S 1 Supporting Information for Novel and Convenient Synthesis of Substituted Quinolines by Copper or PalladiumCatalyzed Cyclodehydration of 1-(2-Aminoaryl)-2-yn-1-ols Bartolo Gabriele,*, Raffaella Mancuso, # Giuseppe Salerno, # Giuseppe Ruffolo, # Pierluigi Plastina # Dipartimento di Scienze Farmaceutiche, Università della Calabria, 8736 Arcavacata di Rende (Cosenza), Italy, and # Dipartimento di Chimica, Università della Calabria, 8736 Arcavacata di Rende (Cosenza), Italy b.gabriele@unical.it Table of Contents Page S2 Tables S1 and S2 Page S3 General Experimental Methods Pages S3-S4 Preparation and Characterization of 2-Amino-3-methoxyacetophenone (1c) Page S4S5 Preparation and Characterization of 2-Amino-5-chloroacetophenone (1d) Pages S5S6 Preparation and Characterization of 2-(2-Aminophenyl)oct-3-yn-2-ol (2aa) Pages S6S1 Characterization Data of Products Page S11 References and Footnotes Pages S12S29 Copy of 1 H and 13 C NMR spectra
S 2 TABLE S1. Cyclodehydration reactions of 2-(2-aminophenyl)oct-3- yn-2-ol 2aa in MeOH to give 2-butyl-4-methylquinoline 3aa in the presence of different catalytic systems a Entry Catalyst t (h) Conversion of 2aa (%) b Yield of 3aa (%) c 1 ZnCl 2 1 43 35 2 ZnI 2 1 5 45 3 PdCl 2 +1KCl 1 54 48 4 PdI 2 +1KI 1 58 46 5 CuCl 1 75 72 6 CuI 1 75 63 7 CuI 5 93 78 8 CuCl 2 2H 2 O 1 86 75 9 CuCl 2 2H 2 O 5 82 1 CuCl 2 1 79 76 11 CuCl 2 3 9 12 CuCl 2 5 85 (78) 13 None 5 d a All reactions were carried out in MeOH at C with a substrate concentration of.22 mmol of 2aa per ml of MeOH in the presence of 2 mol % of catalyst. b Based on starting 2aa, by GLC. c GLC yield (isolated yield) based on 2aa. d Unidentified chromatographically immobile materials were formed under these conditions. TABLE S2. Cyclodehydration reactions of 2-(2- aminophenyl)oct-3-yn-2-ol 2aa in different solvents to give 2- butyl-4-methylquinoline 3aa in the presence of CuCl 2 as the catalyst a a Entry Solvent t (h) Conversion of 2aa (%) b Yield of 3aa (%) c 14 Dioxane 1 45 39 15 DME 1 54 43 16 DME 5 7 56 (46) 17 MeCN 1 44 39 18 DMA 1 19 DMA 5 65 (58) All reactions were carried out at C with a substrate concentration of.22 mmol of 2aa per ml of MeOH in the presence of 2 mol % of CuCl 2. b Based on starting 2aa, by GLC. c GLC yield (isolated yield) based on 2aa.
S 3 General Experimental Methods Melting points are uncorrected. 1 H NMR and 13 C NMR spectra were recorded at 25 C in CDCl 3 solutions at 3 or 5 MHz and 75 or 126 MHz, respectively, with Me 4 Si as internal standard. Chemical shifts () and coupling constants (J) are given in ppm and in Hz, respectively. IR spectra were taken with an FT-IR spectrometer. Mass spectra were obtained using a GC-MS apparatus at 7 ev ionization voltage. Microanalyses were carried out at our analytical laboratory. All reactions were analyzed by TLC on silica gel F 254 and by GLC using a gas chromatograph and capillary columns with polymethylsilicone + 5% phenylsilicone as the stationary phase. Column chromatography was performed on silica gel (7-23 mesh). Evaporation refers to the removal of solvent under reduced pressure. 2-Aminoacetophenone 1a and 2-aminobenzophenone 1b were commercially available and were used as received. 2-Amino-3-methoxyacetophenone 1c was prepared by nitration of commercially available 3-methoxyacetophenone followed by reduction, as described in the literature. 1 2-Amino-5-chloroacetophenone 1d was prepared by nitration of commercially available 3-chloroacetophenone followed by reduction, as described below. Pure 2-(2-aminophenyl)oct-3-yn- 2-ol (2aa) was prepared and characterized as described below. Preparation and Characterization of 2-Amino-3-methoxyacetophenone (1c) Nitration of 3-methoxyacetophenone to give 2-nitro-3-methoxyacetophenone. 1,2 To concd. HNO 3 (12 ml) maintained at 5 C was quickly added 3-methoxyacetophenone (2. g, 13.3 mmol) with stirring. After additional stirring at 5 C for 5 min., the mixture was allowed to warm up to room temperature ant then stirred at room temperature for 54 h. Ice followed by Et 2 O (1 ml) was added. Phases were separated and the aqueous phase was extracted with Et 2 O (3 1 ml). The collected organic layers were washed with water and then dried over Na 2 SO 4. The solvent was evaporated and the residue was taken up with EtOH. Crystallization at C followed by filtration afforded, after drying, 2-nitro-3-methoxyacetophenone as a colorless solid, mp 128-129 C (lit. 4 128-129 C) (778. mg, 3%). IR (KBr): = 1689 (m), 15 (w), 1545 (s), 1458 (m), 1379 (m), 1313 (m), 1291 (s), 148 (m), 977 (m), 864 (m), 789 (m), 614 (w) cm -1 ; 1 H NMR (5 MHz): = 7.55 (dd, J = 8.2, 7.7, 1 H), 7.41 (dd, J = 7.7, 1.1, 1 H), 7.29 (dd, J = 8.2, 1.1, 1 H), 3.92 (s, 3 H),
