N-difluoromethyl hydrazone compound and synthesis method thereof

A technology of difluoromethylhydrazone and its synthesis method, which is applied in the preparation of hydrazone, organic chemistry, sulfonamide preparation, etc., can solve the problems of high toxicity, ozone layer depletion, etc., and achieve no transition metal participation, mild conditions, and substrate adaptation broad effect

Active Publication Date: 2018-11-13
SOUTH CHINA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Trimethylsilyl difluoro(fluorosulfonyl)acetate, methyl difluoro(fluorosulfonyl)acetate, methyl chlorodifluoroacetate, sodium difluorochloroacetate, etc. exist as sources of difluorocarbene to deplete the ozone layer and Due to the problem of greater toxicity, the use is limited (Ni C, Hu J, Synthesis., 2014, 46, 842-863)
However, there is no report on the direct synthesis of N-difluoromethylhydrazone compounds using hydrazone as a raw material

Method used

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  • N-difluoromethyl hydrazone compound and synthesis method thereof
  • N-difluoromethyl hydrazone compound and synthesis method thereof
  • N-difluoromethyl hydrazone compound and synthesis method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] In the reaction tube, add 0.15 mmol acetophenone p-toluenesulfonylhydrazone, 0.1 mmol bromodifluoromethyltrimethylsilane, 0.225 mmol tert-butoxide lithium, 0.005 mmol benzyltriethylammonium chloride ( Benzyltriethylammoniumchloride, TEBAC) and 1.5 ml of toluene were stirred in an open system at 100° C. at 200 rpm for 12 hours, then stopped heating and stirring, and cooled to room temperature. Add 4 mL of water, extract 3 times with ethyl acetate, combine the organic phases and use 0.5 g of anhydrous magnesium sulfate to dry, filter, evaporate the solvent under reduced pressure, and then separate and purify by column chromatography to obtain the target product The column chromatography eluent used was petroleum ether:ethyl acetate mixed solvent with a volume ratio of 100:1, and the yield was 29%.

Embodiment 2

[0039] Add 0.15 mmol of acetophenone p-toluenesulfonylhydrazone, 0.1 mmol of bromodifluoromethyltrimethylsilane, 0.225 mmol of 1,8-diazabicycloundec-7-ene, 0.005 mmoles of benzyltriethylammonium chloride (TEBAC) and 1.5 ml of toluene were stirred and reacted in an open system at 100° C. at a speed of 200 rpm for 12 hours, then heating and stirring were stopped, and cooled to room temperature. Add 4 mL of water, extract 3 times with ethyl acetate, combine the organic phases and use 0.5 g of anhydrous magnesium sulfate to dry, filter, evaporate the solvent under reduced pressure, and then separate and purify by column chromatography to obtain the target product The column chromatography eluent used was petroleum ether:ethyl acetate mixed solvent with a volume ratio of 100:1, and the yield was 12%.

Embodiment 3

[0041] Add 0.15 mmol acetophenone p-toluenesulfonylhydrazone, 0.1 mmol bromodifluoromethyltrimethylsilane, 0.225 mmol cesium carbonate, 0.005 mmol tetrabutylammonium fluoride (TBAF) and 1.5 mmol to the reaction tube Milliliter of toluene was stirred in an open system at 100° C. at 200 rpm for 12 hours, then the heating and stirring were stopped, and cooled to room temperature. Add 4 mL of water, extract 3 times with ethyl acetate, combine the organic phases and use 0.5 g of anhydrous magnesium sulfate to dry, filter, evaporate the solvent under reduced pressure, and then separate and purify by column chromatography to obtain the target product The column chromatography eluent used was petroleum ether:ethyl acetate mixed solvent with a volume ratio of 100:1, and the yield was 38%.

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Abstract

The invention discloses an N-difluoromethyl hydrazone compound and a synthesis method thereof and belongs to the technical field of chemical synthesis of medicines. The synthesis method comprises thefollowing steps: putting a hydrazone compound, bromine difluoromethyl trimethyl silane, a phase transfer catalyst, an alkali and an organic solvent, heating to 25-110 DEG C, stirring to carry out reactions, and after the reactions are completed, cooling to the room temperature, and separating and purifying products, thereby obtaining the N-difluoromethyl hydrazone compound. The synthesis method disclosed by the invention is easy in raw material obtaining, low in cost, simple and safe to operate, free of metal, good in environment protection, high in functional group adaptability, high in substrate adaptability and good in industrial application prospect.

Description

technical field [0001] The invention belongs to the technical field of pharmaceutical chemical synthesis, and in particular relates to an N-difluoromethylhydrazone compound and a synthesis method thereof. Background technique [0002] Fluorine atoms have high electronegativity and small atomic radius, and the introduction of fluorine-containing groups usually changes the physical, chemical and biological properties of the original molecule, thus deriving a large number of fluorine-containing compounds. At present, fluorine-containing compounds account for 20% to 30% of all agricultural chemicals and drugs, such as ciprofloxacin hydrochloride preparations, Lipitor, escitalopram, and Prozac, which also occupy a place in the field of materials, and these Data will have further growth in the 21st century (Yang X., Wu T., PhippsR.J., Toste F.D, Chem.Rev., 2015, 115, 826–870; Barata J.F.B., Neves M.G.P.M.S, Chem.Rev., 2017, 117, 3192–3253). Among them, difluoromethyl is often in...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C303/40C07C311/49C07D333/58C07D307/81C07C249/16
CPCC07C249/16C07C303/40C07D307/81C07D333/58C07C311/49
Inventor 伍婉卿林芝铭江焕峰
Owner SOUTH CHINA UNIV OF TECH
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