CN102381952B - Synthesis method of 1-cyclopropyl-1,3-butanedione - Google Patents
Synthesis method of 1-cyclopropyl-1,3-butanedione Download PDFInfo
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- CN102381952B CN102381952B CN 201110262430 CN201110262430A CN102381952B CN 102381952 B CN102381952 B CN 102381952B CN 201110262430 CN201110262430 CN 201110262430 CN 201110262430 A CN201110262430 A CN 201110262430A CN 102381952 B CN102381952 B CN 102381952B
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Abstract
The invention discloses a synthesis method of 1-cyclopropyl-1, 3-butanedione. The synthesis method comprises the following step of: by taking cyclopropyl ketone and ethyl acetate as raw materials and using polyethylene glycol or polyethylene glycol dimetyl ether as a catalyst, reacting the raw materials with sodium alkoxide at 120 DEG C under the protection of an inert gas to prepare 1-cyclopropyl-1,3-butanedione. In the method, the easy-to-obtain and inexpensive sodium alkoxide is used as an alkali agent, the 1-cyclopropyl-1,3-butanedione with higher yield and higher content can be obtained by adding the catalyst and controlling the proper reaction conditions, the usage of the expensive potassium methoxide or potassium tert-butoxide and the like and unsafe sodium hydride is avoided. The synthesis method has short synthesis route, high yield, low cost, the easy-to-obtain raw material, safety and low production cost and is easy for large-scale production.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of 1-cyclopropyl-1, the synthetic method of 3-dimethyl diketone.
Background technology
1-cyclopropyl-1,3-dimethyl diketone are the important intermediate of synthesizing fungicide cyprodinil.
The US3507958 report is with Cyclopropyl Methyl Ketone and acetic acid ethyl reaction, prepared in reaction in the presence of the hydrogenation soda, J.Org.Chem 17,685, (1952) bibliographical information is with Cyclopropyl Methyl Ketone and acetic acid ethyl reaction, prepared in reaction in the presence of the hydrogenation soda, and it is 40-75% that the product of above-mentioned two kinds of methods preparation produces its yield, the content of product is 75-82%, can not satisfy the specification of quality of synthetic cyprodinil.And the sodium hydride and the sodium amide that use are inflammable, are unfavorable for extensive safety in production.
EP-A-0410726 reports with Cyclopropyl Methyl Ketone and acetic acid ethyl reaction, prepared in reaction 1-cyclopropyl-1 in the presence of the methyl alcohol soda, and 3-dimethyl diketone, yield only are 21%, product purity only is 75%.The 1-cyclopropyl-1 of this method preparation, the 3-dimethyl diketone can not satisfy the specification of quality of synthetic cyprodinil equally.
The US5545762 report is reported with Cyclopropyl Methyl Ketone and acetic acid ethyl reaction, prepared in reaction 1-cyclopropyl-1 in the presence of methyl alcohol potash, and the 3-dimethyl diketone, yield can reach 97.4%, and product purity only is 98.5%.Although the 1-cyclopropyl-1 of this method preparation, the 3-dimethyl diketone can satisfy the specification of quality of synthetic cyprodinil, but because potassium methylate prepares difficult price height, annotate: Dezhou dragon rises 10.8 ten thousand yuan/ton of the 98% potassium methylate prices that chemical industry company limited produces, 1.08 ten thousand yuan/ton of 98% sodium methylates, thereby the 1-cyclopropyl-1 of this method preparation, 3-dimethyl diketone cost is too high, and the product of production does not have the market value advantage.
Summary of the invention
The object of the invention is providing a kind of high yield, the easy preparation 1-cyclopropyl-1 of safety operation, the method for 3-dimethyl diketone, and this method synthetic route is short, yield is high, cost is low, satisfy the mass-producing requirement of safe production.
