(M+ – Br + OCH3 + 3 Ph, 35), 324 (M+– Br + CO2Me + 3 Ph, 10), 207 (M+ + 2 – Ph-CH=CH-CHO + 2 Ph-N-C=O + 2 CO2Me, 7), 205 (M+ – Ph-CH=CH-CHO + 2 Ph-N-C=O + 2 CO2Me, 7), 131 [Ph-CH=CH-C=O+, 100], 119 [ Ph-N-C=O+, 77], 103 [Ph-CH=CH+, 48], 77 [C6H5+, 40], 51 [CH-N-C=C+, 20].
Second diastereomer (4b)II. IR (KBr, cm–1): νmax 3063 (Csp2–H), 2952 (Csp3–H), 1733 (C=O), 1709 (C=O,ester), 1597 (C=C,aromatic), 1492 (C=C,alken), 1226 (Csp2–O), 1071 (Csp3–O) cm–1.
1H NMR (400.13 MHz, DMSO): δ 3.50 (3H, s, OCH3), 3.78 (3H, s, OCH3), 5.70 (1H, dd, 3JHH = 16.0 Hz, 3JHH = 8.0 Hz, CH), 6.41 (1H, d, 3JHH = 8.0 Hz, CH), 6.88 (1H, d, 3JHH = 16.0 Hz, CH), 7.23-7.56 (19H, m, CHaromatic).
13C NMR (100.6 MHz, CDCl3): δ 52.2 and 52.9 (2OCH3), 86.4 (CHNO), 88.0 (Cq), 99.2 (Cspiro), 120.5 (CH), 122.5 (Cq), 126.3 (2CH), 127.1 (2CH), 128.1 (2CH), 128.3 (2CH), 128.7 (2CH), 129.0 (2CH), 129.1 (2CH), 129.2 (CH), 130.6 (2CH), 131.5 (Cq), 132.2 (2CH), 133.5 (Cq), 134.8 (Cq), 137.0 (Cq), 138.6 (CH), 152.5 (Cq), 153.9, 162.6, 163.6 and 169.9 (4C=O).
MS: m/z (%): 695 (M+ + 2, 1), 693 (M+, 1), 563 (M+ + 2 – Ph-CH=CH-CHO, 2), 561 (M+ – Ph-CH=CH-CHO, 2), 504 (M+ + 2 – Ph-CH=CH-CHO + CO2Me, 17), 502 (M+ – CO2Me + Ph-CH=CH-CHO, 17), 412 (M+ + 2 – CO2Me + Me + Ph + Ph-CH=CH-CHO, 43), 410 (M+– CO2Me + Me + Ph + Ph-CH=CH-CHO, 43), 352 (M+– Br + OCH3 + 3 Ph, 48), 324 (M+– Br + CO2Me + 3 Ph, 10), 207 (M+ + 2 – Ph-CH=CH-CHO + 2 Ph-N-C=O + 2 CO2Me, 17), 205 (M+ – Ph-CH=CH-CHO + 2 Ph-N-C=O + 2 CO2Me, 17), 131 [Ph-CH=CH-C=O+, 100], 119 [ Ph-N-C=O+, 64], 103 [Ph-CH=CH+, 50], 91 [Ph-N+, 33], 77 [C6H5+, 56], 51 [CH-N-C=C+, 22].
2-3-4- خواص فیزیکی و مشخصات طیفی دیمتیل-8-(4-کلروفنیل)-2،4-دیاکسو-1،3-دیفنیل-7-](E)-2-فنیلوینیل[-6-اکسا-1،3،8-تریآزا-اسپیرو[4.5]دک-9-ان-9،10-دیکربوکسیلات I](c4) و II(c4)[
از این واکنش دو دیاستریومر (4c)I و (4c)II با بازده برابر 46% از هر کدام بدست آمده است. دیاستریومر (4c)I دارای نقطه ذوب oC 171-169 و دیاستریومر (4c)II دارای نقطه ذوب oC 178-176 میباشد. مشخصات طیفی این ترکیب با استفاده از طیفهای H NMR1، C NMR13، IR و Mass که در صفحات112-107 فصل 3 آورده شده است به شرح زیر میباشند:
First diastereomer (4c)I. IR (KBr, cm–1): νmax 3061 (Csp2–H), 2953 (Csp3–H), 1741 (C=O), 1706 (C=O,ester), 1598 (C=C,aromatic), 1495 (C=C,alken), 1221 (Csp2–O), 1181 (Csp3–O) cm–1.
1H NMR (400.13 MHz, DMSO): δ 3.61 (3H, s, OCH3), 3.87 (3H, s, OCH3), 5.00 (1H, d, 3JHH = 7.6 Hz, CH), 5.74 (1H, dd, 3JHH = 16.0 Hz, 3JHH = 7.6 Hz, CH), 6.50 (1H, d, 3JHH = 16.0 Hz, CH), 7.14-7.60 (19H, m, CHaromatic).
13C NMR (100.6 MHz, CDCl3): δ 52.6 and 53.1 (2OCH3), 87.1 (CHNO), 87.6 (Cq), 106.9 (Cspiro), 120.2 (CH), 126.3 (2CH), 127.1 (2CH), 128.3 (CH), 128.8 (2CH), 129.1 (2CH), 129.2 (CH), 129.3 (CH), 129.4 (2CH), 129.6 (2CH), 129.9 (2CH), 130.1 (2CH), 131.9 (Cq), 134.0 (Cq), 134.5 (Cq), 134.9 (Cq), 136.9 (Cq), 137.5 (CH), 150.5 (Cq), 153.9, 161.0, 164.9 and 168.6 (4C=O).
MS: m/z (%): 651 (M+ + 2, 1), 649 (M+, 1), 519 (M+ – Ph-CH=CH-CHO, 1), 517 (M+ – Ph-CH=CH-CHO, 3), 460 (M+ + 2 – Ph-CH=CH-CHO + CO2Me, 17), 458 (M+ – CO2Me + Ph-CH=CH-CHO, 51), 368 (M+ + 2 – CO2Me + Me + Ph + Ph-CH=CH-CHO, 33), 366 (M+– CO2Me + Me + Ph + Ph-CH=CH-CHO, 100), 337 (M+ + 2 – 2 Ph-N-C=O + Ph-CH=CH-CHO, 2), 335 (M+– Ph-CH=CH-CHO + 2 Ph-N-C=O, 6), 310 (M+ + 2 – Ph-CH=CH + 2 Ph-N-C=O, 31), 308 (M+– 2 Ph-N-C=O + Ph-CH=CH, 93), 229 (M+ – Ph-CH=CH + CO2Me + OCNPhCO + Cl-C6H4, 10), 132 [Ph-CH=CH-CHO+, 22], 119 [ Ph-N-C=O+, 26], 77 [C6H5+, 14].
Second diastereomer (4c)II. IR (KBr, cm–1): νmax 3063 (Csp2–H), 2925 (Csp3–H), 1735 (C=O), 1706 (C=O,ester), 1595 (C=C,aromatic), 1495 (C=C,alken), 1226 (Csp2–O), 1184 (Csp3–O) cm–1.
1H NMR (400.13 MHz, DMSO): δ 3.49 (3H, s, OCH3), 3.78 (3H, s, OCH3), 5.70 (1H, dd, 3JHH = 16.0 Hz, 3JHH = 8.0 Hz, CH), 6.42 (1H, d, 3JHH = 8.0 Hz, CH), 6.88 (1H, d, 3JHH = 16.0 Hz, CH), 6.75, 7.19-7.57 (19H, m, CHaromatic).
13C NMR (100.6 MHz, CDCl3): δ 52.2 (OCH3), 52.8 (OCH3), 86.5 (CHNO), 88.0 (Cq), 99.0 (C spiro), 120.5 (CH), 126.3 (2CH), 127.1 (2CH), 128.1 (2CH), 128.4 (CH), 128.7 (2CH), 129.0 (2CH), 129.1 (2CH), 129.2 (2CH), 130.3 (2CH), 131.5 (Cq), 133.5 (Cq), 134.4 (Cq), 134.8 (Cq), 136.4 (Cq), 138.6 (CH), 152.6 (Cq), 153.9, 162.6, 163.6 and 170.0 (4C=O).
MS: m/z (%): 651 (M+ + 2, 1), 649 (M+, 1), 519 (M+ – Ph-CH=CH-CHO, 1), 517 (M+ – Ph-CH=CH-CHO, 3), 460 (M+ + 2 – Ph-CH=CH-CHO + CO2Me, 8), 458 (M+ – CO2Me + Ph-CH=CH-CHO, 24), 400 (M+ + 2 – Ph-CH=CH-CHO + Ph-N-C=O, 5), 398 (M+ + 2 – Ph-CH=CH-CHO + Ph-N-C=O, 15), 368 (M+ + 2 – CO2Me + Me + Ph + Ph-CH=CH-CHO, 29), 366 (M+– CO2Me + Me + Ph + Ph-CH=CH-CHO, 87), 337 (M+ + 2 – 2 Ph-N + Ph-CH=CH-CHO, 2), 335 (M+– Ph-CH=CH-CHO + 2 Ph-N, 6), 310 (M+ + 2 – Ph-CH=CH + 2 Ph-N-C=O, 33), 308 (M+– 2 Ph-N-C=O + Ph-CH=CH, 100), 229 (M+ – Ph-CH=CH + CO2Me + OCNPhCO + Cl-C6H4, 10), 132 [Ph-CH=CH-CHO+, 45], 119 [ Ph-N-C=O+, 84], 91 [Ph-N+, 37], 77 [C6H5+, 18].
2-3-5- خواص فیزیکی و مشخصات طیفی دیمتیل-8-(4-متیلفنیل)-2،4-دیاکسو-1،3-دیفنیل-7-](E)-2-فنیلوینیل[-6-اکسا-1،3،8-تریآزا-اسپیرو[4.5]دک-9-ان-9،10-دیکربوکسیلات I](d4) و II(d4)[
از این واکنش دو دیاستریومر (4d)I و (4d)II با بازده برابر 49% از هر کدام بدست آمده است. دیاستریومر (4d)I دارای نقطه ذوب oC 173-171 و دیاستریومر (4d)II دارای نقطه ذوب oC 184-182 میباشد. مشخصات طیفی این ترکیب با استفاده از طیفهای H NMR1، C NMR13، IR و Mass که در صفحات113-118 فصل 3 آورده شده است به شرح زیر میباشند:
First diastereomer (4d)I .IR (KBr, cm–1): νmax 3061 (Csp2–H), 2920 (Csp3–H), 1737 (C=O), 1709 (C=O,ester), 1580 (C=C,aromatic), 1496 (C=C,alken), 1181 (Csp2–O), 1122 (Csp3–O) cm–1.
1H NMR (400.13 MHz, DMSO): δ 2.29 (3H, s, CH3), 3.58 (3H, s, OCH3), 3.84 (3H, s, OCH3), 5.05 (1H, d, 3JHH = 7.6 Hz, CH), 5.82 (1H, dd, 3JHH = 15.6 Hz, 3JHH = 7.6 Hz, CH), 6.48 (1H, d, 3JHH = 15.6 Hz, CH), 6.93 -7.60 (19H, m, CHaromatic).
13C NMR (100.6 MHz, CDCl3): δ 21.1 (CH3), 52.4 and 52.9 (2OCH3), 87.0 (CHNO), 87.6 (Cq), 104.7 (Cspiro), 121.0 (CH), 125.4 (2CH), 126.4 (2CH), 127.0 (2CH), 128.3 (CH), 128.7 (2CH), 128.8 (CH), 128.9 (CH), 129.0 (2CH), 129.1 (2CH), 129.7 (2CH), 129.8 (2CH), 132.0 (Cq), 134.1 (Cq), 135.2 (Cq), 136.8 (CH), 138.3 (Cq), 139.1 (Cq), 150.9 (Cq), 154.0, 163.1, 164.9 and 168.8 (4C=O).
MS: m/z (%): 629 (M+, 1), 497 (M+ – Ph-CH=CH-CHO, 2), 438 (M+ – CO2Me + Ph-CH=CH-CHO, 22), 363 (M+– Me + Ph-N-C=O + Ph-CH=CH-CHO, 10), 346 (M+– Me + CO2Me + Ph + Ph-CH=CH-CHO, 100), 315 (M+ – Ph-CH=CH + Ph-N-C=O + Ph + Me, 5), 288 (M+ – Ph-CH=CH + 2 Ph-N-C=O, 100), 260 (M+– Ph-N-C=O + 2 CO2Me + Ph-CH=CH-CHO, 42), 243 (M+ – Ph-CH=CH + 2 Ph-N-C=O + 3 Me, 14), 169 (M+– 2 Ph-N-C=O + CO2Me + Ph-CH=CH-CHO + OMe, 12), 141 (M+– 2 Ph-N-C=O + 2 CO2Me + Ph-CH=CH-CHO, 18), 119 [ Ph-N-C=O+, 73 ], 103 [Ph-CH=CH+, 16], 91 [ Ph-N+, 21 ], 77 [C6H5+, 19].
Second diastereomer (4d)II. IR (KBr, cm–1): νmax 3038 (Csp2–H), 2953 (Csp3–H), 1732 (C=O), 1705 (C=O,ester), 1569 (C=C,aromatic), 1495 (C=C,alken), 1246 (Csp2–O), 1183 (Csp3–O) cm–1.
