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Method for synthesizing N-alkenamide

A technology of alkyl amide and alkyl group, which is applied in the field of synthesizing N-alkyl amide and achieves the effect of broad development prospect and high economy

Inactive Publication Date: 2013-05-22
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] However, the direct synthesis of N-alkylamides from oximes via a transition-metal-catalyzed cascade reaction has not been reported.

Method used

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  • Method for synthesizing N-alkenamide
  • Method for synthesizing N-alkenamide
  • Method for synthesizing N-alkenamide

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Embodiment 1: N-benzylbenzamide

[0033] N-benzylbenzamide

[0034]

[0035] Benzaldoxime (121 mg, 1 mmol), [Ru(p-cymene)Cl 2 ] 2 (3.1 mg, 0.005 mmol, 0.5 mol%), [Cp*IrCl 2 ] 2 (4.0 mg , 0.005 mmol, 0.5 mol%), and toluene (1 ml) were sequentially added to a 25 ml Schlenk reaction flask. mixture at 130 o After 3 h at C, cool to room temperature. Benzyl alcohol (130 mg, 1.2 mmol) and cesium carbonate (65 mg, 0.2 equiv.) were added to the reaction flask, and the mixture was o C for another 12 h, then cooled to room temperature. The solvent was removed by rotary evaporation, and then the pure target compound was obtained by column chromatography (developing solvent: ethyl acetate / petroleum ether), the yield: 90%, and its spectrum is as follows figure 1 and 2 shown.

[0036] mp 103-104 o C; 1 H NMR (500 MHz, CDCl 3 ) δ 7.79 (d, J = 7.2 Hz, 2H, ArH), 7.50 (t, J = 7.4 Hz, 1H, ArH), 7.43 (t, J = 7.5 Hz, 2H, ArH), 7.36-7.35 (m, 4H, ArH), 7.32-7.28 (m, 1H, ArH),...

Embodiment 2

[0037] Embodiment 2: N-(4-methylbenzyl)benzamide

[0038] N-(4-methylbenzyl)benzamide

[0039]

[0040] Benzaldoxime (121 mg, 1 mmol), [Ru(p-cymene)Cl 2 ] 2 (3.1 mg, 0.005 mmol, 0.5 mol%), [Cp*IrCl 2 ] 2 (4.0 mg , 0.005 mmol, 0.5 mol%), and toluene (1 ml) were sequentially added to a 25 ml Schlenk reaction flask. mixture at 130 o After 3 h at C, cool to room temperature. 4-Methylbenzyl alcohol (146 mg, 1.2 mmol) and cesium carbonate (65 mg, 0.2 equiv.) were added to the reaction flask, and the mixture was o C for another 12 h, then cooled to room temperature. The solvent was removed by rotary evaporation, and then the pure target compound was obtained by column chromatography (developing solvent: ethyl acetate / petroleum ether), the yield: 87%, and its spectrum is as follows image 3 and 4 shown.

[0041] mp 142-143 o C; 1 H NMR (500 MHz, CDCl 3 ) δ 7.78 (d, J = 7.3 Hz, 2H, ArH), 7.49 (t, J = 7.4 Hz, 1H, ArH), 7.42 (t, J = 7.6 Hz, 2H, ArH), 7.25 (d, J = 4.3 ...

Embodiment 3

[0042] Embodiment 3: N-(4-isopropylbenzyl)benzamide

[0043] N-(4-isopropylbenzyl)benzamide

[0044]

[0045] Benzaldoxime (121 mg, 1 mmol), [Ru(p-cymene)Cl 2 ] 2 (3.1 mg, 0.005 mmol, 0.5 mol%), [Cp*IrCl 2 ] 2 (4.0 mg , 0.005 mmol, 0.5 mol%), and toluene (1 ml) were sequentially added to a 25 ml Schlenk reaction flask. mixture at 130 o After 3 h at C, cool to room temperature. Add 4-isopropylbenzyl alcohol (180 mg, 1.2 mmol) and cesium carbonate (65 mg, 0.2 equiv.) to the reaction flask, and the mixture is o C for another 12 h, then cooled to room temperature. The solvent was removed by rotary evaporation, and then the pure target compound was obtained by column chromatography (developing solvent: ethyl acetate / petroleum ether) with a yield of 81%.

[0046] mp 103-104 o C; 1 H NMR (500 MHz, CDCl 3 ) δ 7.78 (d, J = 7.2 Hz, 2H, ArH), 7.50 (t, J = 3.8 Hz,1H, ArH), 7.43(t, J = 7.5 Hz, 2H, ArH), 7.30 (d, J = 8.2 Hz, 2H, ArH), 7.22 (d, J = 8.2 Hz, 2H, ArH), 6.36 (b...

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Abstract

The invention discloses a method for synthesizing N-alkenamide. The method comprises the following preparation processes: adding oxime, transition metal catalyst ruthenium, iridium and / or rhodium complex and an organic solvent into a reaction container; reacting the reaction mixture at the temperature of 90-130 DEG C for hours, and cooling to room temperature; adding compound alcohol and alkali, reacting the reaction mixture at the temperature of 90-130 DEG C for hours, and performing separation on columns to obtain a target compound. Compared with the prior art, the method starts from commercial or easily synthesized oxime, rearrangement is generated in the presence of a transition metal catalyst, an amide intermediate is generated, the intermediate and alcohol are subjected to an alkylation reaction so as to obtain N-alkenamide, and the reaction has three obvious advantages that 1) the commercial or easily synthesized oxime and approximately non-toxic alcohol serve as initial raw materials; 2) only the water is generated to serve as a byproduct, and environmental harm is avoided; and 3) the reaction atom is high in economic efficiency. Thus, the reaction meets the green and chemical requirements and has wide development prospects.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry, and in particular relates to a method for synthesizing N-alkyl amides. Background technique [0002] N-Alkylamides are a very important class of nitrogen-containing compounds that are widely used as fine chemicals, natural products, pharmaceutical chemicals, and polymers (a) J. M. Humphrey, A. R. Chamberlin, Chem. Rev. 1997, 97, 2243-2266; b) T. Cupido, J. Tulla-Puche, J. Spengler, F. Albericio, Curr. Opin. Drug Discovery Dev. 2007, 10, 768-783; c) C. L. Allen, J. M. J. Williams, Chem. Soc. Rev. 2011, 40, 3405; d) V.R. Pattabiraman, J. W. Bode, Nature, 2011, 480, 471-479.). The traditional synthesis of N-alkylamides is the synthesis of carboxylic acid derivatives (eg, acid chlorides, carboxylic anhydrides and esters) and N-alkylamines. Beckmann rearrangement, Aube-Schmidt rearrangement and Staudinger ligation reactions are also widely used in the synthesis of N-alkylamides. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B43/06C07C231/08C07C233/65C07C233/73C07C233/66C07C233/05C07D307/68C07D333/38
Inventor 李峰渠攀攀马娟邹小媛孙春楼
Owner NANJING UNIV OF SCI & TECH
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