CN111253233A - Transposition method of acetophenone isomer - Google Patents
Transposition method of acetophenone isomer Download PDFInfo
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- CN111253233A CN111253233A CN202010188539.XA CN202010188539A CN111253233A CN 111253233 A CN111253233 A CN 111253233A CN 202010188539 A CN202010188539 A CN 202010188539A CN 111253233 A CN111253233 A CN 111253233A
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- 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
- C07C45/67—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 isomerisation; by change of size of the carbon skeleton
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- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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Abstract
The invention discloses a transposition method of an acetophenone isomer, which comprises the synthesis and transposition reaction of 2, 4-dichloroacetophenone. The transposition method of the acetophenone isomer can convert the 2, 6-dichloroacetophenone isomer in the 2, 4-dichloroacetophenone crude product into the 2, 4-dichloroacetophenone through transposition reaction, so as to reduce the content of the 2, 6-dichloroacetophenone isomer in the 2, 4-dichloroacetophenone crude product, increase the yield of the 2, 4-dichloroacetophenone, realize the purification of the 2, 4-dichloroacetophenone crude product, and have the advantages of simple reaction and high transposition efficiency.
Description
Technical Field
The invention relates to the technical field of acetophenone purification, and particularly relates to a transposition method of acetophenone isomers.
Background
The 2, 4-dichloroacetophenone is used as raw material for preparing omega-bromo-2, 4-dichloroacetophenone or omega-2, 4-trichloroacetophenone, and the latter two are intermediates for preparing fungicides such as imazalil, propiconazole and etaconazole, and are also intermediates for pesticides such as chlorfenvinphos and herbicide difenzoquat.
The main raw material for synthesizing the 2, 4-dichloroacetophenone is m-dichlorobenzene. However, m-dichlorobenzene is expensive, and occupies a large proportion in production, resulting in a large production cost. Meanwhile, in the process of synthesizing 2, 4-dichloroacetophenone, the content of 2, 4-dichloroacetophenone in the product is low, and the product contains more 2, 6-dichloroacetophenone isomers, in the traditional synthesis process, the purification of the crude product of 2, 4-dichloroacetophenone mainly comprises methods of distillation, rectification, crystallization and the like, only impurities and the like in the crude product of 2, 4-dichloroacetophenone can be separated out, the 2, 6-dichloroacetophenone isomer in the crude 2, 4-dichloroacetophenone cannot be converted into 2, 4-dichloroacetophenone, and therefore, if the 2, 6-dichloroacetophenone isomer can be converted into the 2, 4-dichloroacetophenone, on one hand, the content of the 2, 4-dichloroacetophenone can be improved, on the other hand, the utilization rate of m-dichlorobenzene can be improved, and the resource waste and the cost investment are reduced.
Therefore, the improvement of the purification process of the crude product of the 2, 4-dichloroacetophenone, the reduction of consumption, the improvement of the yield of the 2, 4-dichloroacetophenone and the reduction of cost become problems which need to be solved urgently.
Chinese patent CN102675073A discloses a production method of 2, 4-dichloroacetophenone, which mainly comprises five steps of acylation, hydrolysis, water washing, distillation and crystallization, wherein the acylation reaction comprises the following steps: and (3) carrying out acylation reaction on m-dichlorobenzene and acetic anhydride under the action of anhydrous aluminum trichloride. M-dichlorobenzene is used as a raw material, acetic anhydride is used as an acylating agent, A1C13 is used as a catalyst to react to produce 2, 4-dichloroacetophenone, and the obtained product is higher than acetyl chloride used as the acylating agent; the acetic anhydride is used as an acylating agent, A1C13 is used as a catalyst, and m-dichlorobenzene extracted from chlorinated aromatic hydrocarbon waste is comprehensively utilized as a raw material to produce the 2, 4-dichloroacetophenone, so that the problem of disposal of byproducts in the benzene chlorination process is solved, the cyclic utilization rate of the chlorinated aromatic hydrocarbon is improved, and the method has high social benefit and economic value.
