Preparation method for S-(-)-1,1-diphenyl-1,2-propylene glycol

A technology of propylene glycol and diphenyl, which is applied in the field of organic synthesis, can solve the problems of low yield, long reaction cycle, and low optical purity of products, and achieve the effects of high yield, low cost, and good product purity

Active Publication Date: 2015-07-22
NORTHEAST PHARMA GRP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the chiral reagents used for the synthesis of chiral lactones in existing production are generally dextro-amino compounds. This process has the problems of low product optical purity and low yield, and the reaction cycle is long, requiring 3-4 days.

Method used

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  • Preparation method for S-(-)-1,1-diphenyl-1,2-propylene glycol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0016] 1. Preparation of formatting reagents

[0017] Prepare a mixed solution of 170g (1.08mol) of bromobenzene and 200ml of tetrahydrofuran and shake well for later use. Put 27g (1.11mol) of magnesium and 200ml of tetrahydrofuran into the reaction flask, stir, and add 0.4g (0.0016mol) of iodine. Transfer the prepared bromobenzene-tetrahydrofuran mixture to a constant pressure dropping funnel, add 10-30ml of bromobenzene-tetrahydrofuran mixture dropwise into the reaction vessel, raise the temperature to 35°C, trigger the Grignard reaction, and start adding the remaining bromobenzene - Tetrahydrofuran solution, keeping the reaction temperature not lower than 60°C. After the dropwise addition, keep the reaction for 4 hours, transfer the device to a low-temperature bath, add nitrogen protection, and set aside.

[0018] 2. Preparation of S-(-)-1,1-diphenyl-1,2-propanediol

[0019] Prepare a mixed solution of 34g (0.29mol) of ethyl lactate and 150mL of tetrahydrofuran. Lower t...

Embodiment 2

[0021] 1. Preparation of formatting reagents

[0022] Prepare a mixed solution of 170g (1.08mol) bromobenzene and 200ml ether and shake well for later use. Put 24g (0.99mol) of magnesium and 200ml of ether into the reaction flask, stir, and add 0.3g (0.0012mol) of iodine. Transfer the prepared bromobenzene-ether mixture to a constant pressure dropping funnel, add 10-30ml of bromobenzene-ether mixture dropwise into the reaction vessel, raise the temperature to 30°C, trigger the Grignard reaction, and start adding the remaining bromobenzene - Diethyl ether solution, keeping the reaction temperature not lower than 65°C. After the dropwise addition, keep the temperature for reaction for 3 hours, transfer the device to a low-temperature bath, add nitrogen protection, and wait for use.

[0023] 2. Preparation of S-(-)-1,1-diphenyl-1,2-propanediol

[0024] Other conditions in the preparation steps of S-(-)-1,1-diphenyl-1,2-propanediol are the same as in Example 1, but the reaction...

Embodiment 3

[0026] 1. Preparation of formatting reagents

[0027] Prepare a mixed solution of 170g (1.08mol) bromobenzene and 200ml butyl ether and shake well for later use. Put 31g (1.28mol) of magnesium and 200ml of butyl ether into the reaction flask, stir, and add 0.5g (0.0020mol) of iodine. Transfer the prepared bromobenzene-butyl ether mixture to a constant pressure dropping funnel, add 10-30ml of bromobenzene-butyl ether mixture dropwise into the reaction vessel, raise the temperature to 25°C, trigger the Grignard reaction, and start adding the remaining Bromobenzene-butyl ether solution, keep the reaction temperature not lower than 55°C. After the dropwise addition, keep the reaction for 4 hours, transfer the device to a low-temperature bath, add nitrogen protection, and set aside.

[0028] 2. Preparation of S-(-)-1,1-diphenyl-1,2-propanediol

[0029] Other conditions in the preparation steps of S-(-)-1,1-diphenyl-1,2-propanediol are the same as in Example 1, but the reaction c...

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Abstract

The invention provides a preparation method for S-(-)-1,1-diphenyl-1,2-propylene glycol, which belongs to the field of organic synthesis. The method comprises the following steps: with bromobenzene and magnesium as raw materials and iodine as a catalyst, preparing a Grignard reagent in an organic solvent through a Grignard reaction; with ethyl lactate as a raw material, subjecting ethyl lactate and the Grignard reagent to an addition reaction in the organic solvent under the protection of nitrogen; adding water after the reaction is finished, adjusting a pH value with inorganic acid, carrying out extraction and layering and collecting an organic layer for concentration; and carrying out recrystallization in an organic dissolvent so as to obtain S-(-)-1,1-diphenyl-1,2-propylene glycol. The organic solvent used in the method is an ether, namely, one selected from the group consisting of diethyl ether, butyl ether, amyl ether, tetrahydrofuran and dioxane, reaction temperature is 20 to 70 DEG C, and reaction time is 2 to 6 h, and a mol ratio of bromobenzene to magnesium to iodine is 1: 0.9-1.2: 0.001-0.002. According to the invention, the raw materials are easily available, cost is low, operation in reaction process is clear, the product S-(-)-1,1-diphenyl-1,2-propylene glycol has good purity and higher yield, the method is suitable for industrial production, and production efficiency is improved.

Description

technical field [0001] The invention relates to a method for preparing S-(-)-1,1-diphenyl-1,2-propanediol in the field of organic synthesis. Background technique [0002] S-(-)-1,1-diphenyl-1,2-propanediol is a new type of asymmetric synthetic chiral reagent, which is mainly used for the preparation of biotin synthesis intermediate - chiral lactone, namely In the presence of specific solvents and catalysts, S-(-)-1,1-diphenyl-1,2-propanediol converts cyclic mesogenic carboxylic acid anhydrides into dicarboxylic acid monoesters through ring-opening reactions, and further The reaction converts to biotin key intermediate chiral lactone. However, the chiral reagents used for the synthesis of chiral lactones in existing production are generally dextro-amino compounds. This process has the problems of low product optical purity and low yield, and the reaction cycle is long, requiring 3-4 days. Therefore, research and development of a method for preparing S-(-)-1,1-diphenyl-1,2-p...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C33/26C07C29/36
Inventor 刘永明俎云龙周宏杨青
Owner NORTHEAST PHARMA GRP
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