5060
V.Yu. Korotaev et al. / Tetrahedron 64 (2008) 5055–5060
7.45 (dd, 1H, H-4, J¼8.8, 2.6 Hz), 7.83 (d, 1H, H-6, J¼2.6 Hz), 14.19 (s,
5.64 (dqd, 1H, CH, J¼7.8, 7.0, 4.3 Hz), 6.87–6.93 (m, 2H, H-6, H-8),
7.38–7.41 (m, 1H, H-7), 7.78 (dd, 1H, H-5, J¼8.0, 1.5 Hz), 13.95 (br s,
1H, NH); 19F NMR (376 MHz, DMSO-d6) d 90.12 (d, CF3, J¼7.0 Hz).
13
1H, OH); C NMR (100 MHz, DMSO-d6) d 16.62 (C20), 69.94 (C2),
76.92 (C3), 98.55 (C1), 119.58 (C100), 120.46 (C300), 121.95 (C500),
129.32 (C600), 133.24 (C400), 159.79 (C200), 177.84 (C10). Anal. Calcd for
C
11H10Cl4N2O3: C, 36.70; H, 2.80; N, 7.78. Found: C, 36.66; H, 2.56;
Acknowledgements
N, 7.57.
This work was financially supported by the Russian Foundation
for Basic Research (Grant 06-03-04004).
4.4.5. 1,1,1-Trichloro-3-nitro-N-[1-(4,6-dimethyl-2-hydroxyphenyl)-
ethylidene]propan-2-amine (6e)
Yield 41%, mp 112–113 ꢀC. This compound was obtained
according to the procedure for chromenes 3. IR (KBr) 1636, 1558,
1386 cmꢁ1; 1H NMR (400 MHz, DMSO-d6) (Z-isomer, 80%) d 2.15 (s,
3H, Me-6), 2.21 (s, 3H, Me-4), 2.23 (s, 3H, Me), 4.60 (dd, 1H, CH,
J¼6.9, 1.9 Hz), 4.68 (dd, 1H, CHH, J¼15.9, 1.9 Hz), 5.03 (dd, 1H, CHH,
J¼15.9, 6.9 Hz), 6.52 (s, 1H, H-3), 6.58 (s, 1H, H-5), 9.82 (s, 1H, OH);
(E-isomer, 20%) d 2.06 (s, 3H, Me-6), 2.16 (s, 3H, Me-4), 2.26 (s, 3H,
Me), 4.78 (dd, 1H, CHH, J¼13.5, 8.8 Hz), 5.28 (dd, 1H, CH, J¼8.8,
2.8 Hz), 5.50 (dd, 1H, CHH, J¼13.5, 2.8 Hz), 6.45 (s, 1H, H-3), 6.46 (s,
1H, H-5), 9.36 (s, 1H, OH); (CDCl3) (E-isomer, 95%) d 2.26 (s, 3H, Me),
2.36 (s, 3H, Me), 2.51 (s, 3H, Me), 4.88 (dd, 1H, CHH, J¼13.6, 9.0 Hz),
5.22 (dd, 1H, CHH, J¼13.6, 2.4 Hz), 5.33 (dd, 1H, CH, J¼9.0, 2.4 Hz),
6.57 (s,1H, H-3), 6.63 (s, 1H, H-5), 9.5–12.0 (br s,1H, OH); (Z-isomer,
5%) d 2.23 (s, 3H, Me), 2.29 (s, 3H, Me), 2.34 (s, 3H, Me), 4.66 (dd,1H,
CHH, J¼15.6, 2.0 Hz), 4.78 (dd, 1H, CH, J¼6.3, 2.0 Hz), 4.95 (dd, 1H,
CHH, J¼15.6, 6.3 Hz), 6.44 (s, 1H, H-3), 6.69 (s, 1H, H-5). Anal. Calcd
for C13H15Cl3N2O3: C, 44.15; H, 4.28; N, 7.92. Found: C, 44.10; H,
4.12; N, 7.87.
References and notes
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Marth, G.; Dancso´, A.; Blasko´ , G.; Toke, L. Synlett 2004, 2761–2765.
