Microwave-Promoted Alkynylation-Cyclization
of 2-Aminoaryl Ketones: A Green Strategy for the Synthesis
of 2,4-Disubstituted Quinolines

Iraj Mohammadpoor-Baltork; Shahram Tangestaninejad; Majid Moghadam; Valiollah Mirkhani; Salma Anvar; Arsalan Mirjafari

doi:10.1055/s-0030-1259065

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Synlett 2010(20): 3104-3112
DOI: 10.1055/s-0030-1259065

LETTER

Microwave-Promoted Alkynylation-Cyclization of 2-Aminoaryl Ketones: A Green Strategy for the Synthesis of 2,4-Disubstituted Quinolines

Iraj Mohammadpoor-Baltork*, Shahram Tangestaninejad*, Majid Moghadam, Valiollah Mirkhani, Salma Anvar, Arsalan Mirjafari
Catalysis Division, Department of Chemistry, University of Isfahan, Isfahan 81746-73441, Iran
Fax: +98(311)6689732; e-Mail: imbaltork@sci.ui.ac.ir; e-Mail: stanges@sci.ui.ac.ir;

Further Information

Publication History

Received 19 July 2010
Publication Date:
24 November 2010 (online)

Abstract
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Abstract

A series of 2,4-disubstituted quinolines were easily prepared through a one-pot reaction of structurally diverse 2-aminoaryl ketones with various arylacetylenes in the presence of K₅CoW₁₂O₄₀˙3H₂O as a reusable and environmentally benign catalyst under microwave irradiation and solvent-free conditions.

Key words

2,4-disubstituted quinolines - K₅CoW₁₂O₄₀˙3H₂O - microwave irradiation - 2-aminoaryl ketones - arylacetylenes

References and Notes

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17

The microwave system used in these experiments includes the following items: Micro-SYNTH labstation, equipped with a glass door, a dual magnetron system with pyramid-shaped diffuser, 1000 W delivered power, exhaust system, magnetic stirrer, ‘quality pressure’ sensor for flammable organic solvents, and a ATCFO fiber optic system for automatic temperature control

