A new approach to densely functionalised azepines and dihydroazepines

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

“…In N. A. Nedolya's group it was shown for the first time that conjugated 2-aza-1,3,5-trienes 188, generated from polyunsaturated carbanions and isothiocyanates in a single preparative stage [99,101], can provide a fundamentally new promising source of new families of azacycloheptadienes 189 and trienes 190 [454][455][456] …”

Mass spectra of new heterocycles: IX. Main fragmentaion laws of 7-methyl-2-(methylsulfanyl)-3-(1-ethoxyethoxy)-4,5-dihydro-3H-azepine and its structural isomers (2,3-dihydropyridine, pyrrole, thiophene) under electron impact

“…Compounds I-IV were synthesized by procedures [7,10]. Electron impact mass spectra (70 eV) of compounds I-IV were measured on an instrument Shimadzu GCMS-QP5050A (quadrupole mass analyzer, the range of detected masses 34-650 Da).…”

“…In extension of discovered by us fundamentally new general approach to the selective assembling of important heterocyclic structures from available heterocumulenes and metallated dienes and alkynes [7,8] we synthesized for the first time [from the α-lithiated 1-(1-ethoxyethoxy)-allene, isopropyl isothiocyanate, and methyl iodide along Scheme 1] four structurally isomeric heterocycles containing as one of substituents chemically and biologically active acetal function (1-ethoxy-ethoxy group) [9] and differing both by the character of the heteroatom (in the heterocycle and the hetroatomic substituent) and the size and the nature of the heterocycle, namely, previously unavailable 7-methyl-2-(methylsulfanyl)-3-(1-ethoxyethoxy)-4,5-dihydro-3H-azepine (I) [10], 2,2-dimethyl-6-(methylsulfanyl)-5-(1-ethoxyethoxy)-2,3-dihydropyridine (II), 1-isopropyl-2-(methylsulfanyl)-3-(1-ethoxyethoxy)pyrrole (III), and N-isopropyl-Nmethyl-3-(1-ethoxyethoxy)-2-thiophenamine (IV) [7]. The synthesis of compounds II-IV was performed in a single preparative stage using as the common linear precursor lithium allenylimidothioate (V).…”

Reactions of heterocumulenes with organometallic reagents: XVI. Quantum-chemical study on the mechanisms of formation of homo- and heteroannular azacycloheptadienes in reactions of 2-aza-1,3,5-trienes with potassium tert-butoxide

“…Increased interest in these compounds stimulated search for rational ways of their synthesis, including the synthesis of new derivatives. We recently showed that 2-aza-1,3,5-trienes I available in one preparative step from α-lithiated allenes (e.g., methoxyallene or protected allenyl alcohol) and s-alkyl isothiocyanates (e.g., isopropyl isothiocyanate) (Scheme 1) [3] by the action of potassium tert-butoxide in tetrahydrofuran-dimethyl sulfoxide are readily (-30°C, 30 min) transformed into previously unknown 4,5-dihydro-3H-azepines II (Scheme 2); these results were briefly reported in [4,5].…”