Preparation method of O-diphenylphosphine benzoic acid

A technology of diphenylphosphine and benzoic acid is applied in the field of preparation of organic phosphine ligands, which can solve the problems of consuming sodium diphenylphosphine, low yield, low yield and the like, so as to improve reaction yield and reduce production Cost, effect of suppressing side effects

Inactive Publication Date: 2013-09-25
常州化工研究所有限公司
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  • Abstract
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Problems solved by technology

The deficiency of this method is: (1) yield is low, only 49%
(2) The use of liquid ammonia as a solvent not only has very harsh reaction conditions, but also has great harm to the environment and people, so it is not suitable for industrial production
The deficiency of this method is: the yield is not high equally, only 50%, and in fact according to the method of this document, the applicant also all can't reach the yield of 50% through repeated experiments
[0005] The reasons why the yields of the above two methods are not high mainly contain the following two aspects: (1) on the one hand, since sodium diphenylphosphine (lithium) is an organic base, it can be coupled with O-chlorobenzoic acid In add

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  • Preparation method of O-diphenylphosphine benzoic acid

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Embodiment 1）

[0019] The preparation method of the O-diphenylphosphine benzoic acid of the present embodiment has the following steps:

[0020] ①Under the protection of nitrogen, add 2.24g of lithium metal (0.32mol), 41.96g of triphenylphosphine (0.16mol) and 320mL of 2-methyltetrahydrofuran organic solvent into a 1L three-necked flask. After 5min, the reaction system The color turns red with slight exotherm, and the cracking reaction is carried out at 25±2°C for 3 hours, the color of the solution turns dark red, the metal lithium disappears completely, and diphenylphosphinelithium and phenyllithium are generated.

[0021] ②At a temperature of 25±2°C, slowly drop 16.2g of diisopropylamine (0.16mol) into a three-necked flask within 30min~60min, and keep it warm until the phenyl lithium reaction in the reaction system monitored by HPLC is complete .

[0022] ③Under the protection of nitrogen, cool in an ice-water bath to 5±2°C, and slowly drop 27.3g of methyl O-chlorobenzoate (0.16mol) into ...

Embodiment 2～ Embodiment 5）

[0026] The preparation method of each embodiment is basically the same as that of Example 1, except that see Table 1.

[0027] Table 1

[0028]

[0029]

[0030] .

Embodiment 6）

[0032] The preparation method of the present embodiment is basically the same as that of Example 1, except that step ④:

[0033] ④ After the reaction, the reaction liquid was evaporated to remove the solvent under reduced pressure, and then 48 g of 20 wt % sodium hydroxide aqueous solution (containing 0.24 mol of sodium hydroxide) was added for hydrolysis under reflux for 3 h.

[0034] The hydrolyzed reaction solution was washed with 50 mL of dichloromethane, separated, and the organic layer was discarded (repeated washing twice).

[0035] The aqueous layer was acidified and neutralized with hydrochloric acid with a concentration of 36 wt%, and a pale yellow solid was precipitated. After purification with methanol, 34.84 g of O-diphenylphosphine benzoic acid was obtained, with a yield of 71.1% and a purity of 99.6% (HPLC).

[0036] As can be seen from Example 1 and Example 6, the purity of the hydrolyzed reaction solution after washing with dichloromethane can be increased by ...

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Abstract

The invention discloses a preparation method of O-diphenylphosphine benzoic acid. The preparation method comprises the following steps of: (1) carrying out cracking reaction on alkali metal and triphenylphosphine in an organic solvent to generate diphenylphosphine alkali metal salt and phenyl alkali metal salt; (2) slowly adding diisopropylamine, and enabling diisopropylamine to react with the phenyl alkali metal salt completely; (3) slowly adding O-chlorobenzol formate or O-bromobenzol formate, and enabling the diphenylphosphine alkali metal salt and the O-chlorobenzol formate or the O-bromobenzol formate to carry out coupling reaction and generate O-diphenylphosphino benzoate; (4) firstly hydrolyzing under the alkaline condition, obtaining O-diphenylphosphino sodium benzoate, acidizing and neutralizing under the acid condition, and obtaining the O-diphenylphosphine benzoic acid. The preparation method disclosed by the invention has the advantages that phenyllithium produced by cracking is completely reacted by adding the diisopropylamine, so that the generation of side reaction is effectively suppressed, and the reaction yield is greatly increased; since the triphenylphosphine is adopted as a reaction material, compared with the chlorodiphenylphosphine, the production cost is greatly reduced.

Description

technical field [0001] The invention relates to a preparation method of an organic phosphine ligand, in particular to a preparation method of O-diphenylphosphine benzoic acid. Background technique [0002] O-diphenylphosphine benzoic acid is a water-soluble organic phosphine ligand, which can form a water-soluble phosphine ligand catalyst with transition metals such as palladium and rhodium. [0003] Hoots etc. disclose a kind of preparation method of O-diphenylphosphine benzoic acid in "Inorganic Syntheses" 1982 the 21st volume 178~179 pages, the raw material that this method adopts is metal sodium, triphenylphosphine and O-chloro Benzoic acid, first use liquid ammonia as a solvent, use metal sodium to crack triphenylphosphine to obtain sodium diphenylphosphine and phenylsodium, then react sodium diphenylphosphine with O-chlorobenzoic acid to generate O-diphenylphosphine benzoic acid. The deficiency of this method is: (1) yield is low, only 49%. (2) The use of liquid amm...

Claims

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Application Information

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IPC IPC(8): C07F9/50
Inventor 吴涛徐新马丽
Owner 常州化工研究所有限公司
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