S 4 2.58 (s, 3 H); 13 C NMR (126 MHz): = 195.7, 151.4, 131.4,.9, 117., 56.8, 28.; GC-MS: m/z = 195 (17) [M + ], 1 (), 153 (24), 119 (14), 95 (16), 93 (12), 91 (16), 78 (35), 77 (3), 76 (), 75 (), 74 (17), 67 (1), 65 (22). Reduction of 2-nitro-3-methoxyacetophenone to give 2-amino-3-methoxyacetophenone 1c. The method of Robbins was employed. 3 A mixture of the 2-nitro-3-methoxyacetophenone (2.22 g, 11.4 mmol), Sn powder (3.81 g, 32.1 mmol), and concd. HCl (8.8 ml) was allowed to reflux for 4 h with stirring. After cooling to C, NaOH (pellets) was added to basic ph. Et 2 O (15 ml) was added and phases were separated. The aqueous phase was extracted with Et 2 O (2 15 ml) and the collected organic layers were dried over Na 2 SO 4. After filtration, the solvent was evaporated to give a brown-yellow solid, which was purified by column chromatography (SiO 2, 7:3 hexane-acoet) to give 2-amino-3-methoxyacetophenone as a pale yellow solid, mp 59-61 C (lit. 5.5-61.5 C) (1.41 g, 75%). IR (KBr): = 3476 (s), 3348 (s), 1636 (s), 1545 (s), 1453 (m), 14 (w), 1362 (w), 12 (w), 1243 (m), 1223 (m), 142 (w), 967 (w), 736 (w) cm -1 ; 1 H NMR (5 MHz): = 7.31 (dd, J = 8.2, 1.1, 1 H), 6.82 (dd, J = 7.7, 1.1, 1 H), 6.59 (s, br, 2 H), 6.55 (dd, J = 8.2, 7.7, 1 H), 3.84 (s, 3 H), 2.55 (s, 3 H); 13 C NMR (126 MHz): =.7, 147.2, 141.6, 123.3, 117.5, 114.,112.8, 55.7, 28.1; GC-MS: m/z = 165 (88) [M + ], 15 (), 122 (37), 17 (14), 14 (22), 79 (14), 78 (14), 77 (17), 65 (19). Preparation and Characterization of 2-Amino-5-chloroacetophenone (1d) Nitration of 3-chloroacetophenone to give 5-chloro-2-nitroacetophenone. The method of Robbins was employed. 3 To concd. HNO 3 (8 ml) maintained at C was added in portions with stirring concd. H 2 SO 4 (8 1.25 ml). After additional stirring at C for 45 min., 3- chloroacetophenone (8. g, 52. mmol) was added very slowly at C with vigorous stirring. After additional stirring for 2 h at C, ice was added followed by AcOEt (15 ml). Phases were separated and the aqueous phase was extracted with AcOEt (2 15 ml). The collected organic layers were evaporated and Et 2 O (15 ml) was added to the residue. The orange precipitate was recovered by decantation and then crystallized 2 times from MeOH at ca. 18 C. The crude 5- chloro-2-nitroacetophenone (3.1 g) thus obtained was then used as such for the next step. Reduction of 5-chloro-2-nitroacetophenone to give 2-amino-5-chloroacetophenone 1d. The method of Robbins was employed. 3 A mixture of the 5-chloro-2-nitroacetophenone obtained above, Sn powder (5.36 g, 45.2 mmol), concd. HCl (12.5 ml) was allowed to reflux for 4 h with stirring.
S 5 After cooling to C, NaOH (pellets) was added to basic ph. Et 2 O ( ml) was added and phases were separated. The aqueous phase was extracted with Et 2 O (2 ml) and the collected organic layers were dried over Na 2 SO 4. After filtration, the solvent was evaporated to give a brown-yellow solid, which was purified by column chromatography (SiO 2, 8:2 hexane-acoet) to give a pale yellow solid, mp 63-64 C (lit. 6 65-66 C) (3.97 g, 45% based on 5-chloro-2-nitroacetophenone). IR (KBr): = 3457 (s), 3324 (s), 1654 (s), 1617 (s), 1577 (m), 1544 (m), 1474 (m), 1362 (w), 1231 (m), 11 (w), 958 (w), 824 (w), 628 (w) cm -1 ; 1 H NMR (5 MHz): = 7.62 (d, J = 2.7, 1 H), 7.16 (dd, J = 8.8, 2.7, 1 H), 6.57 (d, J = 8.8, 1 H), 6.3 (s, br, 2 H), 2.53 (s, 3 H); GC-MS: m/z = 171 (29) [M + + 2], 169 (84) [M + ], 156 (33), 154 (), 128 (11), 126 (38), 99 (), 9 (18), 65 (13). Preparation and Characterization of 2-(2-Aminophenyl)oct-3-yn-2-ol (2aa) To a suspension of Mg turnings (7 mg, 28.8 mmol) in anhydrous THF (2. ml), maintained under nitrogen and under reflux, was added pure EtBr (.5 ml) to start the formation of the Grignard reagent. The remaining bromide was added dropwise (ca. min) in THF solution (1.5 ml of EtBr in 15. ml of THF; total amount of EtBr added: 2.92 g, 26.8 mmol). The mixture was then allowed to reflux for additional min. After cooling, the solution of EtMgBr thus obtained was transferred under nitrogen to a dropping funnel and was added dropwise to a solution of the 1- hexyne (2. g, 26.8 mmol) in anhydrous THF (7. ml) at C with stirring. After additional stirring at C for 15 min, the mixture was allowed to warm up to room temperature, maintained at 5 C for 2 h, and then used as such for the next step. 2-Aminoacetophenone 1a (1. g, 8.9 mmol) was dissolved under nitrogen in