Preparation method of diphosphorus ligand

A technology of phosphorus ligand and phosphorus pentachloride is applied in the field of preparation of double phosphorus ligands, and can solve the problems of complex process, high safety risk, difficult preservation and the like, and achieve the effects of easy control of process conditions, simple raw materials, and simple process.

Active Publication Date: 2022-08-02
JIANGSU SINOCOMPOUND CATALYST
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] However, technicians focus on the development of new chiral bisphosphine ligands and explore their specific mechanism of action, and little is involved in their synthesis and preparation. The traditional preparation process is complex and the reaction conditi

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  • Preparation method of diphosphorus ligand
  • Preparation method of diphosphorus ligand
  • Preparation method of diphosphorus ligand

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preparation example Construction

[0078] In the traditional process of preparing chiral double phosphorus ligands, the process is complicated, such as the following preparation route process:

[0079]

[0080]

[0081]

[0082] In the above-mentioned preparation process, it is necessary to first use chiral diol as raw material thionyl chloride to react to obtain a sulfoxide compound, and then the sulfoxide compound is reacted with a phosphorus-hydrogen intermediate. However, the phosphorus-hydrogen bond is very sensitive to water in the air, and it is difficult to It has a bad odor and high safety risk, and the reaction conditions are relatively harsh, which is not conducive to large-scale production.

[0083] Based on this, the technical personnel of the present application propose to improve the above-mentioned synthetic route to obtain a synthetic route that is relatively simple and can be reacted under milder conditions. body preparation method.

[0084] An embodiment of the present invention pro...

Embodiment 1~4

[0187] Compounds (1b) with different structures are synthesized in Examples 1 to 4, which are respectively denoted as compound (1b-1), compound (1b-2), compound (1b-3) and compound (1b-4). The structures are shown in Table 1. Show.

[0188] Specific steps are as follows:

[0189] The 3-L three-necked flask with the magneton was replaced three times with argon, then 1 mol of compound (1a) and methanol (1 L) were added, and cooled to 0°C under an ice-salt bath. Then, under stirring conditions, sodium borohydride (56 g, 1.5 mol) was added in batches, hydrogen was generated during the dropwise addition, and the temperature of the system was controlled not to be higher than 20 °C. After the dropwise addition, the reaction was stirred overnight, and then water (1 L ) to quench the reaction, spin dry methanol, extract with ethyl acetate (1 L×3), take the organic phase and wash with saturated brine, dry over anhydrous sodium sulfate, spin dry the solvent to obtain pure compound (1b)....

Embodiment 5~8

[0197] In Examples 5-8, the compounds (1b) prepared in Examples 1-4 were respectively used to prepare compound (1), and the prepared compounds (1) were denoted as compound (1-1), compound (1-2), compound (1-3) and compound (1-4). The specific steps are as follows: add 1 mol of compound (1b) to a 1 L there-necked flask with magnetic particles, cool to -5°C, and slowly add tribromide to the there-necked flask through a constant pressure dropping funnel under stirring conditions. Phosphorus (600 g, 1.2 mol), the temperature of the system was controlled not to be higher than 5 °C during the dropwise addition. After the dropwise addition, the reaction temperature was gradually raised to room temperature, and the reaction was stirred overnight, and then the reaction solution was poured into 1 L of ice water , the organic phase was washed with 96% concentrated sulfuric acid, water, saturated sodium carbonate and brine respectively, dried over anhydrous sodium sulfate, and then collec...

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Abstract

The invention relates to a preparation method of a diphosphorus ligand, which comprises the following steps: carrying out Grignard reaction on a compound (1) and magnesium metal to prepare a compound (2); carrying out first substitution reaction on the compound (3) and phosphorus pentachloride to prepare a compound (4); then carrying out second substitution reaction on the compound (2) and a compound (4) to prepare a compound (5); finally, the compound (5) is subjected to a reduction reaction, and the diphosphine ligand shown in the formula (6) is obtained. The process is simple, raw materials are simple and easy to obtain, the process conditions in the preparation process are easy to control, phosphorus-hydrogen intermediates do not need to be prepared, the diphosphine ligand can be prepared under the mild process conditions, and large-scale production of the diphosphine ligand is facilitated.

Description

technical field [0001] The invention relates to the technical field of compound synthesis, in particular to a preparation method of a bisphosphorus ligand. Background technique [0002] Asymmetric hydrogenation refers to the reaction of converting latent chiral compounds, such as alkenes, ketones or imines into corresponding chiral reduction products under the condition of hydrogenation catalyst and hydrogen, because green hydrogen is used in asymmetric hydrogenation. As a reducing agent, asymmetric hydrogenation is therefore one of the most efficient and atom-economical methods for building chiral molecules compared to other asymmetric catalytic methods. In addition, asymmetric hydrogenation has the advantages of high reactivity, mild reaction conditions, and environmental friendliness, and is widely used in the synthesis of chiral drugs, fragrances, and agricultural products. [0003] In recent years, asymmetric catalytic hydrogenation has achieved unprecedented developme...

Claims

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Application Information

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IPC IPC(8): C07F9/6568
CPCC07F9/65683C07B2200/07Y02P20/52
Inventor 韩露郑焱孙明明
Owner JIANGSU SINOCOMPOUND CATALYST
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