4.4.6. 1,1,1-Trifluoro-3-nitro-N-[1-(4,6-dimethyl-2-hydroxyphenyl)-
ethylidene]propan-2-amine (6f)
}
7. (a) Bachman, G. B.; Levine, H. A. J. Am. Chem. Soc. 1948, 70, 599–601; (b) Taylor,
H. V.; Tomlinson, M. L. J. Chem. Soc. 1950, 2724–2725; (c) Shimizu, T.; Hayashi,
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Nocanda, X. W.; Robinson, R. S. Org. Biomol. Chem. 2003, 1, 1133–1138; (e) Kaye,
P. T.; Musa, M. A.; Nocanda, X. W. Synthesis 2003, 531–534; (f) Kaye, P. T.;
Nocanda, X. W. Synthesis 2001, 2389–2392.
2'
Me Me
1'
N
6''
1''
1
5''
4''
CF3
2
Me
2'' O
H
3
3''
NO2
9. Larock, R. C.; Wei, L.; Hightower, T. R. Synlett 1998, 522–524.
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11. Talley, J. J. Synthesis 1983, 845–847.
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84, 797–802; (b) Shechter, H.; Ley, D. E.; Roberson, E. B., Jr. J. Am. Chem. Soc.
1956, 78, 4984–4991; (c) Compton, M.; Higgins, H.; MacBeth, L.; Osborn, J.;
Burkett, H. J. Am. Chem. Soc. 1949, 71, 3229–3231; (d) Brower, F.; Burkett, H.
J. Am. Chem. Soc. 1953, 75, 1082–1084.
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2368; (b) Aoyagi, K.; Haga, T.; Toi, H.; Aoyama, Y.; Mizutani, T.; Ogoshi, H. Bull.
Chem. Soc. Jpn. 1997, 70, 937–943; (c) Ratner, V. G.; Lork, E.; Pashkevich, K. I.;
Ro¨schenthaler, G.-V. J. Fluorine Chem. 1997, 85, 129–131; (d) Ratner, V. G.; Lork,
E.; Pashkevich, K. I.; Ro¨schenthaler, G.-V. J. Fluorine Chem. 2000, 102, 73–77; (e)
Khomutov, O. G.; Filyakova, V. I.; Pashkevich, K. I. Izv. Akad. Nauk, Ser. Khim.
1994, 282–284; (Russ. Chem. Bull. 1994, 43, 261–263); (f) Takada, E.; Hara, S.;
Suzuki, A. Tetrahedron Lett. 1993, 34, 7067–7070; (g) Iwata, S.; Ishiguro, Y.;
Utsugi, M.; Mitsuhashi, K.; Tanaka, K. Bull. Chem. Soc. Jpn. 1993, 66, 2432–2435;
(h) Klenz, O.; Evers, R.; Miethchen, R.; Michalik, M. J. Fluorine Chem. 1997, 81,
205–210.
This compound was obtained according to the procedure for
chromenes 3. Yield 60%, mp 171–172 ꢀC; IR (KBr) 1651, 1614, 1565,
1388, 1374 cmꢁ1 1H NMR (400 MHz, DMSO-d6) (Z-isomer, 100%)
;
d 2.05 (s, 3H, Me-6), 2.21 (s, 3H, Me-4), 2.22 (s, 3H, Me), 4.29 (dqd,
1H, CH, J¼7.8, 7.2, 3.4 Hz), 4.61 (dd, 1H, CHH, J¼14.3, 3.4 Hz), 5.04
(dd,1H, CHH, J¼14.3, 7.8 Hz), 6.57 (s, 1H, H-3), 6.58 (s,1H, H-5), 9.81
(s, 1H, OH); (CDCl3) (Z-isomer, 55%) d 2.14 (s, 3H, Me), 2.29 (s, 3H,
Me), 2.33 (s, 3H, Me), 4.45 (dqd, 1H, CH, J¼7.3, 6.7, 3.8 Hz), 4.57 (dd,