Purpose of the present invention can reach by following measure:
A kind of 1-cyclopropyl-1; the synthetic method of 3-dimethyl diketone; it is: in organic solvent; be raw material with cyclopropyl ketone and ethyl acetate; be catalyzer with polyoxyethylene glycol or Polyethylene glycol dimethyl ether; under protection of inert gas, obtain 1-cyclopropyl-1 120 ℃ of following prepared in reaction, the 3-dimethyl diketone with sodium alkoxide.
Reaction equation is as follows:
Wherein organic solvent is inert solvent, as toluene, chlorobenzene, alcohol or aliphatic ether etc., preferably adopts aliphatic ether, most preferably is methyl tertbutyl methyl ether or isopropyl ether.
Described catalyzer can be poly(oxyethylene glycol) 400～2000 or Polyethylene glycol dimethyl ether 400～2000, is preferably Polyethylene Glycol-600～2000 or Polyethylene glycol dimethyl ether 600～2000, more preferably poly(oxyethylene glycol) 400 or Polyethylene Glycol-600.
Sodium alkoxide can be Fatty Alcohol(C12-C14 and C12-C18) sodium, is preferably sodium methylate, sodium ethylate or sodium tert-butoxide, more preferably sodium methylate.
Above-mentioned temperature of reaction is preferably 40 ℃～120 ℃, more preferably 40 ℃～80 ℃, most preferably is 50 ℃～60 ℃.
Synthetic method of the present invention further is in particular: earlier sodium alkoxide is suspended in the organic solvent, add catalyzer again, slowly add the solution that cyclopropyl ketone or cyclopropyl ketone and organic solvent form down at 15～20 ℃ then, add the back insulation reaction, then slowly add ethyl acetate, be warming up to 40 ℃～120 ℃ simultaneously and react, obtain 1-cyclopropyl-1, the 3-dimethyl diketone.The time of described insulation reaction is 0.5～2 hour, stirs fast in the insulation reaction process.
The present invention generates 1-cyclopropyl-1, and the reaction of 3-dimethyl diketone finishes can obtain 1-cyclopropyl-1, the pure product of 3-dimethyl diketone by handling later.A kind of post-treating method is: remove the organic solvent in the solution earlier, the cooling back slowly adds hydrochloric acid to pH value of solution value 1～3 (preferred 1.5～2.0), stirs and the washing oil reservoir 1-cyclopropyl-1 in the rectifying oil-yielding stratum, 3-dimethyl diketone.
The mol ratio of cyclopropyl ketone, ethyl acetate and sodium alkoxide is 1: 1.5～2: 2～2.5 among the present invention, preferred 1: 1.5～2: 2.2～2.5.
It is alkalizing agent that preparation method of the present invention adopts sodium alkoxide cheap and easy to get, by adding catalyzer and controlling the 1-cyclopropyl-1 that proper reaction conditions can obtain higher yields and high level, the 3-dimethyl diketone has been avoided more expensive and unsafe sodium hydrides such as use potassium methylate or potassium tert.-butoxide.This synthetic method has overcome yield and the low problem of purity when adopting sodium alkoxide, and its synthetic route is short, yield is high (can reach more than 90% in its yield of cyclopropyl ketone), cost is low, and the raw material that uses is easy to get, safety, and production cost is low, is easy to scale operation.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
In the 500ml four-hole bottle that thermometer, agitator, water trap (the water trap upper end takes back the stream prolong) are housed, adding 21.60g (0.40mol) sodium methylate is suspended in the 160g methyl tertbutyl methyl ether, add the 0.3g Polyethylene Glycol-600, the solution that 16.8g (0.2mol) Cyclopropyl Methyl Ketone and 20g methyl tertbutyl methyl ether are arranged 15-20 ℃ of dropping, 1 hour dropping time, in 20 ℃ of left and right sides insulation reaction 1 hour (it is fast that stirring velocity is wanted, and prevents the unexpected retrogradation of reaction solution, and the influence reaction is carried out); Then drip 32.0g (0.36mol) ethyl acetate, be warming up to 50 ℃ simultaneously, 1 hour dropping time, drip to finish at 56 ℃ and refluxed 0.5 hour, 30cm rectifying column normal pressure steams except the methyl tertbutyl methyl ether, be cooled to 20-25 ℃ after steaming is finished and drip 2N hydrochloric acid 160ml down, to PH1.5-2.0, stir 10 minutes (orange-yellow emulsion); The oil reservoir of water 100ml washing subsequently, with 20ml * 2 methyl tertbutyl methyl ether aqueous layer extracted, the 30cm rectifying column boils off low-boiling point material and gets 1-cyclopropyl-1,3-dimethyl diketone 22.83g, yield 90.53%, purity 98.56% behind the merging oil reservoir.
