Trifluoromethyl allyl compound as well as preparation method and application thereof

A technology of trifluoromethylpropenyl and methyl methacrylate, which is applied in the field of trifluoromethylpropenyl compounds and their preparation, and can solve by-product halogen salt/high-salt wastewater, cumbersome post-reaction treatment, and reaction conditions Harsh problems, such as excellent stereoselectivity, tolerance to broad-spectrum functional groups, and low preparation cost

Active Publication Date: 2021-08-03
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The primary purpose of the present invention is to provide a method for preparing trifluoromethylpropenyl compounds, which aims to solve the problem of harsh reaction conditions, reliance on transition metal catalysis, cumbersome post-reaction treatment, and quantitative by-product halide salts in existing methods. / The problem of high salt wastewater

Method used

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  • Trifluoromethyl allyl compound as well as preparation method and application thereof
  • Trifluoromethyl allyl compound as well as preparation method and application thereof
  • Trifluoromethyl allyl compound as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] (1) In a 10mL Shrek tube, under argon atmosphere, add 0.2mmol 2-hydroxy (phenyl) methyl methacrylate, 0.3mmol sodium trifluoromethyl sulfinate, 0.008mmol 3,6,-di-tert- Butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate, add 3mL of acetonitrile, stir and react under argon, room temperature and 18W blue light irradiation, the reaction equation is:

[0028] (2) After TLC monitors that the reaction is complete, remove the solvent with a vacuum rotary evaporator, and separate the product by thin-layer chromatography. The developing agent is petroleum ether / ethyl acetate system, and the product is light yellow liquid (E)-2-benzylidene -4,4,4-trifluorobutyric acid methyl ester, yield 71%.

[0029] (E)-2-benzylidene-4,4,4-trifluorobutanoic acid methyl ester was subjected to NMR test, as Figure 1~3 as shown, figure 1 It is the H NMR spectrum of (E)-2-benzylidene-4,4,4-trifluorobutyric acid methyl ester; figure 2 It is the carbon nuclear magnetic resonance spectrum of ...

Embodiment 2

[0031] (1) In a 10mL Shrek tube, under argon atmosphere, add 0.4mmol 2-hydroxyl (2,4-dichlorophenyl)methylcyclohex-2-en-1-one, 0.6mmol trifluoromethyl Sodium sulfinate, 0.016mmol 3,6,-di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate, add 6mL acetonitrile, under argon, room temperature and 18W blue light Stirring reaction under irradiation, the reaction equation is:

[0032]

[0033] (2) After TLC monitors that the reaction is complete, remove the solvent with a vacuum rotary evaporator, and separate the product by thin-layer chromatography. The developer is a sherwood oil / ethyl acetate system, and the product is a light yellow liquid (E)-2-(2, 4-dichlorobenzylidene)-3-(trifluoromethyl)cyclohexan-1-one, yield 74%.

Embodiment 3

[0035] This embodiment is basically the same as the above-mentioned Example 1, except that 10 mmol 2-hydroxy (phenyl) methyl methacrylate, 15 mmol sodium trifluoromethyl sulfinate, 0.4 mmol 3 ,6,-di-tert-butyl-9-mesityl-10-phenylacridine-10-tetrafluoroborate, add 150mL of acetonitrile, stir the reaction under argon, room temperature and 18W blue light irradiation to obtain ( E) 1.76 g of methyl 2-benzylidene-4,4,4-trifluorobutyrate, yield 72%.

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Abstract

The invention discloses a trifluoromethyl allyl compound as well as a preparation method and application thereof. According to the method, allyl alcohol is directly used as a raw material, CF3SO2Na is selected as a trifluoromethylation reagent, a metal-free and cheap photooxidation reduction catalyst is used, and under the catalysis of an organic photooxidation reduction agent, a byproduct SO2 generated in situ is reused as an activated C-OH bond, so that the reaction is carried out in an environment-friendly manner under a mild condition. The allyl alcohol used in the preparation method disclosed by the invention is a MoritA-Baylis-Hillman alcohol allyl alcohol raw material which is simple to synthesize and high in conversion rate, the applicable substrate range is wide, and the preparation cost is low. In addition, the preparation method disclosed by the invention is simple in steps, and has the characteristics of convenience in operation, environment friendliness, excellent stereoselectivity and broad-spectrum functional group tolerance. The trifluoromethyl allyl compound provided by the invention is a general precursor for preparing related CF3 molecules, has potential pharmaceutical activity and biological activity, and can be widely applied to biological and pharmaceutical active molecules.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a trifluoromethylpropenyl compound and a preparation method and application thereof. Background technique [0002] The development of novel synthetic fluorination reactions has important implications in agriculture, medicine, and materials chemistry. Fluorine and fluorinated compounds can affect the properties of organic compounds, and their electronegativity, total hydrophobicity / lipophilicity, and electrostatic interactions can significantly affect chemical reactions. Even a single fluorine atom can completely change the properties of a compound. [0003] Among them, fluorine-containing drugs have invested a lot of resources in academia and industry. Selective fluorination can intentionally improve drug performance, at least prolong the biological half-life of drugs by hindering oxidative metabolism, and increase bioabsorption through lipophilic ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/343C07C69/65C07C45/68C07C49/697C07C67/14C07C69/54C07C69/732C07J9/00C07H13/04C07H1/00
CPCC07C67/343C07C69/65C07C45/68C07C49/697C07C67/14C07J9/00C07H13/04C07H1/00C07C2601/14C07C69/54C07C69/732
Inventor 解沛忠李博文
Owner NANJING UNIV OF TECH
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