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

Fenghai Zhao; Thishana Singh; Yumei Xiao; Wangcang Su; Dongyan Yang; Changqing Jia; Jia-Qi Li; Zhaohai Qin

doi:10.1055/a-1477-4630

Synthesis, Inhaltsverzeichnis

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

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

,

Thishana Singh

^bCollege of Agriculture, Engineering and Science, School of Chemistry and Physics, University of KwaZulu-Natal, Durban 4000, South Africa

,

Yumei Xiao

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

,

Wangcang Su

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

^cInstitute of Plant Protection, Henan Academy of Agricultural Sciences, Zhengzhou 450002, P. R. of China

,

Dongyan Yang

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

^dCollege of Chemistry and Chemical Engineering, Zhongkai University of Agriculture and Engineering, Guangzhou, Guangdong 510225, P. R. of China

,

Changqing Jia

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

^eNational Engineering Research Center, Tongren Polytechnic College, Guizhou 554300, P. R. of China

,

Jia-Qi Li∗

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

,

Zhaohai Qin∗

^aInnovation Center of Pesticide Research, Department of Chemistry, College of Science, China Agricultural University, Beijing 100193, P. R. of China

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Abstract

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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

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Referenzen

References

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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.

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