Synthesis method of organic phosphorus compound

A synthesis method and selected technology, applied in the field of synthesis of organophosphorus compounds, can solve the problems of unsatisfactory industrial application, long reaction route, and high requirements for production equipment, and achieve unique catalytic activity, fewer steps, and easy separation and purification.

Active Publication Date: 2017-03-08
JIANGSU SINOCOMPOUND CATALYST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The current chiral H8-BINAP method is reported by EP839819, using binaphthol as the starting material, through hydrogenation, esterification to obtain the standby product two and diphenylphosphine oxide coupling reaction, trichlorosilane hydrogen reduction, and then use Diphenylphosphine oxide coupling reaction, reduction of trichlorosilane hydrogen, the reaction route is long, in which highly volatile and highly toxic trichlorosilane hydrogen is used, which requires high production equipment, and the products need to be purified by silica gel column chromatography , unable to meet the needs of industrial applications

Method used

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  • Synthesis method of organic phosphorus compound
  • Synthesis method of organic phosphorus compound
  • Synthesis method of organic phosphorus compound

Examples

Experimental program
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Effect test

Embodiment 1

[0031] Add 50g(R)-BINOL, 15g 5%Pd / C (50%wet), 300mL ethanol to a 1L autoclave, seal the autoclave, vacuumize, replace with nitrogen once, then replace with hydrogen three times, adjust the pressure to 60atm, Raise the temperature to 75-80°C, keep the temperature for 8 hours, cool the autoclave to room temperature, filter, and concentrate the filtrate to dryness for later use to obtain a viscous standby product 1.

Embodiment 2

[0033] Dissolve the spare material in Example 1 in 300mL of dichloromethane, add it into 32mL of pyridine solution, cool to below 5°C, add 108g of trifluoroacetic anhydride dropwise, the temperature does not exceed 25°C during the dropwise addition, and stir at room temperature for 24 hours after the dropwise addition , filtered off the insoluble matter, concentrated the filtrate, and when a small amount of solvent remained, add methanol to crystallize, filter, and dry in vacuum at 60-70°C to obtain 70g of yellow standby product 2 with a yield of 72% and a purity of 99.2%.

Embodiment 3

[0035] With the 1.1g spare material two in the example 2, 0.0448gPd (OAc) (10mol%), 0.085gDPPE (10mol%), join in the 5mLDMF solvent, vacuumize, argon replacement is entered reactor, then 0.57gDIPEA and 0.82 Add 1 g of diphenylphosphine to the reaction system, raise the temperature to 120°C with stirring, keep warm and reflux for 72 hours, cool to room temperature, add the reaction solution into 30mL methanol, filter, rinse the filter cake with a small amount of methanol, Dry under vacuum to obtain 0.58g off-white solid, yield 46%, melting point 207~208 ℃, 31 P-NMR (CDCl 3 ):-16.31(S), [] D +69.7 (C 0.5 Toluene).

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Abstract

The invention discloses a synthesis method of 5, 5', 6, 6', 7, 7', 8, 8'-octahydro[1, 1'-binaphthyl]-2, 2'-bis[diphenylphosphine] and belongs to the field of organic synthesis. The method comprises that binaphthol as a starting raw material undergoes a catalytic hydrogenation reaction, the reaction product undergoes an esterification reaction, and the esterification reaction product and diphenylphosphine undergo a C-P bond coupling reaction under co-catalysis of a palladium catalyst and a phosphine ligand to produce a target product. The synthesis method has a product yield of 35%. Compared with the prior art, the synthesis method has few steps, is free of highly toxic raw materials, is easy to separate and purify and is suitable for industrial production. The prepared target product belonging to the field of chiral catalysis and asymmetric cycloaddition has unique catalytic activity and has a wide application prospect in the field of medicine and natural product synthesis.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, and relates to a method for synthesizing organophosphorus compounds, in particular to 5,5',6,6',7,7',8,8'-octahydro-[1,1'-bis A preparation method of naphthalene]-2,2'-bis[diphenylphosphine] (hereinafter referred to as H8-BINAP). Background technique [0002] Binaphthylbisdiphenylphosphine compounds are an important class of catalyst ligands, which are widely used in the synthesis of natural products, drugs, functional materials and biologically active compounds. They can be used in catalytic systems with metal catalysts such as Ru, Rh, and Pd. Catalytic C-C bond coupling [J.Am.Chem.Soc.1998, 120(22), 5579~5580], chiral hydrogenation [J.Am.Chem.Soc.1995, 117(9), 2675~2676] , Cycloaddition [Angew.Chem.Int.Ed.1997,36(5),518~521] and other reactions have their unique catalytic activity. Compared with binaphthylbisdiphenylphosphine, H8-BINAP has a larger chelation angle, and the chiral in...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50
CPCC07F9/5022C07F9/5072
Inventor 赵晓宝张志平陈虎孙明明李娟鲁晓凤王进华
Owner JIANGSU SINOCOMPOUND CATALYST
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