalic acid, 2-5g catalyst is added, 30-40min shapes are mixed
At solution A；
S2, solution A are warming up to 50-60 DEG C under stiring, and a certain amount of by-product suppressor, 200-210g bis- (three is added dropwise
Chloromethyl) carbonic ester and 300ml solvents be mixed to form solution B；
S3, solution B side border ring steam the crude product in system until kettle temperature reach 110 DEG C, generated in reaction process
For gas with water multistage absorption, the aqueous solution of formation is salt soda acid, is sodium chloride after neutralization.
The catalyst is organic amine, and the by-product suppressor is thiourea derivative, the two dosage mass ratio 1: 2-3.
Preferably, the organic amine is pyrazoles, substituted pyrazoles, triethylamine or the different amide of diethyl；The thiocarbamide spreads out
Biology is any one in ethylene thiourea, N- methylthioureas, 4- methyl-thiosemicarbazide or benzoylthioureas.
Catalyst in this patent is organic amine, is catalyzed reaction process, and for the effect of catalyst, presence can be controlled
Potential difference between the group of reaction raw materials processed improves reaction efficiency, but is found in putting into practice, and can synchronize and generate a large amount of side reaction
It is raw, it is added to a certain amount of by-product suppressor thus, the group volume of the thiourea derivative as organic matter is larger, and reaction is former
Bridging action is formed between the group of material, control reaction is carried out toward target product.The collaboration of catalyst and by-product suppressor is made
With so that chlorination reaction is controllable, efficiency of pcr product is high, by-product is few.
It is further preferred that the organic amine is pyrazoles, the thiourea derivative is N- methylthioureas.
Preferably, the solvent is dimethylbenzene (mixing or single composition), toluene and substituted benzene and alkyl halide.
The alkyl halide is 1.1.2- trichloroethanes or 1.1.2.2- tetrachloroethanes.
The beneficial effects of the invention are as follows：
The present invention provides a kind of method preparing oxalyl chloride, this method raw material is easy to get, and post-processing is simple, safe operation,
Using organic amine as catalyst, thiourea derivative allows chlorination reaction is controllable, efficiency of pcr product is high as by-product suppressor, by-product
Object is few, and the water in reaction process absorbs exhaust gas and forms hydrochloric acid, or forms Nacl after neutralizing, and not will produce secondary pollution.
Description of the drawings
Fig. 1 is the reaction equation of oxalyl chloride that oxalic acid is transformed in the case where organic amine is catalyst.
Specific implementation mode
Below by specific embodiment, and in conjunction with attached drawing, technical scheme of the present invention will be further explained in detail.
Embodiment 1：
A method of oxalyl chloride being prepared, steps are as follows for the method：
S1, in reaction bulb, 250ml dimethylbenzene, 90g oxalic acid, 2g pyrazoles is added, 30min is mixed and forms solution A；
S2, it is warming up to 50 DEG C under stiring, a certain amount of by-product suppressor, bis- (trichloromethyl) carbonic acid of 200g is added dropwise
Ester) and 300ml dimethylbenzene be mixed to form solution B；
S3, side border ring steam the crude product in system until kettle temperature reach 110 DEG C, the gas generated in reaction process with
The aqueous solution of water multistage absorption, formation is salt soda acid, is sodium chloride after neutralization；
Specific to the present embodiment, the by-product suppressor is ethylene thiourea, and the ratio between dosage quality and catalyst are 1: 2.
Embodiment 2：
A method of oxalyl chloride being prepared, steps are as follows for the method：
S1, in reaction bulb, 250ml toluene, 100g oxalic acid, 3.5g triethylamines is added, 35min is mixed and forms solution
A；
S2, it is warming up to 55 DEG C under stiring, a certain amount of by-product suppressor, bis- (trichloromethyl) carbonic esters of 205g is added dropwise)
It is mixed to form solution B with 300ml toluene；
S3, side border ring steam the crude product in system until kettle temperature reach 110 DEG C, the gas generated in reaction process with
The aqueous solution of water multistage absorption, formation is salt soda acid, is sodium chloride after neutralization.
Specific to the present embodiment, the by-product suppressor is N- methylthioureas, and the ratio between dosage quality and catalyst are 1:
3。
Embodiment 3：
A method of oxalyl chloride being prepared, steps are as follows for the method：
S1, in reaction bulb, 250ml1.1.2- trichloroethanes, 110g oxalic acid, the different amide of 5g diethyl is added, mixing is stirred
It mixes 40min and forms solution A；
S2, it is warming up to 60 DEG C under stiring, a certain amount of by-product suppressor, bis- (trichloromethyl) carbonic esters of 210g is added dropwise)
It is mixed to form solution B with 300ml1.1.2- trichloroethanes；
S3, side border ring steam the crude product in system until kettle temperature reaches 110 DEG C.The gas generated in reaction process with
The aqueous solution of water multistage absorption, formation is salt soda acid, is sodium chloride after neutralization.
Specific to the present embodiment, the by-product suppressor is 4- methyl-thiosemicarbazide, dosage quality and catalyst it
Than being 2: 5.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, on the premise of not exceeding the technical scheme recorded in the claims also other variations and modifications.
