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Alpha-alkylating method of methyl ketone

A technology for alkylation and methyl ketones, which is applied in the field of α-alkylation of methyl ketones, to achieve the effects of reduced synthesis costs, good research and industrial application prospects, and easy operation of the reaction

Inactive Publication Date: 2013-01-16
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Due to the shortcomings and exposed problems of the transition metal catalysis method, it will be a very worthwhile research topic to find an alternative greener synthesis method that does not even require the participation of transition metal catalysts.
However, among the currently known synthetic methods for preparing long-chain branched-chai

Method used

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  • Alpha-alkylating method of methyl ketone
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  • Alpha-alkylating method of methyl ketone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Reaction of benzyl alcohol with acetophenone

[0021]

[0022] Under nitrogen protection, benzyl alcohol (6.0 mmol, 3.0 equiv.), acetophenone (2.0 mmol, 1.0 equiv.), and NaOH (1.2 mmol, 60 mol%) were sequentially added to a 20 mL Schlenk reaction tube. The reaction mixture was heated to 120°C and stirred for 24 hours. The reaction was quenched with ethyl acetate, the reaction mixture was washed successively with dilute hydrochloric acid, saturated brine, and water, and then washed with MgSO 4 Dry, filter, and concentrate. The product was obtained by flash column chromatography with a GC yield of 99%, a separation yield of 86%, and a product selectivity of 93 / 7. 1 HNMR(500MHz, CDCl 3 ): δ 7.29-7.13 (m, 10H), 4.59-4.56 (m, 1H), 2.71-2.56 (m, 2H), 2.38 (b, 1H), 2.09-1.93 (m, 2H). 13 C NMR(125.4MHz, CDCl 3 ): δ144.5, 141.7, 128.34, 128.33, 128.26, 127.4, 125.8, 125.7, 73.6, 40.3, 31.9. MS (EI): m / z (%) 212(9), 194(20), 107(100 ), 92(20), 91(22), 79(57), 78(10), 77(28), 51(7)....

Embodiment 2

[0024] Reaction of benzyl alcohol with (4-methyl)acetophenone

[0025]

[0026] Under nitrogen protection, benzyl alcohol (6.0 mmol, 3.0 equiv.), (4-methyl)acetophenone (2.0 mmol, 1.0 equiv.), and NaOH (1.2 mmol, 60 mol%) were sequentially added to a 20 mL Schlenk reaction tube. The reaction mixture was heated to 120°C and stirred for 24 hours. The reaction was quenched with ethyl acetate, the reaction mixture was washed successively with dilute hydrochloric acid, saturated brine, and water, and then washed with MgSO 4 Dry, filter, and concentrate. The product was obtained by flash column chromatography with a GC yield of 99%. 1 H NMR(500MHz, CDCl 3 ): δ 7.28-7.14 (m, 9H), 4.64-4.61 (m, 1H), 2.75-2.61 (m, 2H), 2.34 (s, 3H), 2.14-1.96 (m, 2H), 1.92 (b , 1H). 3 CNMR(125.4MHz, CDCl 3 ): δ141.9, 141.6, 137.3, 129.2, 128.5, 128.4, 125.9, 125.8, 73.7, 40.4, 32.1, 21.1. MS (EI): m / z (%) 226(10), 209(3), 208 (15), 121(100), 93(36), 92(10), 91(35), 77(22), 65(9), 51(4).

Embodiment 3

[0028] Reaction of benzyl alcohol with (4-methoxy)acetophenone

[0029]

[0030] Under nitrogen protection, add benzyl alcohol (6.0 mmol, 3.0 equiv.), (4-methoxy)acetophenone (2.0 mmol, 1.0 equiv.), and NaOH (1.2 mmol, 60 mol%) to a 20 mL Schlenk reaction tube in sequence . The reaction mixture was heated to 120°C and stirred for 24 hours. The reaction was quenched with ethyl acetate, the reaction mixture was washed successively with dilute hydrochloric acid, saturated brine, and water, and then washed with MgSO 4 Dry, filter, and concentrate. The product was obtained by flash column chromatography with a GC yield of 99% and a product selectivity of 86 / 14. 1 H NMR(500MHz, CDCl 3 ): δ7.34-7.15 (m, 7H), 6.87-6.85 (m, 2H), 4.61-4.58 (m, 1H), 3.78 (s, 3H), 2.73-2.58 (m, 2H), 2.13-1.95 (m, 2H), 2.10 (b, 1H). 13 C NMR(125.4MHz, CDCl 3 ): δ 159.0, 141.8, 136.7, 128.4, 128.3, 127.2, 125.8, 113.8, 73.4, 55.2, 40.3, 32.1. MS (EI): m / z (%) 242(7), 224(4), 137 (100), 135(6), 109(20), 94(9...

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Abstract

The invention discloses an alpha-alkylating method of methyl ketone. The method is carried out under inert gas or air. The alpha-alkylating method is mild in a reaction condition, a product is simple to process, separate and purify, and a recovery rate of the product is high. Primary alcohol which is cheap and easy to obtain is served as an alkylating agent, therefore, synthesizing cost is greatly reduced. The alpha-alkylating method disclosed by the invention is carried out under a solvent-free condition, thus, possible environmental pollution from an organic solvent can be reduced to a certain extent.

Description

Technical field [0001] The invention relates to a method for α-alkylation of methyl ketones, in particular to a method for synthesizing long-chain secondary alcohol compounds by α-alkylation of methyl ketones using primary alcohols as alkylating agents. Background technique [0002] Various long-chain branched alcohol compounds are important organic chemical raw materials and fine chemical reagents, which are widely used in the production of detergents, lubricants, petroleum product additives, polymer material synthesis, and cosmetics, care products and other fields. Due to the existence of hydrophilic and hydrophobic groups at both ends and the difference in properties, these alcohol compounds and their corresponding acids obtained through oxidation reactions are often used to synthesize various surfactants, phase transfer catalysts, etc., therefore, The synthesis and application of long-chain branched alcohol compounds has always been an important part of the chemical industry....

Claims

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Application Information

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IPC IPC(8): C07B41/02C07C33/24C07C29/38C07C41/30C07C43/23C07C33/46
Inventor 徐清廖诗亨
Owner WENZHOU UNIVERSITY