CN113214074A - Method for producing high-purity 3-chloropropionyl chloride by one-pot method - Google Patents
Method for producing high-purity 3-chloropropionyl chloride by one-pot method Download PDFInfo
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- CN113214074A CN113214074A CN202110460632.6A CN202110460632A CN113214074A CN 113214074 A CN113214074 A CN 113214074A CN 202110460632 A CN202110460632 A CN 202110460632A CN 113214074 A CN113214074 A CN 113214074A
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- 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 invention discloses a method for producing high-purity 3-chloropropionyl chloride by a one-pot method, belonging to the field of fine chemical engineering. Acrylic acid, hydrochloric acid and thionyl chloride are used as raw materials, and 3-chloropropionyl chloride is obtained by addition reaction, dehydration, acyl chlorination reaction and simple distillation in the presence of phenothiazine catalyst. Wherein, the acrylic acid residue in the reaction liquid is strictly controlled to be less than or equal to 2.0 percent and the water content is controlled to be less than or equal to 1.0 percent in the addition stage; the content of 3-chloropropionyl chloride is strictly controlled to be more than or equal to 99.0% in the acyl chlorination stage, the purity of 3-chloropropionyl chloride obtained by distilling the reaction liquid is more than or equal to 99.5%, and the yield is more than 90%. The 3-chloropropionyl chloride product obtained by the process can meet the market demand for high-purity 3-chloropropionyl chloride.
Description
Technical Field
The invention relates to a technical method for producing high-purity 3-chloropropionyl chloride by a one-pot method, belonging to a chemical synthesis technology in fine chemical engineering.
Background
3-chloropropionyl chloride, with a boiling point of 144 ℃, is colorless to light yellow liquid, is a fine chemical intermediate with wide application, and is mainly used in the fields of medicines and pesticides. The current processes mainly comprise the following steps:
1. CN102731369A reports that acrylic acid and phosphorus trichloride react in one pot under the catalysis of trace DMF to obtain 3-chloropropionyl chloride, the yield is 83.6 percent, and the purity is 90.2 percent. The 3-chloropropionyl chloride prepared by the method has low purity, and the purity and yield of the product in the next working procedure can be reduced by carrying out subsequent reaction on the low-purity 3-chloropropionyl chloride.
2. CN103370303A reports that acrylic acid and phosgene react in one pot under the catalysis of trace DMF to obtain 3-chloropropionyl chloride with the yield of 57 percent. The process uses phosgene, a highly toxic reagent, and the yield is only 56% (the purity is unknown).
3. CN107118103A reports the addition of hydrogen chloride gas with acrylic acid to give 3-chloropropionic acid in a yield of 90%. The 3-chloropropionic acid reacts with phosphorus trichloride to obtain 3-chloropropionyl chloride, the yield is 88 percent (the purity is unknown), and the total yield of the two steps is 79 percent. Phosphorous acid generated during phosphorus trichloride chlorination is easy to oxidize and difficult to recover, so that the waste water is greatly increased.
4. CN109534988A reports that 3-chloropropionic acid is obtained by adding acrylic acid and hydrogen chloride gas under the catalysis of an ionic liquid loaded aluminum trioxide special catalyst, and the generated 3-chloropropionic acid reacts with thionyl chloride in situ to obtain 3-chloropropionyl chloride with the best yield of 98%. The method has high yield, but the catalyst preparation process is very complicated, the low temperature of minus 60 ℃ and the ultrahigh temperature of 1000 ℃ are required to be used, and the harsh conditions naturally cause the high cost of the catalyst. In addition, the patent does not report the number of times the catalyst is used, and thus it is impossible to evaluate whether the method has a cost advantage.
5. CN109534971A adopts two gas-liquid reactors to react acrylic acid with hydrogen chloride gas to obtain 3-chloropropionic acid with purity of 77%; 3-chloropropionic acid reacts with thionyl chloride to obtain 3-chloropropionyl chloride with the purity of 99 percent and the yield of 80 percent. The method has low yield, the purity can not reach more than 99.5 percent, and the market has strong demand on high-purity 3-chloropropionyl chloride.
