The reaction of 1,2,3-triazines with Grignard reagents

Abstract

Monocyclic 1,2,3-triazines reacted with Grignard reagents to form adducts due to N-2 and C-5 attack together with p-su bstituted acrylaldehydes and N-substituted pyrazoles; the results show that the N-2, C-4, and C-5 positions are reactive towards Grignard reagents.

Direct Synthesis of β-Aminoenals through Reaction of 1,2,3-Triazine with Secondary Amines

“…The C4 addition of methoxide has been reported, addition of Grignard reagents at C4 (PhMgBr) or C5 (MeMgI) has been disclosed, and the reaction of a lithium reagent (PhLi) at C4 has been described. 16 C4 and C6 disubstitution (methyl) on 1,2,3-triazine has been reported to redirect the addition of a nucleophile to C5 and, remarkably, N2 as well. 16 Like the work detailed herein, C4 addition in these studies has been reported to proceed with in situ loss of nitrogen (N 2 ) and hydrolysis of the resulting imine, providing the corresponding α,β-unsaturated aldehyde.…”

“…This site (C4) also constitutes the most electron-deficient center of the reacting molecular orbital (LUMO) of 1 but it is not the center that bears the largest LUMO molecular orbital coefficient. 16 …”

Facile Access to α-Substituted β-Thio Enals from 1,2,3-Triazines and Thiols

“…1 H and 13 C NMR spectra were recorded on Bruker 500 spectrometer ( 1 H at 500 MHz and 13 C at 125 MHz) and Agilent 400MR DD2 spectrometer…”

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

“…For example, the parent triazine slowly decomposes in methanol at room temperature, which suggests that nucleophilic attack of methanol occurs in the solution. Also, softer nucleophiles undergo a redox reaction with triazine (1) to give 2,5-dihydro derivatives 73 without ring substitution [112] (Scheme 20.16).…”