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A kind of imine compound substituted by difluoroacetate and preparation method thereof

A technology of imine compound and difluoroacetate, which is applied in the preparation of imino compound and organic chemistry, etc., can solve the problem of strong electron-absorbing ability of imine unstable difluoromethylene, difficulty in conversion of functional groups of reaction products, reaction Difficult preparation of substrates and other problems, to achieve the effect of wide application range of substrates, overcoming the limitations of reaction substrates, and easy availability of raw materials

Active Publication Date: 2021-04-30
TIANJIN UNIV OF TRADITIONAL CHINESE MEDICINE
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Problems solved by technology

Organic Letters 2006,8,4767-4770 reported the preparation of imine compounds containing difluoromethylene substitution, but this reaction is limited to imine reaction substrates, and due to the instability of imine and the difluoromethylene Strong electron-withdrawing ability, resulting in the disadvantage of structural instability in both the reaction substrate and the reaction product
J.Fluorine Chem.2014,167,152-158 reported the preparation of imine compounds substituted by difluorophosphate, the reaction substrate is limited to the imine-enaminophosphate reaction substrate, and the preparation of the reaction substrate is difficult, the reaction product The yield is not high, and the conversion of the functional group of the reaction product is not easy, etc.

Method used

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  • A kind of imine compound substituted by difluoroacetate and preparation method thereof
  • A kind of imine compound substituted by difluoroacetate and preparation method thereof
  • A kind of imine compound substituted by difluoroacetate and preparation method thereof

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Experimental program
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Effect test

Embodiment 1

[0018]

[0019] In a dry 25 mL reaction flask, A-1 (179 mg, 0.6 mmol) was dissolved in acetonitrile (6 mL). After the system was cooled to 0 °C, Selectfluor (532 mg, 1.5 mmol) was added at one time, and continued at 0 °C. The reaction was stirred for 1 h. After TLC detected that the reaction was complete, diethyl ether (5 mL) was added to the system, then the insolubles were removed by filtration, the filter cake was washed three times with diethyl ether (5 mL), and the filtrate was spin-dried by column chromatography (eluent: petroleum ether / ethyl acetate) = 20 / 1 to 10 / 1) to obtain the target product (190 mg, yield 95%) as a bright yellow oily liquid. 1 H NMR (500MHz, CDCl 3 )δ(ppm): 7.39–7.32 (m, 3H), 7.28–7.26 (m, 2H), 6.69 (s, 4H), 4.44 (q, J=7Hz, 2H), 3.73 (s, 3H), 1.40 (t, J=7Hz, 3H); 13 C NMR (125MHz, CDCl 3 )δ(ppm): 163.36(t, J=31Hz), 159.81(t, J=30Hz), 157.86, 140.02, 131.00, 130.04, 128.91, 128.72, 123.64, 114.01, 113.13(t, J=253Hz), 63.07 ,55.45,14.19; 19 F...

Embodiment 2

[0021]

[0022] In a dry 25 mL reaction flask, A-1 (179 mg, 0.6 mmol) was dissolved in acetonitrile (6 mL). After the system was cooled to 0 °C, Accufluor (483 mg, 1.5 mmol) was added at one time, and stirring was continued at room temperature. The reaction was carried out for 2h. After TLC detected that the reaction was complete, diethyl ether (5 mL) was added to the system, then the insolubles were removed by filtration, the filter cake was washed three times with diethyl ether (5 mL), and the filtrate was spin-dried by column chromatography (eluent: petroleum ether / ethyl acetate) = 20 / 1 to 10 / 1) to obtain the target product (106 mg, yield 53%) as a bright yellow oily liquid. 1 H NMR (500MHz, CDCl 3 )δ(ppm): 7.39–7.32 (m, 3H), 7.28–7.26 (m, 2H), 6.69 (s, 4H), 4.44 (q, J=7Hz, 2H), 3.73 (s, 3H), 1.40 (t, J=7Hz, 3H); 13 C NMR (125MHz, CDCl 3 )δ(ppm): 163.36(t, J=31Hz), 159.81(t, J=30Hz), 157.86, 140.02, 131.00, 130.04, 128.91, 128.72, 123.64, 114.01, 113.13(t, J=253Hz), ...

Embodiment 3

[0024]

[0025] In a dry 25mL reaction flask, A-1 (179mg, 0.6mmol) was dissolved in 1,4-dioxane (6mL), Selectfluor (532mg, 1.5mmol) was added at one time at room temperature, and the reaction was continued with stirring 1h. After TLC detected that the reaction was complete, diethyl ether (5 mL) was added to the system, then the insolubles were removed by filtration, the filter cake was washed three times with diethyl ether (5 mL), and the filtrate was spin-dried by column chromatography (eluent: petroleum ether / ethyl acetate) = 20 / 1 to 10 / 1) to obtain the target product (137 mg, yield 69%) as a bright yellow oily liquid. 1 H NMR (500MHz, CDCl 3 )δ(ppm): 7.39–7.32 (m, 3H), 7.28–7.26 (m, 2H), 6.69 (s, 4H), 4.44 (q, J=7Hz, 2H), 3.73 (s, 3H), 1.40 (t, J=7Hz, 3H); 13 CNMR (125MHz, CDCl 3 )δ(ppm): 163.36(t, J=31Hz), 159.81(t, J=30Hz), 157.86, 140.02, 131.00, 130.04, 128.91, 128.72, 123.64, 114.01, 113.13(t, J=253Hz), 63.07 ,55.45,14.19; 19 F NMR (376MHz, CDCl 3 )δ(ppm):–10...

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Abstract

The invention relates to a difluoroacetate substituted imine compound and a preparation method. The preparation method comprises the following steps: dissolving the enamine compound shown in formula A in an organic solvent, then adding an electrophilic fluorine reagent, after the reaction is complete, filtering, washing, and separating to obtain the compound containing difluoroethylene as shown in formula B. Ester substituted imine compounds. The preparation method of the invention has simple operation, simple and easy-to-obtain raw materials, few reaction steps, high conversion rate and reaction yield, good functional group compatibility, wide application range of substrates, avoiding the use of alkali and precious metals, and is environmentally friendly. The obtained compound contains imine and difluoroacetate structures, can be used as an important synthetic building block of active molecules, and has great application prospects in the field of biomedicine.

Description

technical field [0001] The invention relates to a difluoroacetate substituted imine compound and a preparation method. Background technique [0002] When a fluorine atom or a fluorine-containing group is introduced into an organic compound molecule, the physical, chemical and physiological properties of the parent compound usually change significantly. In particular, difluoromethylene (-CF 2 -) Due to its good metabolic stability, it is often used in the design and synthesis of drugs and biologically active molecules as the biological isosteres of methylene, oxygen and carbonyl groups. Compared with the methods of introducing difluoromethylene groups at the ortho positions of aldehydes, ketones and hydrazones, the methods for preparing imine compounds containing difluoromethylene groups at the ortho positions are very limited. Organic Letters 2006, 8, 4767-4770 reported the preparation of imine compounds substituted with difluoromethylene, but this reaction is limited to i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C249/02C07C251/24C07D333/22C07D317/58
CPCC07C249/02C07C251/24C07D317/58C07D333/22C07C2601/02
Inventor 李方怿邱昌福郭静敏侯欣鑫尹光伟王春华李正
Owner TIANJIN UNIV OF TRADITIONAL CHINESE MEDICINE
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