Disclosure of Invention
The invention aims to provide a technical method for producing high-purity 3-chloropropionyl chloride, which has the remarkable advantages of simple and convenient operation, high yield and good purity. The operation is simple and convenient and is finished in two steps of reaction and one pot; the yield is high in the technical method, the yield is over 90 percent based on the acrylic acid; the purity is good when the purity of the obtained 3-chloropropionyl chloride reaches over 99.5 percent.
The invention relates to a synthesis method for producing high-purity 3-chloropropionyl chloride by a one-pot method, which is technically characterized by comprising the following steps: under the action of a catalyst, reacting acrylic acid with a chlorinating agent, performing reduced pressure dehydration, dropwise adding thionyl chloride in situ for reaction, and distilling to obtain 3-chloropropionyl chloride.
Further, in the above technical solution, the specific operations are: under the action of 0.01-0.5 part of catalyst, 0.05-3.0 parts of hydrochloric acid reacts with acrylic acid, the temperature is controlled at 25-90 ℃, and 0.5-5 parts of thionyl chloride is dripped; when the content of acrylic acid in the reaction liquid is less than or equal to 2.0 percent, starting to perform reduced pressure dehydration; when the water content is less than or equal to 1.0 percent, controlling the temperature to be between 30 and 100 ℃ and dripping 1.0 to 10.0 parts of thionyl chloride; stopping the reaction when the content of the 3-chloropropionyl chloride in the reaction liquid is more than or equal to 99.0 percent; distilling to obtain high-purity 3-chloropropionyl chloride.
Further, in the above technical solution, the catalyst is selected from phenothiazine, hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, 4-tert-butylcatechol, and other agents for inhibiting polymerization of acrylic acid; the proportion of the catalyst is 0.02-0.10 part.
Further, in the above technical solution, the chlorinating agent is hydrochloric acid and thionyl chloride. The concentration of the hydrochloric acid is 1.0-36%.
Further, in the above technical scheme, the materials acrylic acid, hydrochloric acid and thionyl chloride before dehydration are 1 part: 0.2-0.8 part: 1.0 to 3.0 parts.
Further, in the above technical scheme, the dehydrated material acrylic acid and thionyl chloride is 1 part: 1.5 to 4.0 parts.
Further, in the technical scheme, the reaction temperature before dehydration is 30-60 ℃; the reaction temperature after dehydration is 45-85 ℃.
Further, in the above technical scheme, when chlorination of acrylic acid and a chlorinating agent is finished, acrylic acid residue in a reaction liquid of 3-chloropropionic acid is less than or equal to 2.0%, preferably less than or equal to 1.0%.
The dehydration control standard of the 3-chloropropionic acid is as follows: after the dehydration is finished, the water content of the reaction system is optimally controlled to be less than or equal to 0.5 percent.
Furthermore, in the technical scheme, the 3-chloropropionyl chloride with the purity of more than or equal to 99.5 percent is obtained by distillation, and the yield is more than 90 percent.
The one-pot method is characterized in that under the action of a catalyst, acrylic acid, hydrochloric acid and thionyl chloride react to generate 3-chloropropionic acid, and the 3-chloropropionic acid is subjected to reduced pressure dehydration and in-situ dropwise addition of thionyl chloride to react and then distilled to obtain a product. The method can perform acyl chlorination reaction with thionyl chloride in an original reaction kettle without purifying 3-chloropropionic acid to obtain high-purity 3-chloropropionyl chloride. The method greatly simplifies the operation difficulty, and simultaneously has no material loss and high yield. The control strategy is scientific and appropriate, so that the purity of the obtained product can reach more than 99.5 percent.
Advantageous effects of the invention
The invention effectively solves the problem that high-purity 3-chloropropionyl chloride is difficult to provide in the market, the purity of the 3-chloropropionyl chloride prepared by the method is more than 99.5 percent, meanwhile, the operation of preparing the 3-chloropropionyl chloride by an acrylic acid one-pot method is convenient, and the yield reaches more than 90 percent. In addition, the generated hydrogen chloride is absorbed by a falling film absorption tower to obtain a hydrogen chloride solution for recycling; the generated sulfur dioxide is absorbed by sodium hydroxide solution to obtain sodium bisulfite solution which is used as an effective reagent for removing the oxidant. The technical scheme can realize the operation without three wastes.
