Synthesis and their spectroscopic distinction of. benzonaphthonaphthyridines and its isomer

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1 Synthesis and their spectroscopic distinction of benzonaphthonaphthyridines and its isomer Kolandaivel Prabha and Karnam Jayaramapillai Rajendra Prasad* Department of Chemistry, Bharathiar University Coimbatore, Tamil Nadu, India Preparation of Compound (8) & (9), general procedure; 2-Methyl-N-(1-naphthyl)quinolin-4-amine (3, 2 mmol) and thiophen-2carboxylic acid/furan-2-carboxylic acid (2.5 mmol) were added to polyphosphoric acid (6 g of P 2 O 5 in 3 ml of H 3 PO 4 ) and heated at 110 C for 1 hour. The reaction was monitored by using TLC. After the completion of the reaction, it was poured into ice water, neutralized with saturated sodium bicarbonate solution to remove excess of pyridine-3-carboxylic acid/thiophen- 2carboxylic acid/furan-2-carboxylic acid, extracted with ethyl acetate, purified by column chromatography using silica gel and product eluted with petroleum ether : ethyl acetate (97 : 3) mixture to get 8, 9 which was recrystallised using methanol. Compound 8 Colourless prisms; mp: C; Yield: (49 %); IR (KBr, cm -1 ) ν max : 1637 (C=N), 1599; 1 H NMR (500 MHz, CDCl 3 ) (ppm) δ H : 2.35 (s, 3H, C 4 -CH 3 ), 2.91 (s, 3H, C 6 -CH 3 ), 6.59 (t, 1H, C 4 '-H, J = 3.50 Hz, J = 1.5 Hz), 7.24 (dd, 1H, C 3 -H, J = 9.50 Hz, J = 1.50 Hz), 7.36 (dd, 1H, C 3 '-H, J = 3.50 Hz, J = 1.00 Hz), 7.45 (t, 1H, C 2 -H, J = 8.50 Hz), 7.61 (d, 1H, C 9 -H, J = 8.00 Hz), 7.67 (dd, 1H, C 5 '-H, J = 4.50 Hz, J = 1.50 Hz), (m, 3H, C 8, C 11, C 12 -H), 8.30 (d, 1H, C 10 -H, J = 7.50 Hz), 9.27 (d, 1H, C 1 -H J = 9.00 Hz), 9.69 (d, 1H, C 13 -H J = 8.00 Hz); 13 C NMR (125 MHz, CDCl 3 ) (ppm) δ C : (C 6 -CH 3 ), (C 4 -CH 3 ), (C 4 '), (C 6a ), (C 3 '), (C 1 ), (C 9 ), (C 2 ), (C 8 ),

2 (C 7a ), (C 13 ), (C 14b ), (C 12 ), (C 10 ), (C 3 ), (C 11 ), (C 9a ), (C 13a ), (C 4 ), (C 7 ), (C 5 '), (C 13b ), (C 14a ), (C 2 '), (C 4a ), (C 6 ); MS (EI) m/z (%) 374 (M +, 100); Anal. Calcd. for C 26 H 18 N 2 O (374): C, 83.40; H, 4.85; N, 7.48; Found: C, 83.45; H, 4.88; N, 7.42%. Compound 9 Colourless prisms; mp: C; Yield: (30 %); IR (KBr, cm -1 ) ν max : 1637 (C=N), 1536; 1 H NMR (500 MHz, CDCl 3 ) (ppm) δ H : 2.39 (s, 3H, C 4 -CH 3 ), 2.70 (s, 3H, C 6 -CH 3 ), 7.01 (d, 1H, C 3 -H, J = 8.50 Hz), 7.16 (t, 1H, C 4 '-H, J = 4.50 Hz) 7.41 (t, 1H, C 2 -H J = 9.00 Hz), 7.61 (d, 1H, C 9 -H, J = 8.00 Hz), 7.66 (dd, 1H, C 5 '-H, J = 4.50 Hz, J = 1.00 Hz), (m, 3H, C 8, C 11, C 12 -H), 7.91 (dd, 1H, C 3 '-H J = 3.50 Hz, J = 1.00 Hz), 8.11 (d, 1H, C 10 - H, J = 8.00 Hz), 9.15 (d, 1H, C 1 -H J = 8.00 Hz), 9.47 (d, 1H, C 13 -H J = 8.50 Hz); 13 C NMR (125 MHz, CDCl 3 ) (ppm) δ C : (C 6 -CH 3 ), (C 4 -CH 3 ), (C 6a ), (C 1 ), (C 9 ), (C 2 ), (C 8 ), (C 7a ), (C 13 ), (C 14b ), (C 12 ), (C 10 ), (C 3 '), (C 3 ), (C 11 ), (C 9a ), (C 4 '), (C 13a ), (C 5 '), (C 4 ), (C 2 '), (C 7 ), (C 13b ), (C 14a ), (C 4a ), (C 6 ); MS (EI) m/z (%) 390 (M +, 100); Anal. Calcd. for C 26 H 18 N 2 S (390): C, 79.97; H, 4.65; N, 7.17; S, 8.21; Found: C, 80.01; H, 4.61; N, 7.21; S, 8.17%. Preparation of compound (17) & (18), general procedure; 2-methyl-N-phenylbenzo[h]quinolin-4-amine (15) (2 mmol) and acetic acid/1- naphthoic acid (2.5 mmol) were added to polyphosphoric acid (6 g of P 2 O 5 in 3 ml of H 3 PO 4 ) and heated at 160 C for 3 hours. The reaction was monitored by using TLC. After the completion of the reaction, it was poured into ice water, neutralized with saturated sodium bicarbonate solution to remove excess of benzoic acid/acetic acid/1-naphthoic acid, extracted with ethyl acetate, purified by column chromatography using silica gel and product eluted

