Synthesis method of ortho-benzyl diphosphine compound

A synthesis method and technology of phosphine compounds, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, compounds of Group 5/15 elements of the periodic table, etc., can solve low yield and unfavorable industrialization Production and other issues, to achieve high yield, improve safety and controllability, mild and controllable reaction conditions

Active Publication Date: 2021-03-16
JIANGSU SINOCOMPOUND CATALYST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Compared with the previous process, this reaction has milder reaction conditions, but the yield is very low by about 15%, which is not conducive to industrial production

Method used

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  • Synthesis method of ortho-benzyl diphosphine compound
  • Synthesis method of ortho-benzyl diphosphine compound
  • Synthesis method of ortho-benzyl diphosphine compound

Examples

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preparation example Construction

[0060] One embodiment of the present invention provides a method for synthesizing an ortho-benzyl bisphosphine compound, comprising the following steps:

[0061] In an organic solvent, α,α'-dihalogenated o-xylene and dihydrocarbyl phosphine are subjected to a substitution reaction under the action of a metal salt catalyst, a ligand and a basic compound to obtain an ortho-benzyl bisphosphine compound.

[0062] Wherein, the metal in the metal salt catalyst is a transition metal, and the ligand can coordinate with the metal salt catalyst.

[0063] Dihydrocarbylphosphine is , R is independently selected from: alkyl, aryl or cycloalkyl.

[0064] In some embodiments, metal salt catalysts and ligands can also be added in a pre-coordinated form.

[0065] The structural formula of α,α'-dihalogenated o-xylene is as follows:

[0066]

[0067] Wherein, X is a halogen, further X is independently selected from Cl or Br.

[0068] The reaction formula of this synthetic method is as fo...

Embodiment 1

[0088] This example is a synthesis method of ortho-benzyl bisphosphine compounds, specifically the synthesis steps of bis(diamantylphosphine)-o-xylene. The whole process is carried out in an anhydrous and oxygen-free environment, and the steps are as follows:

[0089] Under Ar atmosphere, add o-dibromobenzyl (300g, 1eq) to 2L toluene solution to dissolve it completely, then add diadamantyl phosphine hydrogen (687g, 2eq), add metal salt catalyst Pd(OAc) 2 (7.6g, 3%eq), ligand DIPPF (15.7g, 3.3%eq) and tBuONa (279g, 2.5eq), heated to reflux, the solid gradually dissolved, reacted for 4h, TLC monitored the reaction was complete, stopped the reaction and cooled to room temperature .

[0090] Remove the solvent by distillation under reduced pressure, then add dichloromethane to dissolve the solid completely (1L), wash with water (1L×3 times), wash with saturated sodium chloride solution (1L×3 times), dry over anhydrous sodium sulfate, filter, and normal pressure The solvent was di...

Embodiment 2

[0092] This embodiment is a synthesis method of ortho-benzyl bisphosphine compounds, specifically the synthesis steps of bis(diphenylphosphine)-o-xylene. The whole process is carried out in an anhydrous and oxygen-free environment, and the steps are as follows:

[0093] Under Ar atmosphere, add o-dibromobenzyl (300g, 1eq) to 2L toluene solution to dissolve it completely, then add diphenylphosphine hydrogen (423g, 2eq), add metal salt catalyst Pd(OAc) 2 (7.6g, 3%eq), ligand DIPPF (15.7g, 3.3%eq) and tBuONa (279g, 2.5eq), heated to reflux, the solid gradually dissolved, reacted for 4h, TLC monitored the reaction was complete, stopped the reaction and cooled to room temperature .

[0094] Remove the solvent by distillation under reduced pressure, then add dichloromethane to dissolve the solid completely (1L), wash with water (1L×3 times), wash with saturated sodium chloride solution (1L×3 times), dry over anhydrous sodium sulfate, filter, and normal pressure The solvent was dist...

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Abstract

The invention relates to a synthesis method of an ortho-benzyl diphosphine compound, which comprises the following steps: in an organic solvent, carrying out substitution reaction on alpha, alpha'-dihalogenated ortho-xylene and dialkyl phosphine under the actions of a metal salt catalyst, a ligand and an alkaline compound to obtain the ortho-benzyl diphosphine compound, wherein metal in the metalsalt catalyst is transition metal, and the ligand can be coordinated with the metal salt catalyst; dialkyl phosphine is PHR2, and R is independently selected from alkyl, aryl or naphthenic base. According to the synthetic method of the ortho-benzyl diphosphine compound, the added ligand can be coordinated with the metal salt catalyst, and through coordination catalysis, the forward proceeding of the reaction under the alkaline condition of the alkaline compound is greatly promoted; meanwhile, a lithium reagent or a Grignard reagent with high risk is reduced or not used, the reaction conditionsare mild and controllable, the yield is high, industrialization is easy, and environmental protection is achieved.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing an ortho-benzyl bisphosphine compound. Background technique [0002] Phosphine generally refers to phosphine (PH 3 ) and its hydrogen atoms are partially or completely replaced by hydrocarbon groups to form a general term for organic compounds. Organic phosphine generally refers to trivalent organic phosphine compounds in which part or all of the hydrogen atoms in the phosphine molecule are substituted by hydrocarbon groups, and can be divided into primary phosphine RPH 2 (A hydrocarbyl phosphine), secondary phosphine R 2 PH (dihydrocarbylphosphine) and tertiary phosphine R 3 P (trihydrocarbyl phosphine) three types. [0003] The ortho-benzyl bisphosphine compound is a very important class of phosphine ligands. It is not only a trihydrocarbylphosphine compound, but also a bisphosphine compound, which can form a catalytic system with a palla...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50B01J31/24B01J31/22
CPCB01J31/2213B01J31/2226B01J31/2295B01J31/2409B01J31/2414B01J2231/4277B01J2531/0225B01J2531/0238B01J2531/824B01J2531/827C07F9/5031C07F9/5072C07F9/5095
Inventor 徐丽湘孙明明郑晟敏
Owner JIANGSU SINOCOMPOUND CATALYST
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