Structural revision in the reactions of 3-cyanochromones with primary aromatic amines. Improved synthesis of 2-amino-3-(aryliminomethyl)chromones

Tetrahedron Letters

Volumn 50, Issue 47, 2009, Pages 6515-6518

  Sosnovskikh, Vyacheslav Ya ^a   Moshkin, Vladimir S ^a   Kodess, Mikhail I ^b  

^a URAL FEDERAL UNIVERSITY   (Russian Federation)

^b INSTITUTE OF ORGANIC SYNTHESIS   (Russian Federation)

Author keywords

[No Author keywords available]

Indexed keywords

2 PHENYLENEDIAMINE; 3 CYANOCHROMONE DERIVATIVE; ALIPHATIC AMINE; AROMATIC AMINE; CHROMONE DERIVATIVE; PHENYLENEDIAMINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS;

EID: 77955717545     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2009.09.028     Document Type: Article

References (14)

1. Ghosh, C. K.; Karak, S. K. J. Heterocycl. Chem. 2005, 42, 1035-1042.
2. Nohara, A.; Ishiguro, T.; Ukawa, K.; Sugihara, H.; Maki, Y.; Sanno, Y. J. Med. Chem. 1985, 28, 559-568.
3. Ghosh, C. K.; Tewari, N. J. Org. Chem. 1980, 45, 1964-1968.
4. Petersen, U.; Heitzer, H. Liebigs Ann. Chem. 1976, 1659-1662.
5. Ghosh, C. K.; Ghosh, C.; Patra, A. Indian J. Chem., Sect B 1998, 37, 387-390.
6. 3-Anilino-2-(2-hydroxy-5-methylbenzoyl) acrylonitrile 2a. This compound was prepared from chromone 1 (R = Me) and aniline according to the procedure described previously for 3.5 Yield 36%, mp 226-228 °C; 1H NMR (400 MHz, CDCl3)(Z-2a, 77%) δ 2.34 (s, 3H, Me), 6.91 (d, 1H, H-3, J = 8.4 Hz), 7.22-7.32 (m, 4H, H-2°, H-6°, H-4°, H-4), 7.46 (t, 2H, H-3', H-5', J =7.9 Hz), 8.05 (d, 1H, =CH, J = 13.4 Hz), 8.19 (br d, 1H, H-6, J =1.5 Hz), 11.17 (s, 1H, OH), 12.45 (br d, 1H, NH, J =13.4 Hz); (E-2a, 23%) δ 2.35 (s, 3H, Me), 6.92 (d, 1H, H-3, J = 8.4 Hz), 7.21-7.50 (m, 6H, H-4, Ar), 8.10 (br d, 1H, H-6, J =1.7 Hz), 8.18 (br d, 1H, NH, J = 15.2 Hz), 8.80 (d, 1H, @CH, J = 15.2 Hz), 11.68 (s, 1H, OH); 13C NMR (100 MHz, CDCl3)(Z-2a) δ 20.60 (Me), 82.38 (C2), 118.05 (C2",C6"), 118.15 (C3'), 119.35 (C1'), 120.34 (CN), 126.92 (C4''), 128.17 (C5'), 129.08 (C6'), 130.22 (C3'',C5''), 136.78 (C4'), 137.84 (C1''), 155.03 (C3), 159.26 (C2'), 193.14 (C1); (E-2a) δ 84.02 (C2), 129.44 (C6'), 137.98 (C1''), 154.45 (C3), 160.06 (C2'), 188.90 (C1) (the remaining carbon atoms were not observed due to their intensities being too low); 1H NMR (400 MHz, DMSO-d6)(Z-2a, 35%) δ 2.23 (s, 3H, Me), 6.81 (d, 1H, H-3, J = 8.2 Hz), 7.10-7.16 (m, 