Synthesis of Substituted Piperidines from N,N-Bis[(benzotriazol-1-yl)methyl]amines

Abstract

N,N-Bis[(benzotriazol-1-yl)methyl]benzylamines and N,N-bis[(benzotriazol-1-yl)methyl](p-N',N'-dimethylphenyl)amine on reaction with allyltrimethylsilanes yielded substituted piperidines. Other N,N-bis[(benzotriazol-1-yl)methyl]anilines (unsubstituted and p-CH(3), OCH(3), Cl) gave julolidines (2,3,6,7-tetrahydro-1H,5H-pyrido[3,2,1-ij] quinoline).

Synthesis and Derivatization of Julolidine: A Powerful Heterocyclic Structure

“…As an example of the application of such strategy, the 1,2,7‐trisubstituted julolidine 117 was obtained in 38 % yield after reaction of benzotriazole 115 with alkene 116 (Scheme ). In this work, tin chloride was also used as catalyst, similarly to the method reported by Katritzky et al (1999) …”

“…Katritzky et al (1996; 1999), reported a different synthetic strategy towards julolidines, making use of benzotriazoles as starting material and obtaining 1‐substituted, 2‐substituted, 1,7‐disubstituted (symmetric and nonsymmetric), 1,2‐and 2,3‐disubstituted, and 1,2,3‐ and 1,7,9‐trisubstituted julolidines.…”

“…By using a similar strategy, p ‐substituted benzotriazole derivatives 93 was also utilized to the synthesis of 1,7,9‐trisubstituted julolidines (Scheme ) . The reaction between 83 and alyltrimethylsilane 94 , in the presence of the Lewis acid SnCl 2 , afforded julolidines 95a ‐ d in 25–78 % yields, although with low diastereoselectivity.…”

“…In spite of the numerous papers reporting the diverse applications for DCVJ ( 2 ), few articles have dealt with the its synthesis. Among those compounds, 192 bearing a colesteryl group presented good sensibility for monitoring interactions between the local anesthetic tetracain and lipid bilayers …”

1,2,3-Triazoles

“…Derivatives of higher aldehydes ( 634 , R 1 ≠ H) allow introduction of an additional substituent into position 2 of tetrahydroquinolines making variation of the tetrahydroquinoline system very versatile <1995JOC7631> . In N,N -bis(benzotriazolylmethyl)anilines 635 , both benzotriazolylmethyl groups may be involved in the cyclocondensation process producing julolidines 1996JOC3117 , 1999JOC3328 . When the nitrogen atom supporting the benzotriazolylalkyl group is already incorporated into a ring, like in structure 636 , an additional ring is added to the heterocyclic ring system 1998S1487 , 1999JHC473 .…”