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Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone

A technology of cyclopropylmethyl ketone and p-chlorobenzaldehyde, which is applied in the efficient preparation of 1--2-cyclopropyl-1-propanone, and in the field of safety, can solve problems such as high cost, difficult raw materials, and high toxicity, and achieve The effects of mild reaction conditions, controllable process and safe operation

Active Publication Date: 2017-10-24
JIANGSU SWORD AGROCHEM
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] In the patent US4664696, it is disclosed that 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone is prepared by reacting 4-chlorophenylacetonitrile and methyl cyclopropyl ketone under the action of sodium hydride. Involving dangerous goods sodium hydride, the problem of uncontrollable reaction is prone to occur in the preparation process, so this method is not suitable for industrial production
[0004] Another example is the method for preparing 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone disclosed in the patent RU2350579, which requires the use of toxic methylene bromide during the preparation process, which has high production costs and low safety performance
[0005] Another example is the method for preparing 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone disclosed in the patent CN101857576. The raw material cyclopropylacetyl chloride used in the preparation process is a raw material that is difficult to obtain, and In the preparation process, high-risk and highly toxic sodium hydride and methyl iodide are used, which makes it difficult to realize industrial production
[0006] In summary, the current production process of 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone generally has the disadvantages of high risk, high toxicity, high cost, and difficulty in industrialized production. Therefore, it is necessary to provide a safe, Efficient method for preparing 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone

Method used

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  • Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone

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Embodiment 1

[0041] Embodiment 1: the preparation of 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone (VI), (the compound of formula (II) is benzyl alcohol, R is hydrogen):

[0042] Throw in benzyl alcohol (II) and trimethyl orthoformate catalyst, add p-chlorobenzaldehyde dropwise after heating up to 68°C, the dropping time lasts for 4 hours, keep warm for 2 hours after the addition, take a sample for detection, when p-chlorobenzaldehyde< At 0.5%, the catalyst trimethyl orthoformate is recovered by distillation to obtain a chlorobenzaldehyde dimethyl acetal (III) solution; 2-methyltetrahydrofuran is added to the chlorobenzaldehyde dimethyl acetal (III) solution, and at 65° C. Add trimethyl phosphite dropwise, and react under the catalysis of boron trifluoride to generate α-benzyloxy dimethyl p-chlorobenzyl phosphonate. When the reaction is over, cool down to 35°C and add tetrabutylammonium bromide, t- Sodium butoxide and 20wt% LiBr, and cyclopropyl methyl ketone is added dropwise at this tempe...

Embodiment 2

[0044] Embodiment 2: the preparation of 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone, (the compound of formula (II) is p-chlorobenzyl alcohol, R is chlorine):

[0045] Put in p-chlorobenzyl alcohol (II) and trimethylchlorosilane catalyst, add p-chlorobenzaldehyde dropwise after heating up to 65°C, the dropping time lasts for 3 hours, keep warm for 1.5 hours after the dropping, take samples for detection, when p-chlorobenzaldehyde When benzaldehyde<0.5%, distillation reclaims catalyst trimethylchlorosilane, obtains chlorobenzaldehyde dimethyl acetal (III) solution; In chlorobenzaldehyde dimethyl acetal (III) solution, add N-methylpyrrolidone, in Add trimethyl phosphite dropwise at 60°C, react under the catalysis of niobium pentachloride to generate α-benzyloxy dimethyl p-chlorobenzylphosphonate, when the reaction is over, cool down to 30°C and add benzyltriethyl Ammonium chloride, sodium methoxide and 15wt% LiCl, and cyclopropyl methyl ketone was added dropwise at this temperat...

Embodiment 3

[0046] Embodiment 3: the preparation of 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone (VI), (the compound of formula (II) is p-methyl benzyl alcohol, R is methyl):

[0047] Throw in p-methyl benzyl alcohol (II) and trimethyl orthoformate catalysts, add p-chlorobenzaldehyde drop by drop after heating up to 70°C, the dropping time lasts for 4 hours, keep warm for 3 hours after the dropping, take samples for detection, when p-chlorobenzaldehyde When benzaldehyde<0.5%, distillation reclaims catalyst trimethyl orthoformate, obtains chlorobenzaldehyde dimethyl acetal (III) solution; In chlorobenzaldehyde dimethyl acetal (III) solution, add dimethyl formamide, in Add trimethyl phosphite dropwise at 70°C, react under the catalysis of aluminum chloride to generate α-benzyloxy-p-chlorobenzyl phosphonic acid dimethyl, when the reaction is over, cool down to 40°C and add tetrabutylammonium chloride , lithium diisopropylamide and 25wt% LiCl, and dropwise add cyclopropyl methyl ketone at thi...

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Abstract

The invention discloses a preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone. The method comprises the steps of preparing acetal by adopting p-chlorobenzaldehyde and phenylcarbinol or a derivative thereof as raw materials under the action of a catalyst, reacting an acetal product with trimethyl phosphite or triethyl phosphite in an environment of a polar solvent under the catalysis of lewis acid to generate alpha-benzyloxy p-chlorobenzyl dimethyl phosphate, further reacting the alpha-benzyloxy p-chlorobenzyl dimethyl phosphate with cyclopropyl methyl ketone under the combined action of a base catalyst, a phase transfer catalyst and a cocatalyst to prepare a benzyloxy-propylene derivative; and then carrying out acidifying hydrolysis on the benzyloxy-propylene derivative to obtain the1-(4-chlorphenyl)-2-cyclopropyl-1-acetone. Compared with the prior art, the method has the advantages of being safe in operation, controllable in process, low in toxicity in the process, mild in reaction condition, suitable for industrial production and high in product purity.

Description

technical field [0001] The invention belongs to the technical field of fine chemicals, and in particular relates to a safe and efficient method for preparing 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone. Background technique [0002] 1-(4-Chlorophenyl)-2-cyclopropyl-1-propanone is an essential intermediate for the synthesis of cyproconazole, a triazole fungicide that can inhibit important substances in fungal cell membranes The demethylation of ergosterol has the effect of preventing and treating fungi. [0003] In the patent US4664696, it is disclosed that 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone is prepared by reacting 4-chlorophenylacetonitrile and methyl cyclopropyl ketone under the action of sodium hydride. Dangerous substance sodium hydride is involved in the process, and the problem of uncontrollable reaction is prone to occur in the preparation process, so this method is not suitable for industrial production. [0004] Another example is the method for preparing 1-...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C41/01C07C43/174C07C41/30C07C43/176C07C45/42C07C49/813C07F9/40
CPCC07C41/01C07C41/30C07C43/176C07C45/42C07F9/4056C07C43/1745C07C49/813
Inventor 刘志勇孙雅泉刘慧吴中明李明
Owner JIANGSU SWORD AGROCHEM
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