Highly active catalyst used for hydrosilation reaction of aldehyde and trimethylsilyl cyanide

A technology of trimethylsilyl cyanide and high-activity catalysts, which is applied in the field of high-activity catalysts, can solve the problems of using organic solvent reaction conditions, large amount of catalysts, nonconformities, etc., and achieves wide application range, simple operation, and mild reaction conditions. Effect

Inactive Publication Date: 2012-01-11
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The above-mentioned catalysts generally have disadvantages such as a large amount of catalyst used, the use of organic solvents in the reaction, or harsh reaction conditions, which do not meet the requirements of "green chemistry"

Method used

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  • Highly active catalyst used for hydrosilation reaction of aldehyde and trimethylsilyl cyanide
  • Highly active catalyst used for hydrosilation reaction of aldehyde and trimethylsilyl cyanide
  • Highly active catalyst used for hydrosilation reaction of aldehyde and trimethylsilyl cyanide

Examples

Experimental program
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Effect test

Embodiment 1

[0020] Preparation of isobutyraldehyde cyanohydrin siloxane

[0021] Add 2.3mL (0.025mol) of freshly distilled isobutyraldehyde to a 25mL one-necked flask, and then add 0.46μL (5.0×10 -8 mol) with a mass fraction of 1% (CH 3 ) 4 Add 3.4mL (0.025mol) trimethylsilyl cyanide (the molar ratio of catalyst, isobutyraldehyde and trimethyl silyl cyanide is 1: 500000: 500000) to the NOH aqueous solution with stirring at room temperature, the reaction is violent (Note : The heat released in the reaction is released naturally by itself), and the reaction ends in 10 minutes. 1 The conversion was determined to be 100% by H NMR.

Embodiment 2

[0023] Preparation of Benzaldehyde Cyanohydrin Silicon Ether

[0024] Add 53g (0.5mol) of freshly distilled benzaldehyde to a 250mL single-necked flask, and then add 0.36μL (1.0×10 -6 mol) with a mass fraction of 25% (CH 3 ) 4 Add 49.5 g (0.5 mol) of trimethylsilyl cyanide to NOH aqueous solution under room temperature and stirring state, the reaction is violent, TLC follows the reaction, after 20 minutes a small amount of sample is taken and sent to NMR, the calculated conversion rate is 98%.

Embodiment 3

[0026] Preparation of Cyclohexylformaldehyde Cyanohydrin Silicon Ether

[0027] Add 60mL (0.5mol) of freshly distilled cyclohexyl formaldehyde to a 250mL one-necked flask, then add 0.26g (1.0×10 -6 mol) n Bu 4 NOH solid, add 66.6mL (0.5mol) trimethylsilyl cyanide under stirring state at room temperature, the reaction is violent, after 10 minutes take a small amount and send it to NMR, the calculated conversion rate is 99%.

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Abstract

Belonging to the field of organic synthesis, the invention relates to a highly active catalyst used for a hydrosilation reaction of aldehyde and trimethylsilyl cyanide so as to synthesize a cyanohydrinsilylether compound. The catalyst is characterized by being a quaternary ammonium base or an alkali metal hydroxide both containing one or two hydroxyl anions. The catalyst can catalyze the hydrosilation reaction of aldehyde and trimethylsilyl cyanide efficiently in a mild condition and at a low catalyst concentration, and a racemic cyanohydrinsilylether compound can be obtained quantificationally, with the activity up to 3000000 turn over number/hour. Characterized by low price and easy availability, mild reaction condition, low catalyst dosage, short reaction time and wide application scope of substrate, the catalyst provided in the invention avoids the disadvantages of severe waterless and anaerobic conditions, high catalyst cost, environmental pollution and the like caused by employment of a metal catalyst, and has strong practicality.

Description

technical field [0001] The invention discloses a high-activity catalyst for synthesizing silicon cyanohydrin silicon ether compounds through the silicocyanation reaction of aldehydes and trimethylsilyl cyanide, belonging to the field of organic synthesis. Background technique [0002] Cyanohydrin compounds are an important class of organic synthesis intermediates, and are direct raw materials for the synthesis of α-hydroxy acids, α-hydroxy aldehydes, β-hydroxy amines, etc. Therefore, the preparation of cyanohydrins has attracted widespread attention, and the addition reaction of carbonyl compounds with trimethylsilyl cyanide (TMSCN) is one of the most effective methods for the synthesis of cyanohydrins. [0003] At present, there are many reports on the preparation of cyanohydrin silicon ethers by the silicocyanation reaction of carbonyl compounds at home and abroad. The commonly used catalysts mainly include Lewis acids, Lewis bases, and inorganic salts. Oxazoline and a ch...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02B01J23/04C07F7/18
Inventor 吕小兵
Owner DALIAN UNIV OF TECH
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