Synthesis of 6-tert-butyl-3-dicyanomethylene-5-silagermyl- and digermyl-1,2,4-triazines

Abstract

Fragmentation of the Ge–Ph bond in 2-(6-tBu-5-triphenylgermyl-2-R-4,5-dihydro-1,2,4-triazin-3(2H)-ylidene)malononitriles (R = Me, nBu) using lithium naphthalenide and further electrophile trapping with H⁺, Ph₃SiCl or Ph₃GeBr furnished the corresponding 5-Ph₂HGe–, Ph₃Si–Ph₂Ge– or Ph₃Ge–Ph₂Ge– derivatives. In the case of R = CH₂CO₂tBu, metalation at the exocyclic methylene group was observed to give tert-butyl 7-amino-3-tBu-8-cyanopyrrolo[1,2-b][1,2,4]triazine-6-carboxylate as a result of cyclization/Ge atom elimination. Structures of the synthesized compounds were confirmed by spectral and XRD data.

Graphical Abstract

Keywords:

• 1,2,4-Triazine
• germanes
• digermanes
• silagermanes
• X-ray diffraction

Acknowledgment

Crystal structure determination was performed in the Department of Structural Studies of Zelinsky Institute of Organic Chemistry, Moscow.

Disclosure statement

The author declares that he has no known competing financial interests or personal relationships that could have appeared to influence the work reported in this article.