2H, H-4, H-6), 7.24 (tt, 1H, H-4', J = 7.4,1.0 Hz), 7.41-7.46 (m, 2H, H-3', H-5'), 7.55-7.59 (m, 2H, H-2', H-6'), 8.54 (d, 1H,=CH, J =13.5 Hz), 9.93 (s, 1H, OH), 12.31 (br d, 1H, NH, J =13.5 Hz); (E-2a, 65%) δ 2.23 (s, 3H, Me), 6.82 (d, 1H, H-3, J = 8.2 Hz), 7.10-7.16 (m, 2H, H-4, H-6), 7.18 (tt, 1H, H-4',J =7.4,1.0 Hz), 7.28-7.32 (m, 2H, H-2', H-6'0), 7.36-7.41 (m, 2H, H-3', H-5'), 8.13 (br s, 1H, =CH), 9.95 (br s, 1H, OH), 10.99 (br s, 1H, NH); 13C NMR (100 MHz, DMSO-d6)(Z-2a) δ 19.91 (Me), 85.48 (C2), 116.27 (C3'), 118.19 (C2'',C6''), 119.92 (CN), 125.77 (C4''), 126.59 (C1'), 127.24 (C5'), 128.24 (C6'), 129.62 (C3'',C5''), 132.45 (C4'), 138.46 (C1''), 152.67 (C2'), 153.59 (C3), 193.05 (C1); (E-2a) δ 19.91 (Me), 86.75 (C2), 116.17 (C3'), 116.73 (CN), 118.33 (C2'',C6''), 125.20 (C4''), 125.63 (C1'), 127.70 (C5'), 129.19 (C6'), 129.62 (C3'',C5''), 132.56 (C4''), 139.78 (C1''), 152.83 (C2'), 154.23 (C3), 189.69 (C1);
7. N NMR (40 MHz, DMSO-d6)(Z-2a) δ 137.6 (NH), (E-2a) 132.1 (NH). Anal. Calcd for C17H14N2O2: C, 73.37; H, 5.07; N, 10.07. Found: C, 73.56; H, 5.33; N, 10.28.
8. (a) Kozerski, L.; Krajewski, P.; Bednarek, E. Magn. Res. Chem. 1995, 33, 745-748;
9. (b) Wójcik, J.; Domalewski, W.; Kamienska-Trela, K.; Stefaniak, L.; Vdovienko, S. I.; Gerus, I. I.; Gorbunova, M. G. Magn. Res. Chem. 1993, 31, 808-814.
10. N2O2 C, 56.00; H, 3.23; N, 8.16. Found: C, 55.86; H, 3.35; N, 7.98.
11. Risitano, F.; Grassi, G.; Foti, F. J. Heterocycl. Chem. 2001, 38, 1083-1085.
12. 2-Amino-3-(2-aminophenyliminomethyl)chromone 4i. This compound was prepared from 3-cyanochromone and o-phenylenediamine according to the procedure described previously for 6.3 mp 217-218 °t.3 lit.7217 °C); IR (KBr) 3330, 3180, 1664, 1601, 1559, 1521, 1498, 1462 cm-1; 1H NMR (400 MHz, DMS0-d6) δ 5.02 (s, 2H, NH2), 6.59 (ddd, 1H, H-5', J = 7.8, 7.3, 1.0 Hz), 6.73 (dd, 1H, H-3', J = 7.8, 0.8 Hz), 6.87 (dd, 1H, H-6', J = 7.8, 0.8 Hz), 6.93 (ddd, 1H, H-4', J =7.8, 7.3, 1.0 Hz), 7.41-7.47 (m, 2H, H-6, H-8), 7.71 (ddd, 1H, H-7, J = 8.2, 7.4, 1.6 Hz), 8.06 (dd, 1H, H-5, J =7.7, 1.6 Hz), 8.91 (s, 1H, =CH), 9.30 (s, 1H, NHa), 10.39 (s, 1H, NHb). Anal. Calcd for C16H13N302: C, 68.81; H, 4.69; N, 15.05. Found: C, 69.04; H, 4.67; N, 15.09.
13. (a) Sigg, I.; Haas, G.; Winkler, T. Helv. Chim. Acta 1982, 65, 275-279;
14. (b) Rihs, G.; Sigg, I.; Haas, G.; Winkler, T. Helv. Chim. Acta 1985, 68, 1933-1935.