CN112480041A - Chlorination process of prothioconazole intermediate - Google Patents
Chlorination process of prothioconazole intermediate Download PDFInfo
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- CN112480041A CN112480041A CN202011463304.3A CN202011463304A CN112480041A CN 112480041 A CN112480041 A CN 112480041A CN 202011463304 A CN202011463304 A CN 202011463304A CN 112480041 A CN112480041 A CN 112480041A
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- butyrolactone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical synthesis, and relates to a chlorination process of a prothioconazole intermediate, in particular to a novel equipment for synthesizing the prothioconazole intermediate.
Description
Technical Field
The invention relates to the field of chemical synthesis, and particularly provides a chlorination process of a prothioconazole intermediate.
Background
Prothioconazole is a novel broad-spectrum triazolethione bactericide developed by Bayer corporation, has low toxicity and is safe to people and environment. Alpha-acetyl-alpha-chloro-gamma-butyrolactone is an important intermediate for the synthesis of prothioconazole, and has the following structural formula:
alpha-acetyl-alpha-chloro-gamma-butyrolactone is now mainly prepared by using alpha-acetyl-gamma-butyrolactone and sulfonyl chloride as raw materials to react, and the reaction is as follows:
the sulfuryl chloride serving as the reaction raw material is a corrosive substance, reacts violently when meeting water and releases hydrogen chloride and sulfur dioxide gas, the sulfur dioxide gas has serious environmental pollution, and meanwhile, the process has the defects of more waste water generated by post-treatment, great environmental pollution, difficulty in treatment and inconvenience for industrial production.
Therefore, how to overcome the above problems becomes one of the technical problems to be solved in the art.
Disclosure of Invention
The invention provides a synthesis method of a new chlorination process of a prothioconazole intermediate, and particularly relates to a novel device for synthesizing the prothioconazole intermediate, wherein a microchannel reactor synthesis device is utilized, an organic solvent solution of raw material alpha-acetyl-gamma-butyrolactone is injected into a microchannel reactor through a metering pump, chlorine is injected into the microchannel reactor, intermediate reaction liquid is obtained through cooling and mixing, and the prothioconazole intermediate is obtained through separation. .
The specific technical scheme of the invention is as follows:
a chlorination process of a prothioconazole intermediate, wherein the prothioconazole intermediate is alpha-acetyl-alpha-chloro-gamma-butyrolactone, and comprises the following specific steps:
the organic solvent solution of raw material alpha-acetyl-gamma-butyrolactone is pumped into a microchannel reactor by a metering pump, a certain proportion of chlorine gas is pumped into the microchannel reactor, the raw material alpha-acetyl-gamma-butyrolactone and the chlorine gas are contacted and reacted for 0.5 to 1.5 hours at the temperature of between 10 ℃ below zero and 5 ℃, and then the target product alpha-acetyl-alpha-chloro-gamma-butyrolactone is separated from the mixture, wherein the reaction equation is as follows:
the invention abandons the original kettle type reaction by utilizing the microchannel reactor, has quicker and more thorough reaction, is easy to operate, has accurate measurement, eliminates the measurement error of personnel and has higher yield.
Wherein the α -acetyl- γ -butyrolactone: the mass ratio of the organic solvent is 1: 0-2; the alpha-acetyl-gamma-butyrolactone: the mol ratio of chlorine is 1: 1-2;
preferred said α -acetyl- γ -butyrolactone: organic solvent: the optimal ratio of chlorine gas addition is 1:2 (mass ratio) to 2 (molar ratio), and the specific results are as follows:
the organic solvent is one or more of toluene, dichloromethane and dichloroethane; because the raw materials in the technical scheme are liquid, a solvent can be optionally not added;
the invention has the advantages that: the sulfuryl chloride raw material of the original process is abandoned, the chlorine is easy to operate and fast in reaction, the generated hydrogen chloride byproduct can be absorbed to prepare hydrochloric acid which can be continuously used in the subsequent process steps, the three wastes are less, the cost is low, the reaction yield is high, and the chlorine is safer and more environment-friendly than the sulfuryl chloride. Aiming at the defects of small contact surface and slow reaction of the traditional kettle-type gas-liquid heterogeneous reaction, the invention adopts the microchannel reactor, greatly increases the gas-liquid two-phase contact surface, improves the reaction efficiency, shortens the reaction period and inhibits the generation of side reactions.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention;
example 1
The prepared dichloromethane solution (50 g of alpha-acetyl-gamma-butyrolactone and 100g of dichloromethane) of the alpha-acetyl-gamma-butyrolactone is pumped into the microchannel reactor through a metering pump, and simultaneously 55-60ml/min of metered chlorine gas is introduced into the microchannel reactor, the two are mixed and reacted at the temperature of-10 ℃, the chlorine gas is continuously introduced for 5h during the reaction, and the byproduct hydrogen chloride after the device is absorbed to prepare hydrochloric acid for recycling; and after the gas phase analysis reaction is finished, performing desolventizing treatment to obtain a product, mechanically applying the desolventizing agent, wherein the content of the product is 98 percent, and the yield is 99 percent.
Example 2
The prepared dichloroethane solution (50 g of alpha-acetyl-gamma-butyrolactone and 100g of dichloromethane) of the alpha-acetyl-gamma-butyrolactone is pumped into the microchannel reactor through a metering pump, and simultaneously 55-60ml/min of metered chlorine gas is introduced into the microchannel reactor, the alpha-acetyl-gamma-butyrolactone and the microchannel reactor are mixed and reacted at minus 10 ℃, the chlorine gas is continuously introduced for 1.5h during the reaction, and the byproduct hydrogen chloride is absorbed to prepare hydrochloric acid and is recycled; hydrochloric acid gas is absorbed after the device, desolventizing treatment is carried out after gas phase analysis reaction is finished to obtain a product, the desolventizing agent is removed for reuse, the product content is 99%, and the yield is 99%.
