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 Affiliations
This 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).


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.

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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  • References

    • 1a Smith CA, Narouz MR, Lummis PA, Singh I, Nazemi A, Li C.-H, Crudden CM. Chem. Rev. 2019; 119: 4986
    • 1b Ghareeb H, Metanis N. Chem. Eur. J. 2020; 26: 10175
    • 2a Li Y.-Q, He Y, Shao T, Pei H.-X, Guo W.-K, Mi D.-Z, Krimm I, Zhang Y.-J, Wang P.-L, Wang X, Liu M.-Y, Yi Z.-F, Chen Y.-H. J. Med. Chem. 2019; 62: 4949
    • 2b Ajmal M, Yunus U, Graham RM, Leblanc RM. ACS Omega 2019; 4: 22280
    • 2c Gao H.-X, Shreeve JM. Chem. Rev. 2011; 111: 7377
    • 3a Romagnoli R, Baraldi PG, Salvador MK, Prencipe F, Bertolasi V, Cancellieri M, Brancale A, Hamel E, Castagliuolo I, Consolaro F, Porcu E, Basso G, Viola G. J. Med. Chem. 2014; 57: 6795
    • 3b El-Sherief HA. M, Youssif BG. M, Bukhari SN. A, Abdelazeem AH, Abdel-Aziz M, Abdel-Rahman HM. Eur. J. Med. Chem. 2018; 156: 774
    • 3c Seth S, McDonald KA, Matzger AJ. Inorg. Chem. 2017; 56: 10151
  • 4 Battaglia U, Moody CJ. J. Nat. Prod. 2010; 73: 1938
  • 5 Ashton TD, Devine SM, Möhrle JJ, Laleu B, Burrows JN, Charman SA, Creek DJ, Sleebs BE. J. Med. Chem. 2019; 62: 10526
  • 6 Li X, Zhang Z, Chen Y, Wan H, Sun J, Wang B, Feng B, Hu B, Shi X, Feng J, Zhang L, He F, Bai C, Zhang L, Tao W. ACS Med. Chem. Lett. 2019; 10: 996
  • 7 Lou K, Yao Y, Hoye AT, James MJ, Cornec AS, Hyde E, Gay B, Lee VM, Trojanowski JQ, Smith AB. III, Brunden KR, Ballatore C. J. Med. Chem. 2014; 57: 6116
  • 8 Zhao XX, Zhang JC, Li SH, Yang QP, Li YC, Pang SP. Org. Process Res. Dev. 2014; 18: 886
  • 9 Yen W.-P, Kung F.-C, Wong FF. Eur. J. Org. Chem. 2016; 2328
  • 10 Yin P, Ma W.-B, Chen Y, Huang W.-C, Deng Y, He L. Org. Lett. 2009; 11: 5482
  • 11 Dolzhenko AV, Pastorin G, Dolzhenko AV, Chui WK. Tetrahedron Lett. 2009; 50: 2124
  • 12 Yin P, Parrish DA, Shreeve JM. Angew. Chem. Int. Ed. 2014; 53: 12889
  • 13 Jia C.-Q, Su W.-C, Xu Y.-J, Liu J.-P, Qin Z.-H. Chin. J. Org. Chem. 2016; 36: 830
  • 14 Su W.-C, Zhou Y.-H, Ma Y.-Q, Wang L, Zhang Z, Rui C.-H, Duan H.-X, Qin Z.-H. J. Agric. Food Chem. 2012; 60: 5028
  • 15 CCDC 1995578 (3a) and 1995580 (8a) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
  • 16 Wang J, Brower KR, Naud DL. J. Org. Chem. 1997; 62: 9055
  • 17 Intermediate 7 is unstable in air and was partially oxidized to compound 8a during the purification. Hence, the isolated yield of intermediate 7 is lower than that of compound 8a if compound 1a is the starting material.
  • 18 The cyclization of 1a with PTSA in methanol was studied by using an in situ ReactIR spectrophotometer to further understand the reaction mechanism. However, besides starting material 1a and product 3a, no intermediates were detected. This result might be the result of the highly reactivities of the reaction intermediates leading to insufficient concentrations.