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Method for preparing tertiary alcohol by means of Grignard reaction

A technology of Grignard reaction and tertiary alcohol, applied in chemical instruments and methods, preparation of hydroxyl compounds, preparation of organic compounds, etc., can solve the problems of expensive additives, unfriendly environment, and reduced drug efficacy, and achieve simple and easy reaction operation Easy to use, low price, and the effect of reducing by-products

Inactive Publication Date: 2012-08-22
FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
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  • Abstract
  • Description
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AI Technical Summary

Problems solved by technology

The disadvantage of the nucleophilic addition reaction of traditional Grignard reagents to ketones is that during the nucleophilic addition reaction, the aldol condensation by-products and reduction by-products of the substrate itself are usually produced, resulting in the loss of the main product. The yield is greatly reduced
Its disadvantages are: 1. The additives are expensive and easy to absorb moisture. They need to be weighed in the glove box, which is not suitable for industrial production.
2. With metal salts as additives, a small amount of metal ions are likely to remain in the product after post-treatment. Ultimately, metal ions remaining in pesticides will be unfriendly to the environment. Residues in pharmaceutical products will not only reduce the efficacy of the medicine but also have a great impact on human health. Impact

Method used

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  • Method for preparing tertiary alcohol by means of Grignard reaction
  • Method for preparing tertiary alcohol by means of Grignard reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Embodiment 1: the preparation of n-BuMgBr Grignard reagent

[0023] In a 250mL three-necked flask, add 2.55g (105mmol) magnesium chips, add 3 iodine particles (as an initiator), and pass through nitrogen protection, add 10mL dry THF to immerse magnesium chips, start stirring, add 1.0mL n-BuBr , heating to initiate the reaction, causing the color of the iodine particles to fade, THF reflux, the surface of the magnesium chips is shiny, and the magnesium chips gradually become less. After initiation, stop heating, slowly add n-BuBr THF solution (containing n-BuBr 9.8mL, dry THF solution 90mL) dropwise, heat to 65°C and reflux for 1h after dropping. The titration of the Grignard reagent refers to the acid-base titration method, and the concentration of n-BuMgBr synthesized according to this operation step and reagent dosage is about 1mol / L.

Embodiment 2

[0024] Embodiment 2: the synthesis of 2-phenyl-2-hexanol

[0025] In a 50mL round-bottomed flask, add the quaternary ammonium salt tetrabutylammonium chloride (TBAC) (27.8mg, 0.1mmol), fill it with nitrogen and seal it, and slowly add the Grignard reagent n-BuMgBr (1.5mL, 1.5mmol , 1.0M in THF), stirred at room temperature for 10min, then added diethylene glycol dimethyl ether (DGDE) (0.21mL, 201mg, 1.5mmol), continued to stir at room temperature for 30min, then gradually cooled from room temperature to 0-5°C , a solution of acetophenone in tetrahydrofuran (120 mg, 1.0 mmol, 1.0 M in THF) was added slowly.

[0026] After the dropwise addition, the reaction solution was gradually raised to room temperature and stirred for 2 hours. After the reaction was completed, 5 mL of saturated NH 4 The reaction was quenched with aqueous Cl solution, extracted with ethyl acetate (10 mL×3), washed with saturated sodium chloride (5 mL), dried over anhydrous sodium sulfate for 20 min, filtere...

Embodiment 3

[0035] Embodiment 3: the synthesis of 3-methyl-2-phenyl-2-butanol

[0036] Replace n-BuMgBr with i-PrMgBr, and the synthesis process is the same as in Example 2. Yield: 82%. The product is a colorless oily liquid. NMR analysis (Burker AVANCE 400 spectrometer): 1 H NMR (400MHz, CDCl 3 , TMS) δ0.82(d, J=6.9Hz, 3H), 0.90(d, J=6.9Hz, 3H), 1.53(s, 3H), 1.73(s, 1H), 2.03(septet, J=6.9 Hz, 1H), 7.20-7.45 (m, 5H); 13 C NMR (100MHz, CDCl 3 )δ 17.2, 17.4, 26.7, 38.6, 76.7, 125.3, 126.4, 127.9, 147.8.

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Abstract

The invention provides a method for preparing tertiary alcohol by means of Grignard reaction, which includes: adding ethers and quaternary ammonium salt compounds into Grignard reagent to serve as addition agent to react with ketone so that the tertiary alcohol is prepared. The method has the advantages of simplicity in operation, mild reaction condition, low cost, high yield, environmental friendliness and suitability for industrial production.

Description

technical field [0001] The invention relates to a method for preparing tertiary alcohol by Grignard reaction. Tertiary alcohol compounds are important intermediates of pesticides, medicines and liquid crystal materials. Background technique [0002] The nucleophilic addition reaction of Grignard reagents to ketones is one of the most important and widely used methods for the preparation of tertiary alcohols. This method not only has easy-to-obtain raw materials and simple operation, but also can increase the carbon chain of the reactant, so it can be used to prepare various tertiary alcohols. The disadvantage of the nucleophilic addition reaction of traditional Grignard reagents to ketones is that in the process of nucleophilic addition reaction, it is usually accompanied by the generation of aldol condensation by-products and reduction by-products of the substrate itself, resulting in the depletion of the main product. The yield is greatly reduced. [0003] In order to p...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/38
Inventor 宋玲宗华黄华银边广岭
Owner FUJIAN INST OF RES ON THE STRUCTURE OF MATTER CHINESE ACAD OF SCI
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