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Method of preparing borate ester based on aldehyde

A technology for boronate ester and borane, which is applied in the field of preparing boronate ester, can solve the problems of weakening the nucleophilic addition activity of carbonyl, weakening the positive charge of carbonyl carbon, reducing the activity of carbonyl, etc., and achieves simple and controllable reaction, good generalization and the like. adaptability, and the effect of reducing pollution

Inactive Publication Date: 2018-08-17
NANTONG TEXTILE & SILK IND TECH RES INST +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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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; while the electron-donating group will weaken the positive charge of the carbonyl carbon. , thereby weakening the nucleophilic addition activity of the carbonyl group, aromatic aldehydes reduce the activity of the carbonyl group 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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  • Method of preparing borate ester based on aldehyde
  • Method of preparing borate ester based on aldehyde
  • Method of preparing borate ester based on aldehyde

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: Lithium anilide catalyzes the hydroboration reaction of cyclohexylbenzaldehyde and pinacol borane

[0026] In the reaction flask that has been dehydrated and deoxygenated, add 20ul tetrahydrofuran solution (0.05M) of lithium anilide (0.1 mol% dosage, the same below) under the protection of argon, then add 0.1596 mL borane with a syringe, mix well, and then use Add 0.095 mL of 2-pyridinecarbaldehyde into the syringe, and stir the mixture at room temperature. After 10 min of reaction, the NMR yield is 99%. After that, a small amount of tetrahydrofuran and excess borane are removed under reduced pressure to obtain the corresponding pinacol borate C 6 h 5 COCH 2 OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 8.61 (d, J = 5.4 Hz, 1H, Ar-H), 7.91 (t, J = 7.7 Hz, 1H, Ar-H), 7.49-7.41 (m, 2H, Ar-H), 5.10 (s, 2H, OCH 2 ), 1.32 (s,12H, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 159.82 (Ar-C), 143.72 (Ar-C), 139.56(Ar-C), 123.39 (Ar-C), 120.09 (Ar-C...

Embodiment 2

[0027] Example 2: Lithium anilide catalyzes the hydroboration reaction of propionaldehyde and pinacol borane

[0028] In the reaction flask that has been dehydrated and deoxygenated, add 20ul tetrahydrofuran solution (0.05M) of lithium anilide (0.1 mol% dosage, the same below) under the protection of argon, then add 0.1596 mL borane with a syringe, mix well, and then use 0.072 mL of propionaldehyde was added into the syringe, and the mixture was stirred at room temperature. After 10 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 CH 3 CH 2 COCH 2 OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 3.80 (t, J = 6.6 Hz, 2H, OCH 2 ), 1.63-1.54 (m,2H, CH 2 ), 1.25 (s, 12H, CH 3 ), 0.91 (t, J = 7.4 Hz, 3H, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 82.04 (OC), 66.02 (OCH 2 ), 24.14 (CH 3 CH 2 ), 24.05 (CH 3 ), 9.55 (CH 2 CH ...

Embodiment 3

[0031] Example 3: Lithium anilide catalyzes the hydroboration reaction of n-heptanal and pinacol borane

[0032] In the reaction flask that has been dehydrated and deoxygenated, add 20ul tetrahydrofuran solution (0.05M) of lithium anilide (0.1 mol% dosage, the same below) under the protection of argon, then add 0.1596 mL borane with a syringe, mix well, and then use 0.1392 mL of n-heptanal was added into the syringe, and the mixture was stirred at room temperature. After 10 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 C 6 h 13 COCH 2 OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 3.82 (t, J = 8Hz, 2H, OCH 2 ), 1.52-1.58 (m,2H, CH 2 ), 1.27-1.34 (m, 8H, CH 2 ), 1.24 (s, 12H, CH 3 ), 0.87 (t, J = 8 Hz, 3H, CH 3 ). 13 C NMR (100 MHz, CDCl 3 ) δ 82.02 (OC), 64.40 (OCH 2 ), 31.29 (CH 2 ), 30.92(CH 2 ), 28.44 (CH ...

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Abstract

The invention relates to application of anilino lithium, in particular to a method of preparing borate ester based on hydroboration reaction of aldehyde and borane. The method comprises the followingsteps of under the conditions without water and oxygen, in an inert gas atmosphere, adding the borane in a reaction bottle subjected to dehydration and deoxygenation treatment, then adding the anilinolithium as a catalyst, performing uniform mixing, then adding the aldehyde for hydroboration reaction, and performing exposure in the air for reaction termination to obtain the borate ester as a product, wherein the aldehyde is selected from fatty aldehydes. By adopting the method provided by the invention, the condition that the anilino lithium can extremely efficiently catalyze cyclohexanecarboxaldehyde, propionaldehyde and heptanal to generate hydroboration reaction with the borane is discovered for the first time, and a new scheme is provided to prepare the borate ester by adopting a carbonyl compound and the borane to generate the hydroboration reaction.

Description

technical field [0001] The invention relates to a method for preparing boric acid ester based on the hydroboration reaction of aldehyde and borane. technical background [0002] 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. 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. 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 variety of catalysts have been used for the hydroboration of aldehydes, and...

Claims

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Application Information

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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 NANTONG TEXTILE & SILK IND TECH RES INST
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