22868-72-0Relevant academic research and scientific papers
Experimental and theoretical characterization of the valence isomerization of Bi-2H-azirin-2-yls to diazabenzenes
Banert, Klaus,Grimme, Stefan,Herges, Rainer,Hess, Kirsten,Koehler, Frank,Mueck-Lichtenfeld, Christian,Wuerthwein, Ernst-Ulrich
, p. 7467 - 7481 (2007/10/03)
3,4-Diazidocyclobutenes 16 were prepared from the corresponding dihalides. Some of these diazides, such as parent compound 16 d and phenyl-substituted derivatives 16c,f, underwent spontaneous stereoselective electrocyclic ring opening below room temperature, whereas the tetraalkyl derivatives of 16 had to be heated to force the same reaction. In most cases, the resulting 1,4-diazidobuta-1,3-dienes 8 were isolated to study their photochemical transformation into bi-2Hazirin-2-yls 9 via intermediate monoazirines 17. Except for starting materials with a low number of substituents such as 9d and 9f, title compounds 9 underwent a thermal valence isomerization which led exclusively to pyridazines 18 at surprisingly low temperatures. Based on quantum-chemical calculations for the parent bi-2H-azirinyl 2-yl 9d at the UB3LYP/6-31+G(d) and MR-MP2/TZV(2df,2p) levels, the valence isomerization process is best explained by simultaneous homolytic cleavage of both C-N single bonds of 9 to generate energetically favorable N,N′ diradicals 26, which cyclize to 18. The theoretical studies indicate also that one stereoisomer of 9, namely, the rac compound, should undergo valence isomerization more easily than the other, which is in conformity with different rates of these rearrangement reactions found experimentally. For the tetramethyl-bi-2H-azirin-2-yls 9g, which are better models for the experimentally studied compounds, simultaneous homolytic cleavage of both C-N single bonds is also predicted by the calculations, although the intermediate diradicals 26 g are significantly higher in energy than those of the parent system 9d.
SYNTHESES AND REACTIONS OF PYRIDAZINE DERIVATIVES XX STUDIES ON THE RADICAL METHYLATION OF THE 1,2-DIAZINE SYSTEM
Heinisch, Gottfried,Loutsch, Gerhard
, p. 1395 - 1402 (2007/10/02)
Protonated pyridazines (1,2,3) on reaction with methyl radical (generated by oxidative decarboxylation of acetic acid or by redox reaction of t-BuOOH/FeSO4*7H2O) are shown mainly to be attacked at positions β to the nitrogen atoms.However, formation of compounds 2, 4, 5, 6, 8, 9 and 10 indicates lower degree of regioselectivity compared with homolytic benzylation or acylation of the 1,2-diazine system.Synthesis of ethyl 5-styryl-4-pyridazinecarboxylates(13,14) was achieved by homolytic methylation of ethyl 4-pyridazinecarboxylate(11) followed by condensation with aromatic carbaldehydes.
