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Synthesis 2021; 53(11): 1901-1910
DOI: 10.1055/a-1477-4630
paper

Divergent Synthesis of Substituted Amino-1,2,4-triazole Derivatives

Fenghai Zhao
a   Innovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
,
Thishana Singh
b   College of Agriculture, Engineering and Science, School of Chemistry and Physics, University of KwaZulu-Natal, Durban 4000, South Africa
,
Yumei Xiao
a   Innovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
,
Wangcang Su
a   Innovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
c   Institute of Plant Protection, Henan Academy of Agricultural Sciences, Zhengzhou 450002, P. R. of China
,
Dongyan Yang
a   Innovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
d   College of Chemistry and Chemical Engineering, Zhongkai University of Agriculture and Engineering, Guangzhou, Guangdong 510225, P. R. of China
,
Changqing Jia
a   Innovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
e   National Engineering Research Center, Tongren Polytechnic College, Guizhou 554300, P. R. of China
,
Jia-Qi Li∗
a   Innovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
,
Zhaohai Qin∗
a   Innovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China
› Author AffiliationsThis work was supported by the National Key Research and Development Plan of China (No 2016YFD0300709) and the National Natural Science Foundation of China (No. 21402234).
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Abstract

A divergent efficient assembly of disubstituted 1,2,4-triazoles was established by cyclization of readily accessible N′-nitro-2-hydrocarbylidene-hydrazinecarboximidamides with moderate to excellent yields under mild reaction conditions. This divergent synthetic strategy was achieved simply by varying the reaction conditions. Under acidic conditions, amino-1,2,4-triazoles were obtained by an intramolecular redox reaction involving the NO2 group. Control experiments and DFT studies revealed that this transformation proceeds via an intramolecular 1,3-hydride transfer pathway leading to HNO2 elimination. Under neutral conditions with water as the solvent, nitroimino-1,2,4-triazoles were obtained by oxidative intramolecular annulation under air.

Key words

1,2,4-triazoles - divergent synthesis - redox chemistry - cyclization - heterocycles

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1477-4630.
  • Supporting Information


Publication History

Received: 20 February 2021

Accepted after revision: 08 April 2021

Accepted Manuscript online:
08 April 2021

Article published online:
03 May 2021

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