Application of anilino lithium to catalysis of ketone and borane to generate hydroboration reaction

A technology of anilinolithium and hydroboration, applied in chemical instruments and methods, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc., can solve the problem of weakening carbonyl nucleophilic addition activity and weakening carbonyl Carbon positive, harsh reaction conditions and other issues, to achieve the effect of simple and controllable reaction, good universality, and short reaction time

Inactive Publication Date: 2018-09-21
ZHANGJIAGANG INST OF IND TECH SOOCHOW UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in the catalytic systems reported so far, the catalysts are relatively expensive, or the reaction conditions are relatively harsh.
[0004] Although both belong to carbonyl compounds, ketones and aldehydes have different reaction properties. This is common knowledge. In the prior art, there are cases where ketones and aldehydes are used as raw materials at the same time but only one raw material reaction occurs; the electron-donating group will weaken the positive charge of the carbonyl carbon. , thereby weakening the nucleophilic addition activity of the carbonyl group, and the aromatic aldehyde reduces the carbonyl activity due to conjugation, so aromatic compounds with different substitution positions and different electronic effects have a large reaction difference with aliphatic compounds

Method used

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  • Application of anilino lithium to catalysis of ketone and borane to generate hydroboration reaction
  • Application of anilino lithium to catalysis of ketone and borane to generate hydroboration reaction
  • Application of anilino lithium to catalysis of ketone and borane to generate hydroboration reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Example 1: Lithium anilide catalyzes the hydroboration reaction of methyl isopropyl ketone and pinacol borane

[0022] In the reaction flask that has been dehydrated and deoxygenated, add 40ul tetrahydrofuran solution (0.05M) of lithium anilide (0.2 mol% dosage) under the protection of argon, then add 0.1596 mL of borane with a syringe, mix well, and then add 0.1072 mL of borane with a syringe. mL of methyl isopropyl ketone, the mixture was stirred at room temperature, and after 30 min of reaction, the NMR yield was 99%, after which a small amount of tetrahydrofuran and excess borane were removed under reduced pressure to obtain the corresponding pinacol borate . 1 H NMR (400 MHz, CDCl 3 ) δ 3.94 (p, J = 6.2 Hz, 1H, OCH), 1.66 (dq, J = 13.5, 6.8 Hz, 1H, CH 3 CH), 1.25 (s, 12H, CH 3 ), 1.14 (d, J = 6.3 Hz, 3H, CH 3 ), 0.91-0.85 (m, 6H,CHCH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 82.34 (OC), 75.40 (OCH), 34.25 (OCHCH), 24.50 (d, J = 7.4 Hz, CH 3 ), 19.30 (CH 3...

Embodiment 2

[0023] Example 2: Lithium anilide catalyzes the hydroboration reaction of 4-heptanone and pinacol borane

[0024] In the reaction flask that has been dehydrated and deoxygenated, add 60ul tetrahydrofuran solution (0.05M) of lithium anilide (0.3 mol% dosage) under the protection of argon, then add 0.1596 mL borane with a syringe, mix well, and then add 0.1398 mL with a syringe mL4-heptanone, and the mixture was stirred at room temperature. After 40 min of reaction, the NMR yield was 99%. After that, a small amount of tetrahydrofuran and excess borane were removed under reduced pressure to obtain the corresponding pinacol borate. 1 H NMR (400 MHz, CDCl 3 ) δ4.03 (td, J = 8.0, 3.9 Hz, 1H, CH), 1.51 – 1.31 (m, 8H, CH 2 ), 1.24 (s, 12H,CH 3 ), 0.90 (t, J = 7.1 Hz, 6H, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 81.82 (OC), 73.55 (OCH), 38.18 (CH2), 23.97 (CH 3 ), 18.10 (CH 3 ), 13.48 (CH 3 ).

[0025] Replacing lithium anilide with the lithium amidide compound of formula I, ...

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Abstract

The invention relates to application of anilino lithium and particularly relates to efficient application of anilino lithium to catalysis of ketone and borane to generate hydroboration reaction. The application comprises the following processes: under the water-free and oxygen-free environment and in the inert gas atmosphere, adding borane to a reaction flask subjected to dehydration and deoxidization treatment, then adding anilino lithium as a catalyst, performing uniform mixing, then adding ketone to generate hydroboration reaction, and exposing to the air to stop the reaction so as to obtain borate, wherein ketone is aliphatic ketone. The catalyst disclosed by the invention has better universality for aliphatic ketones with different structures, thereby providing more options for obtaining borate compounds with different substituent structures.

Description

technical field [0001] The application of anilinolithium involved in the present invention specifically relates to the efficient application of anilinolithium in catalyzing the hydroboration reaction of ketones and boranes. technical background [0002] For the hydroboration reaction of equivalent catalyzed carbonyl compounds, the hydrolysis of the obtained boric acid ester products is also a very effective method for synthesizing alcohols in contemporary organic synthetic chemistry. The boric acid ester compounds produced by the hydroboration reaction can not only be used as polymer additives, gasoline additives, flame retardants, and sterilizers, but also as special surfactants, lubricating oil additives, and automobile brake fluids. very broad. Therefore, the research on the hydroboration reaction of unsaturated bonds is of great significance to modern industry and organic synthetic chemistry, which has attracted extensive attention of scientific researchers. [0003] A...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/04B01J31/02
CPCB01J31/0252C07F5/04
Inventor 薛明强朱章野徐晓娟颜丹丹郑煜沈琪
Owner ZHANGJIAGANG INST OF IND TECH SOOCHOW UNIV
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