| Автор | Reisinger, Ales |
| Автор | Koch, Rainer |
| Автор | Bernhardt, Paul V. |
| Автор | Wentrup, Curt |
| Дата выпуска | 2004 |
| dc.description | Tetrazolo[1,5-a]pyridines/2-azidopyridines 1 undergo photochemical nitrogen elimination and ring expansion to 1,3-diazacyclohepta-1,2,4,6-tetraenes 3, which react with alcohols to afford 2-alkoxy-1H-1,3-diazepines 4 (5), with secondary amines to 2-dialkylamino-5H-1,3-diazepines 16, sometimes via isolable 2-dialkylamino-1H-1,3-diazepines 15, and with water to 1,3-diazepin-2-ones 19. The latter are also obtained by elimination of isobutene or propene from 2-tert-butoxy- or 2-isopropoxy-1H-1,3-diazepines 4 or 5. 1,3-Diazepin-2-one 22B and 1,3-diazepin-4-one 24 were obtained from hydrolysis of the corresponding 4-chlorodiazepines. Diazepinones 19 undergo photochemical ring closure to diazabicycloheptenones 25 in high yields. The 2-alkoxy-1H-1,3-diazepines 4 and 5 interconvert by rapid proton exchange between positions N1 and N3. The free energies of activation for the proton exchange were measured by the Forsénâ Hoffman method as Î G<sup>â ¡</sup>298 = 16.2 ± 0.6 kcal mol<sup>â 1</sup> as an average for 4aâ c in CD2Cl2, acetone-d6, and methanol-d4, and 14.1 ± 0.6 kcal mol<sup>â 1</sup> for 4c in acetone/D2O. The structures of 2-methoxy-5,6-bis(trifluoromethyl)-1H-1,3-diazepine 4k, 1,2-dihydro-4-diethylamino-5H-1,3-diazepin-2-one 22bB, and diazabicycloheptanone 26 were determined by X-ray crystallography. The former represents the first reported X-ray crystal structure of any monocyclic N-unsubstituted 1H-azepine. |
| Формат | application.pdf |
| Издатель | Royal Society of Chemistry |
| Название | 1H-1,3-Diazepines, 5H-1,3-diazepines, 1,3-diazepinones, and 2,4-diazabicyclo[3.2.0]heptenes, |
| Тип | research-article |
| DOI | 10.1039/b317099c |
| Electronic ISSN | 1477-0539 |
| Print ISSN | 1477-0520 |
| Журнал | Organic & Biomolecular Chemistry |
| Том | 2 |
| Первая страница | 1227 |
| Последняя страница | 1238 |
| Аффилиация | Reisinger Ales; Department of Chemistry, School of Molecular and Microbial Sciences, The University of Queensland |
| Аффилиация | Koch Rainer; Institut fürReine und Angewandte Chemie, Carl von Ossietetzky Universität |
| Аффилиация | Bernhardt Paul V.; Department of Chemistry, School of Molecular and Microbial Sciences, The University of Queensland |
| Аффилиация | Wentrup Curt; Department of Chemistry, School of Molecular and Microbial Sciences, The University of Queensland |
| Выпуск | 8 |
| Библиографическая ссылка | Reisinger, J. Chem. Soc., Perkin Trans. 1, 1998, 2247 |
| Библиографическая ссылка | Reisinger, Chem. Commun., 1996, 813 |
| Библиографическая ссылка | Reisinger, Org. Biomol. Chem., 2004, 2, 222 |
| Библиографическая ссылка | D. J. Le Count , Comprehensive Heterocyclic Chemistry II, A. R. Katritzky. C. W. Rees and E. F. V. Scriven, eds, vol 9, p. 139. Elsevier, New York, 1996 |
| Библиографическая ссылка | Lam, Science, 1994, 263, 380 |
| Библиографическая ссылка | Hodge, J. Am. Chem. Soc., 1998, 120, 4570 |
| Библиографическая ссылка | Qian, J. Org. Chem., 2002, 67, 4086 |
| Библиографическая ссылка | Evans, J. Am. Chem. Soc., 1996, 118, 4009 |
| Библиографическая ссылка | Wentrup, J. Am. Chem. Soc., 1980, 102, 6159 |
| Библиографическая ссылка | F. A. Bovey , Nuclear magnetic Resonance Spectroscopy, Academic Press, New York, 2nd edn.; 1988 |
| Библиографическая ссылка | J. Sandström , Dynamic NMR Spectroscopy, Academic Press, New York, 1982 |
| Библиографическая ссылка | Forsén, J. Chem. Phys., 1963, 39, 2892 |
| Библиографическая ссылка | Teulade, Chem. Pharm. Bull., 1989, 37, 2293 |
| Библиографическая ссылка | Molina, J. Chem. Soc., Chem. Commun., 1992, 424 |
| Библиографическая ссылка | Moore, J. Org. Chem., 1978, 43, 787 |
| Библиографическая ссылка | Koch, J. Chem. Soc., Perkin Trans. 2, 1997, 1851 |
| Библиографическая ссылка | Odum, J. Chem. Res. (S), 1997, 276 |
| Библиографическая ссылка | Odum, J. Chem. Res. (M), 1997, 1850 |
| Библиографическая ссылка | Satake, Chem. Commun., 2001, 1382 |
| Библиографическая ссылка | W. J. Hehre , L.Radom, P. v. R.Schleyer and J. A.Pople, Ab Initio Molecular Orbital Theory, Wiley, New York, 1986 |
| Библиографическая ссылка | M. J. Frisch , G. W.Trucks, H. B.Schlegel, G. E.Scuseria, M. A.Robb, J. R.Cheeseman, V. G.Zakrzewski, J. A.Montgomery, R. E.Stratmann, J. C.Burant, S.Dapprich, J. M.Millam, A. D.Daniels, K. N.Kudin, M. C.Strain, O.Farkas, J.Tomasi, V.Barone, M.Cossi, R.Cammi, B.Mennucci, C.Pomelli, C.Adamo, S.Clifford, J.Ochterski, G. A.Petersson, P. Y.Ayala, Q.Cui, K.Morokuma, D. K.Malick, A. D.Rabuck, K.Raghavachari, J. B.Foresman, J.Cioslowski, J. V.Ortiz, B. B.Stefanov, G.Liu, A.Liashenko, P.Piskorz, I.Komaromi, R.Gomperts, R. L.Martin, D. J.Fox, T.Keith, M. A.Al-Laham, C. Y.Peng, A.Nanayakkara, C.Gonzalez, M.Challacombe, P. M. W.Gill, B. G.Johnson, W.Chen, M. W.Wong, J. L.Andres, M.Head-Gordon, E. S.Replogle and J. A.Pople, Gaussian, Inc., Pittsburgh PA, 1998 |
| Библиографическая ссылка | Pople, Isr. J. Chem., 1993, 33, 345 |
| Библиографическая ссылка | Scott, J. Phys. Chem., 1996, 100, 16502 |
| Библиографическая ссылка | Farrugia, J. Appl. Crystallogr., 1999, 32, 837 |
| Библиографическая ссылка | Farrugia, J. Appl. Crystallogr., 1997, 30, 565 |
