Method preparing N-aryl and N-alkyl aromatic amine type compound from phenol type compound

A technology for phenolic compounds and alkylarylamines is applied in the field of preparing N-aryl and N-alkylarylamine compounds and achieves the effects of mild reaction conditions, low cost and pollution avoidance

Inactive Publication Date: 2013-06-05
ZHEJIANG UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the method for the synthesis of N-aryl and N-alkylarylamine compounds with phenolic compounds and ammoniating reagents has not been reported yet.

Method used

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  • Method preparing N-aryl and N-alkyl aromatic amine type compound from phenol type compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Embodiment 1: the synthesis of diphenylamine

[0027] Add phenol (94 mg, 1.0 mmol), KOH (168 mg, 3.0 mmol), 2-chloro-N-phenylpropanamide (549 mg, 3.0 mmol) and toluene (3 ml) to the dry reaction tube, 50 ℃ for 2 hours, add KOH (168 mg, 3.0 mmol), react at 110 ℃ for 24 hours, add 10 ml of water, extract with dichloromethane (3×25ml), and use saturated brine (2×20 ml) for the organic phase ), washed with anhydrous sodium sulfate, filtered, rotary evaporated, and flash silica gel column chromatography (eluent: petroleum ether / ethyl acetate=20 / 1), the product diphenylamine was obtained as a white solid with a yield of 83%.

[0028] 1 H NMR (400 MHz, CDCl 3 , TMS) δ 7.29 (t, J = 8.0 Hz, 4H), 7.09 (d, J = 7.6 Hz, 4H), 6.95 (t, J = 7.6 Hz, 2H), 5.72 (bs, 1H); 13 C NMR (100 MHz, CDCl 3 , TMS) δ 143.0, 129.3, 120.9, 117.8 ppm.

Embodiment 2

[0029] Embodiment 2: the synthesis of 4-chlorodiphenylamine

[0030] Add p-chlorophenol (128 mg, 1.0 mmol), NaOH (80 mg, 2.0 mmol), 2-bromo-N-phenylpropanamide (227 mg, 1.0 mmol) and N-methylpyrrolidone to a dry reaction tube (3 ml), react at 60°C for 4 hours, add NaOH (40 mg, 1.0 mmol), react at 130°C for 2 hours, add 10 ml of water, extract with dichloromethane (3 × 25ml), and use saturated salt for the organic phase Wash with water (2×20 ml), dry over anhydrous sodium sulfate, filter, rotary evaporate, and flash silica gel column chromatography (eluent: petroleum ether / ethyl acetate=20 / 1) to obtain the product 4-chlorodiphenylamine, White solid, yield 75%.

[0031] 1 H NMR (400 MHz, CDCl 3 , TMS) δ 7.32-7.22 (m, 4H), 7.08-6.96 (m, 5H), 5.71(bs, 1H); 13 C NMR (100 MHz, CDCl 3 , TMS) δ 142.5, 141.8, 129.3, 129.1, 125.4, 121.4, 118.7, 118.0 ppm.

Embodiment 3

[0032] Embodiment 3: the synthesis of 3-methoxydiphenylamine

[0033] Add 3-methoxyphenol (124 mg, 1.0 mmol), Na 2 CO 3 (212 mg, 2.0 mmol), 2-iodo-N-phenylpropanamide (522 mg, 2.0 mmol) and N, N-dimethylformamide (3 ml), reacted at 70 ° C for 3 hours, added Na 2 CO 3 (212 mg, 2.0 mmol), reacted at 140 °C for 16 hours, added 10 ml of water, extracted with dichloromethane (3 × 25 ml), washed the organic phase with saturated brine (2 × 20 ml), dried over anhydrous sodium sulfate, and filtered , rotary evaporation, and flash silica gel column chromatography (eluent: petroleum ether / ethyl acetate=20 / 1), the product 3-methoxydiphenylamine was obtained as a light yellow solid with a yield of 48%.

[0034] 1 H NMR (400 MHz, CDCl 3 , TMS) δ 7.29 (t, J = 8.0 Hz, 2H), 7.18 (t, J = 8.0 Hz, 1H), 7.10 (d, J = 7.6 Hz, 2H), 6.96 (t, J = 7.6 Hz, 1H ), 6.67-6.65 (m, 2H), 6.49 (d, J = 8.8Hz, 1H), 5.72 (s, 1H), 3.79 (s, 3H); 13 C NMR (100 MHz, CDCl 3 , TMS) δ 160.6, 144.4, 142.6, 130.0 12...

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Abstract

The invention relates to field of organic synthesis, and aims to provide a method preparing N-aryl and N-alkyl aromatic amine type compound from phenol type compound. The method includes that the phenol type compound and ammoniation reagents are solved in organic solvent or mixed solvent of the organic solvent and cosolvent, alkali is added, reaction is conducted for 2-4 hours under 50-80 DEG C, temperature rises to 100-160 DEG C, stirring reaction is conducted for 2-24 hours, and aromatic primary amine type compound is obtained after postprocessing. Alternatively, part of alkali is added, reaction is conducted for 2-24 hours under 50-80 DEG C, another part of alkali is additionally added, temperature rises to 100-160 DEG C, stirring reaction is conducted for 2-24 hours, and the N-aryl and N-alkyl aromatic amine type compound is obtained after postprocessing. The method is wide in application range, strong in generality, high in yield, and simple and convenient to operate.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a method for preparing N-aryl and N-alkylarylamine compounds starting from phenolic compounds. Background technique [0002] N-aryl and N-alkylarylamine compounds are important chemical intermediates, which are widely used in various industries such as medicine, materials, pesticides, and dyes. The synthesis of N-arylarylamines can be obtained through transition metal-catalyzed coupling reaction between aryl halides and arylamines. There are also reports in the literature on the one-pot synthesis of N-arylaniline compounds using phenol as a raw material. And the synthetic method of N-alkyl arylamine compound mainly contains three kinds, the first kind is that arylamine and alkylating agent take place substitution reaction; The second kind is that arylamine and aldehyde, ketone take place reductive amination reaction; The third kind It is a transition metal-catalyzed coupling re...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B43/04C07C211/55C07C211/58C07C209/60C07C211/56C07C217/84C07C213/02C07C221/00C07C225/22C07C227/04C07C229/60C07C255/58C07C253/30C07D215/40C07D311/16C07D307/52
Inventor 吴军俞建忠张培志商志才
Owner ZHEJIANG UNIV
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