CN105348055B - Synthetic method of pinacolone - Google Patents
Synthetic method of pinacolone Download PDFInfo
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- CN105348055B CN105348055B CN201510848423.3A CN201510848423A CN105348055B CN 105348055 B CN105348055 B CN 105348055B CN 201510848423 A CN201510848423 A CN 201510848423A CN 105348055 B CN105348055 B CN 105348055B
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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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
The invention provides a synthetic method of pinacolone, which comprises the following steps:
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a synthetic method of pinacolone.
Background
Pinacolone is an important fine chemical intermediate, and is particularly used as a synthetic raw material of a bactericide tebuconazole. The molecular formula of pinacolone is: c6H12O, its chemical name is: 3, 3-dimethyl-butan-2-one, english name: pinacolone; the CAS number is: 75-97-8; the structural formula is as follows:
the preparation method of the pinacolone is mainly carried out by a commonly adopted process route taking isoamylene as a starting material, wherein the isoamylene and hydrochloric acid are subjected to addition reaction to generate chloroisopentane, and then the chloroisopentane reacts with formaldehyde under an acidic condition to prepare the pinacolone.
Chinese patent application CN105037118A discloses a method for preparing pinacolone, comprising the steps of: (1) dehydrating isoamyl alcohol to prepare isoamylene, and then carrying out addition reaction with hydrochloric acid to obtain chloroisopentane, wherein the reaction temperature is 5-25 ℃, and the reaction time is 2-8 hours; (2) and reacting the chloroisopentane with a methanol solution of sodium methoxide at the temperature of 0-60 ℃ for 15-35 minutes to obtain the pinacolone. However, the reaction steps are more, the operation is complex, the product has more impurities, and the industrial production is not facilitated.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to overcome the technical problems of low yield and more impurities such as tar and the like in the industrial production of pinacolone, simplifies the process steps, and provides a synthetic method of pinacolone, wherein the synthetic route of the synthetic method is as follows:
and comprises the following steps:
taking 2-chloro-2-methylbutane as a starting material, adding the starting material into a reaction container, dissolving the starting material in a solvent, adding a certain amount of hydrochloric acid, adding a certain amount of polymerization inhibitor and catalyst, adding solid paraformaldehyde into a reaction solution in batches at a reaction temperature of 50-90 ℃, and stirring for reaction until the reaction is complete, wherein the reaction time is 3-10 hours; and (3) carrying out post-treatment, and distilling an organic phase of the reaction solution by using steam to prepare the pinacolone.
Preferably, in the above synthesis method, the amount of the paraformaldehyde is 1.0 to 2.5 times the amount of the 2-chloro-2-methylbutane.
Further preferably, in the above synthesis method, the amount of the material of paraformaldehyde is 1.25 times the amount of the material of 2-chloro-2-methylbutane.
In the above synthesis method, the reaction time is preferably 6 hours.
In the above synthesis method, the reaction temperature is preferably 75 ℃.
Preferably, in the above synthesis method, the solvent is selected from any one of the following: toluene, halogenated toluene, xylene, diphenyl ether, dichloromethane, dichloroethane, chloroform, n-hexane, methylcyclohexane.
Further preferably, in the above synthesis method, the solvent is diphenyl ether.
Further preferably, in the above synthesis method, the catalyst is selected from any one of the following: PEG600, PEG2000, PEG8000, PEG 20000; more preferably PEG 600.
Further preferably, in the above synthesis method, the polymerization inhibitor is selected from any one of: hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone; more preferably hydroquinone.
Further preferably, in the above synthesis method, the interval between the portions of paraformaldehyde added in batches is 10min to 60 min.
Still more preferably, the paraformaldehyde is added in portions with an interval time of 30 min.
More preferably, in the above synthesis method, the mass fraction of the hydrochloric acid is in the range of 20% to 36%, and more preferably 28%. In industrial production, industrial hydrochloric acid is used; the industrial hydrochloric acid can be used repeatedly in multiple batches, and due to the use of the catalyst and the polymerization inhibitor, the tar content is remarkably reduced, the product yield is high, and the post-treatment is convenient.
