130720-50-2Relevant articles and documents
Ring expansions of N-methyl-1,2,5-oxadiazolium and 1,2,3-triazolium perchlorate salts with bases to six-membered azines: Direct detection of an addition intermediate in an addition-elimination mechanism and a degradation of 1,2,5-oxadiazolium salts to aα-cyano nitrones
Butler, Richard N.,McKenna, Elaine C.,McMahon, John M.,Daly, Karen M.,Cunningham, Desmond,McArdle, Patrick
, p. 2919 - 2923 (2007/10/03)
Reactions of 2-methyl-1,2,5-oxadiazolium perchlorate salts and 1-methyl-2-aryl-1,2,3-triazolium perchlorate salts with the bases KCN, NaOEt, KOBuf, LiNPrl2 give ring expansions to substituted 1,2,5-oxadiazines and 1,2,4-triazines. With cyanide as base the reactions follow an addition-elimination pathway and in two cases the addition intermediate has been isolated or directly detected by low-temperature NMR spectroscopy. The oxadiazolium system with cyanide also gives a useful new route to α-cyano nitrones via a ring degradation which competes with ring expansion. The reactions with KOBut and LiNPri2 do not involve an addition of the base to the azolium salt. Reactions have been monitored by 13C NMR spectroscopy by using 13CN-. An X-ray crystal structure is reported for (E)-N-(α-cyanobenzylidene)methylamine N-oxide.
Generation and trapping of a 1,2,3-Triazolium Methanide. A Carbon Analogue of the Azole N-Oxide: Routes to Pyrrolotriazoles and Substituted 1-Aminopyrroles
Butler, Richard N.,McDonald, Peter D.,McArdle, P.,Cunningham, D.
, p. 1653 - 1656 (2007/10/02)
Trapping of the first azole N-unsubstituted methanide species, a carbon analogue of the ubiquitous azole N-oxide system is described; new synthetic routes to pyrrolotriazoles and 1-aminopyrroles have resulted.
Attempted Generation of Substituted 1,2,3-Triazolium-1-methanides: a New Ring Expansion to 2,3-Dihydro-1,2,4-triazines: ab initio Calculations on 1,2,3-Triazolium-1-oxide, -1-imide, and -1-methanide 1,3-Dipoles and a Striking Illustration of the Hammond Principle in the Cyclisation of H.
Butler, Richard N.,Duffy, J. Paul,Cunningham, D.,McArdle, P.,Burke, Luke A.
, p. 882 - 884 (2007/10/02)
Treatment of 1-methyl-1,2,3-triazolium salts with ethoxide gave 2,3-dihydro-1,2,4-triazines via 1,2,5-triazahexa-1,3,5-trienes but the expected 1,2,3-triazolium-1-methanide 1,3-dipoles were not detected and ab initio calculations suggest that they are thermodynamically unfavoured; the X-ray crystal structure of (6a), a dihydro-1,2,4-triazine, is reported.