Method for preparing borate from aliphatic aldehyde

A technology for boronate esters and fatty aldehydes, which is applied in the field of preparing boronate esters, can solve the problems of weakening the nucleophilic addition activity of carbonyl groups, weakening the positive charge of carbonyl carbonyls, reducing the activity of carbonyl groups, etc., and achieves simple and controllable reactions, good generalization, etc. adaptability, and the effect of reducing pollution

Inactive Publication Date: 2018-08-24
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.
[0003] 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 for preparing borate from aliphatic aldehyde
  • Method for preparing borate from aliphatic aldehyde
  • Method for preparing borate from aliphatic aldehyde

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Example 1: Hydroboration reaction of cyclohexylbenzaldehyde and pinacol borane catalyzed by p-methylanilide lithium

[0025] In the reaction flask that has been dehydrated and deoxygenated, add 20ul of tetrahydrofuran solution (0.05M) of p-methylanilinide lithium under the protection of argon (0.1 mol% dosage, the same below), then add 0.1596 mL of borane with a syringe, mix well , then add 0.095 mL of 2-pyridinecarbaldehyde with a syringe, and the mixture is stirred at room temperature. After 10 min of reaction, the NMR yield is 99%, and then a small amount of tetrahydrofuran and excess borane are removed under reduced pressure to obtain the corresponding pinacol boron Ester 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....

Embodiment 2

[0026] Example 2: Lithium p-methylanilide catalyzes the hydroboration reaction of propionaldehyde and pinacol borane

[0027] In the reaction flask that has been dehydrated and deoxygenated, under the protection of argon, add 20ul of tetrahydrofuran solution (0.05M) of p-methylanilinide lithium (0.1 mol% dosage), then add 0.1596 mL of 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 HNMR (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 ) δ82.04 (OC), 66.02 (OCH 2 ), 24.14 (CH 3 CH 2 ), 24.05 (CH 3 ), 9.55 (CH ...

Embodiment 3

[0028] Example 3: Hydroboration reaction of n-heptanal and pinacol borane catalyzed by p-methylanilide lithium

[0029] In the reaction flask that has been dehydrated and deoxygenated, under the protection of argon, add 20ul of tetrahydrofuran solution (0.05M) of p-methylanilinide lithium (0.1 mol% dosage), then add 0.1596 mL of 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....

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Abstract

The invention relates to an application of lithium p-toluidine, in particular to a method for preparing borate from aliphatic aldehyde. Borane is added to a reaction bottle subjected to dehydration and deoxidation treatment in a water-free and oxygen-free environment in an inert gas atmosphere, then, a lithium p-toluidine catalyst is added, the mixture is uniformly mixed, aldehyde is added, a hydroboration reaction is conducted, the reaction is ended by exposing the mixture to the air, and product borate is obtained. The aldehyde is selected from aliphatic aldehyde. It is found for the first time that lithium p-toluidine can extremely efficiently catalyze the hydroboration reaction of borane with cyclohexanecarboxaldehyde, propionaldehyde and n-heptaldehyde, and a new scheme is provided for preparing borate through the hydroboration reaction of a carbonyl compound and borane.

Description

technical field [0001] The invention relates to a method for preparing boric acid esters using fatty aldehydes. 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. A variety of catalysts have been used for the hydroboration of aldehydes, and especially in recent years, there have been numerous reports of such reactions. Due to the absence of catalysts, the hydroboration reaction of carbonyl compounds is difficult to occur. Therefore, the focus of research on this type of reaction is to develop efficient catalytic systems. However, in the catalytic systems reported so far, the catalysts are relatively expensive, or the reaction conditions are relatively harsh. [0003] Although both belong to carbonyl compounds, ketones and aldeh...

Claims

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Application Information

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IPC IPC(8): C07F5/04
CPCC07F5/04
Inventor 薛明强朱章野颜丹丹郑煜陈素芳沈琪
Owner NANTONG TEXTILE & SILK IND TECH RES INST
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