3 with petroleum ether: ethyl acetate (99 : 1) mixture to get 17, 18 which was recrystallised using methanol. Compound 17 Pale yellow prisms; mp: C; Yield : (55 %); IR (KBr, cm -1 ) ν max : 1634 (C=N), 1566, 1521; 1 H NMR (400 MHz, CDCl 3 ) (ppm) δ H : 2.50 (s, 3H, C 6 -CH 3 ), 3.22 (s, 3H, C 9 -CH 3 ), 3.30 (s, 3H, C 7 -CH 3 ), (m, 6H, C 14, C 2, C 3, C 8, C 9, C 10 -H), 8.25 (d, 1H, C 14 -H, J = 8.80 Hz), 9.35 (d, 1H, C 4 -H, J o = 8.00 Hz, J m = 2.00 Hz), 9.42 (d, 1H, C 13 -H, J = 9.20 Hz); 13 C NMR (100 MHz, CDCl 3 ) (ppm) δ C : 18.4 (C 11 -CH 3 ), (C 7 -CH 3 ), (C 6 - CH 3 ), (C 6a ), (C 13 ), (C 7a ), (C 4 ), (C 12b ), (C 3 ), (C 9 ), (C 14 ), (C 8 ), (C 2 ), (C 1 ), (C 4a ), (C 14a ), (C 10 ), (C 11 ), (C 7 ) (C 11a ), (C 4b ), (C 12a ), (C 6 ); MS (EI) m/z (%) 322 (M +, 100); Anal. Calcd. for C 23 H 18 N 2 (322): C, 85.68; H, 5.63; N, 8.69; Found: C, 85.70; H, 5.671; N, Compound 18 Pale yellow prisms; mp: C; Yield : (59 %); IR (KBr, cm -1 ) ν max : (C=N) and 1423; 1 H NMR (500 MHz, CDCl 3 ) (ppm) δ H : 2.43 (s, 3H, C 6 -CH 3 ), 3.09 (s, 3H, C 11 -CH 3 ), 7.34 (t, 1H, C 9 -H, J = 7.50 Hz), (m, 11H, C 2, C 3, C 8, C 10, C 4 ', C 2 ', C 3 ', C 5 ', C 6 ', C 7 ', C 8 ',-H), 8.04 (d, 1H, C 1 -H, J = 7.50 Hz), 8.17 (d, 1H, C 14 -H, J = 7.50 Hz), 9.29 (d, 1H, C 4 -H, J o = 8.50 Hz, J m = 1.50 Hz), 9.43 (d, 1H, C 13 -H, J = 8.00 Hz); 13 C NMR (125 MHz, CDCl 3 ) (ppm) δ C : (C 11 -CH 3 ), (C 6 -CH 3 ), (C 2 '), (C 6a ), (C 13 ), (C 7a ), (C 4 ), (C 12b ), (C 3 ), (C 9 ), (C 14 ), (C 8 ), (C 2 ), (C 1 ), (C 8 '), (C 3 ') (C 4 '), (C 5 '), (C 6 '), (C 7 '), (C 4a ), (C 14a ), (C 10 ), (C 8a '), (C 4a '), (C 11 ), (C 1 '), (C 7 ), (C 11a ), (C 4b ), (C 12a ),