anhydrous THF (7. ml) and then added dropwise to the solution of the 1-hexynylmagnesium bromide in THF (prepared as described above) at 5 C under nitrogen. After stirring at 5 C for 1 h, the mixture was cooled to room temperature. Saturated NH 4 Cl was added with stirring to achieve weakly acidic ph. After additional stirring at room temperature for 15 min., AcOEt (ca. ml) was added and phases were separated. The aqueous phase was extracted with AcOEt (3 3 ml), and the collected organic layers were washed with brine to neutral ph and eventually dried over Na 2 SO 4. After filtration, the solvent was evaporated and the crude product was purified by column chromatography on silica gel (9:1 hexane-acoet) to give pure 2aa as a yellow oil (1.16 g, % based on 1a). Partial decomposition of 2aa usually occurred during the purification procedure, which somewhat affected the final yield obtained. IR (film): = 3451 (m), 3365 (s), 2957 (s), 2932 (s), 2871 (m), 22 (vw), 1614 (s), 1493 (m), 1455 (m), 1368 (w), 137
S 6 (m), 1237 (m), 1159 (w), 192 (m), 153 (m), 95 (w), 751 (s) cm -1 ; 1 H NMR (3 MHz): = 7.48 (dd, J = 7.8, 1.5, 1 H), 7.7 (ddd, J = 7.8, 7.4, 1.5, 1 H), 6.73 (ddd, J = 7.8, 7.4, 1.3, 1 H), 6.63 (dd, J = 7.8, 1.3, 1 H), 4.37 (s, br, 2 H), 2.26 (t, J = 7., 2 H), 1.82 (s, 3 H), 1.58-1.34 (m, 4 H),.91 (t, J = 7.2, 3 H) (Note: the OH signal was too broad to be detected); 13 C NMR (75 MHz): = 144.3, 128.7, 126.4, 118.3, 117.8, 85.9, 83.4, 7.3, 3.7, 28.8, 22., 18.4, 13.6; GC-MS: m/z = 217 (44) [M + ], 2 (15), 199 (18), 184 (19), 171 (12), 17 (53), 158 (), 157 (97), 156 (66), 155 (22), 154 (21), 144 (25), 143 (13), 13 (38), 129 (28), 128 (3), (), 118 (1), 117 (11), 115 (12), 92 (23), 77 (12), 65 (19). Characterization Data of Products 2-Butyl-4-methylquinoline (3aa). Yield: 1.42 g, starting from 1. g of 2-aminoacetophenone 1a (%) (Table 1, entry 21). Yellow oil. IR (film): = 2955 (m), 2929 (s), 2869 (m), 14 (s), 1561 (w), 1465 (m), 1379 (w), 1259 (w), 1123 (w), 861 (w), 758 (m) cm -1 ; 1 H NMR (3 MHz): = 8.5 (ddd, J = 8.5, 1.3,.7, 1 H), 7.94-7.89 (m, 1 H), 7.65 (ddd, J = 8.5, 7., 1.5, 1 H), 7.47 (ddd, J = 8.3, 7., 1.3, 1 H), 7.12 (q, J = 1., 1 H), 2.96-2.88 (m, 2 H), 2.65 (d, J = 1., 3 H), 1.84-1.72 (m, 2 H), 1.51-1.37 (m, 2 H),.96 (t, J = 7.3, 3 H); 13 C NMR (75 MHz): = 162.8, 147.7, 144.2, 129.3, 129., 126.8, 125.4, 123.6, 122.1, 39., 32.2, 22.8, 18.7, 14.; GC-MS: m/z = 199 (1) [M + ], 184 (13), 171 (6), 17 (29), 158 (23), 157 (), 156 (9), 116 (7), 115 (12); anal. calcd for C 14 H 17 N (199.29): C, 84.37; H, 8.; N, 7.3; found C, 84.41; H, 8.59; N, 7.. 2-Butyl-4-phenylquinoline (3ba). Yield: 1.86 g, starting from 1.76 g of 2-aminobenzophenone 1b (%) (Table 1, entry 22). Yellow oil. IR (film): = 2956 (s), 2929 (m), 2871 (w), 1593 (s), 1557 (m), 149 (m), 1444 (m), 8 (m), 1179 (m), 129 (m), 881 (m), 766 (s), 72 (s) cm -1 ; 1 H NMR (3 MHz): 8.12 (ddd, J = 8.4, 1.2,.6, 1 H), 7.86 (ddd, J = 8.4, 1.4,.6, 1 H), 7.66 (ddd, J = 8.4, 6.9, 1.4, 1 H), 7.51-7.44 (m, 5 H), 7. (ddd, J = 8.4, 6.9, 1.2, 1 H), 7.23 (s, 1 H), 3.4-2.96 (m, 2 H), 1.89-1.77 (m, 2 H), 1.53-1.39 (m, 2 H),.96 (t, J = 7.3, 3 H); 13 C NMR (75 MHz): = 162.6, 148.5, 148.4, 138.3, 129.5, 129.2, 128.5, 128.3, 125.7, 125.6, 125.3, 121.6, 39.1, 32.2, 22.7, 14.; GC-MS: m/z = 261 (<.5) [M + ], 232 (15), 2 (19), 219 (), 218 (9), 217 (7); anal. calcd for C 19 H 19 N (261.36): C, 87.31; H, 7.33; N, 5.36; found C, 87.39; H, 7.31; N, 5.3. 2-Butyl-8-methoxy-4-methylquinoline (3ca). Yield: 1.55 g, starting from 1.47 g of 3-methoxy-2- aminoacetophenone 1c (76%) (Table 1, entry 24). Yellow oil. IR (film): = 2954 (s), 2927 (s),
S 7 2858 (m), 16 (m), 1562 (m), 158 (m), 1465 (s), 1442 (w), 7 (w), 12 (s), 115 (m), 146 (m), 747 (m) cm -1 ; 1 H NMR (5 MHz): 7.48 (dd, J = 8.4, 1.1, 1 H), 7.37 (dd, J = 8.4, 7.7, 1 H), 7.16 (s, 1 H), 7. (dd, J = 7.7, 1.1, 1 H), 4.4 (s, 3 H), 3.1-2.97 (m, 2 H), 2.61 (s, 3 H), 1.83-1.75 (m, 2 H), 1.45 (sextuplet, J = 7.5, 2 H),.96 (t, J = 7.5, 3 H); 13 C NMR (126 MHz): = 161.7, 155.4, 144., 139.6, 127.9, 125.3, 122.5, 115.5, 17.4, 56., 39.2, 32.3, 22.9, 19.2, 14.; GC-MS: m/z = 229 (12) [M + ], 228 (29), (29), 188 (18), 187 (), 185 (13), 172 (39), 17 (24), 169 (23), 157 (11), 115 (11); anal. calcd for C 15 H 19 NO (229.32): C, 78.56; H, 8.35; N, 6.11; found C, 78.66; H, 8.33; N, 6.9. 