CN111393325A - Novel method for synthesizing chlorocyanomethane - Google Patents
Novel method for synthesizing chlorocyanomethane Download PDFInfo
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- CN111393325A CN111393325A CN202010365632.3A CN202010365632A CN111393325A CN 111393325 A CN111393325 A CN 111393325A CN 202010365632 A CN202010365632 A CN 202010365632A CN 111393325 A CN111393325 A CN 111393325A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Abstract
The invention discloses a new method for synthesizing chlorocyanomethane, belonging to the technical field of synthesis. The method comprises the following steps: firstly, dissolving a compound raw material with a general formula (II) in a solvent, then adding a chlorination reagent to carry out chlorination reaction, and after the reaction is finished, treating a reaction solution; and then adding a catalyst into water, dropwise adding the reaction solution after the chlorination reaction into the water, performing hydrolysis decarboxylation reaction, and purifying after the reaction is finished to obtain the chlorocyanomethane. The method has the advantages of mild reaction conditions, high product yield and good product quality.
Description
Technical Field
The invention relates to a new method for synthesizing chlorocyanomethane, belonging to the technical field of synthesis.
Background
At present, the preparation of the chlorocyanomethane at home and abroad mainly comprises the following three synthetic methods:
firstly, using dichloroacetic acid as initial raw material, making esterification reaction with methyl alcohol, making reaction with ammonia water, then making amidation, under the action of phosphorus-containing catalyst (phosphorus pentoxide), dewatering so as to obtain the invented chlorocyanomethane. The synthesis method is simple, the raw materials are cheap, but the reaction temperature in the dehydration process needs to reach 270 ℃, the reaction conditions are harsh, and a large amount of phosphorus-containing waste acid is generated after the reaction is finished, so that the environment is polluted;
secondly, the literature (Organic Syntheses, col. Vol.4, p.254) mentions that chlorocyanomethane is obtained by reacting N-chlorosuccinimide with cyanoacetic acid, but the literature mentions that the yield of the route is 75-87%, and the yield is lower;
thirdly, the literature (Journal of physical chemistry1996vol.100#2p.660-668) mentions that chlorocyanomethane is obtained by direct chlorination of acetonitrile, but the chlorocyanomethane is synthesized by the method and at the same time perchlorocyanatomethane is generated, and the mixture cannot be separated by the conventional separation method, thereby resulting in low purity of the product.
Therefore, it is of great significance to find a new method for synthesizing the chlorocyanomethane with mild reaction conditions and high product yield and purity.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a novel method for synthesizing chlorocyanomethane, which has the advantages of mild reaction conditions, high product yield and good product quality.
The structural formula of the chlorocyanomethane synthesized by the method is shown as a formula I.
The structural formula of the raw material adopted by the invention is shown as a formula II, wherein R1 is C1-C4 alkyl;
the structural formula of the intermediate product in the invention is shown as a formula III, wherein R1 is C1-C4 alkyl;
the synthetic reaction formula related by the invention is shown as a formula IV:
in order to achieve the technical purpose, the technical scheme of the invention is as follows:
a new method for synthesizing chlorocyanomethane comprises the following steps:
(1) carrying out chlorination reaction on a compound raw material with a general formula (II) and a chlorination reagent, and directly using a mixed solution for the next reaction without treatment after the reaction is finished;
(2) and (2) adding a catalyst into water, dropwise adding the mixed solution obtained after the reaction in the step (1) into the water, performing hydrolysis decarboxylation reaction, and purifying after the reaction is finished to obtain the chlorocyanomethane.
Preferably, in the step (1), the compound raw material with the general formula (II) is firstly added into a reaction bottle, the solvent is added, and then the chlorination reagent is added for chlorination reaction.
Preferably, the chlorination reaction temperature in the step (1) is 20-60 ℃.
Preferably, the reaction temperature in the step (2) is 30-55 ℃, and the reaction time is 2-8 h.
Preferably, the mass ratio of the raw material to the water is 1 (1-10).
More preferably, the mass ratio of the raw material to the water is 1 (2-5).
Preferably, the ratio of the amount of the raw material to the amount of the catalyst is 1 (0.001 to 3).
More preferably, the mass ratio of the raw material to the catalyst is 1 (0.05 to 0.2).
Preferably, the chlorinating agent can be any one of chlorine, N-chlorosuccinimide, thionyl chloride and sulfuryl chloride.
Preferably, the solvent may be any one of dichloromethane, carbon tetrachloride, chlorobenzene, methanol, and ethanol.
Preferably, the catalyst may be any one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, formic acid, benzoic acid, benzenesulfonic acid, sulfamic acid, ammonium bisulfate, aluminum trichloride, zinc chloride, ferric trichloride, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, magnesium carbonate, calcium bicarbonate, magnesium chloride, calcium chloride, sodium dihydrogen phosphate, disodium hydrogen phosphate, aqueous ammonia, urea, pyridine, dimethylamine, triethylamine, and urea.
