CN102372687A - Production method for spirodiclofen - Google Patents
Production method for spirodiclofen Download PDFInfo
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- CN102372687A CN102372687A CN2010102511713A CN201010251171A CN102372687A CN 102372687 A CN102372687 A CN 102372687A CN 2010102511713 A CN2010102511713 A CN 2010102511713A CN 201010251171 A CN201010251171 A CN 201010251171A CN 102372687 A CN102372687 A CN 102372687A
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- spiral shell
- mite ester
- shell mite
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- spirodiclofen
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Abstract
The present invention discloses a production method for spirodiclofen. According to the production method, cyclohexanone is adopted as a starting raw material, and is subjected to reactions of addition, acylation, esterification, cyclization and the like to obtain a spirodiclofen intermediate 3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]-dec-3-en-4-ol; then the 3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]-dec-3-en-4-ol reacts with 2,2-dimethyl butyryl chloride to prepare 3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]-dec-3-en-4-yl-2,2-dimethyl butyrate, which is the spirodiclofen. The production method of the present invention has characteristics of simple process, available raw materials and easy operation, and is suitable for industrial production of the spirodiclofen. With the present invention, the total yield of the five-step reaction is 36.6%, and is increased by nearly 17% than the yield in the prior art.
Description
Technical field
The present invention relates generally to a kind of production technique of spiral shell mite ester, specifically is a kind ofly to the working method of traditional addition, hydrolysis, esterification, ring-closure reaction, to change hydrolysis process into acidylate, reaches the working method of the spiral shell mite ester of the purpose that improves yield.
Background technology
Traditional technology is to be raw material with the pimelinketone, obtains the midbody of spiral shell mite ester through addition, hydrolysis, esterification, cyclization, again with 2, and 2-dimethyl-butyrylchlorine prepared in reaction spiral shell mite ester.Earlier alcohol hydrolysis of 1-cyanocyclohexanoic and esterification are obtained 1-hydroxyl ethyl formate in this method, carry out esterification with the 24-dichloro phenyllacetyl chloride again.Because this route reaction yield is lower, is merely 20%, makes production cost higher.
Summary of the invention
Main task of the present invention is to provide a kind of production technique of spiral shell mite ester, specifically is a kind of traditional working method to be improved, and reaches the raising reaction yield, reduces production costs, thereby obtains the former medicine of spiral shell mite ester with higher yields.
In order to solve above technical problem; The working method of a kind of spiral shell mite ester of the present invention; It is characterized in that process step is mainly: be starting raw material with the pimelinketone, through addition, acidylate, esterification, ring-closure reaction prepare spiral shell mite ester midbody 3-(2,4 dichloro benzene base)-2-oxo-1-oxaspiro [4.5]-last of the ten Heavenly stems-3-alkene-4-alcohol; With 2, the reaction of 2-dimethyl-butyrylchlorine makes spiral shell mite ester again; Reaction formula is following:
Fenac and thionyl chloride are behind the condition refluxed stirring reaction 4h of heating in the said further acidylate step, and underpressure distillation is removed thionyl chloride and got the 2,4 dichloro benzene Acetyl Chloride 98Min. again.
Further, Heating temperature is 75-100 ℃ in the said acidylate step.
Further, the mol ratio of fenac and thionyl chloride is 1: 1.1 in the said acidylate step.
The invention has the advantages that: technology of the present invention is simple, raw material is easy to get, easy to operate, is fit to industrialization and produces spiral shell mite ester, and five step overall yield of reaction reach 33.7%.Improved nearly 14% than original technology.
Embodiment
The preparation of 1-cyanocyclohexanoic alcohol
Under mechanical stirring, in the there-necked flask of 500ml, add 60.9g pimelinketone, 24.1g sodium cyanide, 80ml water; Maintain the temperature at 5-10 ℃ under the condition of ice bath, slowly drip 40% sulphuric acid soln, keeping the dropping time is 3h, dropwises continued and stirs 30min; Product is used ethyl acetate extraction, the combined ethyl acetate layer with water washing after, use anhydrous sodium sulfate drying; Concentrate the 66.8g product liquid, yield 86.0%, product be not purified to be used for next step reaction.