2-Butyl-6-chloro-4-methylquinoline (3da). Yield: 1.69 g, starting from 1.51 g of 5-chloro-2- aminoacetophenone 1d (81%) (Table 1, entry 25). Yellow oil. IR (film): = 29 (m), 2928 (w), 2535 (w), 14 (m), 1437 (w), 1384 (s), 1262 (m), 188 (s), 124 (s), 877 (w), 2 (s) (m) cm -1 ; 1 H NMR (3 MHz): 8.13 (d, J = 9., 1 H), 7.95 (d, J = 2.2, 1 H), 7.67 (dd, J = 9., 2.2, 1 H), 7.28 (q, J =.9, 1 H), 3.6-2.98 (m, 2 H), 2.7 (d, J =.9, 3 H), 1.87-1.73 (m, 2 H), 1.44 (sextuplet, J = 7.4, 2 H),.96 (t, J = 7.4, 3 H); 13 C NMR (75 MHz): = 162.6, 146.5, 143.7, 132.5, 131.1, 129.2, 127.7, 123., 122.9, 37.6, 31.8, 22.6, 18.8, 13.8; GC-MS: m/z = 235 (<.5) [M + + 2], 233 (2) [M + ], 232 (3), 218 (15), 6 (11), 4 (32), 193 (59), 192 (26), 191 (), 156 (9), 155 (9), 154 (14), 141 (12), (14), 128 (8), 127 (8), 115 (8), 75 (5); anal. calcd for C 14 H 16 ClN (233.74): C, 71.94; H, 6.9; Cl, 15.17; N, 5.99; found C, 71.85; H, 6.92; Cl, 15.18; N, 6.5. 4-Methyl-2-phenylquinoline (3ab). Yield: 1.42 g, starting from 1. g of 2-aminoacetophenone 1a (73%) (Table 1, entry 28). Yellow solid, 65-67 C, lit. 7 64-64.5 C. IR (KBr): = 3 (m), 1597 (s), 1551 (m), 159 (w), 1495 (w), 1451 (m), 1348 (m), 179 (w), 129 (w), 861 (w), 769 (s), 694 (s) cm -1 ; 1 H NMR (3 MHz): = 8.-8.1 (m, 3 H), 7.97-7.92 (m, 1 H), 7.69 (ddd, J = 8.4, 6.9, 1.5, 1 H), 7.68-7.65 (m, 1 H), 7.54-7.39 (m, 4 H), 2.71 (d, J = 1., 3 H); 13 C NMR (75 MHz): = 157., 148.1, 144.8, 139.8, 13.2, 129.3, 129.2, 128.7, 127.5, 127.2, 126., 123.6, 119.7, 19.; GC- MS: m/z = 219 () [M + ], 218 (42), 217 (23), 216 (8), 5 (13), 4 (71), 19 (12); anal. calcd for C 16 H 13 N (219.28): C, 87.64; H, 5.98; N, 6.39; found C, 87.58; H, 5.99; N, 6.43. 2,4-Diphenylquinoline (3bb). Yield: 1.7 g, starting from 1.76 g of 2-aminobenzophenone 1b (68%) (Table 1, entry 3). Yellow solid, mp 17-18 C, lit. 8 15-16 C. IR (KBr): = 354 (m), 159 (s), 1546 (m), 1489 (m), 1445 (m), 7 (m), 1358 (m), 1231 (m), 174 (m), 131 (m), 89 (m), 77 (s), 72 (s) cm -1 ; 1 H NMR (3 MHz): 8.24 (ddd, J = 8.5, 1.1,.6, 1 H), 8.-8.14 (m, 2 H), 7.89-7.84 (m, 1 H), 7.78 (s, 1 H), 7.68 (ddd, J = 8.5, 6.9, 1.5, 1 H), 7.54-7.38 (m, 9 H); 13 C
S 8 NMR (75 MHz): = 156.8, 149.2, 148.8, 139.6, 138.4, 13.1, 129.54, 129.49, 129.3, 128.8, 128.6, 128.4, 127.6, 126.3, 125.8, 125.6, 119.3; GC-MS: m/z = 281 (76) [M + ], 2 (), 278 (7), 2 (16), 176 (6), 139 (1); anal. calcd for C 21 H 15 N (281.35): C, 89.65; H, 5.37; N, 4.98; found C, 89.71; H, 5.35; N, 4.94. 8-Methoxy-4-methyl-2-phenylquinoline (3cb). Yield: 2. g, starting from 1.47 g of 2-amino-3- methoxyacetophenone 1c (9%) (Table 1, entry 32). Yellow solid, mp 96-97 C. IR (KBr): = 1 (m), 1552 (w), 1493 (m), 1468 (s), 7 (w), 135 (w), 1257 (s), 11 (m), 145 (m), 96 (m), 773 (w), 744 (m), 78 (m) cm -1 ; 1 H NMR (5 MHz): = 8.19-8.15 (m, 2 H), 7.72 (s, 1 H), 7.55-7.39 (m, 5 H), 7.4 (d, J = 7.7, 1 H), 4.7 (s, 3 H), 2.71 (s, 3 H); 13 C NMR (126 MHz): = 156., 155.8, 144.7,.1, 139.9, 129., 128.7, 128.4, 127.6, 126.1,.2, 115.5, 17.8, 56.1, 19.5; GC-MS: m/z = 249 (92) [M + ], 248 (), 2 (51), 219 (28), 218 (17), 217 (12), 4 (15), 115 (1), 77 (17); anal. calcd for C 17 H 15 NO (249.31): C, 81.9; H, 6.6; N, 5.62; found C, 81.98; H, 6.5; N, 5.. 6-Chloro-4-methyl-2-phenylquinoline (3db). Yield: 1.76 g, starting from 1.51 g of 2-amino-5- choroacetophenone 1d (78%) (Table 1, entry 33). Yellow solid, mp 89-9 C, lit. 9 92-93 C. IR (KBr): = 1599 (s), 1545 (w), 1491 (m), 1446 (w), 1436 (w), 1384 (s), 1348 (s), 1283 (w), 191 (m), 128 (w), 881 (m), 777 (m), 698 (s), 684 (m) cm -1 ; 1 H NMR (5 MHz): = 8.15-8.1 (m, 3 H), 7.94 (d, J = 2.2, 1 H), 7.71 (s, br, 1 H), 7.65 (dd, J = 9.3, 2.2, 1 H), 7.54-7.44 (m, 3 H), 2.72 (d, J = 1.1, 3 H); 13 C NMR (126 MHz): = 157., 145.8, 144.9, 138.6, 132.1, 131.3, 13.6, 129.8, 128.9, 128., 127.6, 122.8,.6, 19.; GC-MS: m/z = 255 (33) [M + + 2], 254 (27), 253 () [M + ], 252 (22), 2 (15), 238 (46), 218 (1), 217 (24), 216 (14), 3 (11), 19 (23); anal. calcd for C 16 H 12 ClN (253.73): C, 75.74; H, 4.77; Cl, 13.97; N, 5.52; found C, 75.81; H, 4.76; Cl, 13.95; N, 5.48. 2-tert-Butyl-4-methylquinoline (3ac). Yield: 1.33 mg, starting from 1. g of 2- aminoacetophenone 1a (75%) (Table 1, entry 37). Yellow oil. IR (film): = 2956 (s), 2917 (m), 2863 (m), 12 (m), 1557 (m), 156 (m), 1448 (m), 1363 (w), 1153 (m), 117 (m), 932 (w), 863 (w), 757 (s) cm -1 ; 1 H NMR (3 MHz): = 8.6 (ddd, J = 8.4, 1.3,.7, 1 H), 7.93-7.86 (m, 1 H), 7.63 (ddd, J = 8.4, 6.9, 1.5, 1 H), 7.46 (ddd, J = 8.2, 6.9, 1.3, 1 H), 7.33 (q, J =.8, 1 H), 2.66 (d, J =.8, 3 H), 1.45 (s, 9 H); 13 C NMR (75 MHz): = 168.9, 147.3, 143.6, 129.9, 128.7, 126.5, 125.3, 123.3, 118.8, 37.9, 3.1, 18.9; GC-MS: m/z = 199 (36) [M + ], 198 (3), 184 (), 185 (15), 168 (9), 157 (42), 143 (19), 115 (13); anal. calcd for C 14 H 17 N (199.29): C, 84.37; H, 8.; N, 7.3; found C, 84.33; H, 8.62; N, 7.5.