18

Synthesis of 2,4-Disubstituted Quinolines; General Procedure
A mixture of 2-aminoaryl ketone 1 (1 mmol), arylacetylene 2 (1 mmol) and K₅WCo₁₂O₄₀˙3H₂O (10 mol%) was irradiated under solvent-free conditions for the appropriate time (Table [²] ). The progress of the reaction was monitored by TLC (n-hexane-EtOAc, 9:1). After completion of the reaction, the mixture was cooled to r.t. and cold EtOH (20 mL) was added. The residue was filtered, the filtrate was evaporated, and the crude product was purified by recrystal-lization from EtOH to afford the pure product in 75-96% yields.
2,4-Diphenylquinoline (3a) Mp 107-109 ˚C (Lit.^¹¹b 107 ˚C). IR (KBr): 3062, 2922, 1616, 1475, 1317, 1274, 960, 767 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.40-7.45 (m, 2 H), 7.47-7.55 (m, 7 H), 7.70 (t, J = 7.5 Hz, 1 H), 7.77 (s, 1 H), 7.88 (d, J = 3.2 Hz, 1 H), 8.15 (d, J = 8.1 Hz, 2 H), 8.21 (d, J = 8.8 Hz, 1 H). MS: m/z = 281.09 (7.07) [M]⁺, 254.15 (91.45), 179.41 (21.88), 103.16 (35.60), 77.18 (100.00), 51.23 (33.55).
6-Chloro-2,4-diphenylquinoline (3b) Mp 98-99 ˚C (Lit.^¹0g 98 ˚C). IR (KBr): 2922, 2852, 1587, 1543, 1481, 887, 823, 779, 700 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.47-7.50 (m, 1 H), 7.53-7.60 (m, 7 H), 7.68 (dd, ^¹ J = 9.0 Hz, ^² J = 2.2 Hz, 1 H), 7.85 (s, 1 H), 7.87 (d, J = 2.0 Hz, 1 H), 8.17-8.20 (m, 3 H). MS: m/z = 317.08 (2.15) [M + 2]⁺, 315.03 (8.10) [M]⁺, 280.11 (6.22), 238.08 (2.63), 103.05 (20.24), 77.05 (100.00), 51.09 (57.09).
6-Chloro-4-(2-chlorophenyl)-2-phenylquinoline (3c) Mp 112-114 ˚C (Lit.^¹¹b 112 ˚C). IR (KBr): 2951, 1643, 1469, 1365, 1228, 1022, 829 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.39-7.41 (m, 1 H), 7.44-7.50 (m, 4 H), 7.53-7.56 (m, 2 H), 7.62 (d, J = 7.9 Hz, 1 H), 7.67 (dd, ^¹ J = 9.0 Hz, ^² J = 2.1 Hz, 1 H), 7.84 (s, 1 H), 8.19-8.21 (m, 3 H). MS: m/z = 351.02 (11.13) [M + 2]⁺, 349.00 (17.97) [M]⁺, 314.06 (5.91), 279.12 (13.09), 278.13 (38.28), 201.10 (22.46), 102.96 (38.87), 76.96 (81.25), 74.97 (50.78), 50.98 (100.00).
6-Chloro-4-(2′-fluorophenyl)-2-phenylquinoline (3d) Mp 124-126 ˚C (Lit.^¹¹b 125 ˚C). IR (KBr): 3055, 2922, 2850, 1593, 1544, 1481, 1354, 885, 835, 802, 756 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.27-7.37 (m, 2 H), 7.44-7.56 (m, 5 H), 7.66-7.70 (m, 2 H), 7.88 (s, 1 H), 8.19 (d, J = 8.2 Hz, 3 H). MS: m/z = 334.02 (8.59) [M + 2]⁺, 331.98 (21.56) [M]⁺, 298.08 (6.33), 194.07 (14.61), 102.96 (49.38), 76.96 (100.00), 74.95 (65.63), 50.97 (96.25).
