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Method of preparing borate ester by performing hydroboration reaction based on o-toluidine lithium

A technology of o-methylaniline and hydroboration, which is applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, organic chemistry, etc., can solve the problems of harsh reaction conditions and expensive catalysts, and achieve the goal of reaction Short time, good universal applicability, and the effect of reducing pollution

Inactive Publication Date: 2018-08-17
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. Therefore, it is particularly urgent to develop a new catalytic system that can efficiently catalyze the hydroboration reaction of aldehydes under mild conditions.

Method used

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  • Method of preparing borate ester by performing hydroboration reaction based on o-toluidine lithium
  • Method of preparing borate ester by performing hydroboration reaction based on o-toluidine lithium
  • Method of preparing borate ester by performing hydroboration reaction based on o-toluidine lithium

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: Hydroboration reaction of cyclohexylbenzaldehyde and pinacol borane catalyzed by o-methylanilide lithium

[0026] In the reaction flask that has been dehydrated and deoxygenated, add 20ul of tetrahydrofuran solution (0.05M) of lithium o-toluidine under the protection of argon (0.1 mol% dosage, the same below), then add 0.1596 mL of borane with a syringe, and 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), 123.39...

Embodiment 2

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

[0028] In the reaction flask that has been dehydrated and deoxygenated, add 20ul of tetrahydrofuran solution (0.05M) (0.1 mol% dosage) of o-toluidine lithium under the protection of argon, 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 2 CH 3 ). ...

Embodiment 3

[0031] Example 3: Hydroboration reaction of n-heptanal and pinacol borane catalyzed by lithium o-toluide

[0032] In the reaction flask that has been dehydrated and deoxygenated, add 20ul of tetrahydrofuran solution (0.05M) (0.1 mol% dosage) of o-toluidine lithium under the protection of argon, 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 ),28.44 (CH 2 ), ...

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Abstract

The invention discloses a method of preparing borate ester by performing hydroboration reaction based on o-toluidine lithium. The method comprises the following steps of under the conditions without water and oxygen, in an inert gas atmosphere, adding borane in a reaction bottle subjected to dehydration and deoxygenation treatment, then adding the o-toluidine lithium as a catalyst, performing uniform mixing, then adding 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 fromfatty aldehydes. By adopting the method disclosed by the invention, the catalyst has better universality to the fatty aldehydes of different structures, and more selections are provided to obtain borate ester compounds of different substituent group structures.

Description

technical field [0001] The application of the o-tolylanilide lithium involved in the present invention specifically relates to a method for preparing boric acid esters based on the o-tolylanilide lithium hydroboration reaction. technical background [0002] Since Brown et al. discovered in 1956 that borohydride catalyzed the hydroboration reaction of olefins, the hydroboration reaction of unsaturated bonds has become a very effective means for the preparation of various organic synthesis intermediates. The research on hydrogenation reaction is of great significance to both 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 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 focu...

Claims

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Application Information

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IPC IPC(8): C07F5/04B01J31/02
CPCB01J31/0252C07F5/04
Inventor 薛明强朱章野武振杰洪玉标蔡玲霞沈琪
Owner ZHANGJIAGANG INST OF IND TECH SOOCHOW UNIV
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