The reaction mechanism of the present invention is as follows:
because the cyano group and the carbonyl group are strong electron-withdrawing groups, methylene in the raw material (II) is easy to perform a halogenation reaction with a halogenating reagent to obtain an intermediate product shown in a general formula (III), and the intermediate product (III) is subjected to ester hydrolysis and simultaneously is subjected to decarboxylation under the action of a catalyst to obtain a target product of the chlorocyanomethane, wherein the decarboxylation breaks the ester hydrolysis balance, so that the hydrolysis reaction can be performed completely.
From the above description, it can be seen that the present invention has the following advantages:
1. according to the invention, a compound with a structure of a general formula (II) is purposefully selected as a raw material, a methylene structure in the raw material structure is active, which is beneficial to promoting chlorination reaction, an intermediate product generated by the reaction has an active structure, and is easy to carry out hydrolysis and decarboxylation reactions, which is beneficial to improving the yield of the product chlorocyanomethane, and in addition, COOR1 in the raw material structure can protect the methylene before chlorination.
2. The method has the advantages of simple reaction mechanism, mild reaction conditions, clean and environment-friendly reaction process, low operation cost, high product yield, good quality and easy industrialization.
3. The method does not need to treat the reaction liquid after the chlorination reaction, and is simple and convenient to operate.
Detailed Description
The features of the invention will be further elucidated by the following examples, without limiting the claims of the invention in any way.
Example 1:
(1) starting a tail gas absorption system, slowly introducing chlorine gas into a four-neck flask containing 56.5g of ethyl acetonitrile for reaction at the temperature below 75 ℃, sampling and detecting in the reaction process to track the reaction process, and directly using the mixed solution for the next reaction without treatment after the reaction is finished;
(2) adding 30g of water and 5g of sodium carbonate into a four-neck flask, stirring, starting a tail gas absorption system, dropwise adding the mixed solution after the reaction in the step (1) into the water, reacting at 50 ℃ for 3 hours after dropwise adding, standing the mixed solution for layering after the reaction is finished, taking a lower organic layer, washing with water, and rectifying to obtain 45g of colorless liquid chlorocyanomethane.
Example 2:
(1) dissolving 67g of methyl acetonitrile into methanol, slowly adding 26.6g of chlorosuccinimide into a four-neck flask containing methyl acetonitrile solution, reacting at 20 ℃, sampling and detecting in the reaction process to track the reaction process, and directly using the mixed solution for the next reaction without treatment after the reaction is finished;
(2) adding 60g of water and 5g of sodium carbonate into a four-neck flask, stirring, dropwise adding the mixed solution after the reaction in the step (1) into the water, reacting at 30 ℃ for 2 hours after the dropwise adding is finished, standing the mixed solution for layering after the reaction is finished, taking the lower organic layer, washing with water, and rectifying to obtain 63.23g of colorless liquid chlorocyanomethane.
Example 3:
(1) starting a tail gas absorption system, slowly introducing chlorine gas into a four-neck flask containing 99g of methyl acetonitrile to react at 75 ℃, sampling and detecting in the reaction process to track the reaction process, and directly using the mixed solution for the next reaction without treatment after the reaction is finished;
(2) adding 60g of water and 2g of aluminum trichloride into a four-neck flask, stirring, starting a tail gas absorption system, dropwise adding the mixed solution after the reaction in the step (1) into the water, reacting at 50 ℃ for 8 hours after dropwise adding, standing the mixed solution for layering after the reaction is finished, taking a lower organic layer, washing with water, and rectifying to obtain 88g of colorless liquid chlorocyanomethane.
Example 4:
(1) starting a tail gas absorption system, dissolving 56.5g of ethyl ethylcyanoformate in ethanol, slowly introducing chlorine gas into a four-neck flask containing ethyl ethylcyanoformate solution to react at 75 ℃, sampling and detecting in the reaction process to track the reaction process, and directly using the mixed solution for the next reaction without treatment after the reaction is finished;
(2) adding 30g of water and 5g of urea into a four-neck flask, stirring, starting a tail gas absorption system, dropwise adding the mixed solution after the reaction in the step (1) into the water, reacting at 50 ℃ for 3 hours after dropwise adding, standing the mixed solution for layering after the reaction is finished, taking a lower organic layer, washing with water, and rectifying to obtain 46g of colorless liquid chlorocyanomethane.
Example 5:
(1) starting a tail gas absorption system, adding 141g of tert-butyl acetonitrile carbamate into a reaction bottle, slowly introducing chlorine gas into a four-neck flask containing the tert-butyl acetonitrile carbamate for reaction at 70 ℃, sampling and detecting in the reaction process to track the reaction process, and directly using the mixed solution for the next reaction without treatment after the reaction is finished;
(2) adding 60g of water and 5g of acetic acid into a four-neck flask, stirring, starting a tail gas absorption system, dropwise adding the mixed solution after the reaction in the step (1) into the water, reacting at 50 ℃ for 8 hours after dropwise adding, standing the mixed solution for layering after the reaction is finished, taking a lower organic layer, washing with water, and rectifying to obtain 89g of colorless liquid chlorocyanomethane.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (11)
1. The new method for synthesizing the chlorocyanomethane is characterized by comprising the following steps:
(1) carrying out chlorination reaction on a compound raw material with a general formula (II) and a chlorination reagent, and directly using a mixed solution for the next reaction without treatment after the reaction is finished;
(2) adding a catalyst into water, dropwise adding the mixed solution obtained after the reaction in the step (1) into the water, performing hydrolysis and decarboxylation reactions, and purifying after the reaction is finished to obtain the chlorocyanomethane;
wherein R1 is C1-C4 alkyl.
