Synthesis of Acetamides from Aryl Amines and Acetonitrile by Diazotization under Metal-Free Conditions

Yao-Fu Zeng; Yi-Na Li; Na-Na Zhang; Huan Kang; Pan Duan; Fang Xiao; Yu Guo; Xianghao Wen

doi:10.1055/s-0039-1690237

Synlett, Table of Contents

Synlett 2019; 30(19): 2169-2172
DOI: 10.1055/s-0039-1690237

letter

Synthesis of Acetamides from Aryl Amines and Acetonitrile by Diazotization under Metal-Free Conditions

Yao-Fu Zeng

^aInstitute of Pharmacy and Pharmacology, University of South China, Hengyang, 421001, P. R. of China Email: zengyf@usc.edu.cn

^bSchool of Pharmaceutical Science, University of South China, Hengyang, 421001, P. R. of China

,

Yi-Na Li

^aInstitute of Pharmacy and Pharmacology, University of South China, Hengyang, 421001, P. R. of China Email: zengyf@usc.edu.cn

,

Na-Na Zhang

^bSchool of Pharmaceutical Science, University of South China, Hengyang, 421001, P. R. of China

,

Huan Kang

^bSchool of Pharmaceutical Science, University of South China, Hengyang, 421001, P. R. of China

,

Pan Duan

^bSchool of Pharmaceutical Science, University of South China, Hengyang, 421001, P. R. of China

,

Fang Xiao

^aInstitute of Pharmacy and Pharmacology, University of South China, Hengyang, 421001, P. R. of China Email: zengyf@usc.edu.cn

,

Yu Guo

^aInstitute of Pharmacy and Pharmacology, University of South China, Hengyang, 421001, P. R. of China Email: zengyf@usc.edu.cn

^bSchool of Pharmaceutical Science, University of South China, Hengyang, 421001, P. R. of China

,

Xianghao Wen∗

^cAffiliated Nanhua Hospital, University of South China, Hengyang, 421001, P. R. of China

› Author Affiliations

Abstract

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Abstract

An efficient and metal-free coupling reaction has been developed that affords acetamides from the corresponding aryl amines and acetonitrile. This method tolerates a wide range of functional groups and is selective toward aryl amines. Preliminary mechanistic studies were conducted.

Key words

aryl amines - amidation - acetonitrile - diazotization - acetamides - coupling reaction

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References

References and Notes

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16 Acetamides 2a–v; General Procedure To a stirred solution of the appropriate arylamine (1.0 mmol) in CH₃CN (5.0 mL) were added t-BuONO (1.5 mmol, 1.5 equiv), TfOH (1.5 mmol, 1.5 equiv), and H₂O (5.0 mmol, 5.0 equiv). The mixture was stirred under air at 60 °C for 24 h until the reaction was complete. The resulting mixture was purified by flash chromatography (silica gel, PE–EtOAc). N-(4-Tolyl)acetamide (2b) White solid; yield: 83%; 123.8 mg; mp 150–151 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.44 (br s, 1 H), 7.37 (d, J = 8.1 Hz, 2 H), 7.10 (d, J = 8.1 Hz, 2 H), 2.30 (s, 3 H), 2.14 (s, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 168.5, 135.4, 134.1, 129.6, 120.2, 24.6, 21.0. MS (ESI): m/z = 150 [M + H]⁺

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