Embodiment 2
In the 500ml four-hole bottle that thermometer, agitator, water trap (the water trap upper end takes back the stream prolong) are housed, 27.2g (0.40mol) sodium ethylate is suspended in the 160g methyl tertbutyl methyl ether, add the 0.3g Polyethylene Glycol-600,15-20 ℃ of dropping 16.8g (0.2mol) Cyclopropyl Methyl Ketone is arranged, 1 hour dropping time, in 20 ℃ of left and right sides insulation reaction 1 hour (it is fast that stirring velocity is wanted, and prevents the unexpected retrogradation of reaction solution, and the influence reaction is carried out); Then drip 32.0g (0.36mol) ethyl acetate, be warming up to 50 ℃ simultaneously, 1 hour dropping time, drip to finish at 56 ℃ and refluxed 0.5 hour, 30cm rectifying column normal pressure steams except the methyl tertbutyl methyl ether, be cooled to 20-25 ℃ after steaming is finished and drip 2N hydrochloric acid 160ml down, to PH1.5～2.0, stir 10 minutes (orange-yellow emulsion); The oil reservoir of water 100ml washing subsequently, with 20ml * 2 methyl tertbutyl methyl ether aqueous layer extracted, the 30cm rectifying column boils off low-boiling point material and gets 1-cyclopropyl-1,3-dimethyl diketone 20.50g, yield 81.25%, purity 93.27% behind the merging oil reservoir.
Embodiment 3
In the 500ml four-hole bottle that thermometer, agitator, water trap (the water trap upper end takes back the stream prolong) are housed, 21.60g g (0.40mol) sodium methylate is suspended in the 160g isopropyl ether, add the 0.3g Polyethylene Glycol-600, drip 16.8g (0.2mol) Cyclopropyl Methyl Ketone at 15-20 ℃, 1 hour dropping time, in 20 ℃ of left and right sides insulation reaction 1 hour (it is fast that stirring velocity is wanted, and prevents the unexpected retrogradation of reaction solution, and the influence reaction is carried out); Then drip 32.0g (0.36mol) ethyl acetate, be warming up to 50 ℃ simultaneously, 1 hour dropping time, drip to finish at 56 ℃ and refluxed 0.5 hour, 30cm rectifying column normal pressure steams except isopropyl ether, be cooled to 20～25 ℃ after steaming is finished and drip 2N hydrochloric acid 160ml down, to PH1.5～2.0, stir 10 minutes (orange-yellow emulsion); The oil reservoir of water 100ml washing subsequently, with 20ml * 2 isopropyl ether aqueous layer extracted, the 30cm rectifying column boils off low-boiling point material and gets 1-cyclopropyl-1,3-dimethyl diketone 17.57g, yield 69.67%, purity 93.45% behind the merging oil reservoir.
