Synthesis process of bis (tri-tert-butylphosphine) palladium (0)

Abstract

The invention relates to a synthesis process of bis (tri-tert-butylphosphine) palladium (0), which comprises the following steps: reacting in an N,N-dimethyl formamide solvent by taking a palladium substrate and tri-tert-butylphosphine in the mol ratio of 1:2-4 as the main raw materials to generate the bis (tri-tert-butylphosphine) palladium (0) at 20-40 DEG C for 2-4 hours, wherein the reaction formula is as follows: Pd2(dba)3.CHCl3+4P(t-Bu)3, 2Pd[(t-Bu)3P]2+3dba+CHCl3Pd(PPh3)4+2P(t-Bu)3 and Pd[(t-Bu)3P]2+4PPh3. Because tris (dibenzylideneacetone) dipalladium (0) chloroform adducts and tetrakis (triphenylphosphine) palladium (0) are relatively easily obtained raw materials, the process has the characteristics of higher operability, easier commercial production, simple preparation technology, wide raw material sources, low cost, high yield and the like.

Description

technical field

[0001] The invention relates to a synthesis process of bis(tri-tert-butylphosphine)palladium(0), which belongs to the technical field of pharmaceutical and chemical synthesis. Background technique

[0002] Since the 1980s, palladium-catalyzed homogeneous coupling reactions have been increasingly used in pharmaceutical and chemical industries. A large number of drugs are prepared by homogeneously catalyzed coupling reactions. Among various palladium catalysts, bis(tri-tert-butylphosphine)palladium(0), as an emerging third-generation palladium organocatalyst, exhibits excellent performance in various coupling reactions. Therefore, this catalyst plays an extremely important role in basic chemical industry and pharmaceutical chemical industry. With the rapid development of domestic pharmaceutical and chemical industries, the domestic demand for bis(tri-tert-butylphosphine)palladium(0) is increasing day by day.

[0003] There are several literatures related to ...

Examples

Embodiment 1

[0018] In a vacuum glove box, 7 mmol of tris(dibenzylideneacetone) dipalladium (0) chloroform adduct, 31.2 mmol of tri-tert-butylphosphine and 200 mL of anhydrous N,N-dimethylformamide were added to a 500 mL reaction flask, The reaction mixture was stirred at 30°C for 3h, filtered, and the filter cake was washed with N,N-dimethylformamide, dissolved in n-hexane, filtered, and the filtrate was concentrated to obtain white crystal bis(tri-tert-butylphosphine) Palladium (0), the yield is 2.5g, the yield is 70%; the content of Pd element is 20.5% as measured by atomic absorption.

Embodiment 2

[0020] The reaction steps are the same as in Example 1, except that the reaction temperature is 40° C., the reaction time is 4 hours, the post-treatment operation is the same as in Example 1, and the product yield is 65.5%.

Embodiment 3

[0022] In a vacuum glove box, 10mmol tetrakis(triphenylphosphine) palladium (0), 22mmol tri-tert-butylphosphine and 200mL anhydrous N,N-dimethylformamide in a 500mL reaction bottle, the reaction mixture was stirred at room temperature for 3h , filtered, the filter cake was washed with N, N-dimethylformamide, dissolved in n-hexane, filtered, the filtrate was distilled under reduced pressure, filtered after cooling to obtain 0.6g white crystals, the yield was 11%, and the Pd was measured by atomic absorption The element content is 20.6%.

technical field

[0001] The invention relates to a synthesis process of bis(tri-tert-butylphosphine)palladium(0), which belongs to the technical field of pharmaceutical and chemical synthesis. Background technique

[0002] Since the 1980s, palladium-catalyzed homogeneous coupling reactions have been increasingly used in pharmaceutical and chemical industries. A large number of drugs are prepared by homogeneously catalyzed coupling reactions. Among various palladium catalysts, bis(tri-tert-butylphosphine)palladium(0), as an emerging third-generation palladium organocatalyst, exhibits excellent performance in various coupling reactions. Therefore, this catalyst plays an extremely important role in basic chemical industry and pharmaceutical chemical industry. With the rapid development of domestic pharmaceutical and chemical industries, the domestic demand for bis(tri-tert-butylphosphine)palladium(0) is increasing day by day.

[0003] There are several literatures related to ...

Examples

Embodiment 1

[0018] In a vacuum glove box, 7 mmol of tris(dibenzylideneacetone) dipalladium (0) chloroform adduct, 31.2 mmol of tri-tert-butylphosphine and 200 mL of anhydrous N,N-dimethylformamide were added to a 500 mL reaction flask, The reaction mixture was stirred at 30°C for 3h, filtered, and the filter cake was washed with N,N-dimethylformamide, dissolved in n-hexane, filtered, and the filtrate was concentrated to obtain white crystal bis(tri-tert-butylphosphine) Palladium (0), the yield is 2.5g, the yield is 70%; the content of Pd element is 20.5% as measured by atomic absorption.

Embodiment 2

[0020] The reaction steps are the same as in Example 1, except that the reaction temperature is 40° C., the reaction time is 4 hours, the post-treatment operation is the same as in Example 1, and the product yield is 65.5%.

Embodiment 3

[0022] In a vacuum glove box, 10mmol tetrakis(triphenylphosphine) palladium (0), 22mmol tri-tert-butylphosphine and 200mL anhydrous N,N-dimethylformamide in a 500mL reaction bottle, the reaction mixture was stirred at room temperature for 3h , filtered, the filter cake was washed with N, N-dimethylformamide, dissolved in n-hexane, filtered, the filtrate was distilled under reduced pressure, filtered after cooling to obtain 0.6g white crystals, the yield was 11%, and the Pd was measured by atomic absorption The element content is 20.6%.