In conclusion, the following beneficial technical effects can be obtained by using the synthetic method of the pinacolone provided by the invention:
(1) the synthetic method disclosed by the invention is mild in operation condition, low in tar content and higher in product yield;
(2) the synthesis method can realize continuous production, industrial hydrochloric acid solution is repeatedly applied in multiple batches, the catalyst activity is high, the reaction condition is mild, and the environmental protection requirement is met;
(3) the post-treatment of the process is simple, and the reaction solution is distilled by water vapor to obtain the product pinacolone.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the following embodiments.
The invention provides a synthetic method of pinacolone, which comprises the following synthetic route:
and comprises the following steps:
taking 2-chloro-2-methylbutane as a starting material, adding the starting material into a reaction container, dissolving the starting material in a solvent, adding a certain amount of hydrochloric acid, adding a certain amount of polymerization inhibitor and catalyst, adding solid paraformaldehyde into a reaction solution in batches at a reaction temperature of 50-90 ℃, and stirring for reaction until the reaction is complete, wherein the reaction time is 3-10 hours; and (3) carrying out post-treatment, and distilling an organic phase of the reaction solution by using steam to prepare the pinacolone.
In a preferred embodiment, the amount of the paraformaldehyde is 1.0 to 2.5 times the amount of the 2-chloro-2-methylbutane.
In a further preferred embodiment, the amount of the material of paraformaldehyde is 1.25 times the amount of the material of 2-chloro-2-methylbutane.
In a preferred embodiment, the reaction time of the above synthesis method is 6 h.
In a preferred embodiment, the reaction temperature of the above synthesis method is 75 ℃.
In a preferred embodiment, the solvent is selected from any one of the following: toluene, halogenated toluene, xylene, diphenyl ether, dichloromethane, dichloroethane, chloroform, n-hexane, methylcyclohexane.
In a further preferred embodiment, the solvent is diphenyl ether.
In a further preferred embodiment, the catalyst is selected from any one of the following: PEG600, PEG2000, PEG8000, PEG 20000; in a still further preferred embodiment, the catalyst is PEG 600.
In a further preferred embodiment, the polymerization inhibitor is selected from any one of the following: hydroquinone, p-benzoquinone, methylhydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone; in a further preferred embodiment, the polymerization inhibitor is hydroquinone.
In a further preferred embodiment, in the above synthesis method, the paraformaldehyde is added in portions at an interval of 10min to 60 min.
In a further preferred embodiment, the paraformaldehyde is added in portions with an interval of 30 min.
In a further preferred embodiment, the mass fraction of hydrochloric acid ranges between 20% and 36%; in a still further preferred embodiment, the hydrochloric acid is present in a mass fraction of 28%.
The steps in the synthetic method of pinacolone listed below are conventional methods unless otherwise specified, and the starting materials are commercially available from the public unless otherwise specified.
