1064
KHOMUTNIK et al.
phaspiro[4.4]-non-2-ene (IVb). Yield 88%. IR
spectrum (KBr pellet), ν, cm–1: 1630 (C=N), 1745
(C=O). 1H NMR spectrum (CDCl3), δ, ppm: diastereo-
cm–1: 1648 (C=N), 1736 (C=O). 1H NMR spectrum
(CDCl3), δ, ppm: 2.43 s (3H, MeC), 3.82 s (3H, OMe),
7.27 d (2H, Ar, 3JHH 7.4 Hz), 8.02 d (2H, Ar, 3JHH 7.4 Hz).
13C NMR spectrum (CDCl3), δC, ppm: 21.60 (MeC),
52.87 (MeO), 122.25 (CCl2), 129.35, 129.72 (C2,C3,
Ar), 131.58 (=C–N), 135.03 (C1, Ar), 144.03 (C4, Ar),
150.09 (C=N), 161.03 (C=O). Found, %: C 47.24, H
3.12, Cl 34.07, N 4.10. C12H10Cl3NO2. Calculated, %:
C 47.01, H 3.29, Cl 34.69, N 4.57.
3
mer A: 1.03 t (3H, MeCH2, JHH 6.9 Hz), 1.42 t (3H,
3
MeCH2, JHH 6.9 Hz), 2.43 s (3H, MeAr), 2.88–3.02 m
(2H, NCH2), 3.03 s (3H, MeO), 3.65–3.85 m (2H,
NCH2), 6.82–7.02 m (4H, OC6H4), 7.30 d (2H, HTol,
3
3JHH 7.4 Hz), 8.08 d (2H, HTol, JHH 7.4 Hz);
diastereomer B: 0.92 br. (3H, MeCH2), 1.13 br. (3H,
MeCH2), 2.43 s (3H, MeAr), 2.7–3.0 m (2H, NCH2),
3.1–3.3 m (2H, NCH2), 3.90 s (3H, MeO), 6.83–7.03
REFERENCES
3
1. Weinreb, S.M. and Scola, P.M., Chem. Rev., 1989,
vol. 89, no. 7, p. 1525.
2. Weinreb, S.M. and Orr, R.K., Synthesis, 2005, no. 8,
p. 1205.
3. Osipov, S.N., Kolomiets, A.F., and Fokin, A.V., Usp.
Khim., 1992, vol. 61, no. 8, p. 1457.
m (4H, OC6H4), 7.30 d (2H, HTol, JHH 7.4 Hz), 8.08 d
3
(2H, HTol, JHH 7.4 Hz). 31P NMR spectrum (CDCl3),
δP, ppm: –21.0 (A), –19.5 (B). Found, %: C 49.61; H
4.52; Cl 19.85; N 5.21. C22H24Cl3N2O5P. Calculated,
%: C 49.50; H 4.52; C 19.85; N 5.21.
4. Levkovskaya, G.G., Drozdova, T.I., Rozentsveig, I.B.,
and Mirskova, A.N., Usp. Khim., 1999, vol. 68, no. 7,
p. 638.
5. Scerpos, H., Vorob’eva, D.V., Osipov, S.N., Odinets, I.L.,
Breuer, E., and Roschenthaler, G.-V., Org. Biomol.
Chem., 2006, vol. 4, no. 19, p. 3669.
6. Sewald, N., Riede, J., Bissinger, P., Burger, K., J. Chem.
Soc., Perkin Trans. 1, 1992, no. 3, p. 267.
7. Welch, J.T., Tetrahedron, 1987, vol. 43, no. 14, p. 3123.
8. Onys’ko, P.P., Khomutnik, Y.Y., Kim, T.N., Kyselyo-
va, O.L., Rassukana, Yu.V., Brovarets, V.S., and
Synytsya, A.D., Synthesis, 2011, no. 1, p. 65.