Claims (7)
1. a kind of method preparing oxalyl chloride, which is characterized in that include the following steps：
S1, in reaction bulb, be added a certain amount of solvent, oxalic acid, catalyst, 30-40min be mixed and forms solution A；
S2, solution A are warming up to 50-60 DEG C under stiring, and a certain amount of by-product suppressor, double manganese ester and solvent mixing is added dropwise
Form solution B；
S3, solution B side border ring steam the crude product in system until kettle temperature reach 110 DEG C, the gas generated in reaction process
With water multistage absorption, the aqueous solution of formation is salt soda acid, is sodium chloride after neutralization.
2. a kind of method preparing oxalyl chloride as described in claim 1, which is characterized in that in the S1 volume ml of solvent with
The ratio between quality g of oxalic acid is 25: (9-11), the quality of catalyst are the 2-5% of the quality of oxalic acid；Double manganese ester in the S2
Quality is 2-2.5 times of oxalic acid quality, and the ratio between the volume ml of solvent and the quality g of oxalic acid are 30: (9-11).
3. a kind of method preparing oxalyl chloride as claimed in claim 2, which is characterized in that the catalyst is organic amine, institute
It is thiourea derivative, the two dosage mass ratio 1: 2-3 to state by-product suppressor.
4. a kind of method preparing oxalyl chloride as claimed in claim 3, which is characterized in that the organic amine is pyrazoles, substitution
Pyrazoles, triethylamine or the different amide of diethyl；The thiourea derivative is ethylene thiourea, N- methylthioureas, 4- methyl-thio ammonia
Any one in base urea or benzoylthioureas.
5. a kind of method preparing oxalyl chloride as claimed in claim 4, which is characterized in that the organic amine is pyrazoles, described
Thiourea derivative is N- methylthioureas.
6. a kind of method preparing oxalyl chloride as described in claim 1, which is characterized in that the solvent in the S1 and S2 is two
Toluene, toluene and substituted benzene and alkyl halide.
7. a kind of method preparing oxalyl chloride as claimed in claim 6, which is characterized in that the alkyl halide is 1.1.2- trichlorines
Ethane or 1.1.2.2- tetrachloroethanes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724108A (en) * | 2020-12-31 | 2021-04-30 | 山东金城柯瑞化学有限公司 | Preparation method of alpha-oxo-2-furanacetic acid |
| CN114702380A (en) * | 2022-04-07 | 2022-07-05 | 河南特格纳特科技有限公司 | Method for co-producing p-chlorobenzoyl chloride and caproyl chloride and acyl chloride products thereof |
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| US4341720A (en) * | 1978-09-16 | 1982-07-27 | Bayer Aktiengesellschaft | Process for the preparation of oxalyl chloride |
| CN101805257A (en) * | 2010-04-03 | 2010-08-18 | 太原理工大学 | Preparation method for phthalyl chloride, m-phthaloyl chloride and paraphthaloyl chloride |
| CN101817739A (en) * | 2010-05-14 | 2010-09-01 | 山西新天源医药化工有限公司 | Synthesis method of alpha-methacryloylchloride |
| CN105461550A (en) * | 2015-12-17 | 2016-04-06 | 浙江汇能生物股份有限公司 | Preparation method of p-anisoyl chloride |
| CN105481687A (en) * | 2016-01-27 | 2016-04-13 | 浙江汇能生物股份有限公司 | Preparing method for o-methoxybenzoyl chloride |
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2018
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Patent Citations (5)
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|---|---|---|---|---|
| US4341720A (en) * | 1978-09-16 | 1982-07-27 | Bayer Aktiengesellschaft | Process for the preparation of oxalyl chloride |
| CN101805257A (en) * | 2010-04-03 | 2010-08-18 | 太原理工大学 | Preparation method for phthalyl chloride, m-phthaloyl chloride and paraphthaloyl chloride |
| CN101817739A (en) * | 2010-05-14 | 2010-09-01 | 山西新天源医药化工有限公司 | Synthesis method of alpha-methacryloylchloride |
| CN105461550A (en) * | 2015-12-17 | 2016-04-06 | 浙江汇能生物股份有限公司 | Preparation method of p-anisoyl chloride |
| CN105481687A (en) * | 2016-01-27 | 2016-04-13 | 浙江汇能生物股份有限公司 | Preparing method for o-methoxybenzoyl chloride |
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| 陈小春: "固体光气在脂肪族酰氯及酰基硫脲制备中的应用研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724108A (en) * | 2020-12-31 | 2021-04-30 | 山东金城柯瑞化学有限公司 | Preparation method of alpha-oxo-2-furanacetic acid |
| CN114702380A (en) * | 2022-04-07 | 2022-07-05 | 河南特格纳特科技有限公司 | Method for co-producing p-chlorobenzoyl chloride and caproyl chloride and acyl chloride products thereof |
| CN114702380B (en) * | 2022-04-07 | 2024-03-19 | 河南特格纳特科技有限公司 | Method for co-producing p-chlorobenzoyl chloride and hexanoyl chloride and acyl chloride product thereof |
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