Example 1
The synthesis method is used for synthesizing pinacolone, wherein 2-chloro-2-methylbutane is used as a starting material, hydrochloric acid with the same concentration is used, p-benzoquinone is used as a polymerization inhibitor, PEG600 is used as a catalyst, and the pinacolone is reacted with paraformaldehyde with the same equivalent weight in different solvents at the same temperature (75 ℃); wherein, the reaction yields corresponding to different solvents are shown in the following table:
| numbering | Amount of paraformaldehyde | Catalyst and process for preparing same | Temperature (. degree.C.) | Solvent(s) | Yield of |
| 1 | 1.25eq | PEG600 | 75 | Solvent-free | 76％ |
| 2 | 1.25eq | PEG600 | 75 | Diphenyl ether | 91％ |
| 3 | 1.25eq | PEG600 | 75 | Chloroform | 67％ |
| 4 | 1.25eq | PEG600 | 75 | Ortho-xylene | 82％ |
TABLE 1
Example 2
The synthesis method is used for synthesizing pinacolone, wherein 2-chloro-2-methylbutane is used as a starting material, hydrochloric acid with the same concentration is used, p-benzoquinone is used as a polymerization inhibitor, PEG600 is used as a catalyst, and the pinacolone is reacted with paraformaldehyde with different equivalent weights in the same solvent (diphenyl ether) at the same temperature (75 ℃); wherein, the reaction yields corresponding to different equivalents of paraformaldehyde are shown in the following table:
| numbering | Amount of paraformaldehyde | Catalyst and process for preparing same | Temperature (. degree.C.) | Solvent(s) | Yield of |
| 1 | 1.05eq | PEG600 | 75 | Diphenyl ether | 81％ |
| 2 | 1.25eq | PEG600 | 75 | Diphenyl ether | 91％ |
| 3 | 1.50eq | PEG600 | 75 | Diphenyl ether | 65％ |
| 4 | 1.80eq | PEG600 | 75 | Diphenyl ether | 73％ |
TABLE 2
Example 3
The synthesis method is used for synthesizing pinacolone, wherein 2-chloro-2-methylbutane is used as a starting material, hydrochloric acid with the same concentration is used, p-benzoquinone is used as a polymerization inhibitor, PEG600 is used as a catalyst, and the pinacolone is reacted with paraformaldehyde with the same equivalent weight in the same solvent (diphenyl ether) at different temperatures; wherein, the reaction yields corresponding to different temperatures are shown in the following table:
| numbering | Amount of paraformaldehyde | Catalyst and process for preparing same | Temperature (. degree.C.) | Solvent(s) | Yield of |
| 1 | 1.25eq | PEG600 | 55 | Diphenyl ether | 62％ |
| 2 | 1.25eq | PEG600 | 65 | Diphenyl ether | 82％ |
| 3 | 1.25eq | PEG600 | 75 | Diphenyl ether | 91％ |
| 4 | 1.25eq | PEG600 | 80 | Diphenyl ether | 70％ |
TABLE 3
Example 4
The synthesis method is used for synthesizing pinacolone, wherein 2-chloro-2-methylbutane is used as a starting material, hydrochloric acid with the same concentration is used, different polymerization inhibitors are respectively adopted, PEG600 is used as a catalyst, and the pinacolone reacts with paraformaldehyde with the same equivalent weight in the same solvent (diphenyl ether) at the same temperature (75 ℃); wherein, the reaction yields corresponding to different polymerization inhibitors are shown in the following table:
TABLE 4
Example 5
The synthesis method is used for synthesizing pinacolone, wherein 2-chloro-2-methylbutane is used as a starting material, hydrochloric acid with different concentrations is used, hydroquinone is used as a polymerization inhibitor, PEG600 is used as a catalyst, and the pinacolone is reacted with paraformaldehyde with the same equivalent weight in the same solvent (diphenyl ether) at the same temperature (75 ℃); wherein, the reaction yield corresponding to hydrochloric acid with different concentrations is shown in the following table:
| numbering | Amount of paraformaldehyde | HCl concentration | Temperature (. degree.C.) | Solvent(s) | Yield of |
| 1 | 1.25eq | 22％ | 75 | Diphenyl ether | 64％ |
| 2 | 1.25eq | 25％ | 75 | Diphenyl ether | 83％ |
| 3 | 1.25eq | 28％ | 75 | Diphenyl ether | 91％ |
| 4 | 1.25eq | 32％ | 75 | Diphenyl ether | 75％ |
| 5 | 1.25eq | 36％ | 75 | Diphenyl ether | 82％ |
TABLE 5
Example 6