Chinese patent CN102531871A discloses a method for purifying 2, 4-dichloroacetophenone, which comprises the steps of firstly discharging 92-98% by mass of a crude product of 2, 4-dichloroacetophenone to an industrial drum-type slicer through which a flowing medium flows inside for crystallization and slicing. Then directly moving the slices to a centrifuge, and using a solvent to rinse and centrifuge simultaneously; or transferring the slices into a drying room, allowing the surfaces of the slices to sweat, and centrifuging to obtain the 2, 4-dichloroacetophenone with the purity of more than 99%. The centrifugal mother liquor can be recycled. Simple operation, low production cost, high yield, high product purity and stable performance, and is suitable for large-scale industrial production.
Disclosure of Invention
The invention provides a transposition method of acetophenone isomers aiming at the problems.
The technical scheme adopted by the invention for solving the problems is as follows: a transposition method of acetophenone isomers comprises the following steps:
step I, synthesizing 2, 4-dichloroacetophenone: selecting m-dichlorobenzene and acetyl chloride as raw materials, and reacting to obtain a crude product of 2, 4-dichloroacetophenone;
step II, transposition reaction: and (3) adding the 2, 4-dichloroacetophenone crude product obtained in the step (I) into cyclohexane, then adding sulfuric acid with the mass fraction of 98%, and reacting for 3-5 hours at the temperature of 78-82 ℃ to finish transposition.
Further, in the step I, the content of the 2, 4-dichloroacetophenone in the crude product of the 2, 4-dichloroacetophenone is 92.5-94.0%.
Furthermore, in the step I, the content of the 2, 6-dichloroacetophenone in the crude product of the 2, 4-dichloroacetophenone is 5%.
Further, in the step II, the mass ratio of the crude product of 2, 4-dichloroacetophenone, cyclohexane and 98% sulfuric acid is 100: 300: 11.5 to 12.5.
Further, in step II, the purity of cyclohexane was 99.0%.
Further, in step II, the translocation process of the translocation reaction is:
furthermore, in the step II, after transposition is completed, the content of the 2, 4-dichloroacetophenone is 98.5-99.5%, and the content of the 2, 6-dichloroacetophenone is 0.3-0.5%.
The invention has the advantages that:
(1) according to the transposition method of the acetophenone isomer, the 2, 6-dichloroacetophenone isomer in the 2, 4-dichloroacetophenone crude product can be converted into the 2, 4-dichloroacetophenone through transposition reaction, so that the content of the 2, 6-dichloroacetophenone isomer in the 2, 4-dichloroacetophenone crude product is reduced, the yield of the 2, 4-dichloroacetophenone is increased, the purification of the 2, 4-dichloroacetophenone crude product is realized, the reaction is simple, and the transposition efficiency is high;
(2) the transposition method of the acetophenone isomer can improve the utilization rate of the raw material for synthesizing the intermediate dichlorobenzene by using the 2, 4-dichloroacetophenone, reduce the resource waste, reduce the cost and increase the income;
(3) the transposition method of the acetophenone isomer can improve the yield of the 2, 4-dichloroacetophenone, further purify the purity of the 2, 4-dichloroacetophenone, and obtain the 2, 4-dichloroacetophenone with stable performance which can be used as a raw material of various products.
Detailed Description
The following detailed description of embodiments of the invention, but the invention can be practiced in many different ways, as defined and covered by the claims.
Example 1
Transposition method of acetophenone isomer
The method comprises the following steps:
step I, synthesizing 2, 4-dichloroacetophenone: selecting m-dichlorobenzene and acetyl chloride as raw materials, and reacting to obtain a crude product of 2, 4-dichloroacetophenone; in the crude product of the 2, 4-dichloroacetophenone, the content of the 2, 4-dichloroacetophenone is 92.5 percent; the content of the 2, 6-dichloroacetophenone is 5 percent;
step II, transposition reaction: adding the 2, 4-dichloroacetophenone crude product obtained in the step I into cyclohexane with the purity of 99.0%, then adding sulfuric acid with the mass fraction of 98%, and reacting for 3 hours at the temperature of 78 ℃ to finish transposition; wherein the mass ratio of the 2, 4-dichloroacetophenone crude product, cyclohexane with the purity of 99.0 percent and sulfuric acid with the mass fraction of 98 percent is 100: 300: 11.5.
in the above, the process of transposition in the transposition reaction is:
in the above, after the transposition is completed, the content of 2, 4-dichloroacetophenone is 98.5%, and the content of 2, 6-dichloroacetophenone is 0.3%.
