Synthesis method of alpha-keto amide compound

A synthesis method and compound technology, applied in the preparation of sulfonamides, organic chemistry, etc., can solve the problems of expensive gold catalysts, harsh reaction conditions, and complex operations, and achieve high yields, mild reaction conditions, and cheap and easy-to-obtain environments Effect

Inactive Publication Date: 2013-09-04
嘉兴南洋万事兴化工有限公司
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  • Abstract
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Problems solved by technology

[0003] At present, the preparation methods of α-ketoamide mainly include the following types: (1) Using halogenated benzene, carbon monoxide and secondary amine as starting materials and using palladium as a catalyst to synthesize, the disadvantage of this method is that it needs to use expensive precious metals Catalyst, the reaction conditions are harsh, and carbon monoxide gas under high pressure needs to be used. Carbon monoxide is highly toxic, so the operation is complicated and there are safety problems (references can be made to: Ozawa, F., etc., Tetrahed ron Lett., 1982, 23, 3383; Ozawa, F. et al., J. Am. Chem. Soc., 1985, 107, 3235)
(2) Prepare through a multi-step reaction process. This type of method usually has cumbersome steps and needs some special substrates (references can be made to: Wasserman, H.H. et al., J.Org.Chem., 1994,59,4364; U gi, I. et al., Chem. Ber., 1961, 94, 1116; Chen, J.J. et al., Tetrahedron Lett., 2003, 44, 8873)
[0004] In addition to the above literature reports, Xu, C.-F. et al. reported that using gold as a catalyst and diphenylsulfoxide as an oxygen source, α-ketoamides (Org.Lett .,2011,13,1556), it is obvious that the use of expensive gold catalyst, expensive oxygen source and higher temperature are the disadvantages of this method

Method used

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  • Synthesis method of alpha-keto amide compound
  • Synthesis method of alpha-keto amide compound
  • Synthesis method of alpha-keto amide compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030]

[0031] Add 37.4mg (0.2mmol) N-phenylethynyl-oxazolin-2-one, 141.7mg (0.4mmol) S electfluor, 0.64mg (0.01mmol) Cu powder into a 10mL round bottom flask, and then add 2mL Acetonitrile / water (V:V=50:1) was used as solvent. Then, magnetic stirring was performed at room temperature for 9 h. Then, 10 g of column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure. :1) As an eluent, collect the eluate containing the product, and distill the eluate to remove the solvent to obtain the pure product. The material was a pale yellow solid in 92% yield. Characterization data: mp105-107°C; IR(neat)ν=1785,1696(C=O)cm -1 ;. 1 H NMR (CDCl 3 ,500MHz):δ=7.89(d,J=7.0Hz,2H),7.66(t,J=7.5Hz,1H),7.52(t,J=8.0Hz,2H),4.60(t,J=8.0Hz ,2H),4.17(t,J=8.0Hz,2H);MS(EI,70eV):m / z(%)=219(2)[M + ],105(100).

Embodiment 2

[0033] Add 37.4 mg (0.2 mmol) N-phenylethynyl-oxazolin-2-one, 141.7 mg (0.4 mmol) S electfluor, 0.38 mg (0.006) mmol Cu powder into a 10 mL round bottom flask, and then add 2 mL of acetonitrile / water (V:V=50:1) as solvent. Then, the mixture was magnetically stirred for 12 h at room temperature. Then, 10 g of column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure. : 1) As an eluent, collect the eluate containing the product, evaporate the solvent from the eluate to obtain the pure product, and the yield is 90%.

Embodiment 3

[0035]Add 37.4mg (0.2mmol) N-phenylethynyl-oxazolin-2-one, 141.7mg (0.4mmol) S electfluor, 1.28mg (0.02mmol) Cu powder into a 10mL round bottom flask, and then add 2mL Acetonitrile / water (V:V=50:1) was used as solvent. Then, magnetic stirring was performed at room temperature for 16 h. Then, 10 g of column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure. :1) As an eluent, collect the eluate containing the product, evaporate the solvent from the eluate to obtain the pure product, and the yield is 60%.

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Abstract

The invention discloses a synthesis method of an alpha-keto amide compound, which is shown in formula II. According to the synthesis method, an alynyl-amine compound shown in formula I is used as a raw material and then added into a CH3CN / H2O solvent to react so as to obtain the Alpha-keto amide compound shown in formula II under the action of a copper catalyst / Selectfluor oxidant system. The synthesis method provided by the invention has the advantages that the catalyst is low in cost and small in toxicity, the oxygen source is easy to get, environmental protection is realized, the reaction condition is mild, functional groups are good in universality, and the operation is convenient.

Description

(1) Technical field [0001] The invention belongs to the technical field of organic compound synthesis, and in particular relates to a synthesis method of α-ketoamide compounds. (2) Background technology [0002] α-Ketoamides are a very important class of organic compounds. The α-ketoamide structure is an important structural unit of many natural products or artificially synthesized molecules with physiological or pharmacological activity (see Petal. , 2009; Crowley, C.A. et al., PCT Int.Appl.WO2007146712, 2007; Shirasaki Hitohisa et al., authorized invention patent ZL200480036672; Zhang, C. et al., Org. Lett., 2012, 14, 3280). In addition, α-ketoamide itself can also be widely used in the synthesis of some pharmaceutical intermediates. [0003] At present, the preparation methods of α-ketoamide mainly include the following types: (1) Using halogenated benzene, carbon monoxide and secondary amine as starting materials and using palladium as a catalyst to synthesize, the dis...

Claims

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Application Information

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IPC IPC(8): C07D263/26C07C311/16C07C303/40
Inventor 刘运奎张文霞张剑徐振元
Owner 嘉兴南洋万事兴化工有限公司
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