Example 3
The prepared dichloroethane solution (50 g of alpha-acetyl-gamma-butyrolactone and 50g of dichloromethane) of the alpha-acetyl-gamma-butyrolactone is pumped into the microchannel reactor through a metering pump, and simultaneously, 25-30ml/min of metered chlorine gas is introduced into the microchannel reactor, the alpha-acetyl-gamma-butyrolactone and the microchannel reactor are mixed and reacted at the temperature of-5 ℃, the chlorine gas is continuously introduced for 1h during the reaction, and the byproduct hydrogen chloride after the device is absorbed to prepare hydrochloric acid for recycling; hydrochloric acid gas is absorbed after the device, desolventizing treatment is carried out after gas phase analysis reaction is finished to obtain a product, the desolventizing agent is removed for reuse, the product content is 98 percent, and the yield is 99 percent.
Example 4
The prepared dichloromethane and toluene solution (50 g of alpha-acetyl-gamma-butyrolactone, 50g of dichloromethane and 50g of toluene) of alpha-acetyl-gamma-butyrolactone is pumped into the microchannel reactor through a metering pump, and simultaneously, the metered chlorine gas is introduced into the microchannel reactor for 45-50ml/min, the two are mixed and reacted at the temperature of minus 10 ℃, the chlorine gas is continuously introduced for 0.5h to complete the reaction, and the byproduct hydrogen chloride after the device is absorbed to prepare hydrochloric acid for recycling; hydrochloric acid gas is absorbed after the device, desolventizing treatment is carried out after the gas phase analysis reaction is finished to obtain a product, the desolventizing agent is removed for reuse, the product content is 98 percent, and the yield is 98 percent.
Comparative example 5
50g of alpha-acetyl-gamma-butyrolactone and 50g of dichloromethane are put into a 250ml reaction bottle, the temperature is reduced to minus 10 ℃, 54g of sulfonyl chloride is dripped, the temperature is controlled to minus 10 +/-2 ℃, the dripping is completed within 1h, after the gas phase analysis is completed within 20h, 500g of saturated sodium bicarbonate is added for destruction, liquid separation and water washing are carried out twice, the water amount is 100g each time, the product is obtained by desolventizing, the solvent is removed for reuse, the product content is 95%, and the yield is 93%.
The content and yield of the product are obviously improved compared with the prior art by adopting the reactant and the reaction method provided by the application, the hydrochloric acid prepared by absorbing the obtained byproduct hydrogen chloride can be recycled, the three wastes are less, the cost is low, the reaction time is obviously shortened, and the production efficiency is greatly improved.
Claims (2)
1. A chlorination process of a prothioconazole intermediate, wherein the prothioconazole intermediate is alpha-acetyl-alpha-chloro-gamma-butyrolactone, and is characterized in that: the method comprises the following specific steps:
the organic solvent solution of raw material alpha-acetyl-gamma-butyrolactone is pumped into a microchannel reactor by a metering pump, a certain proportion of chlorine gas is pumped into the microchannel reactor, the raw material alpha-acetyl-gamma-butyrolactone and the chlorine gas are contacted and reacted for 0.5 to 1.5 hours at the temperature of between 10 ℃ below zero and 5 ℃, and then the target product alpha-acetyl-alpha-chloro-gamma-butyrolactone is separated from the mixture, wherein the reaction equation is as follows:
wherein the alpha-acetyl-gamma-butyrolactone: the mass ratio of the organic solvent is 1: 0-2; the alpha-acetyl-gamma-butyrolactone: the mol ratio of the chlorine gas is 1: 1-2.
2. The process for chlorinating the prothioconazole intermediate according to claim 1, wherein: the organic solvent is one or more of toluene, dichloromethane and dichloroethane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011463304.3A CN112480041A (en) | 2020-12-09 | 2020-12-09 | Chlorination process of prothioconazole intermediate |
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| CN202011463304.3A CN112480041A (en) | 2020-12-09 | 2020-12-09 | Chlorination process of prothioconazole intermediate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418548A (en) * | 2015-12-11 | 2016-03-23 | 大连世慕化学有限公司 | Microreactor used for alpha-position hydrogen atom chlorination of alpha-dicarbonyl compound and synthesis method |
| CN106588832A (en) * | 2016-12-02 | 2017-04-26 | 连云港市金囤农化有限公司 | Preparation method of alpha-chloro-alpha-acetyl-gamma-butyrolactone |
| CN109400554A (en) * | 2018-12-25 | 2019-03-01 | 江苏兄弟维生素有限公司 | Synthesize alpha-chloro-α-acetyl group-gamma-butyrolacton formate methyl esters method and apparatus |
-
2020
- 2020-12-09 CN CN202011463304.3A patent/CN112480041A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418548A (en) * | 2015-12-11 | 2016-03-23 | 大连世慕化学有限公司 | Microreactor used for alpha-position hydrogen atom chlorination of alpha-dicarbonyl compound and synthesis method |
| CN106588832A (en) * | 2016-12-02 | 2017-04-26 | 连云港市金囤农化有限公司 | Preparation method of alpha-chloro-alpha-acetyl-gamma-butyrolactone |
| CN109400554A (en) * | 2018-12-25 | 2019-03-01 | 江苏兄弟维生素有限公司 | Synthesize alpha-chloro-α-acetyl group-gamma-butyrolacton formate methyl esters method and apparatus |
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Application publication date: 20210312 |