Embodiment 4
In the 500ml four-hole bottle that thermometer, agitator, water trap (the water trap upper end takes back the stream prolong) are housed, 27.2g (0.40mol) sodium ethylate is suspended in the 160g isopropyl ether, add the 0.3g Polyethylene Glycol-600, drip 16.8g (0.2mol) Cyclopropyl Methyl Ketone at 15-20 ℃, 1 hour dropping time, in 20 ℃ of left and right sides insulation reaction 1 hour (it is fast that stirring velocity is wanted, and prevents the unexpected retrogradation of reaction solution, and the influence reaction is carried out); Then drip 32.0g (0.36mol) ethyl acetate, be warming up to 50 ℃ simultaneously, 1 hour dropping time, drip to finish at 56 ℃ and refluxed 0.5 hour, 30cm rectifying column normal pressure steams except isopropyl ether, be cooled to 20～25 ℃ after steaming is finished and drip 2N hydrochloric acid 160ml down, to PH1.5～2.0, stir 10 minutes (orange-yellow emulsion); The oil reservoir of water 100ml washing subsequently, with 20ml * 2 isopropyl ether aqueous layer extracted, the 30cm rectifying column boils off low-boiling point material and gets 1-cyclopropyl-1,3-dimethyl diketone 14.70g, yield 58.29%, purity 91.48% behind the merging oil reservoir.
Embodiment 5
In the 500ml four-hole bottle that thermometer, agitator, water trap (the water trap upper end takes back the stream prolong) are housed, 21.6g (0.40mol) sodium methylate is suspended in the 160g methyl tertbutyl methyl ether, add the 0.3g Macrogol 2000, the solution that 16.8g (0.2mol) Cyclopropyl Methyl Ketone and 20g methyl tertbutyl methyl ether are arranged 15-20 ℃ of dropping, 1 hour dropping time, in 20 ℃ of left and right sides insulation reaction 1 hour (it is fast that stirring velocity is wanted, and prevents the unexpected retrogradation of reaction solution, and the influence reaction is carried out); Then drip 32.0g (0.36mol) ethyl acetate, be warming up to 50 ℃ simultaneously, 1 hour dropping time, drip to finish at 56 ℃ and refluxed 0.5 hour, 30cm rectifying column normal pressure steams except the methyl tertbutyl methyl ether, be cooled to 20～25 ℃ after steaming is finished and drip 2N hydrochloric acid 160ml down, to PH1.5～2.0, stir 10 minutes (orange-yellow emulsion); The oil reservoir of water 100ml washing subsequently, with 20ml * 2 methyl tertbutyl methyl ether aqueous layer extracted, the 30cm rectifying column boils off low-boiling point material and gets 1-cyclopropyl-1,3-dimethyl diketone 22.3g, yield 88.43%, purity 96.28% behind the merging oil reservoir.
Comparative Examples 1
14.2g (0.2mol) potassium methylate is suspended in the 75ml Methyl tertiary butyl ether, adds 8.4g (0.1mol) Cyclopropyl Methyl Ketone, and add 17.6 (0.2mol) ethyl acetate in 45min.Behind reaction 3h under 30 ℃, add concentrated hydrochloric acid in the reaction mixture, extractive distillation goes out low boiling component, product 1-cyclopropyl-1,3-dimethyl diketone 12.18g, yield 97.4%, quality purity 98.5%.
Comparative Examples 2
21.6g (0.4mol) sodium methylate is suspended in the 75ml Methyl tertiary butyl ether, adds 16.8g (0.2mol) Cyclopropyl Methyl Ketone, and adds 32 (0.36mol) ethyl acetate in 45min.Behind reaction 3h under 30 ℃, add concentrated hydrochloric acid in the reaction mixture, extractive distillation goes out low boiling component, product 1-cyclopropyl-1,3-dimethyl diketone 19.52g, yield 77.4%, quality purity 88.5%.Produce 1 ton of 100% products material cost relatively
According to use sodium methylate embodiment 1 of the present invention and use potassium methylate Comparative Examples 1, and Comparative Examples two, produce 1 ton of 100% products material 1-cyclopropyl-1,3-dimethyl diketone cost relatively contrasts as follows:
Comparative Examples 1
Table one, 1 ton of 100%1-cyclopropyl-1 of production, main raw material consumption and the raw materials cost of 3-dimethyl diketone
Embodiment 1
Table two, 1 ton of 100%1-cyclopropyl-1 of production, main raw material consumption and the raw materials cost of 3-dimethyl diketone
Comparative Examples 2
21.6g (0.4mol) sodium methylate is suspended in the 75ml Methyl tertiary butyl ether, adds 16.8g (0.2mol) Cyclopropyl Methyl Ketone, and adds 35.2 (0.4mol) ethyl acetate in 45min.Behind reaction 3h under 30 ℃, add concentrated hydrochloric acid in the reaction mixture, extractive distillation goes out low boiling component, product 1-cyclopropyl-1,3-dimethyl diketone 19.52g, yield 77.4%, quality purity 88.5%.