The preparation of 2,4 dichloro benzene Acetyl Chloride 98Min.
In reaction flask, add 2.6g 2,4 dichloro benzene acetate and 30ml thionyl chloride, heat 75-100 ℃ of refluxing and stirring reaction 4h, thionyl chloride is removed in underpressure distillation, gets yellow liquid 2.80g, yield 98.8%.
The preparation of 2,4 dichloro benzene acetate-1-cyanocyclohexanoic ester
In reaction flask, add 7.9g1-cyanocyclohexanoic alcohol bullion, the pyridine of 13.9g, 60ml methylene dichloride; Room temperature condition drips 20g2 down, and the mixed solution of 4-dichloro phenyllacetyl chloride and 40ml methylene dichloride dropwises about 1h; Continue stirring reaction 12h then, add 100ml 3% hydrochloric acid soln, with ethyl acetate extraction 3 times; Ethyl acetate layer is used water washing at last with 5% sodium carbonate solution washing 2 times, uses anhydrous sodium sulfate drying again; Concentrate the brown mashed prod of 23.2g, can not purifiedly directly be used for step reaction down.
The preparation of 1-[2-(2,4-two chloro-phenyl)-acetoxyl group]-cyclohexyl methyl-formiate
In reaction flask, add 12g2,4-fenac-1-cyanocyclohexanoic ester bullion and 80ml sulfuric acid methyl alcohol mixed liquor (sulfuric acid 5ml, methyl alcohol 75ml) heat 60-80 ℃ and are stirred to backflow; About reaction 22h, steam most of methyl alcohol after, 40 ℃ to be cooled slightly add the 50ml water, with ethyl acetate extraction product 3 times; The combined ethyl acetate layer, with 5% sodium hydrogen carbonate solution washing 3 times, and then with washing; Anhydrous sodium sulfate drying, concentrate the 8.84g crude product, can not purifiedly be used for next step reaction.
3-(2,4 dichloro benzene base)-2-oxo-1-oxaspiro [4.5]-last of the ten Heavenly stems-the pure preparation of 3-alkene-4-
The ethanol that in reaction flask, adds 8.0g1-[2-(2,4-two chloro-phenyl)-acetoxyl group]-cyclohexyl methyl-formiate 1.8g magnesium ethylate and 200ml, 5～10 ℃ of reaction 14h.After steam removing most of solvent, add the hydrochloric acid of 50ml5%, use ethyl acetate extraction, use water washing again, anhydrous sodium sulfate drying, concentrate the 5.3g solid crude product, through 95% ethyl alcohol recrystallization after, get product 5.1g, more than 3 to go on foot total recoverys be 45.3%.
The preparation of spiral shell mite ester
In reaction flask, add under the room temperature 4.6g3-(2,4 dichloro benzene base)-2-oxo-1-oxaspiro [4.5]-last of the ten Heavenly stems-the pure and mild 5ml triethylamine of 3-alkene 4-, 80ml methylene dichloride, drip 2.6g2,2-dimethyl-butyrylchlorine, stirring reaction 2h under the room temperature.Reaction solution with saturated sodium bicarbonate solution washing 2 times, is used water washing 2 times more at last with 1% salt acid elution 3 times, anhydrous sodium sulfate drying, concentrate the 5.8g solid product, must the 5.4g product through 95% ethyl alcohol recrystallization after, yield 94.0%, content 98.4%.
Claims (4)
1. the working method of a spiral shell mite ester; It is characterized in that: process step is mainly: be starting raw material with the pimelinketone; Prepare spiral shell mite ester midbody 3-(2 through addition, acidylate, esterification, ring-closure reaction; The 4-dichlorophenyl)-2-oxo-1-oxaspiro [4.5]-last of the ten Heavenly stems-3-alkene-4-alcohol, again with 2, the reaction of 2-dimethyl-butyrylchlorine makes spiral shell mite ester; Reaction formula is following:
2. the working method of a kind of spiral shell mite ester according to claim 1; It is characterized in that: fenac and thionyl chloride are behind the condition refluxed stirring reaction 4h of heating in the said acidylate step; Underpressure distillation is removed thionyl chloride and is got the 2,4 dichloro benzene Acetyl Chloride 98Min. again.
