KOPTELOV, SAIK
1506
spectrum of isomer mixture), δ, ppm: 0.55 br.s (3H),
6.32 br.s (1H).
H 4.88; N 11.26. C18H18BrN3O. Calculated, %:
C 58.08; H 4.87; N 11.29.
Chromatographic separation of the product mixture
obtained from 500 mg (~2 mmol) of compound Ib and
235 mg (2 mmol) of phenyl isocyanate gave 150 mg
(20.4%) of IVb, 40 mg (5.4%) of Vb, 109 mg (14.8%)
of VIb, and 80 mg (10.9%) of VIIb; in addition,
114 mg (15.5%) of isomer mixtures was isolated. The
overall preparative yield of all isomers was 493 mg
(67.1%). According to the H NMR spectrum of the
reaction mixture, the ratio VIIb/VIb/Vb/IVb was
~0.4:1.1:0.3:1.0.
rel-(3R,5R)-3-(4-Bromophenyl)-5-methyl-2-
phenylperhydropyrazolo[1,2-a][1,2,4]triazol-1-one
(VIIb). mp 176°C. IR spectrum, ν, cm–1: 1025, 1080,
1115, 1135, 1150, 1160, 1265, 1290, 1305, 1390, 1420,
1460, 1510, 1610, 1720 (C=O), 2885, 2915, 2940,
1
2980, 3020, 3040, 3070. H NMR spectrum (55°C), δ,
ppm: 0.60 d (3H, J = ~5.9 Hz), 1.69–1.80 m (1H),
2.25–2.37 m (1H), 3.21–3.33 m (1H, CHMe), 3.45–
3.58 m (1H), 3.61–3.75 m (1H), 6.12 s (1H), 7.02–
7.10 m (1H, Harom), 7.21–7.31 m (6H, Harom), 7.45–
7.51 m (2H, Harom). Found, %: C 58.03; H 4.89;
N 11.22. C18H18BrN3O. Calculated, %: C 58.08;
H 4.87; N 11.29.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 04-03-32898).
1
rel-(3R,7R)-3-(4-Bromophenyl)-7-methyl-2-
phenylperhydropyrazolo[1,2-a][1,2,4]triazol-1-one
(IVb). mp 177–178°C. IR spectrum, ν, cm–1: 1025,
1060, 1085, 1110, 1115, 1160, 1260, 1300, 1330, 1365,
1385, 1415, 1460, 1510, 1610, 1720 (C=O), 2850,
1
2885, 2940, 2990, 3040. H NMR spectrum, δ, ppm:
1.32 d (3H, J = 6.75 Hz), 1.70–1.87 m (1H), 2.36–
2.46 m (1H), 2.71–2.80 m (1H), 3.34–3.39 m (1H),
4.24–4.35 m (1H, CHMe), 5.75 s (1H), 7.06–7.11 m
(1H, Harom), 7.28–7.32 m (4H, Harom), 7.45–7.51 m
(4H, Harom). 13C NMR spectrum, δC, ppm: 22.6, 34.2,
53.1, 54.5, 78.2, 119.5, 123.0, 124.2, 128.6, 129.3,
132.1, 137.0, 138.0, 161.2. Found, %: C 58.12; H 4.94;
N 11.15. C18H18BrN3O. Calculated, %: C 58.08;
H 4.87; N 11.29.
REFERENCES
1. Trofimov, V.V., Koptelov, Yu.B., Molchanov, A.P., and
Kostikov, R.R., Zh. Org. Khim., 1994, vol. 30, p. 1389.
2. Koptelov, Yu.B., Kim, M.Kh., Molchanov, A.P., and
Kostikov, R.R., Russ. J. Org. Chem., 1999, vol. 35,
p. 110; Molchanov, A.P., Sipkin, D.I., Koptelov, Yu.B.,
and Kostikov, R.R., Russ. J. Org. Chem., 2001, vol. 37,
p. 841.
rel-(3R,7S)-3-(4-Bromophenyl)-7-methyl-2-
phenylperhydropyrazolo[1,2-a][1,2,4]triazol-1-one
(Vb). mp 101–102°C. IR spectrum, ν, cm–1: 1025,
1085, 1125, 1140, 1170, 1260, 1290, 1310, 1320, 1380,
1420, 1460, 1515, 1610, 1720 (C=O), 2865, 2880,
3. Molchanov, A.P., Sipkin, D.I., Koptelov, Yu.B., and
Kostikov, R.R., Synlett, 2000, p. 1779.