Table three, 1 ton of 100%1-cyclopropyl-1 of production, main raw material consumption and the raw materials cost of 3-dimethyl diketone
Annotate: Dezhou dragon rises 10.8 ten thousand yuan/ton of the 98% potassium methylate prices that chemical industry company limited produces, 1.08 ten thousand yuan/ton of 98% sodium methylates.
Produce 1 ton of 100%1-cyclopropyl-1, main raw material consumption and the raw materials cost of 3-dimethyl diketone by above-mentioned table one to table three.Embodiments of the invention 1 are produced 1 ton of 100%1-cyclopropyl-1, the raw materials cost of 3-dimethyl diketone is 14.655 ten thousand yuan/ton, product content is 98,56%, and Comparative Examples 1 usefulness potassium methylate is produced 1 ton of 100%1-cyclopropyl-1, the raw materials cost of 3-dimethyl diketone is 26.206 ten thousand yuan/ton, product content is 98,50%, although product content all satisfies ingredient requirement, but the product explicit costs of producing with potassium methylate does not have the market competitiveness than potassium methylate height.And Comparative Examples 2 usefulness sodium methylates are produced 1 ton of 100%1-cyclopropyl-1, the raw materials cost of 3-dimethyl diketone is 18.573 ten thousand yuan/ton, and product content is 88.5%, although product cost is lower than using potassium methylate, but product content has only 88.50%, can't satisfy the raw materials quality requirement.
Claims (3)
1. 1-cyclopropyl-1, the synthetic method of 3-dimethyl diketone, it is characterized in that: in the 500ml four-hole bottle of water trap that thermometer, agitator, upper end take back the stream prolong is housed, adding 21.60g, 0.40mol sodium methylate are suspended in the 160g methyl tertbutyl methyl ether, add the 0.3g Polyethylene Glycol-600, the solution that 16.8g, 0.2mol Cyclopropyl Methyl Ketone and 20g methyl tertbutyl methyl ether are arranged 15-20 ℃ of dropping, 1 hour dropping time, 20 ℃ of left and right sides insulation reaction 1 hour, it is fast that stirring velocity is wanted, prevent the unexpected retrogradation of reaction solution, the influence reaction is carried out; Then drip 32.0g, 0.36mol ethyl acetate, be warming up to 50 ℃ simultaneously, 1 hour dropping time, drip to finish at 56 ℃ and refluxed 0.5 hour, 30cm rectifying column normal pressure steams except the methyl tertbutyl methyl ether, be cooled to 20-25 ℃ after steaming is finished and drip 2N hydrochloric acid 160ml down, to PH1.5-2.0, stir and got orange-yellow emulsion in 10 minutes; The oil reservoir of water 100ml washing subsequently, with 20ml * 2 methyl tertbutyl methyl ether aqueous layer extracted, the 30cm rectifying column boils off low-boiling point material and gets 1-cyclopropyl-1,3-dimethyl diketone 22.83g, yield 90.53%, purity 98.56% behind the merging oil reservoir.