2,4-Diphenyl-6-nitroquinoline (3e) Mp 265-266 ˚C (Lit.^¹0h 264 ˚C). IR (KBr): 2922, 2852, 1595, 1440, 1382, 1338, 883, 846, 771, 752 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 7.54-7.64 (m, 8 H), 7.99 (s, 1 H), 8.26 (d, J = 7.0 Hz, 2 H), 8.35 (d, J = 9.2 Hz, 1 H), 8.50 (dd, ^¹ J = 9.2 Hz, ^² J = 2.4 Hz, 1 H), 8.87 (d, J = 2.4 Hz, 1 H).
MS: m/z = 326.11 (3.20) [M]⁺, 244.02 (13.24), 203.06 (10.96), 146.58 (27.40), 100.66 (25.11), 78.08 (29.68), 77.04 (81.28), 55.10 (100.00).
2-(3-Methoxyphenyl)-4-phenylquinoline (3f) Mp 170 ˚C. IR (KBr): 2922, 2852, 1625, 1544, 1462, 1097 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 3.94 (s, 3 H), 7.04 (d, J = 7.1 Hz, 1 H), 7.44 (t, J = 8.3 Hz, 1 H), 7.49-7.58 (m, 6 H), 7.73-7.78 (m, 2 H), 7.80-7.82 (m, 2 H), 7.92 (d, J = 8.5 Hz, 1 H), 8.28 (s, 1 H). MS: m/z = 311.06 (26.34) [M]⁺, 310.03 (35.61), 281.06 (15.85), 267.10 (4.70), 241.04 (5.03), 204.08 (9.88), 176.04 (21.59), 140.08 (16.95), 57.05 (92.20), 55.05 (100.00).
6-Chloro-2-(3-methoxyphenyl)-4-phenylquinoline (3g) Mp 129-130 ˚C. IR (KBr): 2924, 2831, 1600, 1543, 1485, 1344, 1041, 877, 823, 769 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 3.94 (s, 3 H, OMe), 7.04 (dd, ^¹ J = 8.2 Hz, ^² J = 2.4 Hz, 1 H), 7.44 (t, J = 8.0 Hz, 1 H), 7.54-7.60 (m, 5 H), 7.67 (dd, ^¹ J = 8.2 Hz, ^² J = 2.3 Hz, 1 H), 7.73 (d, J = 7.6 Hz, 1 H), 7.79 (s, 1 H), 7.83 (s, 1 H), 7.87 (d, J = 1.7 Hz, 1 H), 8.18 (d, J = 8.9 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 55.47, 112.72, 115.70, 120.01, 120.14, 124.51, 126.60, 128.75, 128.86, 129.49, 129.90, 130.47, 131.78, 132.29, 137.77, 140.68, 147.19, 148.44, 156.86, 160.23. MS: m/z = 347.98 (5.99) [M + 2]⁺, 345.99 (48.98) [M]⁺, 343.98 (100.00), 317.99 (6.51), 314.99 (27.87), 203.11 (14.34), 155.01 (21.52), 139.04 (23.57), 132.55 (27.66), 77.13 (7.68). Anal. Calcd for C₂₂H₁₆ClNO (345.09): C, 76.41; H, 4.66; N, 4.05. Found: C, 76.28; H, 4.71; N, 3.97.
6-Chloro-4-(2-chlorophenyl)-2-(3-methoxyphenyl)-quinoline (3h) Mp 168-169 ˚C. IR (KBr): 2922, 2850, 1604, 1583, 1544, 1471, 1433, 1282, 1174, 1043, 887, 839, 763, 705 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 3.94 (s, 3 H), 7.04 (dd, ^¹ J = 8.2 Hz, ^² J = 2.5 Hz, 1 H), 7.39 (dd, ^¹ J = 7.4 Hz, ^² J = 1.7 Hz, 1 H), 7.42-7.51 (m, 4 H), 7.61 (d, J = 9.0 Hz, 1 H), 7.67 (dd, ^¹ J = 7.8 Hz, ^² J = 2.2 Hz, 1 H), 7.72 (d, J = 7.6 Hz, 1 H), 7.79-7.81 (m, 2 H), 8.18 (d, J = 9.0 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 55.48, 112.73, 115.81, 