Green method for preparing amine derivatives from alcohols and amines

A green technology of amine derivatives, applied in chemical instruments and methods, preparation of amino compounds, preparation of organic compounds, etc., can solve the problems of low reaction selectivity, high price, and many by-products, and achieve wide application prospects, Effects with a wide range of applications and easy operation

Inactive Publication Date: 2015-03-25
WENZHOU UNIVERSITY
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AI Technical Summary

Problems solved by technology

Therefore, in recent decades, chemists have successively reported new methods for the synthesis of amine compounds catalyzed by various transition metals, but these catalytic methods still have some disadvantages: for example, the method catalyzed by Pd or Cu needs to use an excessive amount of base, reducing the amine The chemical method uses aldehydes and ketones as reaction raw materials and requires a large amount of reducing agent. The transition metal catalyst is expensive, unstable in the air, and difficult to prepare and obtain, which greatly reduces the practicability and promotion potential of the reaction.
However, there are many side reactions and by-products in this method, the reaction selectivity is not high, and the target product is difficult to separate.
But the method has seen little improvement since it was reported by the German chemist Hofmann around 1850

Method used

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  • Green method for preparing amine derivatives from alcohols and amines
  • Green method for preparing amine derivatives from alcohols and amines
  • Green method for preparing amine derivatives from alcohols and amines

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Preparation of N-Benzylaniline from Benzyl Alcohol and Aniline

[0030]

[0031] Benzyl bromide (0.0257g, 7.5mol%), aniline (3mmol, 1.5equiv.) and benzyl alcohol (0.2163g, 2mmol) were successively added into a tubular reactor, sealed directly under air, and then heated under solvent-free conditions Reaction at 160°C for 24h. After the complete reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 82%. 1 H NMR (500MHz, CDCl 3 ): δ7.35-7.30(m, 4H), 7.26-7.24(m, 1H), 7.17-7.14(m, 2H), 6.71-6.68(m, 1H), 6.61-6.59(m, 2H), 4.28 (s, 2H), 3.97(b, 1H). 13 C NMR (125.4MHz, CDCl 3 ): δ148.1, 139.4, 129.2, 128.6, 127.4, 117.5, 112.8, 48.2. MS (EI): m / z (%) 184 (7), 183 (47), 182 (18), 181 (4) , 180(6), 106(18), 104(10), 92(9), 91(100), 89(3), 78(4), 77(23), 65(20), 63(4) , 51(11).

Embodiment 2

[0033] Preparation of N-Benzyl-2-Methylaniline from Benzyl Alcohol and 2-Methylaniline

[0034]

[0035] Add benzyl bromide (0.0257g, 7.5mol%), 2-methylaniline (3mmol, 1.5equiv.) and benzyl alcohol (0.2163g, 2mmol) successively in the tubular reactor, directly seal under the air, then Under solvent conditions, it was heated to 160°C for 24h. After the complete reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 64%. 1 H NMR (500MHz, CDCl 3 ): δ7.44-7.38(m, 4H), 7.34-7.31(m, 1H), 7.16-7.11(m, 2H), 6.72(t, J=7.0Hz, 1H), 6.66(d, J=8.0 Hz, 1H), 4.42(s, 2H), 3.90(b, 1H), 2.21(s, 3H). 13 C NMR (125.4MHz, CDCl 3 ): δ146.1, 139.5, 120.1, 128.6, 127.5, 127.2, 127.1, 121.9, 117.2, 110.0, 48.3, 17.5. MS (EI): m / z (%) 198 (12), 197 (73), 196 (22), 120(15), 118(10), 106(17), 92(9), 91(100), 77(7), 65(16).

Embodiment 3

[0037] Preparation of N-Benzyl-3-Methylaniline from Benzyl Alcohol and 3-Methylaniline

[0038]

[0039]Add benzyl bromide (0.0257g, 7.5mol%), 3-methylaniline (3mmol, 1.5equiv.) and benzyl alcohol (0.2163g, 2mmol) successively in the tubular reactor, directly seal under the air, and then Under solvent conditions, it was heated to 160°C for 24h. After the complete reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 51%. 1 H NMR (500MHz, CDCl 3 ): δ7.35-7.18(m, 5H), 7.05(t, J=7.5Hz, 1H), 7.53(d, J=7.5Hz, 1H), 6.45-6.42(m, 2H), 4.29(s, 2H), 3.83(b, 1H), 2.25(s, 3H). 13 C NMR (125.4MHz, CDCl 3 ): δ148.2, 139.6, 139.0, 129.1, 128.6, 127.5, 127.1, 118.5, 113.6, 110.0, 48.3, 21.6. MS (EI): m / z (%) 198 (16), 197 (100), 196 (49), 194(5), 180(3), 120(26), 118(8), 92(9), 91(99), 89(3), 77(6), 65(15).

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Abstract

The invention discloses a green method for preparing amine derivatives from alcohols and amines. Different amine derivatives are prepared from alcohol and amine compounds by virtue of a controllable high-selectivity alkylation reaction under the catalysis of a nontransition metal catalyst and under the condition of no solvent; the nontransition metal catalyst is a halohydrocarbon and the dosage of the halohydrocarbon is 1-50mol%; a dehydration reaction can be directly performed on the alcohols and the amines under the catalysis of the halohydrocarbon to obtain the amine derivatives, and the reaction temperature ranges from 100 to 180 DEG C, the reaction time is 12-48 hours and the byproduct is water; the reaction needs to be performed under the protection of an inert gas, the conditions are simple and easy to operate, the byproduct is water, the reaction selectivity is controllable and the target selectivity is high. The requirements on the reaction conditions are reduced; the primary alcohol and the secondary alcohol can be used as alkylation reagents and suitable for the dehydration mono-alkylation reaction of the primary amine and the secondary amine and also for the dehydration dual-alkylation reaction of the primary amine; the green method for preparing the amine derivatives from the alcohols and the amines have a wide application range and ought to have certain research and industrial application prospect.

Description

technical field [0001] The invention relates to the technical field of chemical synthesis, in particular to a green method for preparing amine derivatives from alcohols and amines. Background technique [0002] Organic nitrogen compounds such as amines are important synthetic raw materials, which play an important role in organic synthesis and drug synthesis. Almost all drug molecules contain nitrogen atoms; many amine compounds are also widely involved in biochemical processes and natural product synthesis. Such as amino acids and nucleotides necessary to build life, as well as vitamins, hormones, alkaloids and other biologically active substances contain amino functional groups, so various amines and their derivatives are widely used in pesticides, medicines, dyes, polymer materials, Food additives and other various industrial and agricultural production. Therefore, in recent decades, chemists have successively reported new methods for the synthesis of amine compounds cat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C211/48C07C209/18C07C211/52C07C217/84C07C213/02C07D209/86C07D209/08C07D215/06
Inventor 徐清谢华楣张二磊陈建辉
Owner WENZHOU UNIVERSITY
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