4. Molchanov, A.P., Sipkin, D.I., Koptelov, Yu.B., Kosti-
kov, R.R., and Kopf, J., Russ. J. Org. Chem., 2003,
vol. 39, p. 1338; Molchanov, A.P., Sipkin, D.I., Kopte-
lov, Yu.B., and Kostikov, R.R., Russ. J. Org. Chem.,
2004, vol. 40, p. 67.
5. Dorn, H. and Otto, A., Chem. Ber., 1968, vol. 101,
p. 3287.
6. Gomtsyan, A., Koenig, R.J., and Lee, C.-H., J. Org.
Chem., 2001, vol. 66, p. 3613.
7. Turk, C., Svete, J., Stanovnik, B., Goli, L., Golič-
Grdadolnik, S., Golobič, A., and Selič, L., Helv. Chim.
Acta, 2001, vol. 84, p. 146.
8. Rademacher, P., J. Mol. Struct., 1975, vol. 28, p. 97.
9. Rutjes, F.P.J.T., Udding, J.H., Hiemstra, H., and
Speckamp, W.N., Recl. Trav. Chim. Pays–Bas, 1994,
vol. 113, p. 145.
10. Gottlieb, H.E., Kotlyar, V., and Nudelman, A., J. Org.
Chem., 1997, vol. 62, p. 7512.
11. Elguero, J. and Jacquier, R., Bull. Soc. Chim. Fr., 1965,
p. 769.
1
2940, 2988, 3040. H NMR spectrum, δ, ppm: 1.41 d
(3H, J = 6.5 Hz), 1.61–1.74 m (1H), 2.19–2.38 m (2H),
2.54–2.66 m (1H), 4.20–4.33 m (1H, CHMe), 6.21 s
(1H), 6.85–6.92 m (2H, Harom), 7.06–7.14 m (1H,
H
arom), 7.19–7.33 m (6H, Harom), 7.48 d (2H, Harom).
Found, %: C 58.41; H 5.19; N 10.95. C18H18BrN3O.
Calculated, %: C 58.08; H 4.87; N 11.29.
rel-(3R,5S)-3-(4-Bromophenyl)-5-methyl-2-
phenylperhydropyrazolo[1,2-a][1,2,4]triazol-1-one
(VIb). mp 126–128°C. IR spectrum, ν, cm–1: 1025,
1085, 1100, 1115, 1120, 1145, 1160, 1250, 1285, 1300,
1315, 1335, 1350, 1390, 1415, 1460, 1510, 1610, 1720
1
(C=O), 2860, 2885, 2940, 2980, 3025, 3040. H NMR
spectrum, δ, ppm: 1.39 d (3H, J = 6.75 Hz), 1.74–
1.87 m (1H), 2.27–2.37 m (1H), 2.79–2.91 m (1H,
CHMe), 3.25–3.33 m (1H), 3.92–4.01 m (1H), 5.70 s
(1H), 7.07–7.12 m (Harom), 7.26–7.34 m (4H, Harom),
7.48–7.53 m (4H, Harom). 13C NMR spectrum, δC, ppm:
17.1, 33.8, 44.3, 58.8, 76.2, 118.8, 123.1, 124.1, 128.3,
129.3, 132.1, 136.8, 138.1, 161.4. Found, %: C 58.35;
12. Ioffe, B.V. and Burmanova, N.B., Khim. Geterotsikl.
Soedin., 1971, p. 1225.
13. Kost, A.N., Golubeva, G.A., and Stepanov, R.G.,
Zh. Obshch. Khim., 1962, vol. 32, p. 2240.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 10 2006