Application of p-methylanilinyl lithium to catalysis of aldehyde and borane to generate hydroboration reaction

A technology of methylanilino 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, weakening Problems such as carbonyl carbon positive charge and carbonyl activity reduction, etc., to achieve the effect of simple and controllable reaction, good universality, and pollution reduction

Active Publication Date: 2018-09-21
SUZHOU UNIV
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  • 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; 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 p-methylanilinyl lithium to catalysis of aldehyde and borane to generate hydroboration reaction
  • Application of p-methylanilinyl lithium to catalysis of aldehyde and borane to generate hydroboration reaction
  • Application of p-methylanilinyl lithium to catalysis of aldehyde and borane to generate hydroboration reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Example 1: Lithium p-methylanilide catalyzes the hydroboration reaction of benzaldehyde and pinacol borane

[0027] 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 0.1016 mL of benzaldehyde with a syringe, and the mixture is stirred at room temperature. After reacting for 10 min, 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 boronic acid Ester C 6 h 5 CH 2 OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 7.36-7.23 (m, 5H, Ar-H), 4.92 (s, 2H, OCH 2 ), 1.26 (s, 12H, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 138.76 (Ar-C), 127.81 (Ar-C), 126.89 (Ar-C), 126.24 (Ar-C), 82.48 (OC), 66.20 (OCH 2 ), 24.15 (CH 3 ).

[0028] Substitu...

Embodiment 2

[0030] Example 2: Lithium p-methylanilide catalyzes the hydroboration reaction of p-fluorobenzaldehyde and pinacol borane

[0031] 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 0.1072 mL of p-fluorobenzaldehyde was added into the syringe, and the mixture was stirred at room temperature. After 10 minutes 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 p -F-C 6 h 4 CH 2 OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 7.34-7.29 (m, 2H, Ar-H), 7.04-6.98 (m, 2H, Ar-H), 4.87 (s, 2H, OCH2), 1.26 (s, 12H, CH3). 13 C NMR (101 MHz, CDCl 3 ) δ161.71 (ds, Ar-C), 134.50 (d, J = 3.2 Hz, Ar-C), 128.14 (d, J = 8.1 Hz, Ar-C), 114.60 ...

Embodiment 3

[0032] Example 3: Lithium p-methylanilide catalyzes the hydroboration reaction of m-chlorobenzaldehyde and pinacol borane

[0033] 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 Add 0.0899 mL of m-chlorobenzaldehyde into the syringe, and stir the mixture at room temperature. After 10 minutes 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 m -Cl-C 6 h 4 CH 2 OB(OC(CH 3 ) 2 C(CH 3 ) 2 O). 1 H NMR (400 MHz, CDCl 3 ) δ 7.36 (s, 1H, Ar-H), 7.28-7.19 (m, 3H, Ar-H), 4.89 (s, 2H, OCH 2 ), 1.27 (s, 12H,CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) δ 140.75(Ar-C), 133.75 (Ar-C), 129.08 (Ar-C), 126.99 (Ar-C), 126.30 (Ar-C), 124.17(Ar-C), 82.61 (OC), 65....

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Abstract

The invention relates to application of p-methylanilinyl lithium to catalysis of aldehyde 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 p-methylanilinyl lithium as acatalyst, performing uniform mixing, then adding aldehyde to perform hydroboration reaction, and exposing to the air to stop the reaction so as to obtain a product borate, wherein aldehyde is selectedfrom aromatic aldehyde or heterocyclic aldehyde. The catalytic activity in catalysis of aldehyde and borane to generate hydroboration reaction by p-methylanilinyl lithium is high (the dosage of the catalyst is only 0.1%), the reaction conditions are mild (room temperature), the reaction time is short (10 min), the reaction yield is high, the reaction is simple and controllable, the after-treatment is simple, and the reaction adopts a solvent-free system so as to reduce the pollution to the environment.

Description

technical field [0001] The application of the p-toluide lithium involved in the present invention specifically relates to the efficient application of the p-toluide lithium in catalyzing the hydroboration reaction of aldehyde and borane. technical background [0002] 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 aldehydes have different reaction properties. This is common knowledge. In the prior art, there are cases where ketones and aldehydes are used as raw ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07F5/04
CPCB01J31/0252C07F5/04
Inventor 薛明强朱章野颜丹丹郑煜陈素芳沈琪
Owner SUZHOU UNIV
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