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Application of n-butyllithium in catalyzing cyanosilylation reaction of ketone and silane

A technology of n-butyllithium and silane cyanosilane, which is applied in the application field of organolithium compounds, can solve problems such as poor catalytic effect, limited range of substrate trial use, and difficulty in catalyst synthesis, achieving simple structure, simple and controllable reaction process, easy access to effects

Pending Publication Date: 2020-06-19
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, so far, there have been few reports on the cyanosilication of ketones catalyzed by main group metals, and the synthesis of existing catalysts is relatively difficult, and some catalysts only have a good catalytic effect on aldehydes, and the catalytic effect on ketones is poor. The scope of the trial is limited

Method used

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  • Application of n-butyllithium in catalyzing cyanosilylation reaction of ketone and silane
  • Application of n-butyllithium in catalyzing cyanosilylation reaction of ketone and silane
  • Application of n-butyllithium in catalyzing cyanosilylation reaction of ketone and silane

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Embodiment one: n-BuLi catalyzes the reaction of acetophenone and TMSCN

[0029] Under an inert gas atmosphere, add acetophenone (116.6 μL, 1 mmol), trimethylsilyl cyanide (137.6 μL, 1.1 mmol) and finally 0.1 % Catalyst n-BuLi (20 μL, 0.01 M in THF), react at rt for 35 min, pipette a drop into the NMR tube, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 99%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) δ 7.57 – 7.55 (m, 2H, ArH), 7.42-7.33 (m, 3H, ArH), 1.87 (s, 3H, CH 3 ), 0.19 (s,9H, OSiMe 3 ), see the NMR figure 1 .

[0030] Under an inert gas atmosphere, add acetophenone (116.6 μL, 1 mmol), trimethylsilyl cyanide (137.6 μL, 1.1 mmol) and finally 0.01 % Catalyst n-BuLi (2 μL, 0.01 M in THF), react at rt for 60 min, pipette a drop into the NMR tube, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 98%. The NMR data of the product are the same as above.

Embodiment 2

[0031] Embodiment two: n-Butyllithium catalyzes the reaction of acetophenone and TMSCN

[0032] Under an inert gas atmosphere, add acetophenone (116.6 μL, 1 mmol), trimethylsilyl cyanide (137.6 μL, 1.1 mmol) and finally 0.05 % Catalyst n-BuLi (10 μL, 0.01 M in THF), after reacting at rt for 50 minutes, pipette a drop into the NMR tube, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 99%. The NMR data of the product are the same as in Example 1.

[0033] Under an inert gas atmosphere, add acetophenone (116.6 μL, 1 mmol), trimethylsilyl cyanide (1.2 mmol) and finally add 0.05 % catalyst n- BuLi (10 μL, 0.01 M in THF), react at rt for 45 min, pipette a drop into the NMR tube, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 99%. The NMR data of the product are the same as in Example 1.

Embodiment 3

[0037] Embodiment three: n-butyllithium catalyzes the reaction of p-fluoroacetophenone and TMSCN

[0038] Under an inert gas atmosphere, add p-fluoroacetophenone (120.8 μL, 1 mmol), trimethylsilyl cyanide (137.6 μL, 1.1 mmol) to the dehydrated and deoxygenated reaction vial with a pipette gun, and finally add 0.05 % catalyst n-BuLi (10 μL, 0.01 M in THF), after reacting at rt for 60 min, pipette a drop into the NMR tube, add CDCl 3 Dubbed into a solution. Calculated 1 H spectrum yield was 99%. NMR data of the product: 1 H NMR (400 MHz, CDCl 3 ) δ 7.54 – 7.51 (m, 2H, ArH), 7.09-7.05 (m, 2H, ArH), 1.84 (s, 3H, CH 3 ), 0.18 (s,9H, OSiMe 3 ), see NMR figure 2 .

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Abstract

The invention discloses an application of n-butyllithium in catalyzing cyanosilylation reaction of ketone and silane. The n-butyllithium has high catalytic activity, low catalyst dosage and good substrate application range. After n-butyllithium, ketone and silane are mixed, the cyanosilylation reaction is carried out to obtain a cyanohydrin compound. The n-butyllithium reagent disclosed by the invention has the advantages of commercialization, easiness in obtaining, low cost, no need for a solvent, environmental friendliness and the like, has a very good catalytic effect on ketone, and is widein substrate application range. Commercial n-butyllithium is used for efficiently catalyzing the cyanosilylation reaction of ketone by using a relatively low dosage of catalyst.

Description

technical field [0001] The invention relates to the field of application of organolithium compounds, in particular to the application of commercialized n-butyllithium in catalyzing the cyanidation reaction of ketone and trimethylsilyl cyanide. Background technique [0002] In 1832, Winkler first reported the preparation of cyanohydrins by using HCN as a source of cyanide. However, due to the high toxicity of HCN and the difficulty in post-processing, a large number of less harmful and easy-to-control alternative cyanides appeared. Trimethylsilyl cyanide (TMSCN) is by far the most commonly used cyanation reagent, which can be converted to trimethylsilyl cyanohydrin. In recent years, chemists have developed various catalysts, which are used to catalyze the cyanosilication reaction of carbonyl compounds and TMSCN. The cyanosilylation of carbonyl compounds and TMSCN catalyzed by Ca and Ca has only recently attracted increasing attention, especially for the cyanosilylation of al...

Claims

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Application Information

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IPC IPC(8): C07F7/18
CPCC07F7/188
Inventor 薛明强徐晓娟王雨虹康子晗周帅
Owner SUZHOU UNIV
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