Method for reducing amide compounds

A technology of amine compounds and reduction of amides, which is applied in the preparation of organic compounds, preparation of amino compounds, chemical instruments and methods, etc., can solve the problems of post-processing troubles, high reaction costs, C-N bond breakage, etc. The effect of simple operation and mild reaction conditions

Inactive Publication Date: 2015-02-18
SICHUAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In chemical reduction, the method using borohydride (JP Zhao 55-162746A) and aluminum hydride compound as reducing agent is the most widely used, but the reaction is prone to C-N bond breakage (Tetrahedron Lett. 43 (2002) 8867-8869), and post-treatment More troublesome (J. Org. Chem. 47 (1982) 3153-3163)
In addition, trifluoromethanesulfonic anhydride is used as an activator, and triethylsilane and Hantzsch ester are used as a non-metallic reduction method for reducing agents. It is only applicable to secondary and tertiary amides and the reaction cost is relatively high (J. Am. Chem . Soc. 132 (2010) 12817-12819)

Method used

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  • Method for reducing amide compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Example 1: Reduction of benzanilide

[0024]

[0025] Under the protection of Ar gas, Mg powder (10mmol) and THF (60mL) were added to the reaction flask, stirred in an ice bath, and TiCl was injected into the system. 4 (5 mmol), the reaction system was raised to room temperature and reacted for two hours to obtain a black suspension. The system was placed in an ice bath, and a solution of benzanilide (1 mmol) in THF (15 mL) was slowly added dropwise. After the dropwise addition, the mixture was raised to room temperature for reaction. After the reaction was completed, the reactant was placed in an ice bath, and saturated aqueous sodium bicarbonate solution was added thereto, and then 20% aqueous sodium hydroxide solution was added until the pH > 9. The reactant was filtered, the filtrate was extracted with dichloromethane, and the extract was concentrated to obtain a crude amine compound, which was then subjected to silica gel column chromatography to obtain N-ben...

Embodiment 2

[0026] Example 2: Reduction of 4-methyl-N-phenylbenzamide

[0027]

[0028] The experimental operation was similar to that of Example 1, and N-(4-methylbenzyl)aniline was obtained as a colorless oil with a yield of 82%. 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.16 (d, J = 8.0 Hz, 2H), 7.03-7.10 (m, 4H), 6.61 (t, J = 8.0 Hz, 1H), 6.52 (d, J = 8.0 Hz, 2H), 4.15 (s, 2H), 3.77 (brs, 1H), 2.24 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 148.3, 136.9, 136.5, 129.4, 129.3, 127.6, 117.6, 112.9, 48.1, 21.2. HRMS (ESI): m / z calcd for C 14 h 16 N[M+H] + : 198.1283, found: 198.1287.

Embodiment 3

[0029] Example 3: Reduction of 4-methoxy-N-phenylbenzamide

[0030]

[0031] The experimental operation was similar to Example 1, and a colorless solid N-(4-methoxybenzyl)aniline was obtained with a yield of 86%. 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.28 (d, J = 8.0 Hz, 2 H), 7.16 (t, J = 8.0 Hz, 2H), 6.87 (d, J = 8.0 Hz, 2 H), 6.70 (t, J = 8.0 Hz, 1H), 6.63 (d, J = 8.0 Hz, 2H), 4.23 (s, 2H), 3.78 (s, 3H), 3.60 (brs, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ (ppm): 158.9, 148.2, 131.4, 129.3, 128.9, 117.6, 114.1, 112.9, 55.3, 47.9. HRMS (ESI): m / z calcd for C 14 h 16 NO [M+H] + : 214.1232, found: 214.1238.

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Abstract

The invention discloses a method for reducing amide compounds, which reduces various amides through low valent tiron. Low valent tiron prepared by reducing titanium tetrachloride through magnesium powder is reacted with amide in tetrahydrofuran at 0 DEG C or normal temperature so as to obtain corresponding amine. The method has the advantages that the reaction condition is mild, reagent adopted is chip and easy to get, the method is convenient to operate, substrate has a wide applicable scope, functional group has good compatibility, the reaction is rapid, and the yield is high.

Description

technical field [0001] The invention relates to a new method for reducing amides. In the method, low-valent titanium reagent is used as a reducing agent to reduce various types of amides to obtain corresponding amine compounds. Background technique [0002] Amide reduction is one of the important organic reactions, widely used in chemistry, biology, materials and other fields. The partial amide reduction method is widely used, but there are still many shortcomings. [0003] The reduction of amides by catalytic hydrogenation is an earlier and more ideal and economical method. However, the reaction conditions are harsh, and the reaction is generally carried out at high temperature and high pressure (Angew. Chem. Int. Ed. 52 (2013) 2231-2234). Transition metal-catalyzed organosilicon reduction, high reaction temperature, mainly suitable for tertiary amides (J. Am. Chem. Soc. 132 (2010) 1770-1771), partly suitable for secondary amides (J. Am. Chem. Soc . 134 (2012) 11304–1130...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B43/04C07C211/48C07C211/53C07C211/27C07C211/35C07C209/50C07C217/58C07C213/02C07C215/76C07D213/38C07D295/03C07D295/027C07D295/023C07C271/20C07C269/06
Inventor 罗美明张彤鑫张维熙
Owner SICHUAN UNIV
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