CN116283525A - Preparation method of 1, 3-trichloroacetone - Google Patents
Preparation method of 1, 3-trichloroacetone Download PDFInfo
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- CN116283525A CN116283525A CN202310329812.XA CN202310329812A CN116283525A CN 116283525 A CN116283525 A CN 116283525A CN 202310329812 A CN202310329812 A CN 202310329812A CN 116283525 A CN116283525 A CN 116283525A
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- trichloroacetone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
Abstract
The invention relates to the technical field of organic synthesis, and provides a preparation method of 1, 3-trichloroacetone, which is characterized in that water is used as a solvent, acetone is used as a raw material, and the raw material reacts with a chloro reagent under the action of 1-methylpyrazole to obtain the 1, 3-trichloroacetone. By the technical scheme, the problem that the yield and purity of the method for preparing the 1, 3-trichloroacetone in the prior art are not high is solved.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 1, 3-trichloroacetone.
Background
Trichloroacetone can be used for synthesizing and researching anti-HIV medicines, imidazole heterocyclic compounds and polycyclic or bridged ring compounds. Trichloroacetone is also an important intermediate in the production of folic acid. Folic acid is one of the essential vitamins in human body, and deficiency of folic acid can cause diseases such as nerve tube deformity, megaloblastic anemia, cleft lip and palate, depression, tumor and the like. The stability of the synthesized folic acid is higher than that of natural folic acid, and the synthesized folic acid is easy to be absorbed.
The earliest method for producing 1, 3-trichloroacetone adopts chlorine to directly carry out chlorination, has long reaction time and poor selectivity, and the reaction products are difficult to separate, so that the purity is lower. Thus, the skilled person uses triethylamine, diethylamine, pyridine, etc. as catalysts, but the reaction time is long and the 1, 3-trichloroacetone in the product is only 40% -50%. In order to improve the purity and the yield, the Chinese patent document with the application number of 201710257048.4 discloses a method for preparing 1, 3-trichloroacetone, which is characterized in that dichloroacetone and trichloroisocyanuric acid are reacted in the presence of an acid catalyst, so that the reaction time is shortened, the yield is 40-50%, and the purity is 70-80%. Therefore, the yield and purity of the synthesized 1, 3-trichloroacetone have yet to be improved.
Disclosure of Invention
The invention provides a preparation method of 1, 3-trichloroacetone, which solves the problems of low yield and purity of the method for preparing 1, 3-trichloroacetone in the prior art.
The technical scheme of the invention is as follows:
the preparation method of 1, 3-trichloroacetone is characterized in that water is used as a solvent, acetone is used as a raw material, and the raw material reacts with a chloro reagent under the action of 1-methylpyrazole to obtain 1, 3-trichloroacetone.
As a further technical scheme, the chloro reagent is N-chlorosuccinimide.
Compared with the common chloro reagent chlorine, the N-chlorosuccinimide has higher safety, does not need complex experimental operations such as photocatalysis and the like, and is more suitable for large-scale production. And when water is used as a solvent and 1-methylpyrazole is used as a catalyst, N-chlorosuccinimide is used as a chloro reagent, so that the reaction purity can be improved, the yield can be improved, and the production cost can be reduced.
As a further technical scheme, the reaction temperature is 35-40 ℃ during the reaction.
Compared with the existing preparation method of 1, 3-trichloroacetone, the reaction system is more suitable for low-temperature reaction, side reaction can be caused by high temperature, post-treatment is difficult, and the purity of the product is affected.
As a further technical scheme, the molar ratio of the acetone to the chlorinating agent is 1:4-5.
When the molar ratio of acetone to the chlorinating agent is not 1:4-5, especially when the amount of chlorinating agent is increased, more impurities are caused.
As a further technical scheme, the mass of the 1-methylpyrazole is 20% -30% of the mass of the acetone.
As a further technical scheme, the mass of the water is 30-40 times of that of the acetone.
As a further technical scheme, the reaction time is 9-12h.
Aiming at the reaction solvent, the catalyst and the chloro reagent, the 1, 3-trichloroacetone with higher purity can be obtained when the reaction time is controlled to be 9-12 hours, so that the reaction time is prolonged, more byproducts are generated, and the incomplete reaction of the reaction time is shortened.
