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Method for synthesizing tertiary amine derivative by catalyzing hydroboration reaction of tertiary amide by rare earth

A rare earth catalysis and rare earth catalyst technology, applied in the chemical industry, can solve the problems of complex process, low reaction yield, difficult synthesis, etc., and achieve the effects of high quality, stable process and high reaction yield

Active Publication Date: 2020-02-18
WENZHOU MEDICAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

So far, there are only two reports of amide reduction reactions using borane as a reducing agent, all of which are complex catalysts that are difficult to synthesize ( ACS Catal . 2015, 5 , 4219−4226 and Dalton Trans . 2019, 48 , 11978–11984.), the synthesis of the catalyst requires five steps and three steps respectively starting from simple raw materials, the catalyst cannot be purchased commercially directly, and its synthesis is difficult, and it is difficult to realize the expansion of production
[0004] It can be seen that the existing methods for synthesizing tertiary amine derivatives all have certain technical difficulties or application difficulties, or the reaction yield is low, or the source of catalyst is not extensive, or the storage and transportation of raw materials is not easy, or the process is complicated and the reaction time is long.

Method used

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  • Method for synthesizing tertiary amine derivative by catalyzing hydroboration reaction of tertiary amide by rare earth
  • Method for synthesizing tertiary amine derivative by catalyzing hydroboration reaction of tertiary amide by rare earth
  • Method for synthesizing tertiary amine derivative by catalyzing hydroboration reaction of tertiary amide by rare earth

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] The synthesis of tribenzylamine, the chemical structure is as follows:

[0028]

[0029] Under nitrogen protection, add raw materials N , N - Dibenzylbenzamide (0.5 mmol), pinacol borane (1.2 mmol) and catalyst Y [N(SiMe 3 ) 2 ] 3 (5 mol%), reacted in xylene (3 ml) at 100 °C for 20 h, and the isolated yield of the product was 95%.

[0030] 1 H NMR (CDCl 3 , 500 MHz, ppm): δ 7.49-7.47 (m, 6H), 7.38 (t, J = 7.3Hz, 6H), 7.31-7.27 (m, 3H), 3.63 (s, 6H). 13 C NMR (CDCl 3 , 125 MHz, ppm): δ139.8, 128.9, 128.4, 127.0, 58.1.

Embodiment 2

[0032] The synthesis of N,N-dibenzyl-2-cyclopropylethylamine, the chemical structure is as follows:

[0033]

[0034] Under nitrogen protection, N,N-dibenzylcyclopropylformamide (0.5 mmol), pinacol borane (1.2 mmol) and catalyst Y [N(SiMe 3 ) 2 ] 3 (10 mol%), in a mixed solution of toluene and xylene (1.5 mL+1.5 mL), reacted at 60 °C for 24 h, and the isolated yield of the product was 93%.

[0035] 1 H NMR (CDCl 3 , 500 MHz, ppm): δ 7.46-7.44 (m, 4H), 7.35 (t, J = 7.3Hz, 4H), 7.28-7.25 (m, 2H), 3.71 (s, 4H), 2.38 (d, J = 6.5 Hz, 2H), 1.01-0.93(m, 1H), 0.53-0.49 (m, 2H), 0.11-0.06 (m, 2H). 13 C NMR (CDCl 3 , 125 MHz, ppm):δ 140.4, 128.8, 128.3, 126.8, 58.5, 58.4, 8.6, 4.1.

Embodiment 3

[0037] Synthesis of N,N-dibenzyl-1-(4-methoxyphenyl)methanamine, the chemical structure is as follows:

[0038]

[0039] Under nitrogen protection, add raw material N,N-dibenzyl-4-methoxybenzamide (0.5 mmol), pinacol borane (1.2 mmol) and catalyst Y [N(SiMe 3 ) 2 ] 3 (10 mol%), in toluene (3 ml), reacted at 100 ℃ for 24 h, and the isolated yield of the product was 97%.

[0040] 1 H NMR (CDCl 3 , 500 MHz, ppm): δ 7.48-7.46 (m, 4H), 7.40-7.36 (m, 6H),7.31-7.27 (m, 2H), 6.93 (d, J = 8.6 Hz, 2H), 3.84 (s, 3H), 3.61 (s, 4H), 3.57(s, 2H). 13 C NMR (CDCl 3, 125 MHz, ppm): δ 158.8, 139.9, 131.7, 130.0, 128.9,128.3, 126.9, 113.8, 57.9, 57.4, 55.3.

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Abstract

The invention discloses a method for synthesizing a tertiary amine derivative by catalyzing a hydroboration reaction of tertiary amide by rare earth. Under the protection of nitrogen, in a rare earthcatalysis system, the tertiary amine derivative is prepared through a hydrogen transfer reduction reaction catalyzed by rare earth with tertiary amide and pinacol borane as raw materials. The method has the advantages and effects that a novel synthesis process is utilized, and the tertiary amine derivative prepared by using the method disclosed by the invention is high in quality and stable in process; the raw materials are widely sourced or easy to prepare and store, and the reaction yield is high; and in addition, a catalyst can be directly commercially purchased or is easily, directly and simply synthesized, and can be used in actual production.

Description

technical field [0001] The invention relates to the technical field of chemical industry, in particular to a method for synthesizing tertiary amine derivatives by rare earth-catalyzed hydroboration of tertiary amides. Background technique [0002] Tertiary amine derivatives are an important class of organic compounds, which widely exist in the molecular skeletons of biomedicine, food, cosmetics, pesticides and natural products. Therefore, the research on their efficient synthesis methods has great application value and broad application prospects. . [0003] In the existing chemical method preparation technology, the synthetic method of tertiary amine can utilize: (1) amine and halogenated hydrocarbon reaction prepare ( Tetrahedron Lett . 2006, 47 , 4871-4875); (II) Alcohol reacts with amine to prepare new amine, that is, alcohol amination reaction ( Org. Lett. 2017, 19 , 6148-6151); (III) Reaction of amines with alkenes or alkynes, that is, hydroamination reaction, to...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/50C07C211/27C07C211/30C07C211/29C07C213/02C07C217/58C07D295/03C07D307/52
CPCC07C209/50C07C213/02C07D295/03C07D307/52C07C2601/02C07C211/27C07C217/58C07C211/30C07C211/29Y02P20/584
Inventor 章芳俊蔡文选
Owner WENZHOU MEDICAL UNIV
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