4 (C 6 ); MS (EI) m/z (%) 384 (M +, 100), 383 (35), 369 (20), 354 (8), 65 (6), 51 (5) Anal. Calcd. for C 32 H 22 N 2 (384) C, 88.45; H, 5.10; N, 6.45; Found : C, 88.47, H 5.15, N 6.48 %. Preparation of heterosubstituted benzo[b]naphtho[1,2-h][1,6]naphthyridine (19, 20, 21), general procedure; 2-methyl-N-phenylbenzo[h]quinolin-4-amine (15) (2 mmol) and pyridine-3- carboxylic acid /thiophen-2carboxylic acid/furan-2-carboxylic acid (2.5 mmol) were added to polyphosphoric acid (6 g of P 2 O 5 in 3 ml of H 3 PO 4 ) and heated at 160 C for 3 hours. The reaction was monitored by using TLC. After the completion of the reaction, it was poured into ice water, neutralized with saturated sodium bicarbonate solution to remove excess of pyridine-3-carboxylic acid/thiophen-2carboxylic acid/furan-2-carboxylic acid, extracted with ethyl acetate, purified by column chromatography using silica gel and product eluted with petroleum ether: ethyl acetate (99 : 3) mixture to get 19, 20, 21 which was recrystallised using methanol. Compound 19 Pale yellow solid; mp: C; Yield : (51 %); IR (KBr, cm -1 ) ν max : 1626, 1595, 1568(C=N); 1 H NMR (500 MHz CDCl 3 ) δ H : 2.41 (s, 3H, C 6 -CH 3 ), 3.07 (s, 3H, C 11 -CH 3 ), 7.22 (t, 1H, C 5 '-H J = 8.00 Hz, J = 4.50 Hz), 7.34 (t, 1H, C 9 -H, J = 8.00 Hz), ( m, 4H, C 2 C 3, C 8, C 10 -H), 7.79 (dd, 1H, C 6 '-H J = 2.00 Hz, J = 5.50 Hz ), 7.84 (dd, 1H, C 4 '-H J = 2.00 Hz, J = 5.00 Hz ), 7.97 (s, 1H, C 2 '-H), 8.02 (d, 1H, C 1 -H, J = 9.50 Hz), (d, 1H, C 14 -H, J = 7.50 Hz), 9.39 (d, 1H, C 4 -H, J o = 8.00 Hz, J m = 1.50 Hz), 9.52 (d, 1H, C 13 -H, J = 9.00 Hz); 13 C NMR (125 MHz CDCl 3 ) δ C : 18.4 (C 11 -CH 3 ), 29.7 (C 6 -CH 3 ), (C 6a ), (C 13 ), (C 7a ), (C 4 ), (C 12b ), (C 3 ), (C 9 ), (C 14 ), (C 8 ), (C 2 ), (C 1 ), (C 3 ', C 5 '), (C 4 '), (C 4a ), (C 14a ), (C 10 ), (C 11 ), (C 2 '), (C 7 ) (C 11a ), (C 6 ')

5 (C 4b ), (C 12a ), (C 6 ); MS (385) m/z (%) 385 (M +, 100), Anal. Calcd. for C 27 H 19 N 3 (385) C, 84.13; H, 4.97; N, 10.90; Found : C, 84.16, H 4.95, N %. Compound 20 Pale yellow prisms; mp: C; Yield : (50 %); IR (KBr, cm -1 ) ν max : 1633 (C=N), 1560, 1529; 1 H NMR (500 MHz, CDCl 3 ) (ppm) δ H : 2.51 (s, 3H, C 6 -CH 3 ), 3.12 (s, 3H, C 9 -CH 3 ), 6.75 (t, 1H, C 4 '-H, J = 5.50 Hz), 7.37 (d, 1H, C 3 '-H, J = 5.00 Hz), (m, 7H, C 1, C 2, C 3, C 8, C 9, C 10, C 5 '-H), 8.41 (d, 1H, C 14 -H, J = 8.80 Hz), 9.36 (d, 1H, C 4 -H, J o = 8.00 Hz, J m = 2.00 Hz), 9.64 (d, 1H, C 13 -H, J = 9.20 Hz); MS (374) m/z (%) 374 (M +, 100); Anal. Calcd. for C 26 H 18 N 2 O (374): C, 83.40; H, 4.85; N, 7.48; Found : C, 83.37, H 4.78, N 7.43 % Compound 21 Colorless solid; mp: C; Yield : (36 %); IR (KBr, cm -1 ) ν max : 1629 (C=N), 1577, 1519; 1 H NMR (500 MHz, CDCl 3 ) δ H : 2.59 (s, 3H, C 6 -CH 3 ), 2.96 (s, 3H, C 9 -CH 3 ), 7.09 (d, 1H, C 10 -H, J = 8.00 Hz ) 7.20 (t, 1H, C 4 '-H, J = 5.50 Hz), (m, 7H, C 1, C 2, C 3, C 8, C 9, C 3 ', C 5 '-H), 8.51 (d, 1H, C 14 -H, J = 8.80 Hz), 9.22 (d, 1H, C 4 -H, J o = 8.00 Hz), 9.61 (d, 1H, C 13 -H, J = 9.00 Hz); MS (390) m/z (%) 390 (M +, 100); Anal. Calcd. for C 26 H 18 N 2 S (390): C, 79.97; H, 4.65; N, 7.17; S, 8.21; Found : C, 78.01, H 7.15, N 7.15; 8.25 %.

6 Mass fragmentation of 4,6-dimethyl-7-phenylbenzo[h]naphtho[1,2-b][1,6] naphthyridine (5)

7 Mass fragmentation of 6,11-dimethylbenzo[b]naphtho[1,2-h][1,6]naphthyridine (16).

8 1 H- 1 H NMR Spectrum of 6,11-Dimethyl-7-phenylbenzo[b]naphtho[1,2-h][1,6] naphthyridine (16)

9 HSQC NMR Spectrum of 6,11-Dimethyl-7-phenylbenzo[b]naphtho[1,2-h][1,6] naphthyridine (16)

10 HMBC NMR Spectrum of 6,11-Dimethyl-7-phenylbenzo[b]naphtho[1,2-h][1,6] naphthyridine (16)

11 1 H NMR Spectrum of 2-Methyl-N-o-tolylbenzo[h]quinolin-4-amine (15)

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