120.03, 120.70, 124.41, 126.65, 127.04, 129.91, 130.12, 130.17, 130.65, 131.37, 131.76, 132.45, 133.34, 136.34, 140.51, 145.78, 146.90, 156.81, 160.26. MS: m/z = 383.12 (8.09) [M + 4]⁺, 381.14 (4.30) [M + 2]⁺, 379.00 (72.32) [M]⁺, 378.14 (100.00), 350.11 (27.90), 237.12 (15.63), 132.85 (22.99), 75.06 (20.09). Anal. Calcd for C₂₂H₁₅Cl₂NO (379.05): C, 69.49; H, 3.98; N, 3.68. Found: C, 69.32; H, 4.03; N, 3.75.
6-Chloro-4-(2-fluorophenyl)-2-(3-methoxyphenyl)-quinoline (3i) Mp 114-115 ˚C. IR (KBr): 3035, 2935, 2835, 1589, 1544, 1483, 1280, 1043, 887, 761 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 3.94 (s, 3 H), 7.04 (dd, ^¹ J = 8.1 Hz, ^² J = 2.4 Hz, 1 H), 7.30 (t, J = 9.0 Hz, 1 H), 7.35 (t, J = 7.5 Hz, 1 H), 7.42-7.47 (m, 2 H), 7.53-755 (m, 1 H), 7.65 (s, 1 H), 7.68 (dd, ^¹ J = 8.9 Hz, ^² J = 2.2 Hz, 1 H), 7.72 (d, J = 7.7 Hz, 1 H), 7.79 (s, 1 H), 7.86 (s, 1 H), 8.19 (d, J = 8.9 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 55.47, 112.74, 115.75, 116.20, 116.37, 120.01, 121.06, 124.37, 124.59, 125.08, 125.21, 126.72, 129.89, 130.62, 130.85, 130.91, 131.63, 131.65, 131.77, 132.48, 140.54, 142.53, 146.97, 156.84, 158.67, 160.25, 160.65. MS: m/z = 365.15 (44.01) [M + 2]⁺, 363.15 (93.39) [M]⁺, 362.15 (100.00), 334.14 (52.69), 333.14 (60.33), 332.12 (44.01), 296.13 (16.53), 283.13 (15.91), 141.59 (23.35), 99.04 (8.01), 51.10 (5.58). Anal. Calcd for C₂₂H₁₅ClFN (347.09): C, 72.63; H, 4.16; N, 3.85. Found: C, 72.51; H, 4.21; N, 3.78.
2-(3-Methoxyphenyl)-6-nitro-4-phenylquinoline (3j) Mp 194-195 ˚C. IR (KBr): 2922, 2852, 1620, 1597, 1554, 1340, 1267, 1035, 875, 810, 702 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 3.95 (s, 3 H), 7.08 (dd, ^¹ J = 8.17 Hz, ^² J = 2.0 Hz, 1 H), 7.47 (t, J = 8.0 Hz, 1 H), 7.57-7.64 (m, 5 H), 7.79 (d, J = 7.7 Hz, 1 H), 7.85 (s, 1 H), 7.97 (s, 1 H), 8.34 (d, J = 9.3 Hz, 1 H), 8.50 (dd, ^¹ J = 8.8 Hz, ^² J = 1.8 Hz, 1 H), 8.86 (d, J = 2.1 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 55.51, 113.07, 116.47, 120.27, 120.83, 122.91, 123.08, 124.93, 129.16, 129.35, 129.47, 130.04, 131.82, 136.92, 139.98, 145.49, 151.02, 151.27, 159.83, 160.33. MS: m/z = 356.13 (85.19) [M]⁺, 355.11 (100.00), 326.08 (14.89), 241.16 (19.52), 201.16 (25.31), 176.20 (29.32), 139.27 (32.10), 132.61 (31.48), 78.11 (26.85), 77.10 (91.36), 51.13 (51.23). Anal. Calcd for C₂₂H₁₆N₂O (324.13): C, 74.15; H, 4.53; N, 7.86. Found: C, 73.97; H, 4.57; N, 7.92.