7,8-Benzo-5-diethylamino-4-trichloromethyl-2-
phenyl-4-cyano-3-aza-1,6,9-trioxa-5-phosphaspiro
[4.4]-non-2-ene (IVc). Yield 87%, colorless crystals,
mp 149–150°C (CH2Cl2-petroleum ether). IR spectrum
(KBr pellet), ν, cm–1: 1620 (C=N), 2380 (C≡N). 1H
3
NMR spectrum (C6D6), δ, ppm: 1.08 t (6H, Me, JHH
7 Hz), 2.8–3.0 m (2H, NCH2), 3.3–3.7 m (2H, NCH2),
6.8–6.9 m (1H, OC6H4), 6.96 d (2H, OC6H4, J 4.5 Hz),
7.13 d (1H, OC6H4, J 7.9 Hz), 7.33 t (2H, 3,5-HPh, 3JHH
3
~7.5 Hz), 7.39 t (1H, 4-HPh, JHH 7.3 Hz), 8.50 d (2H,
2,6-HPh, 3JHH 7.4 Hz). 13C NMR spectrum (CDCl3), δC,
ppm (numbering of C atoms see in the figure): 15.93
(CH3), 46.23 d (2JCP 3.5 Hz, CH2), 79.50 d (1JCP 151 Hz,
CP), 99.55 d (2JCP 6.8 Hz, CCl3), 111.75 d (3JCP 9 Hz)
and 112.24 d (3JCP 16.8 Hz) (C10, C13), 116.84 d (2JCP
1 Hz, C≡N), 122.43 and 124.39 (C11, C12), 129.30 d
(3JCP 1.5 Hz, C6), 129.5 and 129.5 (C1, C5, and C2, C4),
133.89 (C3), 142.77 d, (2JCP 5.8 Hz) and 147.20 s (C9
and C8), 165.66 d (2JCP 26.9 Hz, C≡N). 31P NMR
spectrum (CDCl3), δP, ppm: –21.7. Found, %: 48.39, H
3.40, Cl 22.57, N 8.95. C19H16Cl3N3O3P. Calculated,
%: C 48.38, H 3.42, Cl 22.55, N 8.91.
9. Onys’ko, P.P., Rassukana, Yu.V., and Sinitsa, A.D.,
Curr. Org. Chem., 2008, vol. 12, no. 1, p. 2.
10. Allen, K.N. and Dunaway-Mariano, D., Trends in
Biochem. Sci., 2004, vol. 29, no. 9, p. 495.
11. Chernega, A.N., Antipin, M.Yu., Struchkov, Yu.T.,
Gololobov, Yu.G., Boldeskul, I.E., Gusar’, N.I., and
Chaus, M.P., Zh. Strukt. Khim., 1984, vol. 25, no. 6, p. 93.
12. Abdrakhamanova, L.M., Mironov, V.F., Baronova, T.A.,
Dimukhametov, M.N., Krivolapov, D.V., Litvinov, I.A.,
Musin, R.Z., and Konovalov, A.I., Mendeleev
Commun., 2007, vol. 17, no. 5, p. 284.
13. Abdrakhamanova, L.M., Mironov, V.F., Baronova, T.A.,
Dimukhametov, M.N., Krivolapov, D.V., Litvinov, I.A.,
Balandina, A.A., Latypov, S.K., and Konovalov, A.I.,
Mendeleev Commun., 2005, vol. 16, no. 6, p. 320.
14. Kolotilo, N.V., Sinitsa, A.A., and Onys’ko, P.P., Izv.
Akad. Nauk, Ser, Khim., 1998, no. 10, p. 2101.
15. Rassukanaya, Yu.V., Sinitsa, A.A., and Onys’ko, P.P.,
Izv. Akad. Nauk, Ser, Khim., 2005, no. 11, p. 2567.
16. Kolotilo, N.V., Sinitsa, A.A., Rassukanaya, Yu.V., and
Onys’ko, P.P., Zh. Obshch. Khim., 2006, vol. 76, no. 8,
p. 1260.
Azadienes (VIII). To a solution of 0.5 mmol of
imine II in 3 ml of diethyl ether 0.5 mmol of tri-
phenylphosphine was added at 5–10°C. After 2 h the
precipitate of triphenylphosphine oxide was filtered
off, the residue was evaporated and extracted with
petroleum ether.
3-Methoxycarbonyl-1,4,4-trichloro-1-phenyl-2-
aza-1,3-diene (VIIIa) [18]. Yield 65%. IR spectrum,
ν, cm–1: 1648 (C=N), 1735 (C=O). Found, %: Cl
35.86. C11H8Cl3NO2. Calculated, %: Cl 36.36.
17. Watkin, D.J., Prout, C.K., Carruthers, J.R., and
Betteridge, P.W., CRYSTALS, issue 19, Chemical
Crystallography Laboratory, Univ. of Oxford.
18. Derach, B.S. and Mis’kevich, G.N., Zh. Org. Khim.,
1978, vol. 14, no. 5, p. 943.
3-Methoxycarbonyl-1-(4-tolyl)-1,4,4-trichloro-2-
aza-1,3-diene (VIIIb). Yield 63%. IR spectrum, ν,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012