Method of synthesizing amide with methyl aromatics and amine in water phase

A technology for synthesizing methyl aromatic hydrocarbons and amides, applied in chemical instruments and methods, formation/introduction of amide groups, preparation of carboxylic acid amides, etc., can solve problems such as applicability limitations, and achieve cost reduction and good application prospects

Inactive Publication Date: 2015-07-08
JIANGXI NORMAL UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, some of the above methods have relatively large restrictions on the conditions of oxidative amidation or the applicabili

Method used

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  • Method of synthesizing amide with methyl aromatics and amine in water phase
  • Method of synthesizing amide with methyl aromatics and amine in water phase
  • Method of synthesizing amide with methyl aromatics and amine in water phase

Examples

Experimental program
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Effect test

example 1

[0018]

[0019] In a clean 10 mL sealed tube add toluene (20 eq) and butylamine (0.24 mmol), TBHP (70% water) 6 eq as oxidant, 30 mol% TBAI and 15 mol% FeCl 3 As catalyst, 100 mg of 4A molecular sieves and 1.5 mL of water. at 60 o C for 24 hours, TLC plate detection, after the reaction, the reaction solution was cooled to room temperature, the reaction solution was extracted with ethyl acetate (3 × 10 mL), the organic phase was combined and washed with anhydrous Na 2 SO 4 After drying, the organic layer was concentrated and subjected to column chromatography to obtain pure N-butylbenzamide as a yellow liquid with a yield of 73%.

[0020] 1 H NMR (400 MHz, CDCl 3 ): δ 7.75 (d, J = 7.7 Hz, 2H), 7.48–7.37(m, 3H), 6.36 (bs, 1H), 3.45–3.40 (m, 2H), 1.64–1.53 (m, 2H), 1.43 –1.36 (m, 2H), 0.93 (t, J = 7.2 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 167.5, 134.9, 131.2, 128.4, 126.8, 39.8, 31.7, 20.1, 13.7.

example 2

[0022]

[0023] In a clean 10 mL sealed tube add p-xylene (20 eq) and butylamine (0.24 mmol), TBHP (70% water) 6 eq as oxidant, 30 mol% TBAI and 15 mol% FeCl 3 As catalyst, 100 mg of 4A molecular sieves and 1.5 mL of water. at 60 o C for 24 hours, TLC plate detection, after the reaction, the reaction solution was cooled to room temperature, the reaction solution was extracted with ethyl acetate (3 × 10 mL), the organic phase was combined and washed with anhydrous Na 2 SO 4 After drying, the organic layer was concentrated and subjected to column chromatography to obtain pure N-butyl-4-methylbenzamide as a yellow solid with a yield of 78%.

[0024] 1 H NMR (400 MHz, CDCl 3 ): δ 7.65 (d, J = 8.2 Hz, 2H), 7.19 (d, J = 7.9 Hz, 2H), 6.30 (bs, 1H), 3.44–3.39 (m, 2H), 2.37 (s, 3H), 1.61–1.54 (m, 2H), 1.43–1.34 (m, 2H), 0.93 (t, J = 7.3 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ 167.4, 141.5, 132.0, 129.1, 126.8, 39.7, 31.7, 21.3, 20.1, 13.7.

example 3

[0026]

[0027] In a clean 10 mL sealed tube add 4-methylanisole (20 eq) and butylamine (0.24 mmol), TBHP (70% water) 6 eq as oxidant, 30 mol% TBAI and 15 mol% FeCl 3 As catalyst, 100 mg of 4A molecular sieves and 1.5 mL of water. at 60 o C for 24 hours, TLC plate detection, after the reaction, the reaction solution was cooled to room temperature, the reaction solution was extracted with ethyl acetate (3 × 10 mL), the organic phase was combined and washed with anhydrous Na 2 SO 4 After drying, the organic layer was concentrated and subjected to column chromatography to obtain pure benzene N-butyl-4-methoxybenzamide as a yellow liquid with a yield of 82%.

[0028] 1 H NMR (400 MHz, CDCl 3 ): δ 7.72 (d, J = 7.7 Hz, 2H), 6.87 (d, J = 7.8 Hz, 2H), 6.31 (bs, 1H), 3.81 (s, 3H), 3.53–3.29 (m, 2H), 1.58–1.52 (m, 2H), 1.40–1.34 (m, 2H), 0.92 (t, J = 6.7 Hz, 3H) 13 C NMR (100 MHz, CDCl 3 ): δ 167.0, 161.9, 128.6, 127.0, 113.5, 55.3, 39.7, 31.7, 20.1, 13.7.

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Abstract

The invention provides a high-efficient method of synthesizing amide with methyl aromatics and amine. In the method, with the methyl aromatics and the amine as the raw materials in the water phase and TBHP and TBAI respectively as an oxidizing agent and a catalyst, a sp3 C-H bond and a sp3 N-H bond are broken and a C-N bond is formed. Compared with a conventional method of synthesizing the amide from oxidized amide, in which an activated acyl group or amine is required, the method is carried out with water as the solvent so that the method is not only economical but also environmental-protective. The method has a very good application prospect in the field of synthesizing polypeptide, protein and drugs in future.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and in particular relates to a method for synthesizing amides with methyl aromatic hydrocarbons and amines in water phase. Background technique [0002] The amide structure is a very special and stable skeleton structure, which is contained in many drug skeletons and peptides and proteins, so the efficient, green, and low-toxic synthesis of such compounds has become a constant challenge in the field of organic chemistry. Although there are many chemical reactions in organic chemistry that can achieve the conversion of amide bonds, traditional chemical synthesis methods require pre-activation of carboxyl moieties or coupling reagents and excess reactants, which will result in high cost and waste. The method of ‘avoiding low atom-economy synthesis of amides’ has become a challenge in organic chemistry and green chemistry. In recent years, Singh et al. used methyl aromatic hydrocarbons and chlorina...

Claims

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Application Information

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IPC IPC(8): C07B43/06C07C231/10C07C233/65C07C235/46C07C235/52C07D333/38
Inventor 王涛袁淋赵振光邵爱龙高梦黄阳妃熊飞张华丽赵军锋
Owner JIANGXI NORMAL UNIV
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