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Rhodium-diphosphine ligand tetrafluoroborate and preparation method thereof

A technology of boron tetrafluoride and phosphorus ligands, applied in the field of medicine and chemical industry, can solve the problems of inactivation of bisphosphorus ligands, easy oxidation, insufficient stability of trivalent phosphorus, etc.

Inactive Publication Date: 2017-05-10
PORTON FINE CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The main defect of this method is that the stability of trivalent phosphorus is insufficient, and it is easy to oxidize, resulting in the inactivation of the dual phosphorus ligand.

Method used

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  • Rhodium-diphosphine ligand tetrafluoroborate and preparation method thereof
  • Rhodium-diphosphine ligand tetrafluoroborate and preparation method thereof
  • Rhodium-diphosphine ligand tetrafluoroborate and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0014] Synthesis of embodiment 1 formula III compound

[0015] 1.1 Preparation of o-toluene magnesium bromide (formula II) solution

[0016] Add magnesium chips (42.1g, 1.75mol), tetrahydrofuran (133g) and 2-bromotoluene (15g) into a 2L three-neck flask. Turn on the stirring, turn on the condensed water, and turn on the nitrogen protection. Adding 1,2-dibromoethane to the reaction system initiates the Grignard reaction. After the reaction is initiated, slowly add a mixed solution of 2-bromotoluene (235g) and tetrahydrofuran (980g) dropwise under temperature control at 65-73°C, reflux for 2-3 hours, and take a sample for control. Under nitrogen protection, cool down to 10-30°C. stand-by.

[0017] The preparation of formula III compound

[0018] Under nitrogen protection, phenylphosphoryl dichloride (285 g) and tetrahydrofuran (2045 g) were added into a 5 L four-neck flask. Start stirring, lower the temperature to -90~-70°C, and add o-toluenemagnesium bromide (Formula II) ...

Embodiment 2

[0019] The preparation of embodiment 2 formula IV compound

[0020] 2.1 Preparation of D-menthol toluene solution

[0021] Add 92.5g (1.59eq) D-menthol and 418.3g toluene to a 1L three-necked flask, stir, raise the temperature to 105-115°C (reflux), and steam 15%-30% of toluene at normal pressure, then cool down to 10 ~ 30 ° C, to obtain D-menthol toluene solution.

[0022] Synthesis of Formula IV Compounds

[0023] Add 85.3g (1.0eq) of the compound of formula III obtained in Example 1 and 501.6g of dichloromethane into a 2L reaction flask, stir for 10-20 minutes, control the temperature at 15-25°C, and add dropwise 95.1g (2.02) of grass acid chloride, reacted overnight. The temperature was lowered to -85~-70°C, and the D-menthol toluene solution obtained in Example 2.1 was added dropwise. After the reaction was completed, the temperature was raised to room temperature, 399.2 g of tert-butanol was added, and the temperature was continued to rise to 60-65° C. to react for 3...

Embodiment 3

[0026] The synthesis of embodiment 3 formula VI compound

[0027] 3.1 Preparation of formula V toluene solution

[0028] Add 49.2g (1.0eq) of the compound of formula IV obtained in Example 2 and 350.0g of toluene to a 1L reaction flask, start stirring, raise the temperature to 115-125°C under nitrogen protection, and reflux to remove 10%-20% of toluene. Under the protection of nitrogen, the temperature was lowered to 10-30°C, and 173.7g (6.0eq) of trichlorosilane was added. Raise the temperature to 50-60°C and react for 12-16 hours, and take samples for control. After passing the test, the temperature is lowered to 10-30°C under the protection of nitrogen. Then the reaction liquid was slowly added dropwise into 1140 g of 25% sodium hydroxide solution, allowed to stand for stratification, extracted with toluene, dried over anhydrous magnesium sulfate, filtered and drained, and the filtrate and washing liquid were set aside.

[0029] The preparation of formula VI compound

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Abstract

The invention discloses a rhodium-diphosphine ligand tetrafluoroborate and a preparation method thereof. According to the method, quinquevalent phenylphosphonyl dichloride is used as a starting raw material; firstly, quinquevalent phosphoryl compounds are prepared; then, a chiral quinquevalent phosphoryl compound is obtained through kinetic resolution; the unstable trivalent phosphorus is avoided; meanwhile, the optical purity of the quinquevalent phosphorus is improved; the EE value can reach 97 or higher; the sufficient space is remained for the optical purity reduction due to subsequent quinquevalent phosphorus reduction and coupling, so that the purity and the yield of the prepared diphosphine ligand are very high; further, the rhodium-diphosphine ligand tetrafluoroborate prepared from the diphosphine ligand has high activity and good optical selectivity.

Description

technical field [0001] The invention belongs to the field of medicine and chemical industry. Background technique [0002] Rhodium-phosphorous ligand catalysts have been widely used in asymmetric hydrogenation. The catalyst rhodium-bisphosphorus ligand boron tetrafluoride salt involved in the invention can be used for the preparation of an anticancer drug intermediate. The preparation of such catalysts or analogues currently reported is mainly based on trivalent phosphorus-containing dichlorophenylphosphorus as raw material, in the presence of Grignard reagent, borane-tetrahydrofuran, through menthol chiral resolution and then coupling to obtain the corresponding The chiral double phosphorus ligand compound is finally complexed with cyclooctadiene rhodium and boron tetrafluoride to form a salt. The reaction process is shown in the following formula. [0003] [0004] The chiral selectivity of the double phosphorus ligand-rhodium boron tetrafluoride catalyst is mainly de...

Claims

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Application Information

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IPC IPC(8): C07F15/00
CPCC07F15/0073
Inventor 彭焕庆徐平洲谈小兵杨格鉴陶文春冯登捷常虎邹卫
Owner PORTON FINE CHEM