S 9 2-tert-Butyl-4-phenylquinoline (3bc). Yield: 1.63 g, starting from 1.76 g of 2-aminobenzophenone 1b (7%) (Table 1, entry 38). Colorless solid, mp 86-87 C, lit. 1 85-88 C. IR (KBr): = 3 (m), 159 (s), 1554 (m), 1488 (m), 1447 (m), 7 (m), 1363 (m), 1252 (m), 116 (m), 127 (m), 886 (m), 839 (w), 779 (m), 762 (s), 77 (s) cm -1 ; 1 H NMR (3 MHz): 8.13 (ddd, J = 8.4, 1.2,.6, 1 H), 7.84 (ddd, J = 8.4, 1.5,.6, 1 H), 7.64 (ddd, J = 8.4, 6.9, 1.5, 1 H), 7.51-7.43 (m, 6 H), 7.39 (ddd, J = 8.4, 6.9, 1.2, 1 H), 1.49 (s, 9 H); 13 C NMR (75 MHz): = 168.7, 148.1, 147.9, 138.8, 129.8, 129.6, 128.9, 128.4, 128.1, 125.7, 125.3, 125., 118.4, 38.1, 3.1; GC-MS: m/z = 261 (44) [M + ], 2 (28), 247 (), 246 (), 2 (1), 219 (48), 5 (13), 4 (18); anal. calcd for C 19 H 19 N (261.36): C, 87.31; H, 7.33; N, 5.36; found C, 87.26; H, 7.35; N, 5.39. 2-tert-Butyl-8-methoxy-4-methylquinoline (3cc). Yield: 1.57 g, starting from 1.47 g of 3- methoxy-2-aminobenzophenone 1c (77%) (Table 1, entry 39). Yellow oil. IR (film): = 2959 (s), 2866 (m), 1598 (m), 1588 (m), 1557 (m), 1494 (m), 9 (s), 1362 (m), 1336 (w), 1258 (s), 2 (w), 148 (m), 932 (w), 87 (w), 731 (m) cm -1 ; 1 H NMR (5 MHz): 7.5 (distorted d, J = 8.2, 1 H), 7.41-7.36 (m, 2 H), 7.1 (d, J = 7.7, 1 H), 4.5 (s, 3 H), 2.65 (s, 3 H), 1.48 (s, 9 H); 13 C NMR (126 MHz): = 167.7, 155.8, 143.6, 139.2, 127.8, 125.4, 119.6, 115.5, 18.2, 56.5, 38.2, 3.2, 19.5; GC-MS: m/z = 229 (99) [M + ], 228 (), 215 (12), 214 (73), 213 (17), 212 (), 21 (12), (63), 199 (73), 198 (47), 197 (1), 196 (33), 187 (11), 185 (13), 184 (32), 183 (15), 173 (23), 169 (1), 115 (17), 17 (11), 77 (1); anal. calcd for C 15 H 19 NO (229.32): C, 78.56; H, 8.35; N, 6.11; found C, 78.62; H, 8.33; N, 6.1. 4-Methylquinoline (3ad). Yield:.93 g, starting from 1. g of 2-aminoacetophenone 1a (73%) (Table 2, entry 42). Yellow oil. IR (film): = 1596 (m), 15 (m), 1524 (s), 1452 (s), 131 (m), 1251 (m), 841 (m), 757 (s) cm -1 ; 1 H NMR (3 MHz): 8.74 (d, J = 4.3, 1 H), 8.14-8.6 (m, 1 H), 7.92 (dd, J = 8.3, 1.4, 1 H), 7.66 (ddd, J = 8.4, 6.9, 1.4, 1 H), 7.5 (ddd, J = 8.3, 6.9, 1., 1 H), 7.14 (d, J = 4.3, 1 H), 2.62 (s, 3 H); 13 C NMR (75 MHz): = 15., 147.8, 144.3, 129.9, 129.1, 128.2, 126.2, 123.8, 121.8, 18.6; GC-MS: m/z = 143 () [M + ], 142 (33), 117 (9), 116 (15), 115 (39), 89 (1); anal. calcd for C 1 H 9 N (143.19): C, 83.88; H, 6.34; N, 9.78; found C, 83.75; H, 6.36; N, 9.89. 4-Phenylquinoline (3bd). Yield: 1. g, starting from 1.76 g of 2-aminobenzophenone 1b (66%) (Table 2, entry 45). Yellow solid, mp. 61-62 C, lit. 11 61 C. IR (KBr): = 1584 (m), 158 (w), 1491 (m), 1391 (m), 1277 (w), 13 (w), 851 (m), 769 (s), 74 (s), 612 (m) cm -1 ; 1 H NMR (3 MHz): 8.94 (d, J = 4.4, 1 H), 8.18 (ddd, J = 8.5, 1.1,.6, 1 H), 7.94-7.89 (m, 1 H), 7.71 (ddd, J = 8.5, 7., 1.5, 1 H), 7.55-7.44 (m, 6 H), 7.32 (d, J = 4.4, 1 H); 13 C NMR (75 MHz): = 149.9, 148.7,
S1 148.6, 138., 129.8, 129.6, 129.3, 128.6, 128.4, 126.8, 126.6, 125.9, 121.3; GC-MS: m/z = 5 (), 4 (97), 3 (1), 178 (13), 177 (12), 176 (3), 151 (12), 12 (14), 88 (12); anal. calcd for C 15 H 11 N (5.25): C, 87.77; H, 5.; N, 6.82; found C, 87.83; H, 5.38; N, 6.79. 2-(1-Methoxy-1-methylhept-2-ynyl)phenylamine (4ac). Yield: 6 mg, starting from 1. g of 2- aminoacetophenone 1a (3%) (Table 1, entry 35). Yellow oil. IR (film): = 347 (m), 3371 (m), 2969 (s), 2934 (m), 2221 (vw), 1614 (s), 1492 (m), 1459 (m), 1364 (w), 131 (w), 1263 (m), 185 (s), 148 (w), 859 (w), 75 (m) cm -1 ; 1 H NMR (3 MHz): = 7.57 (dd, J = 7.7, 1.5, 1 H), 7.8 (ddd, J = 7.9, 7.3, 1.5, 1 H), 6.7 (ddd, J = 7.7, 7.3, 1.2, 1 H), 6.58 (dd, J = 7.9, 1.2, 1 H), 4.45 (s, br, 2 H), 3.24 (s, 3 H), 1.78 (s, 3 H), 1.32 (s, 9 H); 13 C NMR (75 MHz): = 144.7, 129.2, 128.8, 124.4, 117.3, 116.5, 96.7, 78.6, 78.5, 51.9, 31.1, 27.7, 27.6; GC-MS: m/z = 231 (38) [M + ], 216 (28), (21), 199 (63), 198 (16), 185 (19), 184 (), 17 (17), 169 (39), 168 (26), 167 (13), 158 (42), 157 (17), 156 (11), 154 (15), 144 (23), 143 (21), 142 (11), 131 (13), 13 (34), 115 (9), 16 (6), 91 (9), 77 (1); anal. calcd for C 15 H 21 NO (231.33): C, 77.88; H, 9.15; N, 6.5; found C, 77.86; H, 9.13; N, 6.2.
