220555-34-0Relevant articles and documents
Cage-like amines in the synthesis and oxidation of camphor-10-sulfonic acid amides
Kas'yan,Pal'chikov,Turov,Prid'ma,Tokar
, p. 1007 - 1017 (2009)
Reactions of bicyclo[2.2.1]hept-5-en-exo- and -endo-2-ylmethanamines, exo-5,6-epoxybicyclo-[2.2.1]hept-exo-2-ylmethanamine, 1-(bicyclo[2.2.1]hept-2- yl)ethanamine, and 1-(1-adamantyl)ethanamine with camphor-10-sulfonyl chloride in chloroform in the presence of triethylamine gave the corresponding sulfonamides having two cage-like fragments. Stereoisomeric N-(bicyclo[2.2.1] hept-5-en-2-ylmethyl)camphor-10-sulfonamides were oxidized with peroxyphthalic acid generated in situ from phthalic anhydride and 50% hydrogen peroxide. The exo stereoisomer was thus converted into the corresponding 5,6-epoxy derivative, while the endo isomer gave rise to 4-(7,7-dimethyl-2-oxobicyclo[2.2.1]hept-1- ylmethyl)-4-azatricyclo[4.2.1.03,7]-nonan-exo-2-ol (substituted azabrendane). The structure of the synthesized camphor-10-sulfonamides was confirmed by IR and 1H and 13C NMR spectra with the use of homo- (COSY) and heteronuclear 1H-13C correlation techniques (HMQC, HMBC). Heterocyclization of sulfonamides of the norbornene series was also simulated by quantum-chemical calculations at the PM3 and BHandHLYP/6-31G(d) levels of theory.
Epoxy Derivatives of N-Arylsulfonylbicyclohept-2-en-exo-5-ylmethylamines
Kas'yan, L. I.,Kas'yan, A. O.,Gorb, L. G.,Klebanov, B. M.
, p. 626 - 634 (2007/10/03)
Methods have been developed for preparing potentially physiologically active epoxy derivatives of N-arylsulfonylbicyclohept-2-en-exo-5-ylmethylamines.The structure of the sulfonamides and epoxides have been confirmed by their (1)H and (13)C NMR spe
Urea and Thiourea Derivatives Based on Amines of the Norbornene Series
Kas'yan, A. O.,Krasnovskaya, O. Yu.,Okovityi, S. I.,Kas'yan, L. I.
, p. 311 - 319 (2007/10/03)
Electron density distribution in molecules of amino derivatives of norbornene, exo- and endo-5-aminomethylbicyclohept-2-ene, exo-5-aminomethyl-endo-5-methylbicyclohept-2-ene, and their epoxy derivatives was studied by spectral methods (IR and 1H, 13C, and two-dimensional NMR spectroscopy) and by semiempirical (AM1) quantum-chemical calculations.The reactivity of amines was preliminary estimated from the calculated parameters: proton affinity and energies of localized molecular orbitals.The nucleophilic properties of the amines were studied in reactions with acyclic, alicyclic, and aromatic isocyanates and isothiocyanates.In the series of potentially bioactive ureas and thioureas, criteria have been formulated for ascribing the exo and endo structures to these compounds on the basis of the 1H NMR spectra.
Fluorinated Sulfonamides of the Norbornene Series
Kas'yan, A. O.,Maletina, I. I.,Yagupol'skii, L. M.,Markov, V. I.,Kas'yan, L. I.
, p. 320 - 327 (2007/10/03)
Fluorinated sulfonamides derived from exo- and endo-5-aminomethylbicyclohept-2-ene have been prepared and studied.These compounds were synthesized from pure isomers of bicyclohept-2-ene-5-carbonitrile obtained by Diels-Alder reaction from cyclopentadiene and acrylonitrile.The influence of the substituent orientation in the norbornene moiety on the 1H NMR spectra of stereoisomeric sulfonamides has been studied.Reactions of both isomers of N-(perfluorobutylsulfonyl)-5-aminomethylbicyclohept-2-ene with peroxy acids yield epoxides as the only reaction products.The intramolecular cyclization product is not formed, probably owing to the low nucleophilicity (basicity) of the nitrogen atom bearing the perfluorosulfonyl group.