3. the working method of a kind of spiral shell mite ester according to claim 1 is characterized in that: Heating temperature is 75-100 ℃ in the said acidylate step.
4. the working method of a kind of spiral shell mite ester according to claim 1 is characterized in that: the mol ratio of fenac and thionyl chloride is 1: 1.1 in the said acidylate step.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102511713A CN102372687A (en) | 2010-08-12 | 2010-08-12 | Production method for spirodiclofen |
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| CN2010102511713A CN102372687A (en) | 2010-08-12 | 2010-08-12 | Production method for spirodiclofen |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017101515A1 (en) * | 2015-12-14 | 2017-06-22 | Rotam Agrochem International Company Limited | Novel form of spirodiclofen, process for preparation and use thereof |
| CN108840846A (en) * | 2018-08-20 | 2018-11-20 | 山东康乔生物科技有限公司 | A kind of preparation method of Envidor and its intermediate |
| CN108863774A (en) * | 2018-06-09 | 2018-11-23 | 石家庄市绿丰化工有限公司 | A kind of 2,4 dichloro benzene chloroacetic chloride synthetic method |
| CN112745286A (en) * | 2020-12-30 | 2021-05-04 | 杭州宇龙化工有限公司 | Preparation method of spirodiclofen diester derivative |
Citations (3)
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| EP0528156A1 (en) * | 1991-07-16 | 1993-02-24 | Bayer Ag | 3-Aryl-4-hydroxy-delta3-dihydrofuranone and 3-aryl-4-hydroxy-delta3-dihydrothiophenone derivatives |
| CN1336797A (en) * | 1999-01-20 | 2002-02-20 | 拜尔公司 | USe of 3-(2,4,6-trimethylphenyl)-4-neopentylcarbonyloxy-5,5-tetramethylene-delta-dihydrofurance-2-on for controlling the white fly |
| CN101235023A (en) * | 2008-03-04 | 2008-08-06 | 浙江大学 | Method for synthesizing spirodiclofen |
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2010
- 2010-08-12 CN CN2010102511713A patent/CN102372687A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0528156A1 (en) * | 1991-07-16 | 1993-02-24 | Bayer Ag | 3-Aryl-4-hydroxy-delta3-dihydrofuranone and 3-aryl-4-hydroxy-delta3-dihydrothiophenone derivatives |
| CN1336797A (en) * | 1999-01-20 | 2002-02-20 | 拜尔公司 | USe of 3-(2,4,6-trimethylphenyl)-4-neopentylcarbonyloxy-5,5-tetramethylene-delta-dihydrofurance-2-on for controlling the white fly |
| CN101235023A (en) * | 2008-03-04 | 2008-08-06 | 浙江大学 | Method for synthesizing spirodiclofen |
Non-Patent Citations (1)
| Title |
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| 陆一夫，等: "新型杀螨剂螺螨酯的合成", 《精细化工中间体》, vol. 39, no. 2, 30 April 2009 (2009-04-30), pages 20 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017101515A1 (en) * | 2015-12-14 | 2017-06-22 | Rotam Agrochem International Company Limited | Novel form of spirodiclofen, process for preparation and use thereof |
| CN107922368A (en) * | 2015-12-14 | 2018-04-17 | 龙灯农业化工国际有限公司 | The Envidor of new model, preparation method and the usage |
| TWI742024B (en) * | 2015-12-14 | 2021-10-11 | 香港商龍燈農業化工國際有限公司 | A novel form of spirodiclofen, a process for its preparation and use the same |
| CN108863774A (en) * | 2018-06-09 | 2018-11-23 | 石家庄市绿丰化工有限公司 | A kind of 2,4 dichloro benzene chloroacetic chloride synthetic method |
| CN108840846A (en) * | 2018-08-20 | 2018-11-20 | 山东康乔生物科技有限公司 | A kind of preparation method of Envidor and its intermediate |
| CN112745286A (en) * | 2020-12-30 | 2021-05-04 | 杭州宇龙化工有限公司 | Preparation method of spirodiclofen diester derivative |
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Application publication date: 20120314 |