S11 References and Footnotes (1) The only mononitrated product obtained by nitration of 3-methoxyacetophenone was 3- methoxy-2-nitroacetophenone, as confirmed by 1 H NMR. This product was obtained either by using the nitration procedure reported by Alford et. al., 2 or by using the procedure recently reported by Robbins et. al. 3 It is worth noting that in this latter case the Authors have indicated the structure of the mononitrated product as 5-methoxy-2-nitroacetophenone rather than 3-methoxy-2- nitroacetophenone. (2) Alford, E. J.; Irving, H.; Marsh, H. S.; Schofield, K. J. Chem. Soc. 1952, 39 317. (3) Robbins, R. J.; Laman, D. M.; Falvey, D. E. J. Am. Chem. Soc. 1996, 118, 8127 8135. (4) Ames, D. E.; Ansari, H. R.; France, A. D. G.; Lovesey, A. C.; Novitt, B.; Simpson, R. J. Chem. Soc. (C) 1971, 388 397. (5) Georgarakis, E.; Schmid, H.; Hansen, H.-J. Helv. Chim. Acta 1979, 62, 234 27. (6) Leonard, N. J.; Boyd, S. N., Jr. J. Org. Chem. 1946, 11, 5 417. (7) Giezendanner, H.; Rosenkranz, H. J.; Hansen, H. J.; Schmid, H. Helv. Chim. Acta 1973, 56, 2588 2611. (8) Al-Talib, M.; Jochims, J. C.; Wang, Q.; Hamed, A.; Ismail, A. E.-H. Synthesis 1992, 875 878. (9) Makioka, Y.; Shindo, T.; Taniguchi, Y.; Takaki, K.; Fujiwara, Y. Synthesis 1995, 1 4. (1) Kobayashi, K.; Yoneda, K., Miyamoto, K.; Morikawa, O.; Konishi, H. Tetrahedron 4,, 11639 11646. (11) Badger, G. M.; Cook, J. W.; Walker, T. J. Chem. Soc. 1948, 11 13
S12 Copy of 1 H and 13 C NMR spectra 2-Nitro-3-methoxyacetophenone O Me NO 2 OMe 1 HNMR (5 MHz, CDCl 3 ) I n t e g r a l 7. 5 5 3 9 7. 5 3 7 4 7. 4 1 2 3. 9 1 2 7. 3 9 6 9. 9 2 5 5 7. 2 9 9 3. 9 3 1 8 7. 2 8 6 2. 9 9 9 5 4. 1 4 5 3. 9 1 8 2. 9 7 4 2 2. 6 5 8 1 2. 5 7 8. 13 CNMR (126 MHz, CDCl 3 ) 195.719 151.3522 131.3651.9156 116.9814 77.42 77.1468 76.8895 56.8361 27.9658 -. 1 1
S13 2-Amino-3-methoxyacetophenone O Me NH 2 OMe 1 c 1 HNMR (5 MHz, CDCl 3 ) I n t e g r a l. 8 3 2 3. 8 7 3 5 3. 2 8 3 2. 9 9 8 7 3. 2 7. 3 2 1 7. 3 3 7 6. 8 2 4 1 6. 8 8 7 6. 5 7 5 6. 5 5 4 1 6. 5 3 8 7 3. 8 3 7 9 2. 5 5 5. 13 CNMR (126 MHz, CDCl 3 ).63 147.2415 141.5572 123.32 117.53 114.32 112.8119 77.3969 77.1395 76.8895 55.711 28.835 -. 1 1
S14 2-Amino-5-choroacetophenone Cl O Me NH 2 1 d 1 HNMR (5 MHz, CDCl 3 ) I n t e g r a l. 8 9 9 9. 8 9 5 5 1. 1 6 6 7 2. 1 3 7 5 3. 1 7. 6 2 3 7. 6 1 7 5 7. 1 7 6 4 7. 1 7 2 7. 1 5 8 8 7. 1 5 4 4 6. 5 7 9 3 6. 5 6 1 8 2. 7 7 6 6 2. 5 6 9 2 2. 5 2 7 5. 8 7 8 -.