Example 2
Transposition method of acetophenone isomer
The method comprises the following steps:
step I, synthesizing 2, 4-dichloroacetophenone: selecting m-dichlorobenzene and acetyl chloride as raw materials, and reacting to obtain a crude product of 2, 4-dichloroacetophenone; in the crude product of the 2, 4-dichloroacetophenone, the content of the 2, 4-dichloroacetophenone is 94.0 percent; the content of the 2, 6-dichloroacetophenone is 5 percent;
step II, transposition reaction: adding the 2, 4-dichloroacetophenone crude product obtained in the step I into cyclohexane with the purity of 99.0%, then adding sulfuric acid with the mass fraction of 98%, and reacting for 5 hours at the temperature of 82 ℃ to complete transposition; wherein the mass ratio of the 2, 4-dichloroacetophenone crude product, cyclohexane with the purity of 99.0 percent and sulfuric acid with the mass fraction of 98 percent is 100: 300: 12.5.
in the above, the process of transposition in the transposition reaction is:
in the above, after the transposition is completed, the content of 2, 4-dichloroacetophenone is 99.5%, and the content of 2, 6-dichloroacetophenone is 0.5%.
Example 3
Transposition method of acetophenone isomer
The method comprises the following steps:
step I, synthesizing 2, 4-dichloroacetophenone: selecting m-dichlorobenzene and acetyl chloride as raw materials, and reacting to obtain a crude product of 2, 4-dichloroacetophenone; in the crude product of the 2, 4-dichloroacetophenone, the content of the 2, 4-dichloroacetophenone is 93.0 percent; the content of the 2, 6-dichloroacetophenone is 5 percent;
step II, transposition reaction: adding the 2, 4-dichloroacetophenone crude product obtained in the step I into cyclohexane with the purity of 99.0%, then adding sulfuric acid with the mass fraction of 98%, and reacting at the temperature of 79 ℃ for 3.5 hours to complete transposition; wherein the mass ratio of the 2, 4-dichloroacetophenone crude product, cyclohexane with the purity of 99.0 percent and sulfuric acid with the mass fraction of 98 percent is 100: 300: 11.8.
in the above, the process of transposition in the transposition reaction is:
in the above, after the transposition is completed, the content of 2, 4-dichloroacetophenone is 98.8%, and the content of 2, 6-dichloroacetophenone is 0.5%.
Example 4
Transposition method of acetophenone isomer
The method comprises the following steps:
step I, synthesizing 2, 4-dichloroacetophenone: selecting m-dichlorobenzene and acetyl chloride as raw materials, and reacting to obtain a crude product of 2, 4-dichloroacetophenone; in the crude product of the 2, 4-dichloroacetophenone, the content of the 2, 4-dichloroacetophenone is 93.8 percent; the content of the 2, 6-dichloroacetophenone is 5 percent;
step II, transposition reaction: adding the 2, 4-dichloroacetophenone crude product obtained in the step I into cyclohexane with the purity of 99.0%, then adding sulfuric acid with the mass fraction of 98%, and reacting for 4.5 hours at the temperature of 81 ℃ to finish transposition; wherein the mass ratio of the 2, 4-dichloroacetophenone crude product, cyclohexane with the purity of 99.0 percent and sulfuric acid with the mass fraction of 98 percent is 100: 300: 12.3.
in the above, the process of transposition in the transposition reaction is:
in the above, after the transposition is completed, the content of 2, 4-dichloroacetophenone is 99.4%, and the content of 2, 6-dichloroacetophenone is 0.3%.