2. The novel process for synthesizing chlorocyanomethane of claim 1, wherein in step (1), the compound of formula (II) is first introduced into a reaction flask, the solvent is added, and then the chlorinating agent is added to perform the chlorination reaction.
3. The novel process for synthesizing chlorocyanomethane according to claim 1 or 2, wherein the chlorination reaction temperature in the step (1) is 20 to 60 ℃.
4. The novel method for synthesizing chlorocyanomethane according to claim 1 or 2, wherein the reaction temperature in the step (2) is 30-55 ℃ and the reaction time is 2-8 h.
5. The novel method for synthesizing chlorocyanomethane according to claim 1 or 2, wherein the ratio of the amount of the raw material to the amount of water is 1 (1-10).
6. The novel method for synthesizing chlorocyanomethane according to claim 5, wherein the ratio of the amount of the raw material to the amount of the water is 1 (2-5).
7. The novel method for synthesizing chlorocyanomethane according to claim 1, wherein the ratio of the amount of the raw material to the amount of the catalyst is 1 (0.001 to 3).
8. The novel method for synthesizing chlorocyanomethane according to claim 7, wherein the ratio of the amount of the raw material to the amount of the catalyst is 1 (0.05 to 0.2).
9. The novel process for the synthesis of chlorocyanomethane of claim 1 or 2, wherein the chlorinating reagent is any one of chlorine, N-chlorosuccinimide, thionyl chloride and sulfuryl chloride.
10. The novel process for the synthesis of chlorocyanomethane of claim 2, wherein the solvent is any one of dichloromethane, carbon tetrachloride, chlorobenzene, methanol and ethanol.
11. The novel process for synthesizing chlorocyanomethane as claimed in claim 1 or 2, wherein the catalyst is any one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, formic acid, benzoic acid, benzenesulfonic acid, sulfamic acid, ammonium bisulfate, aluminum trichloride, zinc chloride, iron trichloride, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, magnesium carbonate, calcium hydrogencarbonate, magnesium chloride, calcium chloride, sodium dihydrogenphosphate, disodium hydrogenphosphate, aqueous ammonia, urea, pyridine, dimethylamine, triethylamine and urea.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521308A (en) * | 2020-12-01 | 2021-03-19 | 山东国邦药业有限公司 | Synthesis method of dichloroacetonitrile |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278945A (en) * | 2015-05-15 | 2017-01-04 | 湖北文理学院 | Two chloroacetonitrile production new techniques |
| CN107473948A (en) * | 2017-09-26 | 2017-12-15 | 安徽国星生物化学有限公司 | A kind of synthetic method that the pentanone of 3,5 dichloro 2 is prepared by ethyl acetoacetate |
| CN108383744A (en) * | 2018-02-11 | 2018-08-10 | 浙江工业大学 | A kind of preparation method of 2,6- dimethyl-tyrosine |
| CN109608361A (en) * | 2019-01-03 | 2019-04-12 | 山东国邦药业股份有限公司 | A kind of synthetic method of two chloroacetonitriles |
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- 2020-04-30 CN CN202010365632.3A patent/CN111393325A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278945A (en) * | 2015-05-15 | 2017-01-04 | 湖北文理学院 | Two chloroacetonitrile production new techniques |
| CN107473948A (en) * | 2017-09-26 | 2017-12-15 | 安徽国星生物化学有限公司 | A kind of synthetic method that the pentanone of 3,5 dichloro 2 is prepared by ethyl acetoacetate |
| CN108383744A (en) * | 2018-02-11 | 2018-08-10 | 浙江工业大学 | A kind of preparation method of 2,6- dimethyl-tyrosine |
| CN109608361A (en) * | 2019-01-03 | 2019-04-12 | 山东国邦药业股份有限公司 | A kind of synthetic method of two chloroacetonitriles |
Non-Patent Citations (3)
| Title |
|---|
| ED W. B. DE LEER等: "Chlorination of w-Cyanoalkanoic Acids in Aqueous Medium", 《ENVIRON. SCI. TECHNOL.》 * |
| RUUD J. B. PETERS 等: "Chlorination of Cyanoethanoic Acid in Aqueous Medium", 《ENVIRON. SCI. TECHNOL.》 * |
| WILT, JAMES W.等: "Dibromoacetonitrile", 《ORGANIC SYNTHESES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521308A (en) * | 2020-12-01 | 2021-03-19 | 山东国邦药业有限公司 | Synthesis method of dichloroacetonitrile |
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Application publication date: 20200710 |