1H, CHH, J¼13.7, 3.8 Hz), 4.78 (dd, 1H, CHH, J¼13.7, 7.3 Hz), 5.01 (s,
1H, OH), 6.47 (s, 1H, H-3), 6.69 (s, 1H, H-5); (E-isomer, 45%) d 2.26 (s,
3H, Me), 2.34 (s, 3H, Me), 2.44 (s, 3H, Me), 4.87 (dd,1H, CHH, J¼13.8,
5.5 Hz), 4.90 (dd, 1H, CHH, J¼13.8, 3.8 Hz), 5.10–5.20 (m, 1H, CH),
6.57 (s, 1H, H-3), 6.62 (s, 1H, H-5), 9.5–11.0 (br s, 1H, OH); 19F NMR
(376 MHz, DMSO-d6) (Z-isomer) d 89.48 (d, CF3, J¼7.2 Hz); (E-iso-
mer) d 90.81 (d, CF3, J¼7.2 Hz); (CDCl3) (Z-isomer) d 87.42 (d, CF3,
J¼6.7 Hz); (E-isomer) d 88.68 (d, CF3, J¼6.6 Hz); 13C NMR (100 MHz,
DMSO-d6) d 18.14 (Me-C600), 20.84 (Me-C400), 27.98 (C20), 61.44 (q,
14. Korotaev, V. Yu.; Kutyashev, I. B.; Sosnovskikh, V. Ya. Heteroat. Chem. 2005, 16,
492–496.
15. (a) Korotaev, V. Yu.; Sosnovskikh, V. Ya.; Kutyashev, I. B.; Kodess, M. I. Lett. Org.
Chem. 2005, 2, 616–620; (b) Korotaev, V. Yu.; Sosnovskikh, V. Ya.; Kutyashev, I. B.;
Kodess, M. I. Izv. Akad. Nauk, Ser. Khim. 2006, 309–321; (Russ. Chem. Bull., Int. Ed.
2006, 55, 317–330); (c) Korotaev, V. Yu.; Sosnovskikh, V. Ya.; Kutyashev, I. B.;
Kodess, M. I. Izv. Akad. Nauk, Ser. Khim. 2006, 1945–1955; (Russ. Chem. Bull., Int.
Ed. 2006, 55, 2020–2031); (d) Korotaev, V. Yu.; Kutyashev, I. B.; Sosnovskikh, V.
Ya.; Kodess, M. I. Mendeleev Commun. 2007, 17, 52–53.
2
C2, JC,F¼28.4 Hz), 73.62 (C3), 113.29 (C300), 121.10 (C100), 121.85
1
(C500), 124.62 (q, C1, JC,F¼280.7 Hz), 133.75 (C600), 139.30 (C400),
152.42 (C200), 177.25 (C10). Anal. Calcd for C13H15F3N2O3: C, 51.32; H,
4.97; N, 9.21. Found: C, 51.15; H, 5.05; N, 9.10.
16. Bergman, Y.; Perlmutter, P.; Thienthong, N. Green Chem. 2004, 6, 539–540.
17. Nguyen, T. T.; Le, T. N.; Hansen, P. E.; Duus, F. Tetrahedron Lett. 2006, 47, 8433–
8435.
18. Song, A.; Wang, X.; Lam, K. S. Tetrahedron Lett. 2003, 44, 1755–1758.
19. Linderman, R. J.; Jamois, E. A. J. Fluorine Chem. 1991, 53, 79–91.
20. (a) Organofluorine Compounds in Medicinal Chemistry and Biomedical Applica-
tions; Filler, R., Kobayashi, Y., Yagupolskii, L. M., Eds.; Amsterdam: Elsevier,
1993; (b) Hiyama, T. Organofluorine Compounds: Chemistry and Application;
Springer: Berlin, 2000.
4.4.7. (E)-1,1,1-Trifluoro-3-nitro-N-[1-(2-hydroxyphenyl)-
ethylidene]propan-2-amine (6g)
This compound was observed in the 1H NMR spectrum of the
crude chromene 3d; it was not obtained as pure and was not fully
characterized. 1H NMR (400 MHz, DMSO-d6) d 2.56 (s, 3H, Me), 5.18
(dd, 1H, CHH, J¼14.2, 7.8 Hz), 5.32 (dd, 1H, CHH, J¼14.2, 4.3 Hz),