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Difluoromethylene-containing compound and preparation method thereof

A technology of difluoromethylene and compounds, applied in the preparation of carbon-based compounds, organic compounds, steroids, etc., can solve the problems of expensive catalysts, poor broad-spectrum, harsh reaction conditions, etc.

Active Publication Date: 2016-01-27
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The technical problem to be solved by the present invention is to provide a method for overcoming the disadvantages of harsh reaction conditions, expensive catalysts, poor functional group compatibility, and poor broad-spectrum performance in the prior art for the preparation of difluoromethylene-containing compounds. Difluoromethylene-containing compound and its preparation method

Method used

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  • Difluoromethylene-containing compound and preparation method thereof
  • Difluoromethylene-containing compound and preparation method thereof
  • Difluoromethylene-containing compound and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0073]

[0074] In a 25mL reaction tube, add 110mg (0.9mmol) of phenylboronic acid, 4.4mg (2.5mol%, refer to the percentage of phenylboronic acid molar weight) nickel nitrate hexahydrate, 2.4mg (2.5mol%, refer to the percentage of phenylboronic acid molar percentage) bpy (2,2'-bipyridine), 166mg (1.2mmol) K 2 CO 3 , 4mL of 1,4-dioxane, injected 78μL (0.6mmol) ethyl bromodifluoroacetate, after stirring at 60°C for 24 hours, the isolated yield was 87% (when using 0.6mmol ethyl chlorodifluoroacetate, 80 After stirring at °C for 24 hours, the isolated yield was 76%), and the purity was greater than 95% as identified by hydrogen spectroscopy. 1 HNMR (500MHz, CDCl 3 )δ7.62(d, J=7.0Hz, 2H), 7.53–7.41(m, 3H), 4.30(q, J=7.1Hz, 2H), 1.30(t, J=7.2Hz, 3H). 13 CNMR (125.7MHz, CDCl 3 )δ164.2(t, J=35.3Hz), 132.8(t, J=25.5Hz), 130.9(t, J=1.7Hz), 128.6, 125.4(t, J=6.2Hz), 113.4(t, J =251.9Hz), 63.1, 13.8. 19 FNMR (376MHz, CDCl 3 )δ-103.9(s,2F).

Embodiment 2

[0076]

[0077] In a 25mL reaction tube, add 137mg (0.9mmol) 4-methoxyphenylboronic acid, 4.4mg (2.5mol%, refers to the percentage of the molar weight of 4-methoxyphenylboronic acid) nickel nitrate hexahydrate, 2.4mg (2.5mol%, refers to the percentage of the molar weight of 4-methoxyphenylboronic acid) bpy (2,2'-bipyridyl), 166mg (1.2mmol) K 2 CO 3 , 4 mL of 1,4-dioxane, injected 78 μL (0.6 mmol) of ethyl bromodifluoroacetate, and stirred at 60 ° C for 24 hours, the isolated yield was 81% (with 0.6 mmol of ethyl chlorodifluoroacetate, 80 After stirring at °C for 24 hours, the isolated yield was 62%), and the purity was greater than 95% as identified by hydrogen spectroscopy. 1 HNMR (400MHz, CDCl 3 )δ7.53(d, J=8.9Hz, 2H), 6.95(d, J=8.9Hz, 2H), 4.29(q, J=7.1Hz, 2H), 3.84(s, 3H), 1.30(t, J=7.1Hz,3H). 13 CNMR (125.7MHz, CDCl 3 )δ164.4(t, J=36.0Hz), 161.6, 127.0(t, J=6.1Hz), 124.9(t, J=26.2Hz), 114.0, 113.5(t, J=251.5Hz), 63.0, 55.3 ,13.8. 19 FNMR (376MHz, CDCl 3 )δ-102....

Embodiment 3

[0079]

[0080] In the reaction tube of 25mL, add 122mg (0.9mmol) 2-methylphenylboronic acid, 4.4mg (2.5mol%, refer to the percentage of the molar weight of 2-methylphenylboronic acid) nickel nitrate hexahydrate, 2.4mg (2.5 mol%, refers to the percentage of the molar weight of 2-methylphenylboronic acid) bpy (2,2'-bipyridyl), 166mg (1.2mmol) K 2 CO 3 , 4mL of 1,4-dioxane, inject 78μL (0.6mmol) ethyl bromodifluoroacetate, after stirring at 80°C for 24 hours, the isolated yield is 87% (when using 0.6mmol ethyl chlorodifluoroacetate, the isolated The yield is 65%), and the purity is greater than 95% as identified by hydrogen spectrum. 1 HNMR (400MHz, CDCl 3 )δ7.57(d, J=7.9Hz, 1H), 7.37(t, J=7.5Hz, 1H), 7.27(t, J=7.2Hz, 1H), 7.23(d, J=7.5Hz, 1H) ,4.32(q,J=7.1Hz,2H),2.42(s,3H),1.31(t,J=7.1Hz,3H). 13 CNMR (125.7MHz, CDCl 3 )δ164.2(t, J=35.1Hz), 136.4(t, J=3.2Hz), 131.8, 131.1(t, J=23.3Hz), 130.7(t, J=1.4Hz), 126.1(t, J =8.8Hz), 125.9, 114.2(t, J=251.6Hz), 63.0, 19.6(t, J=2....

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Abstract

The invention discloses a difluoromethylene-containing compound and a preparation method thereof. The preparation method of the difluoromethylene-containing compound is characterized in that a Suzuki coupling reaction is carried out on a compound A and a compound B in a solvent in the presence of an alkali, a ligand and a catalyst to obtain a compound C, the catalyst is a nickel salt, and the nickel salt is NiQ2.mH2O, NiLnCl2, NiLnBr2, NiLnI2 or NiLn(OH)2. The preparation method has the advantages of simple and easily available raw materials, few reaction steps, high conversion rate, simple post-treatment operation, low price and low dosage of the catalyst, good compatibility, strong broad spectrum activity, avoiding of use of severely toxic reagents, low production cost and good market application prospect.

Description

technical field [0001] The present invention relates to compounds containing difluoromethylene groups and methods for their preparation. Background technique [0002] Fluoroalkyl-substituted arene compounds have important applications in the fields of medicine, pesticides and materials science. Although the methods of introducing fluoroalkyl groups to aromatic rings have made great progress in recent years, it is still very important to develop some cheap, broad-spectrum and general-purpose methods catalyzed by transition metals. [0003] Among the fluoroalkyl-substituted arene compounds, we focus on a class of difluoromethylene-containing compounds. Because difluoromethylene can be used as a bioisostere of carbonyl, coupled with the unique physical, chemical and biological properties of fluorine atoms, this type of compound has very important applications in the field of life sciences ((a) J.O.Link, J.G. Taylor, L. Xu, M. Mitchell, H. Guo, H. Liu, D. Kato, T. Kirschberg, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/00C07C67/343C07C69/65C07C69/734C07C69/738C07C253/30C07C255/57C07C315/04C07C317/44C07C231/12C07C233/11C07C45/68C07C49/84C07C49/782C07C49/233C07C69/732C07C69/73C07D295/192C07D263/56C07D277/22C07D311/32C07D413/10C07D317/60C07D271/06C07D235/10C07J43/00C07F7/08C07F9/40
Inventor 张新刚肖玉兰
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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