6-Chloro-4-phenyl-2- p -tolylquinoline (3k) Mp 123-124 ˚C (Lit.^¹0i 132 ˚C). IR (KBr): 2922, 2852, 1589, 1539, 1352, 1153, 887, 835 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 2.45 (s, 3 H), 7.34 (d, J = 8.0 Hz, 2 H), 7.53-7.59 (m, 5 H), 7.66 (dd, ^¹ J = 8.9 Hz, ^² J = 1.9 Hz, 1 H), 7.83 (s, 1 H), 7.85 (d, J = 1.9 Hz, 1 H), 8.09 (d, J = 8.0 Hz, 2 H), 8.16 (d, J = 8.9 Hz, 1 H). MS: m/z = 331.04 (34.88) [M + 2]⁺, 329.05 (100.00) [M]⁺, 294.10 (22.84), 201.12 (10.96), 176.12 (12.89), 146.89 (32.10), 91.16 (2.91), 51.13 (4.40).
6-Chloro-4-(2-chlorophenyl)-2- p -tolylquinoline (3l) Mp 125-126 ˚C. IR (KBr): 2922, 2852, 1581, 1350, 1153, 1053, 881, 813 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 2.45 (s, 3 H), 7.34 (d, J = 7.9 Hz, 2 H), 7.38-7.40 (m, 1 H), 7.45-7.49 (m, 3 H), 7.61 (d, J = 7.8 Hz, 1 H), 7.66 (dd, ^¹ J = 9.0 Hz, ^² J = 2.2 Hz, 1 H), 7.81 (s, 1 H), 8.10 (d, J = 8.0 Hz, 2 H), 8.17 (d, J = 8.9 Hz, 1 H). ^¹³C NMR (125 M Hz, CDCl₃): δ = 22.69, 120.41, 124.34, 126.41, 127.44, 129.63, 129.72, 130.01, 130.07, 130.50, 131.35, 131.67, 135.47, 136.28, 139.81, 142.47, 147.05, 157.02, 160.73. MS: m/z = 366.96 (12.71) [M + 4]⁺, 364.96 (65.56) [M + 2]⁺, 362.97 (100.00) [M]⁺, 361.96 (53.06), 327.99 (37.78), 293.05 (3.00), 146.34 (65.83), 145.49 (95.56), 144.50 (33.06), 132.44 (17.78), 91.10 (3.59), 51.06 (4.24). Anal. Calcd for C₂₂H₁₅Cl₂N (363.06): C, 72.54; H, 4.15; N, 3.85. Found: C, 72.43; H, 4.20; N, 3.79.
6-Chloro-4-(2-fluorophenyl)-2- p -tolylquinoline (3m) Mp 162 ˚C. IR (KBr): 3032, 2922, 2852, 1614, 1543, 1479, 1352, 1211, 1151, 887, 754 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 2.44 (s, 3 H), 7.27-7.35 (m, 4 H), 7.44 (s, 1 H), 7.53 (s, 1 H), 7.63-7.67 (m, 2 H), 7.85 (s, 1 H), 8.09 (d, J = 6.9 Hz, 2 H), 8.16 (d, J = 10.3 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 22.69, 116.16, 116.34, 120.77, 124.33, 124.54, 126.54, 127.43, 129.64, 130.50, 130.76, 130.82, 131.67, 132.17, 136.28, 139.81, 142.47, 147.04, 157.02, 160.72. MS: m/z = 349.02 (35.04) [M + 2]⁺, 347.04 (100.00) [M]⁺, 346.03 (78.57), 312.07 (21.21), 155.85 (21.88), 145.49 (19.42), 91.12 (6.92). Anal. Calcd for C₂₂H₁₅ClFN (347.09): C, 75.97; H, 4.35; N, 4.03. Found: C, 75.85; H, 4.41; N, 3.95.
6-Nitro-4-phenyl-2- p -tolylquinoline (3n) Mp 202-203 ˚C. IR (KBr): 2922, 2850, 1593, 1548, 1483, 1336, 1180, 819, 746 cm^-¹. ^¹H NMR (500 MHz, CDCl₃):
