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A kind of method for synthesizing di-tert-butylphosphine biphenyl compounds

A technology of di-tert-butylphosphine biphenyl and di-tert-butylphosphine, which is applied in the field of organic synthesis, can solve the problems of high equipment requirements, difficult post-processing, influence on reaction yield, etc., so as to optimize the reaction process and avoid the use of catalysts. , to avoid the effect of high operating requirements

Active Publication Date: 2020-12-04
HENAN ACADEMY OF SCI CHEM RES INST CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The main disadvantage of this method is that Grignard reagent is needed in the reaction, and the anhydrous and anaerobic operation in the reaction process requires high equipment requirements. In addition, there are a large amount of inorganic salts in the post-reaction treatment process, which makes the post-treatment difficult and affects the yield of the reaction.

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  • A kind of method for synthesizing di-tert-butylphosphine biphenyl compounds

Examples

Experimental program
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Effect test

Embodiment 1

[0016] Example 1: Synthesis of 2-(di-tert-butylphosphine)biphenyl

[0017] Under the protection of argon, add reaction solvent 1L toluene to dry reactor, then add di-tert-butylphosphine (146 g, 1 mol), o-dibromobenzene (236 g, 1 mol), bis[di-tert-butyl base (4-dimethylaminophenyl) phosphine] palladium (0) (6.4 g, 0.01 mol) and sodium carbonate (424 g, 4 mol), then heated to 100 ºC for 6 hours, until the reaction solution cooled to 20-30 ºC Finally, phenylboronic acid (122 g, 1 mol) was added directly to the system, and then heated to 80 ºC for 10 hours; then water was added to quench the reaction, extracted, dried, and the solvent was distilled off under reduced pressure, and recrystallized in methanol to obtain 2 -(di-tert-butylphosphine)biphenyl 262 g, yield 88%. 31 P NMR (121 MHz, CDCl 3 ) δ 18.7; 1 H NMR (300 MHz, CDCl 3 ) δ7.98-7.86 (m, 1H), 7.40-7.22 (m, 8H), 1.16 (d, 18H, J = 11.6 Hz).

Embodiment 2

[0018] Example 2: Synthesis of 2-(di-tert-butylphosphino)-2',4',6'-triisopropylbiphenyl

[0019] Under the protection of argon, add the reaction solvent 1L toluene into the dry reactor, then add di-tert-butylphosphine (146 g, 1 mol), o-dibromobenzene (212 g, 0.9 mol), bis[di-tert-butyl (4-Dimethylaminophenyl)phosphine] palladium (0) (3.2 g, 0.005 mol) and sodium carbonate (530 g, 5 mol), then heated up to 80 ºC for 8 hours, and the temperature of the reaction solution was cooled to 20- After 30ºC, directly add 2,4,6-triisopropylphenylboronic acid (273 g, 1.1 mol) into the system, then raise the temperature to 100ºC for 12 hours; then add water to quench the reaction, extract, dry, and reduce pressure After distilling off the solvent, it was recrystallized in methanol to obtain 364 g of 2-(di-tert-butylphosphino)-2',4',6'-triisopropylbiphenyl with a yield of 86%. 31 P NMR (121 MHz, C 6 D. 6 )δ 21.4; 1 H NMR (300 MHz, C 6 D. 6 ) δ 7.85-7.74 (m, 1H), 7.33-7.24 (m, 1H), 7.14...

Embodiment 3

[0020] Example 3: Synthesis of 2-(di-tert-butylphosphine)-2'-methylbiphenyl

[0021] Under the protection of argon, add the reaction solvent 1L toluene into the dry reactor, then add di-tert-butylphosphine (146 g, 1 mol), o-dibromobenzene (212 g, 0.9 mol), bis[di-tert-butyl (4-Dimethylaminophenyl)phosphine] palladium (0) (3.2 g, 0.005 mol) and sodium carbonate (530 g, 5 mol), then heated to 80 ºC for 6 hours, after the reaction solution cooled to 20- After 30 ºC, directly add 2-methylphenylboronic acid (185g, 1.1 mol) to the system, then raise the temperature to 100 ºC for 10 hours; then add water to quench the reaction, extract, dry, and distill under reduced pressure to remove the solvent in methanol Recrystallization gave 281 g of 2-(di-tert-butylphosphine)-2'-methylbiphenyl with a yield of 90%. 31 P NMR (121 MHz, C 6 D. 6 ) δ 20.8; 1 H NMR (300MHz, CDCl 3 ) δ 7.90-7.84 (m, 1H), 7.37-7.08 (m, 7H), 2.12 (s, 3H), 1.17 (d, J=11.5 Hz, 9H), 1.16 (d, J=11.3 Hz, 9H) .

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Abstract

The invention discloses a method for synthesizing a di-tert-butylphosphine biphenyl compound, and belongs to the field of organic synthesis. In an anhydrous and anaerobic atmosphere, di-tert-butylphosphine is taken as a raw material and reacts with o-dibromobenzene under the effect of a palladium catalyst, and then coupling with arylboronic acid is conducted to obtain the di-tert-butylphosphine biphenyl compound. Compared with the prior art, the reaction steps of the method are less, operation is easy, the yield is high, and the method is more suitable for industrial production.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a synthesis method of a class of organic phosphine compounds, in particular to a synthesis method of di-tert-butylphosphine biphenyl compounds. Background technique [0002] With the development of organometallic chemistry, transition metal-catalyzed coupling reactions for the synthesis of C-C, C-N and C-O bonds have become one of the most effective synthetic methods. During the development of coupling reactions, ligands have attracted great attention because they can activate transition metals to become more effective catalysts. Although a large number of different types of ligands have been used in transition metal-catalyzed reactions, phosphine-containing compounds with different structures and functional groups are still the most important type of ligands, and their steric effects and electronic properties can be changed. By fine-tuning the properties of the resulting compound...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/50
CPCC07F9/5022
Inventor 陈辉赵顺伟李云飞周铎孙敏青杨振强张金强杨瑞娜段征
Owner HENAN ACADEMY OF SCI CHEM RES INST CO LTD