As a further technical scheme, the chloro reagent is added for 4-5 times; the chlorinated reagent is added in batches so as to make the reaction more complete.
As a further technical scheme, the post-treatment is carried out after the reaction is completed.
As a further technical scheme, the post-treatment specifically comprises: filtering the reaction solution to obtain a filter cake, washing the filter cake with acetone, merging the filtrates, and rectifying to obtain the 1, 3-trichloroacetone.
The working principle and the beneficial effects of the invention are as follows:
1. in the invention, water is used as a solvent, and 1-methylpyrazole is used as a catalyst to catalyze acetone to carry out chlorination reaction, so that 1, 3-trichloroacetone is prepared, the reaction condition is mild, and the reaction time is short. The water is used as solvent to obtain a product with less byproducts and less impurities, and the conventional rectification is adopted to carry out post-treatment to ensure that the purity of the 1, 3-trichloroacetone is high. The 1-methylpyrazole is used as a catalyst, so that the reaction rate is promoted, the reaction time is shortened, the product selectivity is improved, and the production and the application of 1, 3-trichloroacetone are facilitated.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
58g of acetone is added into 2000mL of water, 12g of 1-methylpyrazole is added, 267g N-chlorosuccinimide is then added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 3h; then 133g N-chlorosuccinimide is added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 3 hours; continuously adding 67g N-chlorosuccinimide, controlling the temperature to be 35-40 ℃, and continuously stirring for 1h; finally 67g of N-chlorosuccinimide is added, the temperature is controlled to be 35-40 ℃, the stirring is continued for 2 hours, the reaction is stopped, the filter cake is obtained by suction filtration, the filter cake is washed by acetone, the filter cake is combined, the filter cake is rectified and dried, and 121.2g of powder is obtained, the purity of 1, 3-trichloroacetone is 86.5%, and the yield of 1, 3-trichloroacetone is 64.9%.
Example 2
58g of acetone and 17g of 1-methylpyrazole are added into 2300mL of water, 267g N-chlorosuccinimide is then added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 3 hours; then 133g N-chlorosuccinimide is added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 3 hours; continuously adding 133g N-chlorosuccinimide, controlling the temperature to be 35-40 ℃, and continuously stirring for 2 hours; continuously adding 67g N-chlorosuccinimide, controlling the temperature to be 35-40 ℃, and continuously stirring for 2 hours; finally 67g N-chlorosuccinimide is added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 2 hours; stopping the reaction, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, merging the filtrates, rectifying and drying to obtain 125.6g of powder, wherein the purity of 1, 3-trichloroacetone is 85.3%, and the yield of 1, 3-trichloroacetone is 66.4%.
Example 3
To 2300mL of water, 58g of acetone was added, 15g of 1-methylpyrazole was added, 267g N-chlorosuccinimide was then added, the temperature was controlled at 35-40℃and stirring was continued for 3h; then 133g N-chlorosuccinimide is added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 3 hours; continuously adding 133g N-chlorosuccinimide, controlling the temperature to be 35-40 ℃, and continuously stirring for 3 hours; finally 67g N-chlorosuccinimide is added, the temperature is controlled at 35-40 ℃, stirring is continued for 2 hours, and the reaction is stopped; stopping the reaction, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, merging the filtrates, rectifying and drying to obtain 132g of powder, wherein the purity of 1, 3-trichloroacetone is 82.9%, and the yield of 1, 3-trichloroacetone is 67.8%.
Example 4
58g of acetone is added into 2000mL of water, 12g of 1-methylpyrazole is added, 155g of trichloroisocyanuric acid is then added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 3 hours; then 78g of trichloroisocyanuric acid is added, the temperature is controlled at 35-40 ℃, and stirring is continued for 3 hours; continuously adding 39g of trichloroisocyanuric acid, controlling the temperature to be 35-40 ℃, and continuously stirring for 1h; finally, 39g of trichloroisocyanuric acid is added, the temperature is controlled to be 35-40 ℃, stirring is continued for 2 hours, the reaction is stopped, a filter cake is obtained through suction filtration, the filter cake is washed by acetone, the filter cake is rectified after being combined, and the powder is dried, so that 112.3g of powder, the purity of 1, 3-trichloroacetone is 75.6%, and the yield of 1, 3-trichloroacetone is 52.6%.