δ = 2.46 (s, 3 H), 7.37 (d, J = 8.0 Hz, 2 H), 7.56-7.64 (m, 5 H), 7.97 (s, 1 H), 8.16 (d, J = 8.0 Hz, 2 H), 8.32 (d, J = 9.2 Hz, 1 H), 8.48 (dd, ^¹ J = 9.2 Hz, ^² J = 2.5 Hz, 1 H), 8.85 (d, J = 2.5 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 22.70, 120.53, 122.91, 123.03, 124.74, 127.77, 129.13, 129.29, 129.48, 129.82, 131.67, 135.72, 137.02, 140.87, 145.30, 151.14, 159.99. MS: m/z = 340.07 (100.00) [M]⁺, 310.09 (7.43), 294.10 (25.54), 293.10 (60.75), 202.05 (24.60), 176.02 (45.16), 145.72 (38.17), 139.18 (19.35), 91.04 (11.96), 77.03 (8.60), 57.01 (50.54). Anal. Calcd for C₂₂H₁₆N₂O₂ (340.12): C, 77.63; H, 4.74; N, 3.23. Found: C, 77.50; H, 4.80; N, 8.14.
6-Chloro-2-(4-methoxyphenyl)-4-phenylquinoline (3o) Mp 135-136 ˚C (Lit.^¹0j 135 ˚C). IR (KBr): 2916, 2850, 1587, 1516, 1026, 825, 777, 704 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 3.89 (s, 3 H), 7.04 (d, J = 8.7 Hz, 2 H), 7.54-7.57 (m, 5 H), 7.65 (dd, ^¹ J = 9.1 Hz, ^² J = 2.1 Hz, 1 H), 7.79 (s, 1 H), 7.84 (d, J = 2.2 Hz, 1 H), 8.14-8.18 (m, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 55.42, 114.32, 119.55, 124.48, 126.26, 128.67, 128.81, 128.92, 129.46, 130.36, 131.50, 131.72, 131.80, 137.89, 147.22, 148.32, 156.60, 161.10. MS: m/z = 347.02 (35.27) [M + 2]⁺, 345.03 (100.00) [M]⁺, 344.02 (52.05), 310.06 (9.08), 301.06 (7.79), 155.21 (21.32), 132.71 (33.22), 120.50 (8.82), 99.17 (2.70).
6-Chloro-4-(2-chlorophenyl)-2-(4-methoxyphenyl) quinoline (3p) Mp 140-141 ˚C. IR (KBr): 2958, 2852, 1602, 1541, 1469, 1373, 1247, 1157, 1022, 889, 771 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 3.89 (s, 3 H), 7.05 (d, J = 8.8 Hz, 2 H), 7.39 (dd, ^¹ J = 7.3 Hz, ^² J = 2.2 Hz, 1 H), 7.44-7.50 (m, 3 H), 7.61 (dd, ^¹ J = 7.5 Hz, ^² J = 1.4 Hz, 1 H), 7.65 (dd, ^¹ J = 9.6 Hz, ^² J = 2.2 Hz, 1 H), 7.78 (s, 1 H), 8.13-8.17 (m, 3 H).^¹³C NMR (125 MHz, CDCl₃): δ = 55.42, 120.10, 124.36, 126.27, 126.99, 128.94, 130.08, 130.50, 131.36, 131.52, 131.66, 131.92, 133.35, 136.49, 145.59, 146.99, 156.58, 161.14. MS: m/z = 381.93 (17.57) [M + 2]⁺, 379.92 (39.53) [M]⁺, 378.93 (100.00), 343.96 (10.35), 265.02 (12.67), 176.09 (8.70), 154.29 (9.97), 132.51 (10.43), 99.14 (7.77), 57.12 (43.92), 55.13 (47.97). Anal. Calcd for C₂₂H₁₅Cl₂NO (379.05): C, 69.49; H, 3.98; N, 3.68. Found: C, 69.31; H, 4.05; N, 3.60.
6-Chloro-4-(2-fluorophenyl)-2-(4-methoxyphenyl) quinoline (3q) Mp 121 ˚C. IR (KBr): 2924, 2852, 1608, 1463, 1355, 1253, 1174, 1022, 825, 761 cm^-¹. ^¹H NMR (500 MHz, CDCl₃):
