Preparing method for di-tertiary butyl-4-dimethylamino phenylphosphine and bis(di-tertiary butyl-4-dimethylamino phenylphosphine) palladium chloride

A technology of dimethylaminophenylphosphine and di-tert-butylphosphine, which is applied in the field of preparing di-tert-butyl-4-dimethylaminophenylphosphine and palladium dichloride, and can solve the problem of high product prices and preparation Problems such as high cost and low product purity have achieved the effect of being suitable for large-scale industrial production, reducing preparation costs and high product purity

Active Publication Date: 2016-01-13
BEIJING GREENCHEM TECH
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AI Technical Summary

Problems solved by technology

This method has few reaction steps and is relatively easy to control, but the disadvantage is that the loss of palladium is increased because the di-tert-butyl-4-dimethylaminophenylphosphine ligand is not purified, and the obtained product has low purity and low quality. Poor, product yield is only about 70%
And this method needs to use expensive palladium catalysts such as tris(dibenzylideneacetone) dipalladium in the process of preparing di-tert-butyl-4-dimethylaminophenylphosphine ligand, so the preparation cost of this method is relatively high. High, resulting in high product prices

Method used

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  • Preparing method for di-tertiary butyl-4-dimethylamino phenylphosphine and bis(di-tertiary butyl-4-dimethylamino phenylphosphine) palladium chloride
  • Preparing method for di-tertiary butyl-4-dimethylamino phenylphosphine and bis(di-tertiary butyl-4-dimethylamino phenylphosphine) palladium chloride
  • Preparing method for di-tertiary butyl-4-dimethylamino phenylphosphine and bis(di-tertiary butyl-4-dimethylamino phenylphosphine) palladium chloride

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0062] Preparation of di-tert-butyl-4-dimethylaminophenylphosphine

[0063] Replace the reaction bottle with a nitrogen atmosphere, add 32g of di-tert-butylphosphine and 200mL of toluene into a 1L reaction bottle, start magnetic stirring, add 96mL of 2.5M n-butyllithium dropwise at -10°C, and raise the temperature to 50°C for 12 hours , the temperature of the reaction solution was lowered to -10°C, 200mL of toluene solution of 40g N,N-dimethyl-p-bromoaniline was added dropwise, raised to 50°C and reacted for 12 hours, after which the reaction solution was lowered to room temperature, and dropped in an ice-water bath Add 10g of triethylamine aqueous solution 100mL, desolventize the upper organic phase under nitrogen protection, and distill under reduced pressure to collect 49.2g of di-tert-butyl-4-dimethylaminophenylphosphine at 120°C (15mmHg).

Embodiment 2

[0065] Preparation of bis(di-tert-butyl-4-dimethylaminophenylphosphine)palladium chloride

[0066] Add 10g (1,5-cyclooctadiene) palladium dichloride to a 500mL reaction, replace the reaction bottle with a nitrogen atmosphere, and add di-tert-butyl-4-dimethylaminophenylphosphine 19.6 prepared in Example 1 g and anhydrous tetrahydrofuran 200mL, stirred at room temperature for 16 hours, a solid was precipitated, filtered and dried to obtain a light yellow powder product bis(di-tert-butyl-4-dimethylaminophenylphosphine)palladium chloride 24.1g, the yield was 97% (The yield is calculated based on (1,5-cyclooctadiene) palladium dichloride). The purity of the product obtained by XY-1A intelligent elemental analyzer is 99.8%.

[0067] figure 1 and figure 2 Respectively the two (di-tert-butyl-4-dimethylaminophenylphosphine) palladium chloride prepared 1 H-NMR spectrum and 31 P-NMR spectrum, the characterization results are as follows: 400MHz- 1 H-NMR (CDCl 3 ): δ=1.57-1.61 (m, 3...

Embodiment 3

[0070] Replace the reaction bottle with a nitrogen atmosphere, add 31g of di-tert-butylphosphine and 200mL of xylene into a 1L reaction bottle, start magnetic stirring, add 90mL of 2.5M n-butyllithium dropwise at 0°C, and raise the temperature to 55°C to react 8 hour, the temperature of the reaction solution was lowered to -5°C, and 200 mL of a xylene solution of 40 g N,N-dimethyl-p-bromoaniline was added dropwise. 100 mL of 6 g of ammonium chloride aqueous solution was added dropwise, and the upper organic phase was desolvated under nitrogen protection, and distilled under reduced pressure to collect 48 g of di-tert-butyl-4-dimethylaminophenylphosphine at 120° C. (15 mmHg).

[0071] Add 10g (1,5-cyclooctadiene)palladium dichloride to another 500mL reaction, replace the reaction bottle with nitrogen atmosphere, add 19.6g di-tert-butyl-4-dimethylaminophenylphosphine and anhydrous Methyltetrahydrofuran 200mL, stirred at room temperature for 12 hours, solids were precipitated, fi...

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Abstract

The invention provides a preparing method for di-tertiary butyl-4-dimethylamino phenylphosphine. Di-tertiary butylphosphine is subjected to low-temperature lithiation under shielding of inert gas and then reacts with N,N-dimethyl p-chloroaniline, and di-tertiary butyl-4-dimethylamino phenylphosphine is obtained. According to the preparing method, di-tertiary butyl-4-dimethylamino phenylphosphine is purified after a quenching reaction. The invention further provides a preparing method for bis(di-tertiary butyl-4-dimethylamino phenylphosphine) palladium chloride. Di-tertiary butyl-4-dimethylamino phenylphosphine obtained through the preparing method is further subjected to complexation with (1,5-cyclooctadiene) palladium dichloride or bispalladium dichloride. A di-tertiary butyl-4-dimethylamino phenylphosphine ligand is prepared through the novel method, purified and then subjected to palladium complexation, and the preparing yield is greatly increased; meanwhile, the loss of palladium is reduced, the preparing cost is greatly reduced, and the obtained products are high in purity and good in quality.

Description

technical field [0001] The invention relates to a method for preparing di-tert-butyl-4-dimethylaminophenylphosphine and a method for preparing bis(di-tert-butyl-4-dimethylaminophenylphosphine)palladium chloride, which belong to the technical field of organic synthesis . Background technique [0002] Bis(di-tert-butyl-4-dimethylaminophenylphosphine)palladium chloride plays an important role in modern organic synthesis and practical application. It is mainly used as a catalyst in coupling reactions such as Suzuki, in liquid crystal materials, It has a very wide range of applications in the synthesis of substances such as photofunctional complexes. Di-tert-butyl-4-dimethylaminophenylphosphine is used as an intermediate ligand in the preparation process of bis(di-tert-butyl-4-dimethylaminophenylphosphine)palladium chloride. In practical applications, the purity and quality of bis(di-tert-butyl-4-dimethylaminophenylphosphine)palladium chloride are generally high. [0003] So f...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/50C07F15/00
Inventor 饶志华宫宁瑞
Owner BEIJING GREENCHEM TECH
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