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Difluoromethylphosphonium salt and its preparation method and application

A technology of difluoromethyl phosphonium salt and difluoromethylene phosphonium is applied in the field of difluoromethyl phosphonium salt and preparation and application thereof, and can solve the problems of expensive, complicated preparation method, harsh reaction conditions and the like

Inactive Publication Date: 2018-09-21
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0016] The technical problem to be solved by the present invention is to overcome the difluoromethyl phosphonium salt anions prepared by the preparation method of difluoromethyl phosphonium salt only limited to a few kinds, such as Br - , OTf - , BF 4 - and FSO 2 - ; and the preparation methods are more loaded down with trivial details, some methods use more expensive raw materials, and the reaction conditions are harsher, unfavorable for the defects of industrial production, etc., and provide a kind of difluoromethyl phosphonium salt and its preparation method and application

Method used

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  • Difluoromethylphosphonium salt and its preparation method and application
  • Difluoromethylphosphonium salt and its preparation method and application
  • Difluoromethylphosphonium salt and its preparation method and application

Examples

Experimental program
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Effect test

Embodiment 1

[0078] Synthesis

[0079] In a 100mL single-mouth bottle, first add difluoromethyl phosphonium internal salt ( 7.12g, 0.02mol), then add THF (50mL), slowly add 40% hydrogen bromide aqueous solution (2.9mL, 0.024mol) while stirring. When the acid is added, all the solids are dissolved and the mixture is stirred. Reflux for 1 hour to stop the reaction; cool the system to room temperature and concentrate with a rotary evaporator; then add ether (20 mL) to the concentrated solution, stir for a while, the solution is divided into two layers, decant the upper solution, and repeat Five times; THF (20mL) was added and stirred until a white solid precipitated, filtered under reduced pressure, washed with THF (5mL) three times, and finally a white solid was obtained. The yield was 90%, and the purity was> 99.9% (nuclear magnetic purity).

[0080] White solid, 1 H NMR (400MHz, DMF) δ 9.50 (td, J = 46.6, 29.6 Hz, 1H), 8.16-8.06 (m, 9H), 7.94 (m, 6H). 19 F NMR (376MHz, DMF) δ-127.58 (dd, J=77...

Embodiment 2

[0084] Synthesis

[0085] In a 100mL single-mouth bottle, first add difluoromethyl phosphonium internal salt ( 7.12g, 0.02mol), then add THF (50mL), slowly add 60% hexafluorophosphoric acid aqueous solution (2.4mL, 0.024mol) while stirring, when the acid is added, all the solids are dissolved, and the mixture is stirred Reflux for 1 hour to stop the reaction; cool the system to room temperature and concentrate with a rotary evaporator; then add diethyl ether (20 mL) to the concentrated solution, stir for a while, a white solid precipitates, pour out the diethyl ether solution, repeat this three times THF (20mL) was added and stirred, filtered under reduced pressure, washed with THF (5mL) three times, and finally a white solid was obtained. The obtained solid was dissolved in dichloromethane (10mL), ion exchange was performed with 1mol / L potassium hexafluorophosphate aqueous solution (10mL×3), and finally dichloromethane was removed under reduced pressure to obtain the product w...

Embodiment 3

[0088] Synthesis.

[0089] In a 100mL single-mouth bottle, first add difluoromethyl phosphonium internal salt ( 7.12g, 0.02mol), and then add THF (50mL), under stirring, slowly add bis(trifluoromethanesulfonyl)imine (6.7g, 0.024mol), when the imine is added, all the solids are dissolved , Reflux for 1 hour under stirring, stop the reaction; cool the system to room temperature and concentrate with a rotary evaporator; then add ether (20mL) to the concentrated solution, stir for a while, a white solid precipitates out, pour out the ether solution , Repeat this three times; add THF (20mL) and stir, filter under reduced pressure, wash with THF (5mL) three times, finally get a white solid, the yield is 70%, the purity is> 99.9% (nuclear magnetic purity).

[0090] White solid, M.P.: 75.0-75.5℃. 1 H NMR (400MHz, DMF): δ9.50 (td, J = 46.8, 29.6Hz, 1H), 8.16-8.06 (m, 9H), 7.94 (m, 6H). 19 F NMR (376MHz, DMF): δ-127.25 (dd, J = 77.7, 46.8 Hz, 2F), -79.72 (s, 6F). 31 P NMR (162MHz, DMF): δ1...

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Abstract

The invention discloses difluromethylphosphonium salt, and a preparation method and application thereof. A synthetic method of the difluromethylphosphonium salt disclosed by the invention comprises the following steps of in a solvent, carrying out a reaction shown as follows on gem-difluoromethylenated phosphonium inner salt as shown in a formula II and protonic acid, and preparing a compound as shown in a formula I. The invention discloses application of the compound as shown in the formula I in difluromethylation reaction with a compound as shown in a formula III or a compound as shown in a formula IV. The preparation method of the difluromethylphosphonium salt provided by the invention is simple and convenient to operate and wide in substrate applicability, can be carried out with the existence of water and oxygen, and is moderate in reaction condition and high in yield and purity. The difluromethylphosphonium salt provided by the invention can be used for directly difluromethylating aldehyde, ketone and imine compounds, and the method is simple to operate, moderate in condition, and high in reaction yield when a substrate is a ketone compound containing alpha-H.

Description

Technical field [0001] The invention relates to a difluoromethyl phosphonium salt and a preparation method and application thereof. Background technique [0002] The introduction of fluorine atoms or fluorine-containing building blocks into the molecule usually enhances the hydrophobicity of the molecule and the drug activity of the molecule. Therefore, the application of fluorine-containing compounds in medicine, pesticides, and materials has become more and more extensive. In fluorinated building blocks, difluoromethyl (-CF 2 H) is very polar, and the hydrogen atoms in difluoromethyl are very active. Its structure and properties are similar to those of alcohols and can be used as hydrogen bond donors. Since a large number of drug molecules contain hydroxyl groups, the introduction of difluoromethyl groups into drug molecules is of great significance for studying the biological activity of drug molecules and developing new drugs. At present, people have developed difluoromethyl...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/54C07C33/46C07C29/38C07C205/26C07C201/12C07C255/53C07C253/30C07D215/14C07D307/80C07D333/56C07C69/732C07C67/343C07C317/36C07C315/04
Inventor 肖吉昌邓祖勇林锦鸿
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI