Electronic Supplementary information C-H Functionalization of Tertiary Amines by Cross Dehydrogenative Coupling Reactions: Solvent-Free Synthesis of α-amino Nitriles and β-nitro Amines under Aerobic Condition Kaliyamoorthy Alagiri, and Kandikere Ramaiah Prabhu* Department of rganic Chemistry, Indian Institute of Science, Bangalore 560 012, Karnataka, India. Contents 1 Typical experimental procedure the preparation of N-aryl tetrahydroisoquinoline Page no SI 2 - SI 3 2 Characterization data for N-Aryl Tetrahydroisoquinoline SI 3 SI 5 3 Typical experimental procedure for the synthesis of α-amino nitrile SI - 5 4 References SI 5 5 1 H and 13 C NMR spectra SI 6 SI 41
ESI - 2 Typical experimental procedure for the Preparation of Nitroolefin H CH 3 N 2 AcH N 2 Heliotropin (5 g, 33.3 mmol) and ammonium acetate (2.56 g, 33.3 mmol) were taken into the RB flask. Nitromethane (8.9 ml, 166.5 mmol) and glacial acetic (10 ml) acid were added at room temperature. The reaction mixture was refluxed for 1.5h, and then reaction mixture was cooled in an ice bath, filtered through sintered crucible and washed successively with water, hexane and 1% ethanol in hexane. The crude mixture was concentrated under vacuo. Typical experimental procedure for the reduction of nitroolefin N 2 LiAlH 4 NH 2 The crude nitroolefin (2 g, 10.3 mmol) in dry THF (10 ml) was added drop wise to a stirred solution of LiAlH 4 (0.98 g, 25.9 mmol) in THF (20 ml). The reaction mixture was refluxed for 4h and then cooled in ice bath, quenched with saturated solution of Na 2 S 4 until effervescence ceases completely. Then filtered through sintered crucible and washed successively with ethyl acetate and concentrated under vacuo. Typical experimental procedure for the preparation of [1, 3]dioxolo[7, 8-g]- 1, 2, 3, 4- tetrahydroisoquinoline NH 2 (CH 2 )n HCH NH The amine (1.35 g, 8.18 mmol) obtained in previous step was added to formic acid (3.5 ml) at 0 o C and stirred for 10 min at same temperature until complete dissolution of amine. Then paraformaldehyde (0.25 g, 8.18 mmol) was added and stirred at 50 o C for 24h, added saturated
ESI - 3 NaH solution and extracted with DCM. The combined organic layer was dried over Na 2 S 4 and concentrated under reduced pressure. Then purified by column chromatography on silica gel using MeH/ CHCl 3. Typical experimental procedure for the preparation of N-phenyl Tetrahydroisoquinoline. CuI K 3 P 4 NH PhI Ethylene glycol N Ph Copper (I) iodide (0.21g, 1.13 mmol) and potassium phosphate (4.8 g, 22.6 mmol) were taken into the RB flask filled with nitrogen. 2-Propanol (10 ml), ethylene glycol (1.24 ml, 22.6 mmol), 1,2,3,4-tetrahydro-isoquinoline (2 g, 11.3 mmol) and iodobenzene (1.26 ml, 11.3 mmol) were added successively at room temperature. The reaction mixture was heated at 90 C for 24 h and then allowed to cool to room temperature. The solvent was removed under vacuo, added water (20 ml) and extracted with dichloromethane (3x 30 ml). The organic layer was dried over sodium sulfate. The solvent was concentrated under reduced pressure and purified by column chromatography on silica gel (hexane/ethyl acetate=95:5), to give the desired product 4a with 30% isolated yields. Characterization data for N-Aryl Tetrahydroisoquinoline 1, 2, 3, 4-Tetrahydro-2-phenylisoquinoline (1a) 1 1a N Ph Pale yellow solid; Yield - 60%; mp: 44-46 C (lit. 1 45 C); R f (20% EtAc/Hexane) 0.7; Prepared as shown in general experimental procedure. IR (KBr, cm -1 ): 2824, 1599, 1505, 1388, 1238, 1156, 1034, 934, 873, 749; 1 H NMR (400 MHz, CDCl 3 ): δ 7.27 (2H, t, J = 7.9Hz), 7.15 (4H, d, J = 3.8Hz), 6.97 (2H, d, J = 8.1Hz), 6.81 (1H, t, J = 7.2Hz), 4.39 (2H, s), 3.54 (2H, t, J = 5.8Hz), 2.96 (2H, t, J = 5.7Hz); 13 C NMR (100MHz, CDCl 3 ): 150.5, 134.8, 134.4, 129.1, 128.4, 126.4, 126.2, 125.9, 118.6, 115.0, 50.6, 46.4, 29.0; HRESI-MS (m/z): Calculated for C 15 H 15 N (M + H): 210.1283, found (M + H): 210.1286.
ESI - 4 1, 2, 3, 4-Tetrahydro-2- (4-methoxyphenyl)isoquinoline (1b) 1 1b N PMP Pale yellow solid; Yield - 50%; mp: 93-95 C (lit. 1 95 C); R f (20% EtAc/Hexane) 0.7; Prepared as shown in general experimental procedure. IR (KBr, cm -1 ): 3456, 1584, 1510, 1459, 1384, 1273, 1242, 1151, 1036, 823, 755; 1 H NMR (400 MHz, CDCl 3 ): δ 7.11 7.18 (4H, m), 6.98 (2H, d, J = 8.8Hz), 6.86 (2H, d, J = 8.8Hz), 4.29 (2H, s), 3.77 (3H, s), 3.43 (2H, t, J = 5.8Hz), 2.98 (2H, t, J = 5.7Hz); 13 C NMR (100MHz, CDCl 3 ): 153.4, 145.2, 134.5, 134.4, 128.6, 126.4, 126.2, 125.8, 118.0, 114.5, 55.5, 52.6, 48.4, 29.0; HRESI-MS (m/z): Calculated for C 16 H 17 N (M + H): 240.1388, found (M + H): 240.1387. 6, 7-dimethoxy-2-phenyl-1, 2, 3, 4-tetrahydroisoquinoline (1c) 2 1c N Ph Pale yellow solid; Yield - 30%; mp: 91-93 C; R f (20% EtAc/Hexane) 0.7; Prepared as shown in general experimental procedure. IR (KBr, cm -1 ): 3446, 1601, 1519, 1466, 1384, 1271, 1238, 1116, 1025, 861, 761; 1 H NMR (400 MHz, CDCl 3 ): δ 7.28 (2H, t, J = 7.8Hz), 6.98 (2H, d, J = 8.2Hz), 6.82 (1H, t, J = 7.2Hz), 6.64 (2H, d, J = 4.2Hz), 4.33(2H, s), 3.87 (3H, s), 3.86 (3H,s), 3.54 (2H, t, J = 5.8Hz), 2.89 (2H, t, J = 5.7Hz); 13 C NMR (100MHz, CDCl 3 ): 150.5, 147.5, 147.4, 129.1, 126.6, 126.1, 118.7, 115.3, 111.2, 109.3, 55.94, 55.90, 50.4, 46.7, 28.5; HRESI- MS (m/z): Calculated for C 17 H 19 N 2 (M + Na): 292.1313, found (M + Na): 292.1314. [1,3]dioxolo[7, 8-g]-2-phenyl-1, 2, 3, 4-tetrahydroisoquinoline (1d) 1d N Ph Pale yellow solid; Yield - 30%; mp: 65-66 C R f (20% EtAc/Hexane) 0.7; Prepared as shown in general experimental procedure. IR (KBr, cm -1 ): 2807, 1583, 1508, 1460, 1385, 1273, 1241,
ESI - 5 1207, 1190, 1036, 823, 755; 1 H NMR (400 MHz, CDCl 3 ): δ 7.27 (2H, t, J = 7.8Hz), 6.95 (2H, d, J = 8.1Hz), 6.82 (1H, t, J = 7.2Hz), 6.61 (2H, s), 5.90 (2H, s), 4.29 (2H, s), 3.51 (2H, t, J = 5.8Hz), 2.86 (2H, t, J = 5.7Hz); 13 C NMR (100MHz, CDCl 3 ): 150.3, 146.1, 145.9, 129.1, 127.8, 127.2, 118.7, 115.2, 108.3, 106.4, 100.6, 50.7, 46.6, 28.9; HRESI-MS (m/z): Calculated for C 16 H 15 N 2 (M + H): 254.1181, found (M + H): 254.1185. Typical experimental procedure for the synthesis of α-amino nitrile To the 10 mol% of Mo 2 (acac) 2 (0.05 mmol) and N-phenyltetrahydroisoquinoline (0.5 mmol) was added TMSCN (1.0 mmol). The reaction mixture was stirred at 80 o C under oxygen atmosphere (oxygen balloon) for 17 h. The reaction mixture was cooled to room temperature, added saturated NaHC 3 solution and extracted with DCM (3 X 10 ml). The combined organic layer was dried over Na 2 S 4 and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel using Hexane / Ethyl acetate (95 : 5) and furnished pale yellow solid (78%, NMR conversion = 96%). References 1) M. Jerome, H. Philippe, T. Christophe,G. R. Sylviane, -P. H. Henri, Synth. Commun., 2001, 31, 987 992. 2) A. Sud, D. Sureshkumar, M. Klussmann, Chem. Commun. 2009, 3169
ESI - 6 1.99 2.04 1.95 2.00 2.04 2.01 2.03 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 CDCl 3 400MHz 1 HNMR 1d N 7.3009 7.2815 7.2621 6.9848 6.9646 6.8563 6.8382 6.8200 6.6109 5.9030 4.2967 3.5296 3.5152 3.5007 2.8842 2.8700 2.8558-0.0002-0.5-1.0
ESI - 7 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 CDCl 3 100MHz 13 CNMR 1d N 150.1163 146.1437 145.9813 129.1837 127.7042 127.0459 119.0269 115.3891 108.3719 106.4193 100.7076 77.3175 76.9999 76.6822 50.8600 46.7882 28.8099
ESI - 8 2.13 2.86 1.15 2.04 1.03 1.04 1.04 1.04 10 9 8 7 6 5 4 3 2 1 0 CDCl 3 400MHz 1 HNMR N Ph 3a CN 7.3759 7.3709 7.3574 7.3544 7.3493 7.3407 7.3359 7.3263 7.3096 7.3041 7.2969 7.2863 7.2844 7.2798 7.2754 7.2637 7.2363 7.2181 7.0894 7.0698 7.0273 7.0090 6.9907 5.5044 3.7932 3.7907 3.7857 3.7830 3.7784 3.7758 3.7708 3.7682 3.7622 3.7596 3.7547 3.7520 3.7474 3.7448 3.7399 3.7374 3.5133 3.5030 3.4865 3.4823 3.4763 3.4721 3.4555 3.4453 3.1916 3.1767 3.1649 3.1505 3.1359 3.1242 3.1093 2.9885 2.9797 2.9709 2.9477 2.9390 2.9301 0.0001
ESI - 9 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR N Ph 3a CN 148.35 134.59 129.58 129.54 129.32 128.72 127.03 126.82 121.85 117.71 117.56 77.32 77.00 76.68 53.17 44.16 28.50
ESI - 10 4.21 2.05 2.05 3.08 1.06 1.08 1.07 1.04 10 9 8 7 6 5 4 3 2 1 CDCl 3 400MHz 1 HNMR N PMP CN 3b 7.2866 7.2763 7.2549 7.2443 7.2254 7.2072 7.0903 7.0681 6.9214 6.8992 5.3574 3.7889 3.5958 3.5802 3.5655 3.5504 3.4617 3.4519 3.4324 3.4230 3.4033 3.3936 3.1953 3.1795 3.1674 3.1534 3.1385 3.1266 3.1108 2.9405 2.8996-0.0001
ESI - 11 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR N PMP CN 3b 155.64 142.54 134.30 129.66 129.42 128.61 127.03 126.65 120.93 117.56 114.75 77.32 77.00 76.68 55.51 55.49 44.86 28.65
ESI - 12 2.07 2.05 1.01 1.03 1.04 6.20 1.10 1.04 1.05 1.07 10 9 8 7 6 5 4 3 2 1 CDCl 3 400MHz 1 HNMR N Ph 3c CN 7.3704 7.3513 7.3309 7.0865 7.0856 7.0656 7.0068 6.7478 6.6794 5.4427 3.8780 3.7868 3.7781 3.7720 3.7615 3.7556 3.7468 3.7410 3.4713 3.4612 3.4428 3.4328 3.4124 3.4024 3.1166 3.1018 3.0890 3.0757 3.0616 3.0488 3.0340 2.8707 2.8627 2.8546 2.8305 2.8228 2.8145-0.0000
ESI - 13 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR N Ph 3c CN 149.35 148.39 148.04 129.49 126.84 121.86 121.07 117.83 117.67 111.51 109.31 77.32 77.00 76.68 56.03 55.90 53.00 44.15 28.04
ESI - 14 2.02 3.03 0.98 1.01 2.05 1.02 1.02 1.02 1.03 10 9 8 7 6 5 4 3 2 1 CDCl 3 400MHz 1 HNMR N Ph 3d CN 7.3724 7.3531 7.3332 7.0691 7.0490 7.0277 7.0093 6.9910 6.7252 6.6586 5.9623 5.3850 3.7462 3.7393 3.7323 3.7222 3.7156 3.7083 3.7020 3.4613 3.4511 3.4331 3.4233 3.4034 3.3934 3.0899 3.0752 3.0631 3.0492 3.0348 3.0228 3.0081 2.8581 2.8503 2.8253 2.8177 0.0001
ESI - 15 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR N Ph 3d CN 148.24 148.10 146.63 129.53 128.31 122.14 121.88 117.67 117.54 108.84 106.65 101.32 77.32 77.00 76.68 53.23 44.11 28.49
ESI - 16 1.92 0.96 1.91 2.00 2.97 10 9 8 7 6 5 4 3 2 1 CDCl 3 400MHz 1 HNMR 3e N CN 7.3298 7.3108 7.3094 7.2897 6.9367 6.9183 6.9000 6.8765 6.8557 4.1577 2.9992-0.0002
ESI - 17 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR 3e N CN 147.75 129.43 120.16 115.45 114.85 77.32 77.00 76.69 42.24 39.21
ESI - 18 1.93 1.95 2.00 2.99 3.00 10 9 8 7 6 5 4 3 2 1 CDCl 3,400MHz, 1 HNMR 3f N CN 7.1179 7.0975 6.7935 6.7720 4.0990 2.9392 2.2770-0.0000
ESI - 19 220 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR 3f N CN 145.60 129.89 129.74 115.44 115.31 77.32 77.00 76.68 42.70 39.36 20.30
ESI - 20 2.00 2.02 1.04 1.07 4.26 10 9 8 7 6 5 4 3 2 1 0 CDCl 3,400MHz, 1 HNMR 3g CN N 7.3159 7.2955 7.2767 6.8477 6.8295 6.8111 6.7011 6.6807 4.4358 4.4179 3.4787 3.4709 3.4566 3.4511 3.4378 3.4321 3.3893 3.3690 3.3498 3.3296 2.4380 2.4174 2.4109 2.4013 2.3732 2.3331 2.3147 2.3070 2.2889 2.2718 2.2561 2.2377 2.2327 2.2225 2.2134 2.2037 2.1914 2.1783 2.1603-0.0001
ESI - 21 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR 3g CN N 145.1047 129.3253 119.1931 118.0512 112.5860 77.3186 77.0006 76.6821 48.9457 47.3286 31.3837 23.8004-20
ESI - 22 1.96 1.98 1.08 3.48 1.10 1.01 1.15 1.01 1.01 10 9 8 7 6 5 4 3 2 1 N Ph 4 CDCl 3,400MHz, 1 HNMR 7.9925 7.9896 7.9693 7.4781 7.4735 7.4606 7.4402 7.4170 7.4044 7.3993 7.3930 7.3810 7.2896 7.2828 7.2747 7.2702 7.2587 7.2539 7.2486 7.2437 7.2325 7.2177 7.0949 7.0637 7.0453 5.0677 5.0296 4.5919 4.5538 4.1675 4.1563 4.1436 4.1397 4.1324 4.1285 4.1161 4.1042 3.8084 3.7946 3.7855 3.7689 3.7527 3.7295 3.6827 3.6717 3.6576 3.6431 3.6323 3.6294 2.8649 2.8535 2.8423 2.8226 2.8114-0.0001
ESI - 23 200 180 160 140 120 100 80 60 40 20 0 N Ph 4 CDCl 3,100MHz, 13 CNMR 154.05 131.23 130.04 129.08 128.90 128.53 127.43 126.68 126.26 120.52 77.32 77.00 76.68 71.45 65.54 28.45 26.25
ESI - 24 5.43 1.03 2.15 1.09 1.01 2.12 1.06 1.09 10 9 8 7 6 5 4 3 2 1 7.2702 7.2493 7.2307 7.2236 7.2038 7.1929 7.1748 7.1622 7.1449 7.1093 7.0911 6.9680 6.9467 6.8441 6.8258 6.8077 5.5423 5.5243 5.5064 4.8489 4.8294 4.8193 4.7999 4.5438 4.5272 4.5141 4.4977 3.6622 3.6486 3.6297 3.6159 3.6062 3.6032 3.5954 3.5850 3.5737 3.5626 3.5524 3.5408 3.0881 3.0738 3.0666 3.0482 3.0330 3.0256 3.0113 2.7851 2.7729 2.7606 2.7444 2.7321 2.7198-0.0001
ESI - 25 200 180 160 140 120 100 80 60 40 20 0 148.37 135.21 132.85 129.43 129.12 128.03 126.92 126.61 119.35 115.04 78.68 77.31 77.00 76.68 58.11 41.97 26.35
ESI - 26 2.37 2.12 2.18 2.02 1.02 1.01 3.08 1.96 1.08 1.04 10 9 8 7 6 5 4 3 2 1 0 CDCl 3,400MHz, 1 HNMR 6b N 2 PMP N 7.2486 7.2352 7.2204 7.2180 7.2030 7.1664 7.1434 7.1251 6.9218 6.8993 6.8201 6.7975 5.4006 5.3855 5.3796 5.3647 4.8425 4.8211 4.8127 4.7913 4.5732 4.5587 4.5434 4.5289 3.7420 3.5699 3.5658 3.5596 3.5480 3.0475 3.0303 3.0248 3.0067 2.9839 2.9664 2.7197 2.7098 2.6999 2.6785 2.6685 2.6586-0.0001-1
ESI - 27 200 180 160 140 120 100 80 60 40 20 0 153.96 143.03 135.41 132.86 129.43 127.87 126.89 126.59 118.84 114.68 78.93 77.32 77.00 76.68 58.89 55.56 43.12 25.77
ESI - 28 2.22 2.02 0.98 1.04 6.24 1.09 1.02 1.09 1.03 10 9 8 7 6 5 4 3 2 1 7.2784 7.2582 7.2395 6.9782 6.9573 6.8604 6.8422 6.8240 6.6434 6.6017 5.4750 5.4569 5.4392 4.8694 4.8493 4.8399 4.8199 4.5837 4.5679 4.5543 4.5384 3.8519 3.8442 3.8308 3.7010 3.6883 3.6754 3.6681 3.6553 3.6428 3.6022 3.5910 3.5785 3.5677 3.5581 3.5454 3.5341 3.0307 3.0171 3.0074 2.9914 2.9766 2.9669 2.9530 2.6995 2.6883 2.6769 2.6592 2.6479 2.6366-0.0004
ESI - 29 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR N Ph 6c N 2 148.76 148.57 147.71 129.41 127.40 124.55 119.54 115.51 111.72 109.63 78.76 77.32 77.00 76.68 57.95 56.04 55.88 42.04 25.79
ESI - 30 2.16 1.99 1.02 1.97 2.02 2.07 1.08 1.04 10 9 8 7 6 5 4 3 2 1 7.2794 7.2581 7.2399 6.9537 6.9330 6.8593 6.8410 6.8228 6.6174 6.5879 6.5720 5.9127 5.8805 5.8752 5.4206 5.4026 5.3848 4.8367 4.8173 4.8071 4.7877 4.5276 4.5111 4.4980 4.4815 3.6256 3.6118 3.5932 3.5788 3.5660 3.5570 3.5452 3.5341 3.5244 3.5126 2.9890 2.9743 2.9683 2.9491 2.9337 2.9275 2.9128 2.6892 2.6769 2.6643 2.6487 2.6363 2.6239 0.0000
ESI - 31 200 180 160 140 120 100 80 60 40 20 0 148.38 147.43 146.33 129.44 128.78 125.67 119.46 115.18 108.95 106.92 101.09 78.71 77.32 77.00 76.68 58.14 42.15 26.39
ESI - 32 6.02 2.43 0.61 0.39 0.63 1.44 1.05 1.04 1.17 2.24 10 9 8 7 6 5 4 3 2 1 7.2883 7.2679 7.2486 7.2385 7.2276 7.2089 7.1912 7.1661 7.1474 7.1202 7.1038 7.0851 7.0122 6.9928 6.9723 6.8344 6.8175 6.8045 6.7867 5.2592 5.2359 5.2142 5.0738 5.0569 5.0381 5.0205 5.0034 4.8983 4.8782 4.8599 3.8586 3.8443 3.8390 3.8249 3.8112 3.8060 3.7912 3.6093 3.5946 3.5862 3.5694 3.5624 3.5535 3.5375 3.5214 3.5058 3.0801 3.0632 3.0394 3.0221 3.0043 2.9337 2.9194 2.9041 2.8796 2.8650 2.8418 2.8265 1.6970 1.6799 1.5488 1.5361 1.5195
ESI - 33 200 180 160 140 120 100 80 60 40 20 0 149.113 148.833 135.575 134.741 133.771 131.979 129.389 129.269 129.064 128.675 128.309 128.162 127.210 126.555 126.086 119.281 118.741 115.374 114.442 88.911 85.394 77.318 77.000 76.682 62.698 61.111 43.506 42.625 26.703 26.342 17.384 16.347
ESI - 34 4.37 2.25 2.14 1.63 0.42 3.95 1.38 1.11 1.01 2.01 10 9 8 7 6 5 4 3 2 1 7.2458 7.2391 7.2212 7.2007 7.1799 7.1516 7.1348 7.1116 7.0931 6.9222 6.9003 6.8275 6.7894 6.7669 5.0683 5.0474 5.0312 5.0090 4.9907 4.9747 4.9695 4.9537 4.8920 4.8749 4.8572 4.8392 4.8209 4.8129 4.7913 4.5728 4.5583 3.7442 3.7238 3.5213 3.5081 3.4972 3.4863 3.4741 3.4612 3.0127 2.9982 2.9897 2.9713 2.9560 2.9484 2.9336 2.8417 2.8289 2.8160 2.7878 2.7524 2.7391 1.6761 1.6592 1.5318 1.5170-0.0002
ESI - 35 200 180 160 140 120 100 80 60 40 20 0 153.77 153.53 143.47 135.79 135.00 133.64 132.02 129.23 128.93 128.35 127.98 127.94 127.16 126.48 126.00 118.85 118.82 118.20 114.67 114.54 88.78 85.73 77.32 77.00 76.68 63.43 62.14 55.57 55.51 44.98 43.97 26.22 25.99 17.06 16.54
ESI - 36 2.02 1.90 0.96 0.98 0.58 0.32 0.90 0.58 0.33 6.30 1.34 0.99 0.91 1.77 10 9 8 7 6 5 4 3 2 1 0 CDCl 3,400MHz, 1 HNMR N 2 6g Ph N 7.2785 7.2557 7.2482 7.2342 7.2148 7.0053 6.9837 6.9619 6.8324 6.8143 6.7961 6.6339 6.6249 6.5628 6.4940 5.1664 5.1464 5.1374 5.1145 5.0689 5.0523 5.0340 5.0166 4.9057 4.8885 4.8844 4.8667 3.8649 3.8471 3.8421 3.8319 3.8160 3.8000 3.7815 3.7684 3.7611 3.7472 3.6305 3.6089 3.5945 3.5793 3.5602 3.5460 3.5391 3.5325 3.5198 3.5108 3.4984 3.4871 3.4782 2.9961 2.9791 2.9567 2.9381 2.9188 2.8200 2.8064 2.7928 2.7790 2.7653 2.7515 2.7381 2.7249 2.6976 1.6975 1.6806 1.5376 1.5211 0.0000
ESI - 37 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR N Ph 6g N 2 149.25 148.87 148.80 148.60 147.32 147.06 129.32 129.23 127.81 126.78 125.50 123.50 119.36 118.95 115.61 115.03 111.53 111.48 111.13 110.17 88.90 85.31 77.32 77.00 76.68 62.44 60.90 56.00 55.89 55.79 55.76 43.28 42.56 25.89 25.79 17.47 16.15
ESI - 38 2.25 1.87 1.04 0.94 0.62 2.00 0.91 0.57 0.36 0.58 1.39 1.06 0.97 1.10 2.63 10 9 8 7 6 5 4 3 2 1 7.2863 7.2662 7.2510 7.2487 7.2267 7.2077 6.9680 6.9477 6.8421 6.8318 6.8242 6.8136 6.7955 6.6110 6.5785 5.9280 5.9174 5.9153 5.8979 5.1296 5.1052 5.0826 5.0414 5.0250 5.0085 4.9883 4.8722 4.8552 4.8507 4.8333 3.8018 3.7877 3.7813 3.7678 3.7546 3.7483 3.7340 3.5690 3.5542 3.5378 3.5207 3.5045 3.4859 2.9717 2.9556 2.9308 2.9145 2.8961 2.8150 2.8005 2.7859 2.7800 2.7594 2.7440 1.6852 1.6682 1.5682 1.5515 1.5352-0.0001
ESI - 39 200 180 160 140 120 100 80 60 40 20 0 149.14 148.88 147.51 147.41 146.14 145.89 129.39 129.27 129.16 128.36 126.74 124.77 119.44 118.88 115.59 114.63 108.93 108.74 108.27 107.61 101.07 101.01 88.98 85.53 77.32 77.00 76.68 62.76 61.11 43.63 42.65 26.69 26.37 17.49 16.47
ESI - 40 2.05 2.04 2.00 2.03 3.02 3.39 10 9 8 7 6 5 4 3 2 1 CDCl 3,400MHz, 1 HNMR 6i N 2 N 7.0876 7.0669 6.6761 6.6551 4.5656 4.5497 4.5339 3.9739 3.9580 3.9422 2.9439 2.2632-0.0001
ESI - 41 200 180 160 140 120 100 80 60 40 20 0 CDCl 3 100MHz 13 CNMR 6i N 2 N 145.83 129.99 127.49 113.18 77.31 77.00 76.68 72.59 50.98 38.96 20.20