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Production method for cycloalkyl(trifluoromethyl)benzene

A technology of trifluoromethyl and manufacturing method, which is applied in the direction of organic chemical methods, chemical instruments and methods, preparation of halogenated hydrocarbons, etc., can solve the problem of expensive cycloalkyl (trifluoromethyl) benzene, expensive ligands, and low productivity. Not advanced question

Active Publication Date: 2020-01-24
TORAY FINE CHEMICALS CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] However, the method described in Patent Document 1 requires a dehydration reaction, a hydrogenation reaction, and a multi-stage reaction process after that, in addition to the lithiation reaction at an extremely low temperature of -78°C.
[0008] Also in Patent Document 2, since dilute isopropylmagnesium bromide is used, a dehydration reaction, a hydrogenation reaction, and a multistage reaction process are required after the Grignard exchange reaction, which is not very productive.
[0009] Since these methods involve low-productivity reaction steps in extremely low temperature and dilute solutions, the resulting cycloalkyl(trifluoromethyl)benzenes become expensive through complex multi-stage reaction steps.
[0010] The method described in Non-Patent Document 1 discloses that expensive N,N,N',N'-tetramethylethylenediamine is coordinated with ferric chloride to pass The cross-coupling reaction of 4-(trifluoromethyl)phenylmagnesium bromide and cyclohexyl bromide obtained 1-cyclohexyl-4-(trifluoromethyl)benzene with a yield of 67%, but using 1.5 equivalents of Excess 4-(trifluoromethyl)phenylmagnesium bromide, if converted into the yield of 4-(trifluoromethyl)phenylmagnesium bromide benchmark, the yield is as low as 44%
[0011] The ligands disclosed in Non-Patent Documents 2, 3, and 4 are expensive or unavailable, and there are problems in industrial use, and it is not clear whether they can be applied to the cycloalkyl(trifluoromethyl)benzene of the present invention

Method used

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  • Production method for cycloalkyl(trifluoromethyl)benzene
  • Production method for cycloalkyl(trifluoromethyl)benzene
  • Production method for cycloalkyl(trifluoromethyl)benzene

Examples

Experimental program
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Embodiment 1

[0071] Tetrahydrofuran (hereinafter referred to as "THF") 75.0 g (1.04 mol; manufactured by Nacalai Tesque Co.), magnesium powder 5.1 g (0.208 mol; manufactured by Chuo Kosan Co.), LiCl 2.5 g (0.06 mol; manufactured by Nacalai Tesque Co. ) into a 200ml four-necked flask with a thermometer, and the system was replaced with nitrogen while stirring. 0.5 g of 1 mol / L ethylmagnesium bromide THF solution (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the moisture in the system was removed. Next, 0.44 g (0.004 mol; manufactured by Wako Pure Chemical Industries, Ltd.) of bromoethane was added. After stirring for a while, generation of heat generation was confirmed. Next, 36.1 g (0.2 mol; manufactured by Wako Pure Chemical Industries, Ltd.) of o-chlorobenzotrifluoride was slowly added dropwise while keeping the temperature of the reaction liquid at 45 to 50°C. After completion of the dropwise addition, it was aged while stirring at 45° C. for 5 hours. Aft...

Embodiment 2

[0076] In Example 1, the temperature at which the Grignard reagent solution was added dropwise was changed from 70°C to 75°C, and after the entire amount of the Grignard reagent solution was added dropwise, the aging temperature was changed from 70°C to 75°C. In addition, The reaction was carried out in the same manner as in Example 1.

[0077] The obtained oil phase was analyzed by gas chromatography. As a result, the reaction yield of 1-cyclopentyl-2-(trifluoromethyl)benzene was 60.0% (based on the raw material o-chlorobenzotrifluoride).

Embodiment 3

[0088]In Example 1, 1.6 g of ferric chloride (0.05 mol times / o-chlorobenzotrifluoride: manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 1.3 g of ferrous chloride (0.05 mol times / o-chlorobenzotrifluoride: Wako Pure Chemical Industries, Ltd. Yakusha-manufactured), except that, it reacted similarly to Example 1.

[0089] The obtained oil phase was analyzed by gas chromatography. As a result, the reaction yield of 1-cyclopentyl-2-(trifluoromethyl)benzene was 55.6% (based on the raw material o-chlorobenzotrifluoride).

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Abstract

The present invention provides an industrially excellent method for highly efficiently producing a cycloalkyl(trifluoromethyl)benzene without any complicated step and through a small number of steps.A halogen-substituted trifluoromethylbenzene is reacted with magnesium metal to convert the compound into a Grignard reagent. The Grignard reagent is cross-coupled with a cycloalkyl halide in the presence of an iron salt or a cobalt salt at a reaction temperature of 60-80 DEG C to produce a cycloalkyl(trifluoromethyl)benzene.

Description

technical field [0001] The present invention relates to a method for producing cycloalkyl(trifluoromethyl)benzene, and more specifically, relates to a method for producing an industrially excellent cycloalkyl(trifluoromethyl)benzene. Background technique [0002] Cycloalkyl(trifluoromethyl)benzene is a compound useful in fine chemicals, pharmaceutical and agricultural chemical raw materials, resin / plastic raw materials, electronic information materials, optical materials, and the like. [0003] As a method for producing cycloalkyl(trifluoromethyl)benzene, in Patent Document 1, 1-bromo-2-(trifluoromethyl)benzene is lithiated with butyllithium, and cyclopentanone is reacted with it, 1-(2-(Trifluoromethyl)phenyl)cyclopentanol is produced. This was further dehydrated and hydrogenated to obtain 1-cyclopentyl-2-(trifluoromethyl)benzene. [0004] In Patent Document 2, after Grignard exchange of 1-bromo-2-(trifluoromethyl)benzene with isopropylmagnesium bromide, it is reacted with...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/26C07C22/08C07B61/00
CPCC07B61/00C07C17/26C07C22/08C07C17/2632C07C2601/08C07C17/278C07F3/02B01J37/16B01J23/745B01J23/75
Inventor 中谷仁郎
Owner TORAY FINE CHEMICALS CO LTD