2. 1-cyclopropyl-1, the synthetic method of 3-dimethyl diketone, it is characterized in that: in the 500ml four-hole bottle of water trap that thermometer, agitator, upper end take back the stream prolong is housed, 27.2g, the 0.40mol sodium ethylate is suspended in the 160g methyl tertbutyl methyl ether, add the 0.3g Polyethylene Glycol-600,15-20 ℃ of dropping 16.8g, 0.2mol Cyclopropyl Methyl Ketone are arranged, 1 hour dropping time, 20 ℃ of left and right sides insulation reaction 1 hour, it is fast that stirring velocity is wanted, prevent the unexpected retrogradation of reaction solution, the influence reaction is carried out; Then drip 32.0g, 0.36mol ethyl acetate, be warming up to 50 ℃ simultaneously, 1 hour dropping time, drip to finish at 56 ℃ and refluxed 0.5 hour, 30cm rectifying column normal pressure steams except the methyl tertbutyl methyl ether, be cooled to 20-25 ℃ after steaming is finished and drip 2N hydrochloric acid 160ml down, to PH1.5 ~ 2.0, stir and got orange-yellow emulsion in 10 minutes; The oil reservoir of water 100ml washing subsequently, with 20ml * 2 methyl tertbutyl methyl ether aqueous layer extracted, the 30cm rectifying column boils off low-boiling point material and gets 1-cyclopropyl-1,3-dimethyl diketone 20.50g, yield 81.25%, purity 93.27% behind the merging oil reservoir.
3. 1-cyclopropyl-1, the synthetic method of 3-dimethyl diketone, it is characterized in that: in the 500ml four-hole bottle of water trap that thermometer, agitator, upper end take back the stream prolong is housed, 21.6g, the 0.40mol sodium methylate is suspended in the 160g methyl tertbutyl methyl ether, add the 0.3g Macrogol 2000, the solution that 16.8g, 0.2mol Cyclopropyl Methyl Ketone and 20g methyl tertbutyl methyl ether are arranged 15-20 ℃ of dropping, 1 hour dropping time, 20 ℃ of left and right sides insulation reaction 1 hour, it is fast that stirring velocity is wanted, prevent the unexpected retrogradation of reaction solution, the influence reaction is carried out; Then drip 32.0g, 0.36mol ethyl acetate, be warming up to 50 ℃ simultaneously, 1 hour dropping time, drip to finish at 56 ℃ and refluxed 0.5 hour, 30cm rectifying column normal pressure steams except the methyl tertbutyl methyl ether, be cooled to 20 ~ 25 ℃ after steaming is finished and drip 2N hydrochloric acid 160ml down, to PH1.5 ~ 2.0, stir and got orange-yellow emulsion in 10 minutes; The oil reservoir of water 100ml washing subsequently, with 20ml * 2 methyl tertbutyl methyl ether aqueous layer extracted, the 30cm rectifying column boils off low-boiling point material and gets 1-cyclopropyl-1,3-dimethyl diketone 22.3g, yield 88.43%, purity 96.28% behind the merging oil reservoir.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5545762A (en) * | 1994-02-09 | 1996-08-13 | Huels Aktiengesellschaft | Process for preparing 1-cyclopropylalkane-1,3-diones |
| CN1259113A (en) * | 1997-06-03 | 2000-07-05 | 伊斯曼化学公司 | Process for the preparation of 1,3-dicarbonyl compounds |
| JP2008120759A (en) * | 2006-11-15 | 2008-05-29 | Ube Ind Ltd | METHOD FOR PRODUCING beta-DIKETONE COMPOUND HAVING ETHER GROUP |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5545762A (en) * | 1994-02-09 | 1996-08-13 | Huels Aktiengesellschaft | Process for preparing 1-cyclopropylalkane-1,3-diones |
| CN1259113A (en) * | 1997-06-03 | 2000-07-05 | 伊斯曼化学公司 | Process for the preparation of 1,3-dicarbonyl compounds |
| JP2008120759A (en) * | 2006-11-15 | 2008-05-29 | Ube Ind Ltd | METHOD FOR PRODUCING beta-DIKETONE COMPOUND HAVING ETHER GROUP |
Non-Patent Citations (1)
| Title |
|---|
| 柴宝山等.嘧菌环胺的合成与杀菌活性.《农药》.2007,第46卷(第6期),377-378. * |
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