After a series of experiments, and further verification and data analysis, the inventors obtained the best implementation conditions of the method for synthesizing pinacolone of the present invention, as follows:
600.0g of 2-chloro-2-methylbutane, 1700mL of hydrochloric acid (28%), 20g of PEG600, 1.5g of hydroquinone and 500mL of diphenyl ether are placed in a 5L three-necked flask and mechanically stirred. The temperature is raised to 75 ℃, 185g of solid paraformaldehyde is added into the reaction liquid in batches, 30g of solid paraformaldehyde is added into each batch, and one batch is added at intervals of 30 min. After the addition, the reaction was stopped by keeping the temperature at 75 ℃ for 6 hours. The reaction solution was transferred to a 10L separatory funnel, allowed to stand, and the acid aqueous phase was separated off, and the acid aqueous phase was used successively. The organic phase was distilled with steam to give 524.4g of a colorless liquid, normalized content 97.8%, overall yield 91.1%.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (3)
1. A synthetic method of pinacolone is characterized in that the synthetic route of the synthetic method is as follows:
and comprises the following steps:
taking 2-chloro-2-methylbutane as a starting material, adding the starting material into a reaction vessel, dissolving the starting material in a solvent, adding a certain amount of hydrochloric acid, adding a certain amount of polymerization inhibitor and a catalyst PEG600, adding solid paraformaldehyde into a reaction solution in batches at a reaction temperature of 75 ℃, and stirring for reaction until the reaction is complete, wherein the reaction time is 6 hours; post-treatment, namely distilling an organic phase of the reaction solution by using steam to prepare the pinacolone; the amount of the material of paraformaldehyde is 1.25 times the amount of the material of 2-chloro-2-methylbutane;
the solvent is diphenyl ether, the polymerization inhibitor is hydroquinone, and the mass fraction of the hydrochloric acid is within 28%.
2. The method for synthesizing pinacolone according to claim 1, wherein the interval between the addition of paraformaldehyde in portions is 10 to 60 min.
3. The method according to claim 2, wherein paraformaldehyde is added in portions at 30min intervals.
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| CN106365964A (en) * | 2016-08-26 | 2017-02-01 | 张家港市振方化工有限公司 | Synthesis method of high-purity pinacolone |
| CN113956142B (en) * | 2021-11-22 | 2022-04-29 | 山东省科学院菏泽分院 | Preparation method of pinacolone |
| CN114646714A (en) * | 2022-03-28 | 2022-06-21 | 酒泉市尚上化工有限公司 | Rapid analysis method for detecting content of pinacolone |
Citations (4)
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|---|---|---|---|---|
| US4057583A (en) * | 1974-12-27 | 1977-11-08 | Bayer Aktiengesellschaft | Process for the preparation of pinacolone |
| CN102557905A (en) * | 2012-01-17 | 2012-07-11 | 盐城利民农化有限公司 | Clean production process for pinacoline |
| CN103240094A (en) * | 2013-05-20 | 2013-08-14 | 张家港市振方化工有限公司 | Process for preparing pinacolone and compound catalyst |
| CN104961634A (en) * | 2015-05-25 | 2015-10-07 | 张家港市振方化工有限公司 | Method for preparing high yield pinacolone, and pesticide bactericide |
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2015
- 2015-11-26 CN CN201510848423.3A patent/CN105348055B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4057583A (en) * | 1974-12-27 | 1977-11-08 | Bayer Aktiengesellschaft | Process for the preparation of pinacolone |
| CN102557905A (en) * | 2012-01-17 | 2012-07-11 | 盐城利民农化有限公司 | Clean production process for pinacoline |
| CN103240094A (en) * | 2013-05-20 | 2013-08-14 | 张家港市振方化工有限公司 | Process for preparing pinacolone and compound catalyst |
| CN104961634A (en) * | 2015-05-25 | 2015-10-07 | 张家港市振方化工有限公司 | Method for preparing high yield pinacolone, and pesticide bactericide |
Non-Patent Citations (2)
| Title |
|---|
| 频呐酮合成工艺的研究;陈学林;《华东理工大学硕士学位论文》;20130131;全文 * |
| 频哪酮的合成方法;道兴;《世界农药》;19831227;第5卷(第06期);29-31 * |
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