Example 5
Transposition method of acetophenone isomer
The method comprises the following steps:
step I, synthesizing 2, 4-dichloroacetophenone: selecting m-dichlorobenzene and acetyl chloride as raw materials, and reacting to obtain a crude product of 2, 4-dichloroacetophenone; in the crude product of the 2, 4-dichloroacetophenone, the content of the 2, 4-dichloroacetophenone is 93.6 percent; the content of the 2, 6-dichloroacetophenone is 5 percent;
step II, transposition reaction: adding the 2, 4-dichloroacetophenone crude product obtained in the step I into cyclohexane with the purity of 99.0%, then adding sulfuric acid with the mass fraction of 98%, and reacting for 4 hours at the temperature of 80 ℃ to complete transposition; wherein the mass ratio of the 2, 4-dichloroacetophenone crude product, cyclohexane with the purity of 99.0 percent and sulfuric acid with the mass fraction of 98 percent is 100: 300: 12.0.
in the above, the process of transposition in the transposition reaction is:
in the above, after the transposition is completed, the content of 2, 4-dichloroacetophenone is 99.3%, and the content of 2, 6-dichloroacetophenone is 0.4%.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A transposition method of acetophenone isomers is characterized by comprising the following steps:
step I, synthesizing 2, 4-dichloroacetophenone: selecting m-dichlorobenzene and acetyl chloride as raw materials, and reacting to obtain a crude product of 2, 4-dichloroacetophenone;
step II, transposition reaction: and (3) adding the 2, 4-dichloroacetophenone crude product obtained in the step (I) into cyclohexane, then adding sulfuric acid with the mass fraction of 98%, and reacting for 3-5 hours at the temperature of 78-82 ℃ to finish transposition.
2. An indexing method according to claim 1, wherein in step I, the 2, 4-dichloroacetophenone content in the crude 2, 4-dichloroacetophenone is 92.5% to 94.0%.
3. An indexing method according to claim 1, wherein in step I, the crude 2, 4-dichloroacetophenone has a 2, 6-dichloroacetophenone content of 5%.
4. An indexing method according to claim 1, wherein in step II, the mass ratio of the crude 2, 4-dichloroacetophenone, cyclohexane and 98% sulfuric acid is 100: 300: 11.5 to 12.5.
5. An indexing method according to claim 1, wherein in step II, the cyclohexane is 99.0% pure.
6. A method according to claim 1, wherein in step II, the process of translocating the translocating reaction is:
7. an indexing method according to claim 1, wherein in step II, after indexing is completed, the content of 2, 4-dichloroacetophenone is 98.5% to 99.5% and the content of 2, 6-dichloroacetophenone is 0.3% to 0.5%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500277A (en) * | 2021-01-04 | 2021-03-16 | 江西永通科技股份有限公司 | Synthetic method of 2, 4-dichloroacetophenone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2643900A1 (en) * | 1989-03-03 | 1990-09-07 | Rhone Poulenc Chimie | FUNCTIONALIZATION IN THE N + 1 POSITION OF DISINFECTED ARYLIC DERIVATIVES IN THE N AND N + 2 POSITION |
| CN101898947A (en) * | 2010-08-19 | 2010-12-01 | 江苏隆昌化工有限公司 | Method for producing 2,4-dichloroacetophenone by using solid waste chlorobenzene tar as raw material |
| CN102675073A (en) * | 2012-05-24 | 2012-09-19 | 江苏隆昌化工有限公司 | Method for preparing 2, 4-dichloroacetophenone |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2643900A1 (en) * | 1989-03-03 | 1990-09-07 | Rhone Poulenc Chimie | FUNCTIONALIZATION IN THE N + 1 POSITION OF DISINFECTED ARYLIC DERIVATIVES IN THE N AND N + 2 POSITION |
| CN101898947A (en) * | 2010-08-19 | 2010-12-01 | 江苏隆昌化工有限公司 | Method for producing 2,4-dichloroacetophenone by using solid waste chlorobenzene tar as raw material |
| CN102675073A (en) * | 2012-05-24 | 2012-09-19 | 江苏隆昌化工有限公司 | Method for preparing 2, 4-dichloroacetophenone |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112500277A (en) * | 2021-01-04 | 2021-03-16 | 江西永通科技股份有限公司 | Synthetic method of 2, 4-dichloroacetophenone |
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