Drawings
FIG. 1 shows the GC spectrum of the product obtained in example 4 by the methanol derivatization method.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Into a 1000mL reaction flask, 200g of acrylic acid, 120g of 30% hydrochloric acid, and 6g of phenothiazine were charged. Stirring and heating to 40-50 ℃, controlling the temperature and dripping 200g of thionyl chloride, and finishing dripping within 6 hours. After finishing dropping, the reaction is kept for 2 hours, the residual acrylic acid in the reaction solution is detected to be less than 1.0 percent, and the temperature is controlled to be less than 50 ℃ for decompression and dehydration. When the water content is lower than 0.50%, 350g of thionyl chloride is dripped at the temperature of 55-65 ℃ for 4 hours. After the dripping is finished, the reaction is carried out for 2 hours, the content of the 3-chloropropionyl chloride in the reaction liquid is detected to be 99.2 percent, and the reaction is stopped. The colorless liquid 3-chloropropionyl chloride is obtained by reduced pressure distillation with the yield of 90.1 percent and the purity of 99.6 percent (3-chloropropionyl chloride is detected by GC through a methanol derivation method).
Example 2
Into a 1000mL reaction flask, 200g of acrylic acid, 160g of 30% hydrochloric acid, and 6g of phenothiazine were charged. Stirring and heating to 40-50 ℃, controlling the temperature and dripping 200g of thionyl chloride, and finishing dripping within 6 hours. After finishing dropping, the reaction is kept for 2 hours, and when the residual acrylic acid in the reaction liquid is detected to be below 0.5 percent, the temperature is controlled to be below 50 ℃ for decompression and dehydration. When the water content is lower than 0.50%, controlling the temperature at 65-75 ℃, and dropwise adding 300g of thionyl chloride for 3 hours. After the dripping is finished, the reaction is kept for 2 hours, and the reaction is stopped when the content of the 3-chloropropionyl chloride in the reaction liquid is detected to be 99.1 percent. The colorless liquid 3-chloropropionyl chloride is obtained by reduced pressure distillation, the yield is 90.8 percent, and the purity is 99.5 percent (3-chloropropionyl chloride is detected by a methanol derivative method GC).
Example 3
Into a 1000mL reaction flask, 200g of acrylic acid, 160g of 30% hydrochloric acid, and 6g of phenothiazine were charged. Stirring and heating to 40-50 ℃, controlling the temperature and dripping 200g of thionyl chloride, and finishing dripping within 6 hours. After finishing dropping, controlling the temperature below 50 ℃ for decompression and dehydration when detecting that the acrylic acid in the reaction solution is below 0.5 percent. When the water content is lower than 0.50%, controlling the temperature to be 55-75 ℃, and dropwise adding 600g of thionyl chloride for 5 hours. After the dripping is finished, the reaction is carried out for 2 hours, and the reaction is stopped when the content of the 3-chloropropionyl chloride in the reaction liquid is detected to be more than 99.4 percent. The colorless liquid 3-chloropropionyl chloride is obtained by reduced pressure distillation, the yield is 92.5 percent, and the purity is 99.7 percent (3-chloropropionyl chloride is detected by a methanol derivative method GC).
Example 4
2000kg of acrylic acid, 1600kg of 30% hydrochloric acid and 60kg of phenothiazine were charged into a 5000L reactor. Stirring and heating to 40-50 deg.c, dropping 2000kg of thionyl chloride at controlled temperature for over 12 hr. After finishing dropping, the reaction is kept for 2 hours, and when the residual acrylic acid in the reaction liquid is detected to be below 0.5 percent, the temperature is controlled to be below 50 ℃ for decompression and dehydration. When the water content is lower than 0.50%, 3500kg of thionyl chloride is dripped at the temperature of 55-75 ℃ for 10 hours. After the dropwise addition, the reaction is carried out for 2 hours under the condition of heat preservation, and the reaction is stopped when the content of the 3-chloropropionyl chloride in the reaction liquid is detected to be 99.1 percent. The colorless liquid 3-chloropropionyl chloride product is obtained by reduced pressure distillation, the yield is 92 percent, and the purity is 99.6 percent (figure 1, 3-chloropropionyl chloride is detected by a methanol derivation method GC). The hydrogen chloride generated in the reaction process is absorbed by a falling film absorption tower, and the generated sulfur dioxide is absorbed by 30 percent sodium hydroxide.
