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Method for preparing biphenyl diphosphine ligand

A technology of diphosphine ligand and biphenyl, which is applied in the field of synthesis of organic compounds, can solve the problems of cumbersome post-treatment, low yield, oxidation of phosphine ligand, etc., and achieve the effect of simple operation and cheap and easy-to-obtain reagents

Active Publication Date: 2011-04-13
成都欣华源科技有限责任公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The post-treatment of this method is cumbersome, the yield is low, it needs to be carried out at a higher temperature, and it is easy to cause the oxidation of the phosphine ligand

Method used

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  • Method for preparing biphenyl diphosphine ligand
  • Method for preparing biphenyl diphosphine ligand
  • Method for preparing biphenyl diphosphine ligand

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Add 50 parts of triphenylphosphine and 260 parts of tetrahydrofuran into the dry reaction bottle under the protection of nitrogen, stir and dissolve, add 14 parts of metal sodium, heat, stir and reflux for 12 hours. Cool to 0°C, add 15 parts of tert-butyl chloride dropwise, heat the reaction solution under reflux for 0.5h after addition, then cool to 0°C again, add dropwise 2,2'-dibromomethyl-1,1'- Biphenyl II (R = R 1 =R 2 =-H, X=Br) 20 parts and 20 parts of tetrahydrofuran in a mixed solution, add to room temperature and stir for 12h. The reaction solution was extracted, dried, and concentrated to obtain a crude product, which was recrystallized from absolute ethanol to obtain a white solid (BISBI), with a yield of 78%, Mp: 83.2-85.4°C.

[0027] 1 H NMR (CDCl 3 , 400MHz) δ7.53~7.00 (m, 28H), 3.26~3.02 (m, 4H).

[0028] 31 P NMR (CDCl 3 , 161.7MHz) δ-10.56(s).

Embodiment 2

[0030] Add 60 parts of triphenylphosphine and 290 parts of tetrahydrofuran into a dry reaction flask under the protection of nitrogen, stir and dissolve, add 20 parts of sodium metal, and 3.0 parts of naphthalene, heat and stir to reflux for 2 hours. Cool to 0°C, add 19 parts of tert-butyl chloride dropwise, heat the reaction solution under reflux for 0.5h after addition, then cool to 0°C again, add dropwise 2,2′-dimethylsulfonate-1,1 '-biphenyl II (R = R 1 =R 2 =-H, X=-CH 2 OSO 2 CH 3 ) 30 parts and THF 30 parts of the mixed solution, after adding, it was raised to room temperature and stirred for 12h. The reaction solution was extracted, dried, and concentrated to obtain a crude product, which was recrystallized from isopropanol to obtain a white solid (BISBI), with a yield of 80%, Mp: 84.2-86.2°C.

[0031] 1 H NMR and 31 The P NMR spectrum is consistent with Example 1.

Embodiment 3

[0033] Add 50 parts of triphenylphosphine and 295 parts of 2-methyltetrahydrofuran into the dry reaction bottle under the protection of nitrogen, stir and dissolve, add 3.3 parts of metal lithium, and stir at room temperature for 12 hours. Cool to 0°C, add 17 parts of tert-butyl chloride dropwise, heat the reaction solution under reflux for 0.5h after addition, then cool to 0°C again, add dropwise 2,2′-di-p-toluenesulfonate methyl-1, 1'-biphenyl II (R = R 1 =R 2 =-H, X=-CH 2 OSO 2 PhCH 3 -p) A mixed solution consisting of 40 parts of 2-methyltetrahydrofuran and 40 parts of 2-methyltetrahydrofuran was added and raised to room temperature and stirred for 6 hours. The reaction solution was extracted, dried, and concentrated to obtain a crude product, which was recrystallized from acetone to obtain a white solid (BISBI), with a yield of 75%, Mp: 83.8-86.1°C.

[0034] 1 H NMR and 31 The P NMR spectrum is consistent with Example 1.

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Abstract

The invention discloses a new method for preparing a biphenyl diphosphine ligand 2,2'-diphenylphosphinomethyl-1,1'-biphenyl (BISBI) and derivatives thereof. The method is characterized by comprising the following steps: (1) under the protection of inert gases, adding 40-60 parts of triphenylphosphine and 250-360 parts of ether solvents to a reaction flask, stirring the mixture to dissolve the mixture and adding 3-20 parts of alkali metals and 0-5 parts of electron-rich aromatics to the reaction flask to react for 2-24 hours at 20-120 DEG C to prepare a diphenulphosphine metal compound and a phenyl metal compound; (2) dropwise adding 15-20 parts of tertiary butyl chloride to the reaction solution to remove the generated phenyl metal compound; and (3) dropwise adding the solution formed by 15-40 parts of 2,2'-disubstituted methyl-1,1'-biaryl compound and 20-40 parts of ether solvent to the reaction solution with phenyl metal compound removed to react for 6-24 hours at 0-40 DEG C and carrying out extraction, drying, concentration and recrystallization to obtain the diphosphine ligand 2,2'-diphenylphosphinomethyl-1,1'-biphenyl (BISBI) and the derivatives thereof. The method has the characteristics of cheap and easily obtained raw materials and mild reaction conditions, is simple and convenient for operation, and is easy to realize industrial production.

Description

technical field [0001] The invention relates to a preparation method of biphenyl bisphosphine ligand 2,2'-diphenylphosphinomethyl-1,1'-biphenyl (BISBI) and its derivatives, belonging to the field of organic compound synthesis. Background technique [0002] 2,2′-Diphenylphosphinomethyl-1,1′-biphenyl (BISBI) and its derivatives are excellent bisphosphine ligands, which show good activity in the hydroformylation of alkenes Catalytic activity and selectivity. [0003] U.S. Patents US4694109 and US8701362 describe the use of butyllithium and diphenylphosphine hydrogen at -70 ° C to prepare diphenylphosphine lithium, which is combined with 2,2'-halomethyl-1,1'-biphenyl Method of reaction preparation (BISBI). U.S. Patent US4879416 and European Patent EP0375576 ​​use metal lithium and triphenylphosphine to react at room temperature to prepare diphenylphosphine lithium, and then react with 2,2'-dihalomethyl-1,1'-biphenyl to prepare BISBI. European patents EP0491240 and EP0326286 u...

Claims

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Application Information

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IPC IPC(8): C07F9/50
Inventor 黄建李贤均
Owner 成都欣华源科技有限责任公司
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