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Difluromethylphosphonium salt, and preparation method and application thereof

A technology of difluoromethylphosphonium salt and difluoromethylenephosphonium, which is applied in the field of difluoromethylphosphonium salt and its preparation and application, and can solve the problems of expensive, cumbersome preparation methods, harsh reaction conditions, etc.

Inactive Publication Date: 2016-11-23
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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  • Difluromethylphosphonium salt, and preparation method and application thereof
  • Difluromethylphosphonium salt, and preparation method and application thereof
  • Difluromethylphosphonium salt, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0077] Synthesis

[0078] In a 100mL single-necked bottle, first add difluoromethylphosphonium inner salt ( 7.12g, 0.02mol), then add THF (50mL), under stirring, slowly add 40% aqueous hydrogen bromide (2.9mL, 0.024mol), when the acid is added, all the solids are dissolved, and under stirring Under reflux for 1 hour, the reaction was stopped; the system was cooled to room temperature and then concentrated with a rotary evaporator; then ether (20 mL) was added to the concentrated solution, stirred for a while, the solution was divided into two layers, and the upper layer solution was poured out, and so on. Five times; THF (20 mL) was added and stirred until a white solid precipitated, filtered under reduced pressure, washed three times with THF (5 mL), and finally a white solid was obtained with a yield of 90% and a purity >99.9% (NMR purity).

[0079] white solid, 1 H NMR (400MHz, DMF) δ9.50 (td, J = 46.6, 29.6Hz, 1H), 8.16–8.06 (m, 9H), 7.94 (m, 6H). 19 F NMR (376MHz, D...

Embodiment 2

[0083] Synthesis

[0084] In a 100mL single-necked bottle, first add difluoromethylphosphonium inner salt ( 7.12g, 0.02mol), then add THF (50mL), under stirring, slowly add 60% hexafluorophosphoric acid aqueous solution (2.4mL, 0.024mol), when the acid is added, all the solids dissolve, and under stirring Under reflux for 1 hour, the reaction was stopped; the system was cooled to room temperature and then concentrated with a rotary evaporator; then ether (20 mL) was added to the concentrated solution, stirred for a while, a white solid was precipitated, and the ether solution was poured out, and this was repeated three times Add THF (20mL) and stir, filter under reduced pressure, wash with THF (5mL) three times, and finally obtain a white solid. The resulting solid was dissolved in dichloromethane (10 mL), ion-exchanged with 1 mol / L potassium hexafluorophosphate aqueous solution (10 mL×3), and finally the dichloromethane was removed under reduced pressure to obtain the pro...

Embodiment 3

[0087] Synthesis.

[0088] In a 100mL single-necked bottle, first add difluoromethylphosphonium inner salt ( 7.12g, 0.02mol), then THF (50mL) was added, under stirring, bis(trifluoromethanesulfonyl)imide (6.7g, 0.024mol) was added slowly, when the imine was added, all the solids were dissolved , refluxed for 1 hour under stirring, and stopped the reaction; the system was cooled to room temperature and then concentrated with a rotary evaporator; then, ether (20 mL) was added to the concentrated solution, stirred for a while, and a white solid was precipitated, and the ether solution was poured out , so repeated three times; add THF (20mL) and stir, filter under reduced pressure, wash with THF (5mL) three times, and finally obtain a white solid with a yield of 70% and a purity of >99.9% (NMR purity).

[0089] 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, 46.8H...

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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 difluoromethylphosphonium salt, 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, so fluorine-containing compounds are more and more widely used in medicine, pesticides, materials, etc. In fluorine-containing building blocks, difluoromethyl (-CF 2 The polarity of H) is very large, and the hydrogen atom in the difluoromethyl group is very active. Its structure and properties are similar to alcohols, and it can be used as a hydrogen bond donor. Since a large number of drug molecules contain hydroxyl groups, the introduction of difluoromethyl groups into drug molecules is of great significance for the study of the biological activity of drug molecules and the development of new drugs. At present, the drug molecules contai...

Claims

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Application Information

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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
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