1H NMR (400.13 MHz, DMSO): δ 2.26 (3H, s, CH3), 3.46 (3H, s, OCH3), 3.77 (3H, s, OCH3), 5.72 (1H, dd, 3JHH = 16.0 Hz, 3JHH = 8.0 Hz, CH), 6.41 (1H, d, 3JHH = 8.0 Hz, CH), 6.87 (1H, d, 3JHH = 16.0 Hz, CH), 6.61-6.69 , 7.06-7.57 (19H, m, CHaromatic).
13C NMR (100.6 MHz, CDCl3): δ 21.1 (CH3), 52.1 and 52.6 (2OCH3), 86.3 (CHNO), 88.2 (Cq), 97.7 (Cspiro), 121.1 (CH), 126.0 (2CH), 126.3 (2CH), 127.0 (2CH), 127.9 (2CH), 128.2 (CH), 128.3 (CH), 128.6 (2CH), 129.0 (2CH), 129.1 (2CH), 129.2 (2CH), 129.5 (CH), 131.6 (Cq), 133.7 (Cq), 135.1 (Cq), 137.7 (Cq), 138.0 (CH), 138.9 (Cq), 153.1 (Cq), 154.0, 162.7, 163.7 and 170.1 (4C=O).
MS: m/z (%): 629 (M+, 1), 497 (M+ – Ph-CH=CH-CHO, 8), 438 (M+ – CO2Me + Ph-CH=CH-CHO, 100), 363 (M+– Me + Ph-N-C=O + Ph-CH=CH-CHO, 58), 286 (M+– 2 Me + Ph-N + Ph-CH=CH + Ph-N-C=O, 36), 244 (M+ – Ph-CH=CH-CHO + 2 Ph-N-C=O + Me, 74), 131 [ Ph-CH=CH-C=O+, 100], 119 [Ph-N-C=O+, 19], 103 [ Ph-CH=CH+, 45], 84 [ N-CO-N-CO+, 50], 77 [C6H5+, 30].
2-3-6- خواص فیزیکی و مشخصات طیفی دیمتیل-8-(3-کلروفنیل)-2،4-دیاکسو-1،3-دیفنیل-7-](E)-2-فنیلوینیل[-6-اکسا-1،3،8-تریآزا-اسپیرو[4.5]دک-9-ان-9،10-دیکربوکسیلات I](e4) و II(e4)[
از این واکنش دو دیاستریومر (4e)I و (4e)II با بازده برابر 42% از هر کدام بدست آمده است. دیاستریومر (4e)I دارای نقطه ذوب oC 145-143 و دیاستریومر (4e)II دارای نقطه ذوب oC 185-183 میباشد. مشخصات طیفی این ترکیب با استفاده از طیفهای H NMR1، C NMR13، IR و Mass که در صفحات 124-119 فصل 3 آورده شده است به شرح زیر میباشند:
First diastereomer (4e)I .IR (KBr, cm–1): νmax 3064 (Csp2–H), 2952 (Csp3–H), 1739 (C=O), 1707 (C=O,ester), 1579 (C=C,aromatic), 1496 (C=C,alken), 1270 (Csp2–O), 1098 (Csp3–O) cm–1.
1H NMR (400.13 MHz, DMSO): δ 3.62 (3H, s, OCH3), 3.86 (3H, s, OCH3), 5.04 (1H, d, 3JHH = 7.6 Hz, CH), 5.81 (1H, dd, 3JHH = 16.0 Hz, 3JHH = 7.6 Hz, CH), 6.52 (1H, d, 3JHH = 16.0 Hz, CH), 7.07-7.60 (19H, m, CHaromatic).
13C NMR (100.6 MHz, CDCl3): δ 52.6 and 53.1 (2OCH3), 87.1 (CHNO), 87.5 (Cq), 106.9 (Cspiro), 120.4 (CH), 126.4 (2CH), 126.7 (CH), 127.1 (2CH), 128.4 (CH), 128.6 (CH), 128.7 (CH), 128.8 (2CH), 129.0 (2CH), 129.1 (CH), 129.3 (CH), 129.6 (2CH), 129.8 (2CH), 130.0 (CH), 131.8 (Cq), 133.9 (Cq), 134.7 (Cq), 134.9 (Cq), 137.3 (CH), 139.7 (Cq), 150.1 (Cq), 154.0, 162.9, 164.7 and 168.5 (4C=O).
MS: m/z (%): 651 (M+ + 2, 1), 649 (M+, 1), 519 (M+ – Ph-CH=CH-CHO, 1), 517 (M+ – Ph-CH=CH-CHO, 3), ), 460 (M+ + 2 – Ph-CH=CH-CHO + CO2Me, 6), 458 (M+ – CO2Me + Ph-CH=CH-CHO, 18), 368 (M+ + 2 – CO2Me + Me + Ph + Ph-CH=CH-CHO, 7), 366