δ = 3.90 (s, 3 H), 7.05 (d, J = 8.7, 2 H), 7.28-7.32 (m, 1 H), 7.35 (t, J = 7.3, 1 H), 7.44 (dt, ^¹ J = 7.3 Hz, ^² J = 1.7 Hz, 1 H), 7.51-7.56 (m, 1 H), 7.61 (d, J = 1.9 Hz, 1 H), 7.65 (dd, ^¹ J = 8.9 Hz, ^² J = 2.2 Hz, 1 H), 7.82 (s, 1 H), 8.15 (t, J = 9.0 Hz, 3 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 55.42, 114.32, 116.17, 116.34, 120.47, 124.33, 124.51, 124.54, 126.36, 126.54, 128.93, 130.49, 130.75, 130.82, 131.53, 131.62, 131.65, 131.97, 142.35, 156.61, 160.67, 161.13. MS: m/z = 365.01 (25.00) [M + 2]⁺, 363.04 (96.00) [M]⁺, 362.02 (30.25), 319.00 (35.50), 285.09 (50.50), 149.12 (67.00), 141.42 (55.75), 99.00 (26.50), 95.20 (65.00), 85.21 (70.00), 83.19 (95.00), 81.19 (87.00), 77.15 (27.00), 57.21 (95.00), 55.17 (100.00). Anal. Calcd for C₂₂H₁₅ClFNO (363.08): C, 72.63; H, 4.16; N, 3.85. Found: C, 72.50; H, 4.21; N, 3.77.
2-(4-Methoxyphenyl)-6-nitro-4-phenylquinoline (3r) Mp 221 ˚C. IR (KBr): 2922, 2852, 1643, 1593, 1479, 1253, 1095, 954, 796, 761 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 3.91 (s, 3 H), 7.07 (d, J = 8.8, 2 H), 7.56-7.64 (m, 5 H), 7.94 (s, 1 H), 8.24 (d, J = 8.8 Hz, 2 H), 8.29 (d, J = 9.3 Hz, 1 H), 8.47 (dd, 1 H, ^¹ J = 9.3 Hz, ^² J = 2.5 Hz, 1 H), 8.80 (d, J = 2.5 Hz, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 55.48, 114.48, 120.19, 122.92, 123.04, 124.54, 129.12, 129.26, 129.37, 129.45, 131.01, 131.48, 137.07, 145.15, 151.02, 151.20, 159.53, 161.81. MS: m/z = MS: 356.06 (100.00) [M]⁺, 326.06 (2.85), 309.09 (25.00), 267.11 (6.84), 241.11 (5.38), 202.09 (8.29), 176.08 (12.95), 169.68 (8.10), 132.79 (16.58), 120.54 (9.20), 63.03 (8.00), 57.11 (4.81). Anal. Calcd for C₂₂H₁₆N₂O₃ (356.12): C, 74.15; H, 4.53; N, 7.86. Found: C, 74.29; H, 4.48; N, 7.78.
4-Methyl-2-phenylquinoline (3s) Mp 63-65 ˚C (Lit.^¹0k 65-67 ˚C). IR (KBr): 2924, 2854, 1648, 1553, 1458, 1242, 1161, 950, 748 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 2.72 (s, 3 H), 7.37-7.40 (m, 1 H), 7.44-7.51 (m, 3 H), 7.65-7.72 (m, 2 H), 7.95 (d, J = 8.3 Hz, 1 H), 8.08-8.14 (m, 3 H). MS: m/z = 219.00(100) [M]⁺, 203.98 (12.68), 134.90 (48.59), 119.87 (67.61), 91.86 (80.28), 88.85 (78.87), 76.82 (85.21), 64.83 (83.80). 4-Methyl-2- p -tolylquinoline (3t) Mp 53-54 ˚C (Lit.^¹0l 51-53 ˚C). IR (KBr): 2925, 2854, 1658, 1615, 1462, 1245, 1162, 1112, 874, 754 cm^-¹. ^¹H NMR (500 MHz, CDCl₃): δ = 2.44 (s, 3 H), 2.70 (s, 3 H), 7.30-733 (m, 2 H), 7.48-7.52 (m, 1 H), 7.69-7.74 (m, 2 H), 7.97 (d, J = 8.3 Hz, 1 H), 8.07-8.10 (m, 2 H), 8.15-8.18 (m, 1 H). MS: m/z = 233.00 (62.28) [M]⁺, 218.98 (60.53), 217.97 (35.53), 134.88 (30.26), 119.82 (53.95), 90.84 (75.00), 88.81 (84.65), 76.80 (67.54), 64.81 (100.00).