S15 2-(2-Aminophenyl)oct-3-yn-2-ol Me OH NH 2 Bu 2aa 1 HNMR (3 MHz, CDCl 3 ). 9 5 9 3. 9 8 2 1 1. 3 4 1. 1 1 7 1. 9 2 7 9 2. 3 6 3 2. 9 9 4 3 4. 3 1 6 2 3. 2 7 3 6 7. 4 9 1 6 7. 4 6 5 6 7. 6 7 7 6. 7 3 2 6. 6 3 6 9 6. 6 1 4 2. 2 8 1 2 2. 2 5 8 3 2. 2 3 4 5 1. 8 2 3 4 1. 5 2 1 6 1. 4 9 8 2 1. 4 2 4 6 1. 1 8 9 1. 9 3 7 5. 9 1 3 3. 8 8 9 5 -. 13 CNMR (75 MHz, CDCl 3 ) 144.2824 128.6598 126.3665 118.384 117.7829 85.8687 83.4322 77.5398 77.199 76.6799 7.2939 3.738 28.87 22.246 18.4414 13.61 -. 13 11 9 7 5 3 1
S16 2-Butyl-4-methylquinoline Me N Bu 3aa 1 HNMR (3 MHz, CDCl 3 ). 8 3 1 7. 8 6 3. 8 3 7 4. 8 9 3. 8 5 1. 9 9 9 3. 8 6 1. 9 6 7 4 2. 1 4 2 1 3. 1 8 7 9 7. 9 3 2 7. 9 2 6 7. 6 5 3 8 7. 6 3 6 7. 4 9 6 8 7. 4 7 3 6 7. 1 1 9 8 3. 2 4 9 8 2. 9 4 3 6 2. 9 1 7 6 2. 8 9 1 2. 6 4 6 2 2. 6 4 3 4 1. 8 7 6 1. 7 8 5 1. 7 5 5 1 1. 7 2 9 1 1. 4 7 5 9 1. 4 5 1 6 1. 4 2 5 6 1. 4 7. 9 8 1 2. 9 5 6 9. 9 3 2 5. 9 1 2 -. 13 CNMR (75 MHz, CDCl 3 ) 162.7557 147.6745 144.171 129.2968 129.12 126.7647 125.3792 123.5797 122.668 77.5 77.7 76.66 39.168 32.2486 22.7572 18.6962 14.31. 1
S17 2-Butyl-4-phenylquinoline Ph N Bu 3ba 1 HNMR (3 MHz, CDCl 3 ) I n t e g r a l 8. 1 8 1 7. 8 6 8 1. 1 1 1 9 7. 8 4 2 9 1. 1 5 8 9 7. 6 6 1 3 7. 4 8 5 7 1. 2 1 8 9 7. 4 7 7 4. 9 3 2 8 7. 4 2 7 6 1. 2 1 1 1 7. 3 9 9 7 7. 2 3 4 2. 9 9 9 6 2. 4 2 2 3 3. 2 6 2 3. 1 2. 9 7 3 6 2. 4 6 9 2. 1 5 1 4 3. 1 7 4 4 1. 8 3 2 1 1. 8 6 1. 5 1 1. 4 7 6 3 1. 4 5 1 1 1. 2 5 5 4. 9 8 8 8. 9 6 4 5. 9 3 9 8 -. 13 CNMR (75 MHz, CDCl 3 ) 162.5964 148.4867 148.3911 138.2786 129.5197 129.1853 128.4846 128.2616 125.6818 125.5862 125.2518 121.573 77.5 77.7 76.66 39.964 32.2326 22.7412 14.142 -. 1
S18 2-Butyl-8-methoxy-4-methylquinoline Me N OMe Bu 3ca 1 HNMR (5 MHz, CDCl 3 ) I n t e g r a l 7. 4 8 1 4 7. 4 6 3 9 7. 3 8 4 9. 9 6 6 6 7. 3 6 8 4 7. 3 5 3. 9 4 3 4 7. 1 5 5 5. 9 1 9 3 6. 9 9 7 5 6. 9 8 2 1. 9 5 2 9 2. 9 4 8 1 4. 3 4 3 2. 2 3 3 5 3. 2 7 2. 9 8 6 2 2. 9 6 9 7 3. 3 2 7 8 2. 6 7 6 2. 2 1 2 5 2. 2 4 4 8 3. 1 9 2 2 1. 8 1 8 5 1. 8 3 1 1. 7 8 6 7 1. 7 7 1 3 1. 7 5 5 9 1. 4 7 6 1. 4 5 5 2 1. 4 4 1 1. 4 2 5 6. 9 7 2. 9 5 5 9. 9 4 1 6 -. 13 CNMR (126 MHz, CDCl 3 ) 161.6693 155.3746 143.9912 139.6232 127.8721 125.291 122.4525 115.4592 17.4143 77.4998 77.2498 76.9924 56.493 39.1948 32.344 22.8624 19.1561 14.3 -. 1
S19 2-Butyl-6-chloro-4-methylquinoline Cl Me N Bu 3da 1 HNMR (3 MHz, CDCl 3 ) 1. 2 1 1. 4 5 2 1. 1 6 1. 2. 2 1 1 2. 9 5 8 4 2. 3 4 7 5 2. 2 3 1 5 3. 1 8. 1 2 6 9 8. 9 6 2 7. 9 4 5 7. 6 7 7 6 7. 6 4 6 9 7. 2 6 1 3. 3 1 3. 4 9 2. 9 7 7 5 2. 6 9 4 7 1. 8 2 1 3 1. 7 9 6 1 1. 7 6 9 8 1. 4 5 3 1 1. 4 2 7 9. 9 8 4 1. 9 5 8 9. 9 3 4 8. 8 6 6 -. 13 CNMR (75 MHz, CDCl 3 ) 162.5871 146.537 143.727 132.59 131.1238 129.2449 127.6685 123.828 122.9554 77.5278 77.94 76.6839 37.5617 31.8136 22.613 18.8366 13.5 -. 1
S 4-Methyl-2-phenylquinoline Me N Ph 3ab 1 HNMR (3 MHz, CDCl 3 ) I n t e g r a l 2. 8 9 5 7 1. 5 4 2. 5 8 1 3. 2 3 3. 1 6 9 8. 1 8 5 8. 1 4 8 8 8. 1 4 3 3 8. 1 2 9 7. 9 6 9 7. 9 3 3 4 7. 6 8 7 8 7. 6 6 5 4 7. 5 2 8 2 7. 4 9 9 9 7. 4 7 4 7 7. 4 5 1 4 7. 4 2 8 1 2. 7 8 8 2. 7 5 6. 13 CNMR (75 MHz, CDCl 3 ) 157.385 148.885 144.72 139.7915 13.2364 129.2968 129.1535 128.7394 127.5132 127.216 125.9843 123.5796 119.7257 77.4762 77.462 76.6162 18.9669. 1
S21 2,4-Diphenylquinoline Ph N Ph 3bb 1 HNMR (5 MHz, CDCl 3 ) I n t e g r a l 8. 2 3 5 4 8. 1 8 3 8 8. 1 6 9 6 7. 8 9 8. 8 7 7 4 7. 8 7 4 3 2. 6 4 7. 7 9 4 2. 9 2 3 8 7. 7 1 5 2 7. 6 9 8 8 1. 7. 6 8 5 6 1. 2 2 3 6 7. 5 2 6 4 7. 5 1 2 2 1. 7. 4 9 9 7. 4 8 4 7 7. 4 4 9 6 7. 4 3 4 3 7. 4 2 1 1. 1 1. 9. 13 CNMR (126 MHz, CDCl 3 ) 156.81 149.1535 148.79 139.6379 138.3951 13.1223 129.5487 129.4973 129.3281 128.8134 128.577 128.3795 127.5853 126.3131 125.7616 125.6145 119.3272 77.2939 77.365 76.7792. 1
