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Method for synthesizing bis(diphenylphosphino)-alkane

A technology of diphenylphosphine and triphenylphosphine, which is applied in the synthesis of organic phosphine compounds and the field of bis-alkane compounds. It can solve the problem that the amount of tert-chlorobutane added is difficult to control, by-products are produced, and ultrasonic radiation methods cannot be widely used in industrialization. and other problems, to achieve the effects of easy control of the reaction, less by-products, and reduced separation costs

Active Publication Date: 2012-08-15
河南惠成新材料有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The process uses ultrasonic radiation to speed up the reaction speed and improve the yield of the product, but the amount of tert-butyl chloride added in the middle process is not easy to control. Adding too much will consume the diphenylphosphine lithium of the system, and adding too much will lead to benzene The base lithium reacts with the subsequent raw material dihaloalkane to produce by-products. In addition, the ultrasonic radiation method cannot be widely used in industrialization at present.

Method used

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  • Method for synthesizing bis(diphenylphosphino)-alkane

Examples

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example 1

[0016] Under the protection of argon, add 200 mL THF and 104.9 g (0.4 mol) triphenylphosphine to the dry reactor, then add 3.18 g (0.4 mol) lithium hydride solution in 200 mL THF dropwise under cooling in a water bath, and then stir at room temperature After reacting overnight, after HPLC detected that there was no triphenylphosphine in the reaction system, 62.5 g (0.36 mol) of dibromomethane was added dropwise to the reaction system. After washing with hydrochloric acid, water, and methanol, recrystallize from a mixed solvent of chloroform and methanol to obtain 125.9 g of off-white solid product 1, 1-bisdiphenylphosphine methane, content 98% (HPLC), yield 91%, product melting point 116-118 ℃. Characterization results: GC-MS (EI, m / z): 384 (M ＋ ); 31 P NMR (300MHz, d 6 -DMSO), δ: -23.048; 1 H NMR (300MHz, CDCl 3 ), δ: 7.426-7.352 (s, 20H), 2.912 (s, 2H).

example 2

[0018] Under the protection of argon, 200 mL THF and 104.9 g (0.4 mol) triphenylphosphine were added to the dry reactor, and 3.18 g (0.4 mol) lithium hydride solution in 200 mL THF was added dropwise under cooling in a water bath, and the reaction was stirred at room temperature overnight , after detecting that there is no triphenylphosphine in the reaction system by HPLC, 67.6 g (0.36 mol) 1,2-dibromoethane was added dropwise to the reaction system, and the temperature was raised to reflux after the drop, and the solvent THF was recovered under reduced pressure to obtain a viscous solid , washed with dilute hydrochloric acid, water and methanol in sequence, recrystallized from a mixed solvent of chloroform and methanol to obtain 133.4 g of off-white solid product 1, 2-bisdiphenylphosphineethane, content 98% (HPLC), yield 93%, The melting point of the product is 139-140°C. Characterization results: GC-MS (EI, m / z): 398 (M ＋ ); 31 P NMR (300MHz, d 6 -DMSO), δ: -13.747; 1 H ...

example 3

[0020] Under the protection of argon, add solvent 200 mL THF and 104.9 g (0.4 mol) triphenylphosphine to the dry reactor, drop 3.18 g (0.4 mol) lithium hydride solution in 200 mL THF under cooling in a water bath, and then stir at room temperature After reacting overnight, after HPLC detected that there was no triphenylphosphine in the reaction system, 72.7 g (0.36 mol) of 1,3-dibromopropane was added dropwise to the reaction system. The solid was washed with dilute hydrochloric acid, water, and methanol in sequence, and then recrystallized from a mixed solvent of chloroform and methanol to obtain 132 g of off-white solid product 1, 3-bisdiphenylphosphinopropane, with a content of 98% (HPLC), and a yield of 89%. The melting point of the product is 63-65°C. Characterization results: GC-MS (EI, m / z): 412 (M ＋ ); 31 P NMR (300MHz, d 6 -DMSO), δ: -18.019; 1 H NMR (300MHz, CDCl 3 ), δ: 7.342-7.330 (s, 20H), 2.252-2.198 (t, 4H), 1.589-1.442 (m, 2H).

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Abstract

The invention discloses a method for synthesizing bis(diphenylphosphino)-alkane, belonging to the field of organic synthesis. The method comprises the following steps of: enabling triphenylphosphine to react with lithium hydride to generate a lithium diphenylphosphide intermediate under anhydrous and anoxybiotic conditions, and then directly reacting with dibromoalkane to synthesize a bis(diphenylphosphino)-alkane compound. According to the method disclosed by the invention, the intermediate generated during the preparation of lithium diphenylphosphide by using the lithium hydride has no affects on follow-up reaction, the reaction process is optimized, the reaction is easier to control, the separation cost is reduced, and the method is more suitable for industrial production.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a synthesis method of a class of organic phosphine compounds, and is especially suitable for bis(diphenylphosphine)alkane compounds. Background technique [0002] Bis(diphenylphosphine)alkanes are an important class of intermediates and catalyst ligands, which can be reacted with transition metal compounds to produce homogeneous catalysts. They are widely used in the field of industrial catalysis, especially in coupling reactions in the field of organic synthesis. Coupling reaction is an effective method for forming C-C, C-N, C-S bonds in organic synthesis, and it has a very wide range of applications in the synthesis of natural products, functional materials, drugs, liquid crystal molecules and biologically active compounds. [0003] At present, there have been a large number of literature reports on the research on bis(diphenylphosphine) alkane compounds, and U.S. Patent 4,618,72...

Claims

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Application Information

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IPC IPC(8): C07F9/50
Inventor 杨振强杨瑞娜王中锋崔富民冯培培周铎张鹏可
Owner 河南惠成新材料有限公司
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