A kind of synthetic method of organophosphorus compound

A synthesis method and selected technology, applied in the field of synthesis of organophosphorus compounds, can solve problems such as high requirements for production equipment, inability to meet industrial applications, and long reaction routes, and achieve the effects of easy separation and purification, unique catalytic activity, and fewer steps

Active Publication Date: 2018-09-28
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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  • A kind of synthetic method of organophosphorus compound
  • A kind of synthetic method of organophosphorus compound
  • A kind of synthetic method of organophosphorus compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Add 50g (R)-BINOL, 15g 5%Pd / C (50%wet), 300mL ethanol to a 1L autoclave, seal the autoclave, evacuate, replace with nitrogen once, and replace with hydrogen 3 times, adjust the pressure to 60atm, The temperature was raised to 75-80° C., the reaction was kept for 8 hours, the autoclave was cooled to room temperature, filtered, and the filtrate was concentrated to dryness for later use, to obtain a viscous standby material 1.

Embodiment 2

[0033] Dissolve the standby material in Example 1 in 300 mL of dichloromethane, add 32 mL of pyridine solution, cool to below 5 ° C, add 108 g 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, added methanol for crystallization, filtered, and vacuum-dried at 60-70° C. to obtain 70 g of yellow ready-to-use product 2 with a yield of 72% and a purity of 99.2%.

Embodiment 3

[0035] In Example 2, 1.1g of standby material two, 0.0448g of Pd(OAc) (10mol%), 0.085g of DPPE (10mol%) were added to 5mL of DMF solvent, evacuated, and argon was replaced into the reactor, then 0.57g of DIPEA and 0.82 g diphenylphosphine was added to the reaction system, heated to 120°C with stirring, kept at reflux for 72 hours, cooled to room temperature, the reaction solution was added to 30 mL of methanol, filtered, and the filter cake was rinsed with a small amount of methanol at 60-70°C Under vacuum drying, 0.58g of off-white solid was obtained, the yield was 46%, and the melting point was 207-208°C. 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 organic phosphorus compounds, in particular to 5,5',6,6',7,7',8,8'-octahydro-[1,1'-linked 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 have a wide range of uses in the synthesis of natural products, drugs, functional materials and biologically active compounds. 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 chirality induction effect is more prominent, such as Pd(CF 3 COO) 2 The catalyti...

Claims

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Application Information

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Patent Type & Authority Patents(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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