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A method for preparing triphosphine by metal-free reduction of triphosphine oxide

A phosphine oxide and non-metallic technology, which is applied in the field of reducing tertiary phosphine oxides to tertiary phosphine, can solve the problems of harsh hydrogen reduction reaction conditions, not in line with economic and environmental protection, flammable and explosive reactions, etc., and achieve cheap reagents , high yield and easy access to reagents

Inactive Publication Date: 2015-11-11
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although the existing reduction methods can obtain the corresponding tertiary phosphine compounds, most of the reactions require metal reagents or metal catalysts, which do not meet the requirements of economic and environmental protection
In addition, the method of non-metal reduction also has shortcomings. For example, although the reaction using highly active silane as a reducing agent has no metal participation, some reactions are flammable and explosive, and produce toxic SiH 4 Gas (J.Org.Chem.58 (1993) 3221); Mercaptan has avoided the participation of metal as reducing agent, and reaction condition is gentle simultaneously, but the stench smell of mercaptan makes the operation of reaction very difficult (ChemistryLett.(1977) 151 -152); hydrogen reduction reaction conditions are harsh, generally need high temperature and high pressure (Angew.Chem.100 (1988) 699-702)

Method used

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  • A method for preparing triphosphine by metal-free reduction of triphosphine oxide
  • A method for preparing triphosphine by metal-free reduction of triphosphine oxide
  • A method for preparing triphosphine by metal-free reduction of triphosphine oxide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Embodiment 1: the reduction of triphenylphosphine oxide

[0022]

[0023] In the reaction bottle, 0.4 mmol of triphenylphosphine oxide was dissolved in 2 mL of dichloromethane, and 0.4 mmol of oxalyl chloride was added at room temperature to react for 0.5 hours. Add 1mmol Hantzsch ester and 3mmol triethylamine to the system, 40 oC The starting material disappeared after 2 hours under stirring. The reaction system was diluted with water, then extracted with dichloromethane, and the extract was concentrated to obtain a crude product of triphenylphosphine, which was then subjected to silica gel column chromatography to obtain 97 mg of pure white solid triphenylphosphine, with a yield of 92%, Mp: 78- 80°C. 1 HNMR (400MHz, CDCl 3 )δ:7.29-7.31(m,15H). 13 CNMR (100MHz, CDCl 3 )δ: 137.3, 137.2, 133.7, 128.8, 128.6, 128.5. 31 PNMR (202MHz, CDCl 3 )δ: -5.40.

Embodiment 2

[0024] Example 2: Reduction of Tris(4-methoxyphenyl)phosphine oxide

[0025]

[0026] The experimental operation was similar to Example 1, and 117 mg of pure white solid tris(4-methoxyphenyl)phosphine was obtained, with a yield of 83%, Mp: 131-134°C. 1 HNMR (400MHz, CDCl 3 )δ:7.21-7.25(m,6H),6.88(d, J =8.0Hz,6H),3.79(s,9H). 13 CNMR (100MHz, CDCl 3 )δ: 160.2, 135.1, 134.9, 128.8, 128.7, 114.2, 114.1, 55.2. 31 PNMR (202MHz, CDCl 3 )δ: -10.25.

Embodiment 3

[0027] Example 3: Reduction of three (4-methylphenyl) phosphine oxides

[0028]

[0029] The experimental operation was similar to Example 1, and 103.5 mg of pure white solid tris(4-methylphenyl)phosphine was obtained, with a yield of 85%, Mp: 145-148°C. 1 HNMR (400MHz, CDCl 3 )δ:7.10-7.15(m,6H),7.05(d, J =8Hz,6H),2.25(s,9H). 13 CNMR (100MHz, CDCl 3 )δ: 137.6, 132.5, 128.3, 128.2, 20.3. 31 PNMR (202MHz, CDCl 3 )δ: -7.98.

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Abstract

The invention adopts a (COCl)2 / Hantzsch ester non-metal reduction system to reduce tertiary phosphine oxide. The tertiary phosphine oxide is activated by (COCl)2 and then reduced by Hantzsch ester, and is subjected to one-pot reduction to obtain the corresponding tertiary phosphine compound. The method has the advantages of mild reaction conditions, economic and accessible reagents, simple operation process, high reaction speed and the like.

Description

technical field [0001] The present invention relates to the method for reducing tertiary phosphine oxide to tertiary phosphine, the method adopts (COCl) 2 / Hantzsch ester non-metal reduction system, reducing the three-level phosphine oxide to obtain the corresponding three-level phosphine compound. Background technique [0002] The reduction of tertiary phosphine oxides is one of the important organic reactions, and the product tertiary phosphine is an important intermediate and ligand in organic synthesis. Existing reduction method at present is divided into direct reduction method and indirect reduction method two classes, and wherein the reducing agent commonly used of direct reduction method has: aluminum hydride reagent (Org.Lett.3 (2001) 87-90), silane reagent (Tetrahedron68 ( 2012) 3151-3155) and highly active low-valent metal reagents (Tetrahedron Lett.38 (1997) 5997-6000); the indirect reduction method activates the tertiary phosphine oxide by oxalyl chloride to ob...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/50
Inventor 罗美明张维熙张彤鑫
Owner SICHUAN UNIV