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Method for synthesizing amine compounds through alcohol and amine dehydration

A technology for synthesizing amines and compounds, applied in the field of synthesis of amine compounds, can solve the problems of high price of transition metal catalysts, reduced practicality and promotion potential, difficult preparation and acquisition, etc., achieves good research and industrial application prospects, reduces synthetic The effect of low cost and low price

Inactive Publication Date: 2014-12-24
WENZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These methods catalyzed by transition metals have many disadvantages: as the method catalyzed by Pd or Cu needs to use an excessive amount of alkali, the reductive amination method uses aldehydes and ketones as reaction raw materials and requires a large amount of reducing agent, and the transition metal catalyst is expensive. Unstable, difficult to prepare and obtain, greatly reducing the practicability and promotion potential of the reaction
[0004] Among the currently known synthetic methods for preparing amine derivatives by reacting alcohols with amines, there is still no one that can be compared with the reaction catalyzed by transition metals, and a wide range of applications, green, mild, efficient, economical, simple and easy catalytic system can Catalyzed direct dehydration coupling reaction of alcohols and amines to synthesize amines

Method used

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  • Method for synthesizing amine compounds through alcohol and amine dehydration
  • Method for synthesizing amine compounds through alcohol and amine dehydration
  • Method for synthesizing amine compounds through alcohol and amine dehydration

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020]

[0021] Weigh successively benzyl alcohol (3.9mmol, 1.3 equiv.), benzenesulfonamide (3.0mmol, 1.0equiv.), K 2 CO 3 (0.3mmol, 10mol%), absolute benzaldehyde (0.3mmol, 10mol%) in a 20mL Shlenk reactor, seal the tube, stir and heat to 135°C. Follow up detection with GC-MS and TLC. The reaction crude product was separated by flash column chromatography, and the mixture of petroleum ether and ethyl acetate was used as the eluent to purify to obtain the target product, and the separation yield was 91%. White solid. 1 H NMR (500MHz, CDCl 3 ): δ7.87-7.85(m, 2H), 7.59-7.56(m, 1H), 7.51-7.48(m, 2H), 7.27-7.17(m, 5H), 5.02(b, 1H), 4.13(s , 2H). 13 C NMR (125.4MHz, CDCl 3 ): δ139.9, 136.2, 132.7, 129.1, 128.7, 127.91, 127.86, 127.1, 47.3. 5), 106(100), 104(11), 91(14), 79(23), 78(14), 77(40), 65(5), 51(14).

Embodiment 2

[0023]

[0024] Take by weighing p-methyl benzyl alcohol (4.5mmol, 1.5equiv.), benzenesulfonamide (3.0mmol, 1.0equiv.), K 2 CO 3 (0.6mmol, 20mol%) and p-tolualdehyde (0.6mmol, 20mol%) were placed in a 20mL Shlenk reactor, sealed, stirred, and heated to 150°C. Follow up detection with GC-MS and TLC. The reaction crude product was separated by flash column chromatography, and the mixture of petroleum ether and ethyl acetate was used as eluent to purify to obtain the target product with an isolation yield of 88%. White solid. 1 H NMR (500MHz, CDCl 3 ): δ7.88-7.86(m, 2H), 7.60-7.57(m, 1H), 7.53-7.50(m, 2H), 7.09-7.05(m, 4H), 4.65(b, 1H), 4.10(d , J=6.1Hz, 2H), 2.30(s, 3H). 13 C NMR (125.4MHz, CDCl 3 ): δ140.1, 137.8, 133.2, 132.7, 129.4, 129.1, 127.9, 127.2, 47.1, 21.1. MS (EI): m / z (%) 261 (0.5), 246 (0.1), 195 (0.3), 165(0.3), 143(3), 125(3), 120(100), 118(30), 105(13), 91(18), 93(17.5), 77(33), 65(9), 51(10).

Embodiment 3

[0026]

[0027] Take by weighing p-methoxybenzyl alcohol (3.9mmol, 1.3 equiv.), benzenesulfonamide (3.0mmol, 1.0equiv.), K 2 CO 3 (0.3mmol, 10mol%), p-methoxybenzaldehyde (0.3mmol, 10mol%) in a 20mL Shlenk reactor, sealed, heated to 135°C, and stirred. Follow up detection with GC-MS and TLC. The reaction crude product was separated by flash column chromatography, and the mixture of petroleum ether and ethyl acetate was used as the eluent to purify to obtain the target product, and the separation yield was 67%. White solid. 1 H NMR (500MHz, CDCl 3 ): δ7.84-7.82(m, 2H), 7.57-7.54(m, 1H), 7.48-7.45(m, 2H), 7.07(d, J=8.5Hz, 2H), 6.75(d, J=8.6 Hz, 2H), 5.15(b, 1H), 4.04(d, J=6.1Hz, 2H), 3.73(s, 3H). 13 C NMR (125.4MHz, CDCl 3 ): δ159.3, 140.0, 132.6, 129.3, 129.1, 128.4, 127.1, 114.1, 55.3, 46.8. MS (EI): m / z (%) 277(5), 141(2), 136(64), 135(100), 134(54), 121(27), 109(9), 94(5), 77(29), 65(5), 51(8).

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Abstract

The invention discloses a method for synthesizing amine compounds through alcohol and amine dehydration. According to the method, nonmetal elements are used as catalysts for reaction in inert gas or air. The price of nontransition metal element catalysts used in the method is low, the reaction conditions in a catalytic system are mild, the treatment, the separation and the purification of products are simple, and the product yield is high. The low-price and easy-to-obtain alcohol is used as alkylation reagents, so that the synthesis cost is greatly reduced. The method has the advantages that the operation is carried out under the solvent-free condition, so that the pollution possibly caused by organic solvents on the environment can be reduced to a certain degree.

Description

technical field [0001] The invention relates to a method for synthesizing amine compounds, in particular to a method for synthesizing amine compounds through dehydration coupling of alcohol and amine. Background technique [0002] Amine compounds are important raw materials for the synthesis of many nitrogen-containing compounds, not only occupy an important position in organic and pharmaceutical synthesis, but also widely participate in many biochemical processes and natural product synthesis. For example, amino acids and nucleotides necessary for the construction of living organisms, as well as biologically active substances such as vitamins, hormones, and alkaloids, all contain amino functional groups. This is why various amines and their derivatives are widely used in various industrial and agricultural productions such as pesticides, medicines, dyes, polymer materials, and food additives. Systematic and in-depth research. [0003] In recent decades, in addition to the...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B43/04C07C303/40C07C311/16C07C311/17C07D213/42C07C311/29C07D333/34C07C311/03C07C313/06C07D239/42C07D213/74C07D277/82C07C209/18C07C211/45C07C211/52
Inventor 徐清余小春李强
Owner WENZHOU UNIV