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (8)
1. The method for producing high-purity 3-chloropropionyl chloride by a one-pot method is characterized by comprising the following steps of: under the action of a catalyst, reacting acrylic acid with a chlorinating agent, performing reduced pressure dehydration, dropwise adding thionyl chloride in situ for reaction, and distilling to obtain 3-chloropropionyl chloride.
2. The one-pot process of claim 1 for producing high purity 3-chloropropionyl chloride, characterized in that: under the action of 0.01-0.5 part of catalyst, 0.05-3.0 parts of hydrochloric acid reacts with acrylic acid, the temperature is controlled at 25-90 ℃, and 0.5-5 parts of thionyl chloride is dripped; when the content of acrylic acid in the reaction liquid is less than or equal to 2.0 percent, starting to perform reduced pressure dehydration; when the water content is less than or equal to 1.0 percent, controlling the temperature to be between 30 and 100 ℃ and dripping 1.0 to 10.0 parts of thionyl chloride; stopping the reaction when the content of the 3-chloropropionyl chloride in the reaction liquid is more than or equal to 99.0 percent; distilling to obtain high-purity 3-chloropropionyl chloride.
3. The one-pot process for producing high-purity 3-chloropropionyl chloride according to claim 1 or 2, characterized in that: the catalyst is selected from phenothiazine, hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone or 4-tert-butylcatechol; the proportion of the catalyst is 0.02-0.10 part.
4. The one-pot process of claim 2 for producing high purity 3-chloropropionyl chloride, characterized in that: the materials of acrylic acid, hydrochloric acid and thionyl chloride before dehydration are 1 part: 0.2-0.8 part: 1.0 to 3.0 parts.
5. The one-pot process of claim 2 for producing high purity 3-chloropropionyl chloride, characterized in that: the dehydrated materials of acrylic acid and thionyl chloride are 1 part: 1.5 to 4.0 parts.
6. The one-pot process of claim 2 for producing high purity 3-chloropropionyl chloride, characterized in that: the reaction temperature before dehydration is 30-60 ℃; the reaction temperature after dehydration is 45-85 ℃.
7. The one-pot process of claim 2 for producing high purity 3-chloropropionyl chloride, characterized in that: hydrochloric acid and thionyl chloride are used as chlorination reagents and react with acrylic acid, and the acrylic acid residue in the reaction liquid is less than or equal to 1.0 percent; the water content of the reaction system is less than or equal to 0.5 percent.
8. The one-pot process of claim 2 for producing high purity 3-chloropropionyl chloride, characterized in that: distilling to obtain 3-chloropropionyl chloride with purity not less than 99.5% and yield over 90%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260026A (en) * | 2022-04-29 | 2022-11-01 | 浙江沙星科技有限公司 | Green synthesis method of 4-chlorobutyryl chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349969A (en) * | 2000-10-20 | 2002-05-22 | 敖枝平 | Prepn of 3-chloropropionyl chloride |
| CN109553526A (en) * | 2018-12-18 | 2019-04-02 | 杭州盛弗泰新材料科技有限公司 | A kind of continuous producing method of acryloyl chloride |
| CN111777505A (en) * | 2020-07-17 | 2020-10-16 | 宿迁市科莱博生物化学有限公司 | Preparation method of 3-chloropropionyl chloride |
| CN112409166A (en) * | 2020-10-17 | 2021-02-26 | 张掖耀邦化工科技有限公司 | Synthetic method of 3-chloropropionyl chloride |
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- 2021-04-27 CN CN202110460632.6A patent/CN113214074A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349969A (en) * | 2000-10-20 | 2002-05-22 | 敖枝平 | Prepn of 3-chloropropionyl chloride |
| CN109553526A (en) * | 2018-12-18 | 2019-04-02 | 杭州盛弗泰新材料科技有限公司 | A kind of continuous producing method of acryloyl chloride |
| CN111777505A (en) * | 2020-07-17 | 2020-10-16 | 宿迁市科莱博生物化学有限公司 | Preparation method of 3-chloropropionyl chloride |
| CN112409166A (en) * | 2020-10-17 | 2021-02-26 | 张掖耀邦化工科技有限公司 | Synthetic method of 3-chloropropionyl chloride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260026A (en) * | 2022-04-29 | 2022-11-01 | 浙江沙星科技有限公司 | Green synthesis method of 4-chlorobutyryl chloride |
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Application publication date: 20210806 |