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Method for synthesizing remote fluorinated aryl olefin

A substituted aryl olefin, remote technology, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problem of not being applicable to the preparation of remote fluoro aryl olefins, etc.

Active Publication Date: 2020-04-14
XINYANG NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Although this route realizes the synthesis of ortho-difluoroalkenes, its method is not suitable for the preparation of remote fluoroaryl olefins, so it is still necessary to develop a new research method for the synthesis of remote fluoroalkenes

Method used

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  • Method for synthesizing remote fluorinated aryl olefin
  • Method for synthesizing remote fluorinated aryl olefin
  • Method for synthesizing remote fluorinated aryl olefin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030]

[0031] In the reaction flask, continuously bubble nitrogen into the reaction flask, then add 2-allyl-2-phenylethylmalonate 2a (30.4 mg, 0.1 mmol), ethyl bromodifluoroacetate 3a (40.2mg), bis(triphenylphosphine)palladium dichloride (3.5mg), 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (5.78), potassium carbonate (27.6mg ) and 1.0 mL of acetonitrile, stirred and mixed evenly, reacted at 80 degrees for 12 hours, and separated directly by column chromatography to obtain the target product 1a with a yield of 72%. 1 H NMR (600MHz, CDCl 3 )δ7.41(d, J=7.4Hz, 2H), 7.32(t, J=7.4Hz, 2H), 7.26(t, J=7.5Hz, 1H), 6.74(d, J=16.6Hz, 1H) ,6.49(d,J=16.6Hz,1H),4.29-4.21(m,6H),2.20(t,J=8.5Hz,2H),2.13-2.04(m,2H),1.49-1.43(m,2H ),1.30-1.25(m,9H); 19 F NMR (564MHz, CDCl 3 )δ-105.86(t, J=16.9Hz, 2F); 13 C NMR (150MHz, CDCl 3 )δ170.18, 164.08(t, J=32.9Hz), 136.30, 131.56, 128.55, 127.99, 126.52, 125.73, 115.87(t, J=249.1Hz), 62.79, 61.70, 59.21, 34.95, 34.49(t, J=23.1 Hz), 16.64, 13...

Embodiment 2

[0034]

[0035] In the reaction flask, continuously bubble nitrogen into the reaction flask, then add 2-allyl-2-(4-methoxy) phenethyl malonate 2b (32.0mg, 0.1mmol), bromine Ethyl difluoroacetate 3a (40.2mg), bis(triphenylphosphine) palladium dichloride (3.5mg), 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (5.78 ), potassium carbonate (27.6 mg) and 1.0 mL of acetonitrile, stirred and mixed evenly, reacted at 80 degrees for 12 hours, and separated directly by column chromatography to obtain the target product 1b with a yield of 78%. 1 HNMR (600MHz, CDCl 3)δ7.35(d, J=8.8Hz, 2H), 6.86(d, J=8.6Hz, 2H), 6.58(d, J=16.6Hz, 1H), 6.42(d, J=16.6Hz, 1H) ,4.29(q,J=7.3Hz,2H),4.24–4.20(m,4H),3.81(s,3H),2.18(t,J=8.5Hz,2H),2.12-2.04(m,2H), 1.47-1.42(m,2H),1.29(t,J=7.0Hz,3H),1.25(t,J=7.0Hz,6H); 19 F NMR (564MHz, CDCl 3 )δ-105.87(t, J=15.9Hz, 2F); 13 C NMR (150MHz, CDCl 3 )δ170.34, 164.10(t, J=32.9Hz), 159.48, 130.96, 129.11, 127.75, 123.36, 115.90(t, J=248.9Hz), 113.94, 62.79, 61.65, ...

Embodiment 3

[0037] Adopt the identical reaction conditions of embodiment 1-2, only change substrate 2, obtain serial product 1c-1o, concrete result is as follows: (wherein, Rf=CF 2 CO 2 Et)

[0038]

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PUM

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Abstract

The invention discloses a method for synthesizing remote fluorinated aryl olefin, and belongs to the field of organic chemistry. The preparation method comprises the following steps: carrying out a reaction by taking 2-allyl-2-phenethyl diethyl malonate and a derivative thereof as raw materials in the presence of a phosphorus ligand, an inorganic alkali and an organic solvent to obtain the fluorinated olefin compound triethyl (E)-1,1-difluoro-7-phenylhept-6-ene-1,5,5-tricarboxylic acid. According to the method, the method can be completed in one step under the catalysis of palladium, difluoroalkylation is achieved while olefin isomerization is conducted, and a direct and effective way is provided for synthesis of the compound.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry and relates to a method for fluoroalkylation of olefins, in particular to providing a method for synthesizing remote fluorinated aryl olefins. Background technique [0002] Fluorine-containing functional groups have a profound impact on medicinal chemistry and biochemistry. Fluorine-containing groups can change the absorption, distribution, metabolism and excretion of molecules in the body. Fluorine-containing olefin compounds have a wide range of transformation characteristics, and can introduce different functional groups, such as phenyl, hydroxyl, amino, cyano, etc., through the difunctionalization of olefins to further realize the transformation and application of fluorine-containing compounds. Activity studies provide powerful tools. [0003] Traditionally, the synthesis of fluoroalkenes mostly relies on transition metal catalysis. The reaction process requires a large amount of ox...

Claims

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Application Information

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IPC IPC(8): C07C67/00C07C67/343C07C69/734C07C69/618C07C69/65C07D307/79C07D319/06
CPCC07C67/00C07C67/343C07D307/79C07D319/06C07C69/734C07C69/618C07C69/65
Inventor 李立新赵争光罗浩天李勇
Owner XINYANG NORMAL UNIVERSITY
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