Preparation method of phosphinobenzene compound

A compound and chlorine compound technology, applied in the field of preparation of phosphine and benzene compounds, can solve problems affecting product purity and quality, inconvenient scale-up production operation, troublesome post-processing, etc., to achieve guaranteed purity and quality, high yield, and easy operation Effect

Active Publication Date: 2016-08-17
BEIJING GREENCHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the yield of this method is not too high, only about 80%; and cuprous chloride is used as a catalyst, aftertreatment needs to be washed repeatedly with ammonia water to remove

Method used

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  • Preparation method of phosphinobenzene compound
  • Preparation method of phosphinobenzene compound
  • Preparation method of phosphinobenzene compound

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preparation example Construction

[0043] The preparation method of the present invention comprises:

[0044]

[0045] Under the protection of inert gas such as nitrogen, the bromobenzene compound of general formula (III), wherein R 1 , R 2 , R 3 , R 4 and R 5 The definition is as before, reacts with magnesium chips and organic solvents such as anhydrous tetrahydrofuran (THF) or anhydrous methyl tetrahydrofuran to make the bromobenzene compound Grignard reagent of general formula (II), wherein R 1 , R 2 , R 3 , R 4 and R 5 As defined above, reflux for 2-10 hours; Add tetrakis(triphenylphosphine) palladium at room temperature, stir for 10 minutes to 3 hours, add dropwise the phosphine chloride compound of general formula (IV) at room temperature, wherein R 6 and R 7 The definition is as before, reflux reaction 1-10 hour; Under ice-water bath, dropwise add saturated weak acid and weak base salt solution such as saturated ammonium chloride aqueous solution to the reaction solution to quench the reactio...

Embodiment 1

[0059] Preparation of di-tert-butylphenylphosphine

[0060]

[0061] Under the protection of nitrogen, in a 1L three-necked flask, a Grignard reagent was made from 27g of bromobenzene, 5g of magnesium chips and 400mL of anhydrous THF, refluxed for 2 hours, cooled to room temperature, added 2g of tetrakis(triphenylphosphine) palladium, After stirring for 10 minutes, 33 g of di-tert-butylphosphine chloride was added dropwise at room temperature, and the mixture was refluxed for 3 hours. In an ice-water bath, 200 mL of saturated ammonium chloride aqueous solution was added dropwise to the reaction solution to quench, the liquid was separated, the organic phase was desolvated, crystallized by adding methanol, and filtered to obtain 36 g of white di-tert-butylphenylphosphine, with a yield of 94.7%.

Embodiment 2

[0063] Preparation of 2-(di-tert-butylphosphine)biphenyl

[0064]

[0065] Under nitrogen protection, in a 1L three-neck flask, Grignard reagent was made from 40g of 2-bromobiphenyl, 5g of magnesium chips and 400mL of anhydrous THF, refluxed for 2 hours, cooled to room temperature, and 2g of tetrakis(triphenylphosphine ) palladium, stirred for 30 minutes, added dropwise the di-tert-butylphosphine chloride of 33g at room temperature, and refluxed for 2 hours. Add dropwise 200mL of saturated ammonium chloride aqueous solution to the reaction solution under an ice-water bath to quench, separate the liquids, desolventize the organic phase, add methanol to crystallize, and filter to obtain 49g of white 2-(di-tert-butylphosphine)biphenyl. 95.7%.

[0066] figure 1 and figure 2 The prepared 2-(di-tert-butylphosphine)biphenyl 1 H-NMR spectrum and 31 P-NMR spectrum, the characterization results are as follows:

[0067] 400MHz- 1 H-NMR (CDCl3): δ=1.1-1.2 (m, 18H); 7.8-7.9 (s, ...

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Abstract

The invention relates to a preparation method of a phosphinobenzene compound. The method is characterized in that a bromobenzene compound reacts with magnesium to prepare a Grignard reagent, and the Grignard reagent reacts with a chlorophosphine compound under the catalysis of tetrakis(triphenylphosphine)palladium to obtain the phosphinobenzene compound. The method concretely comprises the following steps: preparing the Grignard reagent from the bromobenzene compound, magnesium chips and an organic solvent under the protection of insert gas, and refluxing for 2-10h; adding tetrakis(triphenylphosphine)palladium at room temperature, stirring for 10min-3h, adding the chlorophosphine compound at room temperature in a dropwise manner, and carrying out a refluxing reaction for 1-10h; and adding an aqueous solution of saturated weakly-acidic and weakly-alkaline salt to the above obtained reaction solution in a dropwise manner in ice-water bath, carrying out liquid separation, removing the solvent from the obtained organic phase, adding an alcohol solvent for crystallizing, and filtering obtained crystals to obtain the phosphinobenzene compound. The preparation method has the advantages of great increase of the preparation yield, simple post-treatment, omitting of the repeated ammonia water washing process, preparation process simplification, and facilitation of large-scale industrial production.

Description

technical field [0001] The invention relates to a preparation method of phosphine and benzene compounds, belonging to the technical field of organic synthesis. Background technique [0002] Phosphine benzene compounds with the following general formula (I) [0003] [0004] Among them, R 1 , R 2 , R 3 , R 4 and R 5 independently represent a hydrogen atom, C 1 ~C 4 Alkyl, phenyl, one or more C 1 ~C 3 Alkyl substituted phenyl or -NR 1 R 2 , where R 1 and R 2 independently represent C 1 ~C 3 Alkyl; R 6 and R 7 independently represent tert-butyl or phenyl, and R 6 and R 7 It is the same substituent, and it is an important class of organic phosphine ligands, which play an important role in modern organic synthesis and practical applications. This type of compound can be used as a catalyst in coordination with palladium in coupling reactions such as Suzuki and Buchwald, as well as in reactions such as C-arylation and N-arylation. [0005] The existing method...

Claims

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Application Information

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IPC IPC(8): C07F9/50
CPCC07F9/5022C07F9/5068
Inventor 饶志华宫宁瑞
Owner BEIJING GREENCHEM TECH
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