1326
BAGDASARYAN et al.
under reflux. The solvent was removed, and the re-
sidue was washed with anhydrous diethyl ether, dis-
solved in water, and extracted with chloroform to
isolate 3.35 g of a mixture of salts IIId and I at a ratio
of 80:20. Yield of salt IIId 77.4%. Attempts to
separate the salt mixture by recrystallization were
[2-(1H-Imidazol-1-yl)-1,2-diphenylethyl]diphe-
nylphosphine oxide (IVc) was synthesized from
2.3 g of salt IIIc. The product was recrystallized from
anhydrous alcohol. Yield 0.7 g (34.7%). H NMR
spectrum (CDCl3), , ppm (J, Hz): 4.43 d.d (1H, PCH,
1
3
3
2JPH = 7.0, J = 10.9); 6.18 d.d (1H, NCH, J = 10.9,
8.2); 6.74 s (1H, CH, imidazole); 6.88 s (1H, CH,
imidazole); 6.95 7.06 m (6H), 7.09 7.29 m (8H),
7.30 7.42 m (5H), and 7.47 7.55 m (2H, C6H5 and
1
unsuccessful. IR spectrum: (C=C) 1590 cm .
31P NMR spectrum (CDCl3):
17.7 ppm.
P
[1,2-Diphenyl-2-(1H-pyrazol-1-yl)ethyl]diphe-
nylphosphine oxide (IVa). A mixture of 2.0 g of
I/IIIa salt mixture and 50 ml of 3.5% aqueous sodium
hydroxide was heated for 13.5 h at the boiling point
under stirring. The mixture was cooled and extracted
with diethyl ether. The white solid separated at the
diethyl ether water phase boundary was washed with
diethyl ether and dried. Yield of IVa 0.65 g (62%,
CH, imidazole). 31P NMR spectrum (CDCl3):
P
29.7 ppm.
Removal of the solvent from the combined extracts
gave 0.2 g (17%) of triphenylphosphine oxide with
mp 152 154 C, which showed no depression of the
melting point on mixing with an authentic sample.
1
calculated on IIIa), mp 280 282 C. H NMR spec-
Diphenyl[1,2-diphenyl-2-(1H-1,2,4-triazol-1-yl)-
ethyl]phosphine oxide (IVd) was obtained from
2.0 g of salt IIId (reaction time 17 h). Yield 0.35 g
2
trum (CDCl3), , ppm (J, Hz): 4.93 d.d (0.5H, JPH
=
3
2
5.6, J = 11.3) and 5.09 d.d (0.5H, PCH, JPH = 4.8,
3J = 11.0), 5.66 d.d (0.5H, J = 2.5, 1.8) and 5.83 d.d
3
1
(25%). H NMR spectrum (CDCl3), , ppm (J, Hz):
3
2
3
(0.5H, 4-H, pyrazole, J = 2.5, 1.8), 6.10 d.d (0.5H,
3J = 11.3, JPH = 6.1) and 6.34 d.d (0.5H, NCH, J =
11.0, JPH = 10.5), 6.83 7.76 m (22H, C6H5; 3-H and
4.81 d.d (1H, PCH, JPH = 5.8, J = 11.3); 6.25 d.d
3
3
3
3
(1H, NCH, J = 11.3, JPH = 6.3); 7.73 s (1H, CH,
triazol); 7.73 s (1H, CH, triazole); 6.92 7.04 m (6H),
7.08 7.24 m (6H), 7.29 7.38 m (2H), 7.38 7.54 m
(4H), and 7.59 7.65 m (2H, C6H5). 31P NMR spec-
3
5-H, pyrazole). 31P NMR spectrum (CDCl3):
29.4,
30.7 ppm. 13C NMR spectrum (CDCl3), C, pPpm (J,
trum (CDCl3):
29.3 ppm.
1
Hz): 50.47 d (1JPC = 64.2) and 51.64 d (PCH, JPC
=
P
2
66.9), 65.60 d and 69.11 d (NCH, JPC = 4.3),
105.15 d (JPC = 3.4) and 105.53 d (JPC = 3.7, C4,
pyrazole), 127 139 (Carom). Found: M+ 448; cal-
culated: M 448.
Removal of the solvent from the combined extracts
gave 0.15 g (14.7%) of triphenylphosphine oxide with
mp 152 154 C, which showed no depression of the
melting point on mixing with an authentic sample.
Removal of the solvent from the combined extracts
gave 0.15 g (15%) of triphenylphosphine oxide with
mp 152 154 C, which showed no depression of the
melting point on mixing with an authentic sample.
REFERENCES
1. Norobu, M., Dickstein, J.L., and Miller, S.J., J. Chem.
Soc., Perkin Trans. 1, 1979, no. 9, p. 2103.
Compounds IVb IVd were obtained in a similar
2. Schweiser, E.E. and De Voc Coff, S., J. Org. Chem.,
way.
1978, vol. 43, no. 15, p. 2972.
[2-(3,5-Dimethyl-1H-pyrazol-1-yl)-1,2-diphenyl-
ethyl]diphenylphosphine oxide (IVb) was synthe-
sized from 0.9 g of salt mixture I/IIIb by heating for
7 h at the boiling point. The product was recrystal-
3. Hoffmann, H. and Foerster, H., Tetrahedron Lett., 1964,
nos. 17 18, p. 983.
4. Shutt, J.R. and Trippett, S., J. Chem. Soc. C, 1969,
1
no. 15, p. 2038.
lized from alcohol. Yield 0.3 g (42.2%). H NMR
spectrum (DMSO-d6/CCl4, 1:3), , ppm (J, Hz):
5. Khachatryan, R.A., Zalinyan, S.A., Bagdasaryan, G.B.,
Sarkisova, E.A., and Indzhikyan, M.G., Izv. Ross. Akad.
Nauk, Ser. Khim., 2002, no. 1, p. 139.
2.01 s (3H, CH3), 2.08 s (3H, CH3), 5.03 d.d (1H,
2
3
PCH, JPH = 5.2, J = 11.2), 5.30 s (1H, 4-H, pyra-
3
3
zole), 5.86 d.d (1H, NCH, J = 11.2, JPH = 5.7),
6. Khachatryan, R.A., Khachikyan, R.Dzh., Zalinyan, S.A.,
Gevorkyan, G.A., Karamyan, N.V., and Indzhi-
kyan, M.G., Arm. Khim. Zh., 2001, vol. 54, nos. 3 4,
p. 41.
6.77 6.98 m (6H), 7.04 7.19 m (6H) and 7.41
7.55 m (7H, C6H5). 31P NMR spectrum (CDCl3):
P
29.8 ppm. 13C NMR spectrum (CDCl3), C, ppm (J,
1
Hz): 10.19 (CH3), 13.17 (CH3), 50.95 d (PCH, JPC
=
2
68.2), 62.74 d (NCH, JPC = 5.0), 103.51 (C4, pyra-
7. Dickstein, J.L. and Miller, S.J., J. Org. Chem., 1972,
zole), 126 146 (Carom).
vol. 37, no. 13, p. 2168.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 8 2006