阅读说明：本技术 一种1,1,1-三氟-4-乙氧基戊-3-烯-2-酮的制备方法 (A kind of preparation method of the amyl- 3- alkene -2- ketone of the fluoro- 4- ethyoxyl of 1,1,1- tri- ) 是由 徐卫国 蒋强 陈伟 于 2018-05-25 设计创作，主要内容包括：本发明公开了一种在有机溶剂中、在碱性条件下、使三氟乙酰氯与2-乙氧基丙烯反应得到1,1,1-三氟-4-乙氧基戊-3-烯-2-酮的方法。本发明提供的方法反应收率高、原料简单易得、反应条件温和和易于工业化生产的优点。(The invention discloses it is a kind of in organic solvent, under alkaline condition, the method that makes trifluoro-acetyl chloride and 2- ethoxy-c alkene reaction obtain the amyl- 3- alkene -2- ketone of the fluoro- 4- ethyoxyl of 1,1,1- tri-.Method reaction yield provided by the invention is high, raw material is simple and easy to get, reaction condition is mild and advantage easy to industrialized production.)

1. a kind of method for preparing 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl, it is characterised in that the described method includes:

In organic solvent, under alkaline condition, trifluoro-acetyl chloride and 2- ethoxy-c alkene reaction is made to obtain 1,1,1- tri- fluoro- 4- The amyl- 3- alkene -2- ketone of ethyoxyl.

2. the method for 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl of preparation described in accordance with the claim 1, it is characterised in that The organic solvent is selected from least one of methyl tertiary butyl ether, hexamethylene, toluene and Trifluoroacetic Acid Ethyl Ester.

3. the method for 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl of preparation described in accordance with the claim 1, it is characterised in that The alkaline condition includes that alkali is added into reaction system, and the alkali is in triethylamine, diethylamine, isopropylamine and cyclohexylamine It is at least one.

4. the method for 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl of preparation described in accordance with the claim 1, feature exist In:

The molar ratio of 2- ethoxy propylene and trifluoro-acetyl chloride is 1.0~5.0:1；

The dosage of alkali is 1.0~4.0 times of trifluoro-acetyl chloride mole；

The dosage of organic solvent is 2.0~10.0 times of trifluoro-acetyl chloride weight.

5. preparing 1 according to claim 4, the method for 1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl, feature exists In:

The molar ratio of 2- ethoxy propylene and trifluoro-acetyl chloride is 1.0~2.5:1；

The dosage of alkali is 1.0~2.5 times of trifluoro-acetyl chloride mole；

The dosage of organic solvent is 2.5~5.0 times of trifluoro-acetyl chloride weight.

6. the method for 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl of preparation described in accordance with the claim 1, it is characterised in that The reaction temperature is -10~30 DEG C.

7. preparing 1 according to claim 6, the method for 1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl, it is characterised in that The reaction temperature is 0~20 DEG C.

8. the method for 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl of preparation described in accordance with the claim 1, feature exist In:

After reaction, the reaction solution containing 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl is obtained, is first added into reaction solution Water collects the organic phase for containing 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl after standing liquid separation, then organic phase is depressurized Rectifying obtains the 1 of purity >=99.0%, 1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone product of 4- ethyoxyl.

9. preparing 1 according to claim 8, the method for 1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl, feature exists In:

The dosage of the water is the 30%~70% of reaction solution gross mass；

The vacuum degree of rectification under vacuum is -100~-50KPa.

10. preparing 1 according to claim 9, the method for 1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl, feature exists In:

The dosage of the water is the 40~60% of reaction solution gross mass；

The vacuum degree of rectification under vacuum is 95~-80KPa.

Technical field

The present invention relates to a kind of preparation methods of the amyl- 3- alkene -2- ketone of the fluoro- 4- ethyoxyl of 1,1,1- tri-.

Background technique

The amyl- 3- alkene -2- ketone of the fluoro- 4- ethyoxyl of 1,1,1- tri- is in the activity of a kind of highly useful pesticide and field of medicaments Mesosome can be used for preparing the heterocyclic compound of trifluoromethyl substitution, as pyrazole derivatives, pyrrole derivatives, quinolines are spread out Biology.

