Photochemistry of 2-azido-4,6-dichloro-s-triazine: matrix isolation of a strained cyclic carbodiimide containing four nitrogen atoms in a seven-membered ring

Abstract

2-Azido-4,6-dichloro-s-triazine 1, matrix-isolated in Ar at 10 K, yields triplet nitrene 2 and the strained cyclic carbodiimide 3 upon photolysis.

Dicyanocarbodiimide and Trinitreno‐s‐triazine Generated by Consecutive Photolysis of Triazido‐s‐triazine in a Low‐Temperature Nitrogen Matrix

“…[11]. 13 C-Labeled 1 was synthesized from sodium azide and the 13 C isotopomer of cyanuric chloride (Isotec.…”

“…Previously reported results for the photolyses of the related species [6,10,11] indicate that the most probable candidate for the first photoproduct is the triplet mononitrene 2. In the theoretical IR spectrum of 2 at the B3LYP/6-31G* level, the most intense band is at around 1340 cm À1 for all three isomers.…”

“…In the theoretical IR spectrum of 2 at the B3LYP/6-31G* level, the most intense band is at around 1340 cm À1 for all three isomers. [12] Previously reported results for an azido-s-triazine derivative [11] indicate that ring expansion of the nitrene produces didehydrotetrazepine. However, the characteristic IR band (around 1900 cm À1 ) of didehydrotetrazepine was extremely weak in our case, indicating that subsequent photoreaction of the nitrene was preferred over ring expansion.…”

Controlled Covalent Functionalization of Thermally Reduced Graphene Oxide To Generate Defined Bifunctional 2D Nanomaterials

“…2,4,6-Trichloro-1,3,5-triazine is ac heap,c ommercially available compound and is highly reactive towards nucleophiles such as amines.The reaction between sodium azide and 2,4,6trichloro-1,3,5-triazine at low temperature results in 2-azido-4,6-dichloro-1,3,5-triazine,w hich is ap recursor to the highly reactive nitrene intermediates. [19] Inspired by perfluoroazides, [20,21] the lifetime of these electron-poor nitrenes could be long enough to conjugate to the p-system of graphene through a[2 + +1] cycloaddition reaction.…”

Six‐Membered Heterocycles: Triazines, Tetrazines and Other Polyaza Systems

“…Photolysis of 2-azido-4,6-dichloro-1,3,5-triazine, in a low temperature argon matrix, yields a cyclic carbodiimide containing four nitrogen atoms in a sevenmembered ring [668]. Consecutive photolysis of triazido-1,3,5-triazine, in a low temperature nitrogen matrix, has been studied [669,670].…”