Example 5
58g of acetone and 17g of 1-methylpyrazole are added into 2300mL of water, 267g N-chlorosuccinimide is then added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 3 hours; then 133g N-chlorosuccinimide is added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 3 hours; continuously adding 133g N-chlorosuccinimide, controlling the temperature to be 35-40 ℃, and continuously stirring for 2 hours; continuously adding 133g N-chlorosuccinimide, controlling the temperature to be 35-40 ℃, and continuously stirring for 2 hours; finally 67g N-chlorosuccinimide is added, the temperature is controlled to be 35-40 ℃, and stirring is continued for 2 hours; stopping the reaction, carrying out suction filtration to obtain a filter cake, washing the filter cake with acetone, merging the filtrates, rectifying and drying to obtain 126.4g of powder, wherein the purity of 1, 3-trichloroacetone is 79.2%, and the yield of 1, 3-trichloroacetone is 62.0%.
Comparative example 1
In comparison with example 1, the same procedure as in example 1 was repeated except that water was replaced with methanol to obtain 130.9g of powder, which had a purity of 60.3% and a yield of 48.9% of 1, 3-trichloroacetone.
Comparative example 2
In comparison with example 1, the same procedure as in example 1 was repeated except that chloroform was used instead of water, whereby 128.3g of powder was obtained, the purity of 1, 3-trichloroacetone was 53.5%, and the yield of 1, 3-trichloroacetone was 42.5%.
Comparative example 3
In comparison with example 1, the same procedure as in example 1 was repeated except that 1-methylpyrazole was replaced with triethylamine, whereby 111.3g of powder was obtained, the purity of 1, 3-trichloroacetone was 74.1%, and the yield of 1, 3-trichloroacetone was 51.1%.
When other solvents are adjusted for the reactants and the reaction conditions, the purity of the product is affected, and the obtained powder has more byproducts and impurities. When the catalyst is changed, the yield is greatly reduced, and the purity is changed.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
- The 1.1,1,3-trichloroacetone preparing process features that water as solvent and acetone as material are reacted with chloro reagent to obtain 1, 3-trichloroacetone.
- 2. The method for preparing 1, 3-trichloroacetone according to claim 1, wherein the chlorinating agent is N-chlorosuccinimide.
- 3. The process for preparing 1, 3-trichloroacetone according to claim 1, wherein the reaction temperature is 35 to 40 ℃.
- 4. The process for the preparation of 1, 3-trichloroacetone according to claim 1, wherein the molar ratio of acetone to chlorinated reagent is 1:4-5.
- 5. The method for preparing 1, 3-trichloroacetone according to claim 1, wherein the mass of the 1-methylpyrazole is 20% -30% of the mass of the acetone.
- 6. The method for preparing 1, 3-trichloroacetone according to claim 1, wherein the mass of the water is 30-40 times of the mass of the acetone.
- 7. The process for preparing 1, 3-trichloroacetone according to claim 1, wherein the reaction time is 9 to 12 hours.
- 8. The process for preparing 1, 3-trichloroacetone according to claim 1, wherein the chlorinating agent is added in 4 to 5 portions.
- 9. The process for preparing 1, 3-trichloroacetone according to claim 1, wherein the reaction is carried out after completion of the work-up.
- 10. The process for the preparation of 1, 3-trichloroacetone according to claim 9, characterized in that the post-treatment is in particular: filtering the reaction solution to obtain a filter cake, washing the filter cake with acetone, merging the filtrates, and rectifying to obtain the 1, 3-trichloroacetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310329812.XA CN116283525A (en) | 2023-03-30 | 2023-03-30 | Preparation method of 1, 3-trichloroacetone |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310329812.XA CN116283525A (en) | 2023-03-30 | 2023-03-30 | Preparation method of 1, 3-trichloroacetone |
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| CN202310329812.XA Pending CN116283525A (en) | 2023-03-30 | 2023-03-30 | Preparation method of 1, 3-trichloroacetone |
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