摘要:

ExperimentalGeneral methodsMelting points were taken in an open capillary tube on a Buchi 510 apparatus and are uncorrected. Spectra were recorded with the following instruments:1H NMR spectra: Brücker AC‐250,13C NMR spectra: Brücker WP‐200, mass spectra: Jeol JMS DX 300. TMS was used as an internal reference. Column chromatography was carried out using E‐Merck silica gel 60F254 . Reagents and solvents were purified in the usual way.General procedure for preparation of products5–7To a solution of 1,4‐diazepines1–3(3.50 mmol) in dry diethyl ether (20 mL) was added mesitonitrile oxide (7 mmol, 2 equiv.).11The reaction mixture was stirred for 7 days at room temperature. The mixture was concentrated under reduced pressure. Solid products were purified by chromatography on silica gel (CH2Cl2) and recrystallized in ethanol. Compounds6a,bwere purified by flash chromatography (hexane–CHCl31 : 9).3‐Mesityl‐7‐methyl‐8,9a‐diphenyl‐4,5,6,9a‐tetrahydro‐7H‐[1,2,4]oxadiazolo[4,5‐d][1,4]diazepine 5This product was obtained in 95% yield; m.p. 211–213 °C;1H NMR (CDCl3):δ2.31, 2.38, 2.45 (3 CCH3 , 3s, 9H), 2.52 (NCH3 , s, 3H), 2.79–3.65 (NCH2CH2N, m, 4H), 5.12 (&z.dbd6;CH9, s, 1H), 6.91–7.90 (ArH, m, 12H);13C NMR (CDCl3):δ19.70, 20.10, 21.15 (3 CCH3), 37.33 (NCH3), 42.25, 51.02 (2‐CH2–), 99.61 (C9a), 106.91 (C9), 121.82, 127.78, 127.97, 128.24, 128.39, 128.56, 128.91, 137.78, 138.26, 138.98, 139.70,142.04, 150.80, 154.56 (C&z.dbd6;); MS:m/z423 [M]+; anal. calc. for C28H29N3O: C, 79.43; H, 6.86; N, 9.93; found: C, 79.29; H, 6.70; N, 10.01%.3‐Mesityl‐7,8,9a‐trimethyl‐4,5,6,9a‐tetrahydro‐7H‐[1,2,4]‐oxadiazolo[4,5‐d][1,4]diazepine6aThis compound was obtained in 30% yield as an oil;1H NMR (CDCl3):δ1.63, 2.22, 2.23, 2.28 (5 CCH3 , 4s, 15H), 2.30 (NCH3 , s, 3H), 2.9–3.4 (NCH2CH2N, m, 4H), 3.97 (&z.dbd6;CH9, s, 1H), 6.87 (ArH, s, 2H);13C NMR (CDCl3):δ19.52, 20.21, 21.06, 23.57, 35.31, 35.93 (6 CH3), 41.40, 50.48 (NCH2CH2N), 98.55 (C9a), 106.00 (C9), 121.43, 128.35, 136.96, 137.79, 138.51, 139.92, 155.67, 162.33, 167.47 (C&z.dbd6;); MS:m/z299 [M]+;anal. calc. for C18H25N3O: C, 72.24; H, 8.36; N, 14.05; found: C, 72.39; H, 8.18; N, 14.18%.3,3′‐Dimesityl‐7,9a‐dimethyl‐4,4′,5,5′,6,8,9,9a‐octahydro‐7H‐[1,2,4]oxadiazolo[4,5‐d][1,4]diazepine‐8‐spiro‐5′‐isoxazole 7aThis compound was obtained in 60% yield; m.p. 203–205 °C;1H NMR (CDCl3):δ1.75, 2.25, 2.26, 2.28, 2.35 (7 CCH3 , 5s, 21H), 2.53 (NCH3 , s, 3H), 2.4–3.5 (4‐CH2–, m, 8H), 6.9 (ArH, s, 4H);13C NMR (CDCl3):δ19.14, 19.53, 19.95, 29.96, 21.11, 21.30 (7 CCH3), 37.45 (NCH3), 44.11, 48.60, 51.84, 53.10 (4‐CH2–), 96.30 (C8), 102.30 (C9a), 121.17, 126.32, 128.26,128.41, 128.60, 136.50, 137.77, 137.84, 138.78, 139.79, 154.15, 155.45 (C&z.dbd6;); MS:m/z460 [M]+; anal. calc. for C28H36N4O2 : C, 73.04; H, 7.83; N, 12.17; found: C, 73.20; H, 7.71; N, 12.05%.3‐Mesityl‐7,8‐dimethyl‐9a‐phenyl‐4,5,6,9a‐tetrahydro‐7H‐[1,2,4]oxadiazolo[4,5‐d][1,4]diazepine6bThis compound was obtained in 27% yield as an oil;1H NMR (CDCl3):δ1.96, 2.16, 2.47 (4 CCH3 , NCH3 , 3s, 15H), 2.93–3.07 (NCH2CH2N, m, 4H), 3.97 (&z.dbd6;CH9, s, 1H), 6.93–7.50 (ArH, m, 7H);13C NMR (CDCl3):δ19.31, 19.83, 20.83, 33.92 (4 CCH3), 35.47 (NCH3), 41.75, 50.23 (NCH2CH2N), 99.44 (C9a), 106.14 (C9, d,J = 27 Hz), 120.96, 126.25, 127.93, 128.27, 128.75, 136.79, 137.84, 138.18, 138.76,139.79, 154.82, 167.04 (C&z.dbd6;); MS:m/z361 [M]+.3,3′‐Dimesityl‐7‐methyl‐9a‐phenyl‐4,4′,5,5′,6,8,9,9a‐octahydro‐7H‐[1,2,4]oxadiazolo[4,5‐d][1,4]diazepine‐8‐spiro‐5′‐isoxazole7bThis compound was obtained in 50% yield; m.p. 184–186 °C;1H NMR (CDCl3):δ1.90, 2.16, 2.32, 2.47 (6 CCH3 , 4s, 18H), 2.60 (NCH3 , s, 3H), 2.87, 2.90, 3.37, 3.83, 4.16 (4 –CH2–, 5m, 8H), 6.90–7.50 (ArH, m, 9H);13C NMR (CDCl3):δ19.25, 19.52, 20.00, 20.93 (6 CCH3), 37.53 (NCH3), 42.61, 45.92, 46.63, 49.52 (4‐CH2–), 97.79 (C8), 102.71 (C9a),121.01, 124.57, 126.24, 126.65, 127.96, 128.21, 128.41, 128.54, 128.67, 136.42, 138.16, 138.51, 138.88, 139.74, 144.01, 155.75, 157.23 (C&z.dbd6;); MS:m/z522 [M]+.

ISSN:1144-0546    

DOI:10.1039/b107409c

出版商:RSC    

年代:2001

数据来源: RSC