The chemistry of N-substituted benzotriazoles. Part 14. Novel routes to secondary and tertiary amines and to N, N-disubstituted hydroxylamines

Abstract

Tertiary amines of types R4R3CHNR'R2 (2), (R2CH,),NR1 (10) and (11), or (R2CH2),N (12), secondary amines of type ( R2CH,),NH (8), and N,N-disubstituted hydroxylamines of type ( R2CH,),NOH (9), are prepared in high yield by the action of Grignard reagents or sodium borohydride on easily available N,Ndialkyl-N-[benzotriazolylalkyl-(or arylalkyl-)lamines (I ) or tris(benzotriazoly1methyl)amine ( 7 ) , on bis( bentotriazolylmethyl)amines (3), (5), and ( 6 ) , and on N,Nbis( benzotriazolylmethyl) hydroxylamine

A versatile method for the N, N-dialkylation of aromatic amines via Grignard reactions on N,N-bis(benzotriazolylmethyl)arylamines

“…Treatment of these adducts with Grignard reagents leads to substitution of the benzotriazolyl moiety by an alkyl or aryl group, and this is in many cases the preferred method for the N-monoalkylation of arylamines (2). Under similar conditions, alkylamines, hydroxylamines, and hydrazines give their N,N-bis(benzotriazolylmethylated) derivatives, which upon treatment with Grignard reagents are transformed into the corresponding N,N-dialkylated alkylamines (3), hydroxylamines (3), and hydrazines (4).…”

o‐(α‐Benzotriazolylalkyl)phenols: Versatile Intermediates for the Synthesis of Substituted Phenols

“…Anilines were readily alkylated with 1-(hydroxymethy1)-lH-benzotriazole (13) to afford 9 which in turn underwent smooth lithiation and subsequent reaction with an electrophile at the methylene carbon to give derivatives 10. Subsequent displacement of the benzotriazole group in compounds 9 and 10 by anilines and other electron-rich aromatic compounds such as indoles, pyrroles, etc.…”

Magnetogenese unter physiologischen Bedingungen mit molekularen Sonden, die auf (bio‐)chemische Analyten ansprechen

“…Seine extreme Empfindlichkeit gegen hydrolytischen Zerfall wird durch Literaturberichte bestätigt. [31][32][33] Die Synthese gelang schließlich, indem wir die rohe Reaktionslçsung der Dreikomponentenreaktion mit einer wasserfreien Lçsung von Eisen(II)-tetrafluoroborat titrierten; den Endpunkt bestimmten wir mit LCMS.…”