The preparation method of the amyl- 3- alkene -2- ketone of 4- ethyoxyl fluoro- for 1,1,1- tri-, prior art report is less, only, E.G.Mkrtchyan et al. (Russian Chemical Bulletin, International Edition, Vol.54, No.9, pp.2150-2156, September, 2005) system of the amyl- 3- alkene-2- ketone of the fluoro- 4- ethyoxyl of 1,1,1- tri- is disclosed on Preparation Method.The method is with 1,1,1- trifluoroacetylacetone (TFA) and triethyl orthoformate for raw material, and using perchloric acid as catalyst, ethyl alcohol is Solvent prepares 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl by esterification.Yield only 27%, and raw material 1,1,1- Trifluoroacetylacetone (TFA) is expensive and is not easy to obtain, and is not suitable for carrying out industrialized production.

Therefore, it is necessary to which the preparation method of 1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl is for further study to 1.

Summary of the invention

The preparation 1,1,1- tri- of industrialized production is easy to get and is suitble to the purpose of the present invention is to provide a kind of high income, raw material The method of the fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl.

The invention provides the following technical scheme:

A kind of method preparing 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl, which comprises

In organic solvent, under alkaline condition, trifluoro-acetyl chloride and 2- ethoxy-c alkene reaction is made to obtain 1,1,1- tri- The fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl.

Preparation method provided by the invention, reaction equation are as follows:

Preparation method provided by the invention, raw material trifluoro-acetyl chloride need to react under alkaline condition with 2- ethoxy propylene. The alkaline condition can be, and the compound that reaction system can be made to have alkalinity commonly used in the art is added into reaction.

Preferably, the alkaline condition can be, and alkali is added into reaction system.

It may further be preferable that the alkaline condition can be and organic base is added into reaction system.

It is even furthermore preferable that the organic base can be in triethylamine, diethylamine, isopropylamine and cyclohexylamine It is at least one.

The dosage satisfaction of the alkali used goes on smoothly reaction.

Preferably, the dosage of alkali is 1.0~4.0 times of trifluoro-acetyl chloride mole.

It may further be preferable that the dosage of alkali is 1.0~2.5 times of trifluoro-acetyl chloride mole.

Preparation method provided by the invention, raw material trifluoro-acetyl chloride need to react in organic solvent with 2- ethoxy propylene. The organic solvent can be organic solvent commonly used in the art.

Preferably, the organic solvent in methyl tertiary butyl ether, hexamethylene, toluene and Trifluoroacetic Acid Ethyl Ester at least It is a kind of.

The dosage satisfaction of the organic solvent used goes on smoothly reaction.

Preferably, the dosage of the organic solvent is 2.0~10.0 times of trifluoro-acetyl chloride weight.

It may further be preferable that the dosage of the organic solvent is 2.5~5.0 times of trifluoro-acetyl chloride weight.

Preparation method provided by the invention, the proportion between raw material trifluoro-acetyl chloride and 2- ethoxy propylene meet thing and react It goes on smoothly.

Preferably, the molar ratio of the 2- ethoxy propylene and trifluoro-acetyl chloride is 1.0~5.0:1.

It may further be preferable that the molar ratio of the 2- ethoxy propylene and trifluoro-acetyl chloride is 1.0~2.5:1.

Preparation method provided by the invention, reaction temperature satisfaction go on smoothly reaction.

Preferably, the reaction temperature is -10~30 DEG C.

It may further be preferable that the reaction temperature is 0~20 DEG C.

Preparation method provided by the invention, when after reaction, obtaining containing 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- of 4- ethyoxyl Water is first added in the reaction solution of ketone into reaction solution, collects after standing liquid separation containing 1,1, the 1- tri- fluoro- amyl- 3- alkene -2- ketone of 4- ethyoxyl Organic phase, then organic phase is subjected to rectification under vacuum, obtains the 1 of purity >=99.0%, 1, the 1- tri- fluoro- amyl- 3- alkene-of 4- ethyoxyl 2- ketone product.

The amount of above-mentioned addition water need to make be collected into after standing liquid separation containing 1,1, the 1- tri- fluoro- amyl- 3- of 4- ethyoxyl The organic phase of alkene -2- ketone.

Preferably, the dosage of the water is the 30%~70% of reaction solution gross mass.

It may further be preferable that the dosage of the water is the 40~60% of reaction solution gross mass.

Above-mentioned rectification under vacuum, vacuum degree preferably -100~-50KPa, and further preferably 95~-80KPa.

Preparation method provided by the invention has the advantage that compared with prior art

(1) reaction yield is high；

(2) raw material is simple and easy to get, and price is lower；

(3) reaction condition is mild, easy to industrialized production.

Specific embodiment

Next combined with specific embodiments below invention is further explained, but does not limit the invention to these tools Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope All alternatives, improvement project and equivalent scheme.