S22 8-Methoxy-4-methyl-2-phenylquinoline Me N OMe Ph 3cb 1 HNMR (5 MHz, CDCl 3 ) I n t e g r a l 8. 1 7 7 2 8. 1 6 8 7. 7 2 4 7. 5 3 7 4 7. 5 1 9 9 2. 3 5 5 7. 4 9 9 7. 4 8 3 6 1. 2 4 8 7. 4 6 8 3 7. 4 4 3 5. 9 9 4 7. 4 2 5 5 7. 4 1 1 1. 1 4 2 7. 4 6 9 7. 3 1 5 3. 3 5 2 8 4. 7 2 7 3. 3 7 3 2 2. 7 5 3 1. 2 5 3 3. 8 8 9. 9. 13 CNMR (126 MHz, CDCl 3 ) 155.9997 155.7717 144.7413.865 139.926 129.3 128.6737 128.3574 127.6368 126.778.2243 115.4666 17.8482 77.33 77.7 76.8233 56.1449 19.4871. 1
S23 6-Chloro-4-methyl-2-phenylquinoline Cl Me N Ph 3db 1 HNMR (5 MHz, CDCl 3 ) 2. 8 3 8. 8 6 9 5 1. 1 6 9 2. 8 6 2 8 3. 2 5 5 3. 2 8. 1 2 2 4 8. 1 8 1 7. 9 4 2 4 7. 9 3 8 7. 7 1 8 7. 6 5 9 2 7. 5 1 6 6 7. 5 1 2 2. 7 1 6 2 2. 7 1 4. 8 1. 13 CNMR (126 MHz, CDCl 3 ) 157.419 157.366 145.7782 144.9252 138.6379 132.1299 131.2769 13.5562 129.7547 128.9237 127.74 122.82.5774 77.2866 77.366 76.7792 19.312. 1
S24 2-tert-Butyl-4-methylquinoline Me N t-bu 3ac 1 HNMR (3 MHz, CDCl 3 ) I n t e g r a l 7. 6 6 1 3 7. 6 5 6 3. 8 4 1 9 7. 6 3 8 4. 9 1 2 1 7. 6 3 3 4. 9 2 5 8 7. 6 1 1 7. 6 5 5. 8 8 7. 4 8 8. 8 3 9 3 7. 4 8 3 4 7. 4 6 1 7. 4 5 6 7. 4 3 7 2 7. 3 3 3 4 2. 9 9 8 1 2. 6 5 7 6 2. 6 5 4 8 9. 6 7 1. 4 5 4 3 1. 2 5 4. 13 CNMR (75 MHz, CDCl 3 ) 168.8869 147.2923 143.5658 129.9179 128.6598 126.599 125.3473 123.38 118.8498 77.4443 77.143 76.3 37.8861 3.1146 18.9192. 1 1
S25 2-tert-Butyl-4-phenylquinoline Ph N t-bu 3bc 1 HNMR (3 MHz, CDCl 3 ) I n t e g r a l 8. 1 4 6 1 8. 1 1 8 2 1. 9 6 7. 8 4 7 4 7. 8 1 9 1 1. 9 1 1 7. 6 4 1 2 1. 1 9 2 7 7. 4 9 5 3 7. 4 8 6 6 6. 2 4 7. 4 4 2 2 1. 1 9 6 7. 4 7 9 7. 3 8 4 6 9. 4 7 7 1. 6 5 4 2 1. 4 9 3 2 1. 4 8 6 3. 13 CNMR (75 MHz, CDCl 3 ) 168.7275 148.3 147.8814 138.7722 129.7745 129.5675 128.8667 128.4527 128.1183 125.6658 125.3314 124.9651 118.4357 77.4283 77.143 76.5843 38.19 3.1623 -. 1
S26 2-tert-Butyl-8-methoxy-4-methylquinoline Me N OMe t-bu 3cc 1 HNMR (5 MHz, CDCl 3 ) I n t e g r a l 7. 5 5 6 7. 4 8 9 1. 9 2 6 7. 3 8 6 1. 2 9 9 7. 3 7 3 9 7. 2 5. 8 9 5 7 7. 5 1 2. 8 9 3 4 4. 5 4 2. 9 6 9 4 2. 6 4 7 1 8. 9 9 4 1. 4 7 7 2. 8 7 8 -. 13 CNMR (126 MHz, CDCl 3 ) 167.6626 155.8232 143.15 139.1526 127.7545 125.13 119.6434 115.51 18.1644 77.3233 77.733 76.8159 56.5199 38.21 3.1572 19.465. 1
S27 4-Methylquinoline Me N 3ad 1 HNMR (3 MHz, CDCl 3 ) I n t e g r a l 8. 7 2 9 2 8. 1 1 5. 9 8 1 2 8. 8 7 5 8. 8 7 1 7. 9 3 7. 9 1 2 3 7. 9 2 7 7. 9 2 8. 9 4 7 7. 8 9 9 1. 9 1 7 3 7. 6 8 5 1. 8 9 6 2 7. 6 6 1 3 7. 6 3 3 9 1. 8 7. 5 2 6 4 7. 4 9 9 7. 4 7 5 6 7. 1 4 9 5 7. 1 3 8 1 2. 9 9 8 3 2. 6 1 6 9. 9. 13 CNMR (75 MHz, CDCl 3 ) 15.473 147.8337 144.2664 129.871 129.579 128.1979 126.2232 123.777 121.79 77.6194 77.1895 76.7595 18.5688 -.
S28 4-Phenylquinoline Ph N 3bd 1 HNMR (3 MHz, CDCl 3 ) I n t e g r a l 1. 9 1 1. 2 9 9 6 1. 3 4 5 1. 4 1 8 6. 1 2 4. 8 9 3 8. 9 4 3 2 8. 9 2 8 6 8. 1 9 8 7 8. 1 7 3 7. 9 2 7 7. 9 1 4 7. 7 3 9 7. 7 1 1 2 7. 6 8 7 8 7. 4 9 3 5 7. 3 2 3 3 7. 3 8 2 1. 2 5 3 6 -. 9. 13 CNMR (75 MHz, CDCl 3 ) 149.9477 148.6682 148.5726 129.8355 129.5561 129.352 128.5854 128.4457 126.6441 125.89 121.3421 77.2866 77.365 76.7792 -. 1
S29 2-(1-Methoxy-1-methylhept-2-ynyl)phenylamine Me OMe t-bu NH 2 4ac 1 HNMR (3 MHz, CDCl 3 ). 9 6 8 4. 9 6 1. 8 7 8 7. 9 2 6 6 1. 9 1 2 3 2. 5 4 5 6 2. 8 1 8 5 9. 2 1 7. 5 5 5 2 7. 1 2 7. 7 4 1 7. 4 9 8 6. 7 1 7 8 6. 6 9 2 2 6. 6 6 7 5 6. 5 9 1 6 6. 5 6 5 1 3. 2 3 6 1 2. 1 5 1 3 1. 7 8 4 1 1. 3 1 7 1. 7 9 1 -. 13 CNMR (75 MHz, CDCl 3 ) 144.6487 129.2171 128.7712 124.4237 117.351 116.4929 96.7297 78.6387 78.5272 77.4761 77.621 76.6321 51.8843 31.542 27.67 27.5825 -.