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Preparation method of amide

A technology of amide and formamide, which is applied in the field of amide preparation, can solve the problems of restricting large-scale application, narrow use range of substrates, troublesome preparation of reactants, etc., and achieve the effects of improving utilization efficiency, wide use range and excellent yield

Active Publication Date: 2012-07-18
铜陵市官作文化有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0013] Although there are many methods for synthesizing amides, some catalysts used in these methods are more expensive (such as Ru, Rh, Pd, Ni, Cu), some catalytic systems are more loaded down with trivial details, some reactants are troublesome to prepare, and the price is more expensive. The scope of use is narrow and has relatively large limitations, which limit its large-scale application

Method used

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  • Preparation method of amide
  • Preparation method of amide
  • Preparation method of amide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038]

[0039] The reaction flasks were sequentially charged with Bu 4 NI (20 mol%), compound 1a (2 mmol, 312 mg), TBHP (11.6 mmol), N,N-dimethylformamide (2.4 mL), acetonitrile 8 mL. Then the system was heated at 100°C in air for about 24 hours, quenched with saturated sodium sulfite, washed with water, extracted with ethyl acetate (40 mL×3), and the oxidized product 3a was obtained by simple column chromatography with a yield of 79%.

[0040] The product was analyzed and the results were as follows: 1 HNMR (300MHz, CDCl 3 ): δ7.88-7.64(m, 3H), 7.48-7.26(m, 4H), 3.16(s, 3H), 2.71(s, 3H). 13 CNMR (75MHz, CDCl 3): 170.8, 134.6, 133.3, 129.3, 128.9, 128.3, 126.9, 126.2, 125.1, 124.7, 123.8, 38.8, 34.8. MS: Anal.Calcd.For C 13 H 12 NO: 199, Found: 199 (M + ); IR(KBr, cm -1 ): v1621. The above data proves that the obtained compound is the target product.

Embodiment 2

[0042]

[0043] The reaction flasks were sequentially charged with Bu 4 NI (20 mol%), compound 1a (2 mmol, 312 mg), TBHP (2 mmol), N,N-dimethylformamide (2.4 mL), toluene 8 mL. Then the system was heated at 90°C in the air for about 24 hours, quenched with saturated sodium sulfite, washed with water, extracted with ethyl acetate (40 mL×3), and the oxidized product 3a was obtained by simple column chromatography with a yield of 85%.

[0044] The product was analyzed and the results were as follows: 1 HNMR (300MHz, CDCl 3 ): δ7.88-7.64(m, 3H), 7.48-7.26(m, 4H), 3.16(s, 3H), 2.71(s, 3H). 13 CNMR (75MHz, CDCl 3 ): 170.8, 134.6, 133.3, 129.3, 128.9, 128.3, 126.9, 126.2, 125.1, 124.7, 123.8, 38.8, 34.8. MS: Anal.Calcd.For C 13 H 12 NO: 199, Found: 199 (M + ); IR(KBr, cm -1 ): v1621. The above data proves that the obtained compound is the target product.

Embodiment 3

[0046]

[0047] The reaction flasks were sequentially charged with Bu 4 NI (20 mol%), compound 1a (2 mmol, 312 mg), TBHP (2 mmol), N,N-dimethylformamide (2.4 mL), acetonitrile 8 mL. Then the system was heated at 90°C in the air for about 24 hours, quenched with saturated sodium sulfite, washed with water, extracted with ethyl acetate (40 mL×3), and the oxidized product 3a was obtained by simple column chromatography with a yield of 59%.

[0048] The product was analyzed and the results were as follows: 1 HNMR (300MHz, CDCl 3 ): δ7.88-7.64(m, 3H), 7.48-7.26(m, 4H), 3.16(s, 3H), 2.71(s, 3H). 13 CNMR (75MHz, CDCl 3 ): 170.8, 134.6, 133.3, 129.3, 128.9, 128.3, 126.9, 126.2, 125.1, 124.7, 123.8, 38.8, 34.8. MS: Anal.Calcd.For C 13 H 12 NO: 199, Found: 199 (M + ); IR(KBr, cm -1 ): v1621. The above data proves that the obtained compound is the target product.

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Abstract

The invention discloses a preparation method of amide. With an aldehyde derivative and a formamide derivative as a reaction substrate, iodide as catalyst and tert-butanol hydrogen peroxide as an oxidizing agent, the amide is prepared through decarbonylation double free radical cross-coupling reaction, wherein the chemical structural formula of the aldehyde derivative is shown in the description, R1 is selected from a naphthyl, a heterlcyclic ring, an alkylene or a mono-substituted aryl; and the iodide is one selected from sodium iodide, potassium iodide, cuprous iodide, lithium iodate, an iodine elementary substance, tetrabutyl ammonium iodide, tetraheptylammonium iodide, tetramethylammonium iodide and benzyltrimethylammonium iodide. According to the invention, because the amide is prepared by using the iodide as the catalyst and using the double free radical cross-coupling method, the use of the traditional metal catalyst with expensive price and larger toxicity as well as a complicated experiment method is avoided so that the reaction is simpler, more convenient, easier, safer, greener and more economic; moreover, the preparation method of the amide disclosed by the invention has the advantages of quite moderate reaction condition, simpler post-treatment and potential industrial application value.

Description

technical field [0001] The present invention relates to a method for preparing amides. Background technique [0002] Amides are a kind of very important structural units, widely present in physiologically active natural products, drug molecules, and often found in synthetic intermediates. [0003] At present, the method for preparing amide has the disadvantages of large amount of catalyst, high price, high toxicity, harsh reaction conditions, low selectivity, and narrow use range of substrates. E.g: [0004] (1) J.M.J.Williams et al. reported the preparation of amides by coupling reaction of carboxylic acids and their derivatives with amines, (see: C.L.Allen, J.M.J.Williams, Chem.Soc.Rev 2011, 40, 3405); [0005] (2) H.Alper et al. reported the selective synthesis of a class of amides through the aminocarboxylation of halogenated aromatic hydrocarbons (see: Y.-S.Lin, H.Alper, Angew.Chem.2001, 113 , 801; Angew. Chem. Int. Ed. 2001, 40, 779); [0006] (3) S.Murahashi et al...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/00C07C231/12C07C233/65C07C253/30C07C255/57C07C319/20C07C323/62C07C303/30C07C309/73C07C237/42C07C235/46C07D307/68C07D333/38C07D277/56C07D213/81C07C233/09C07C233/11C07D295/192C07D211/46C07D231/12C07D207/16
Inventor 万小兵刘召军张杰陈书林时二波徐元
Owner 铜陵市官作文化有限公司
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