840
BADEEVA et al.
The coordinates of atoms and their thermal parameters
are listed in Table 1, and the geometric parameters of
the structure, in Table 2. The drawings were per-
formed and the intermolecular interactions were
calculated by the PLATON program [13].
was heated for 8 h at 60 80 C. 31P NMR spectrum
of the reaction mixture, P, ppm (%): 131.9 (3.2); 56.4
(66.5); 46.5 (16); 23.3 (5.3); 7.4 (9). The solvent was
removed, and the reaction mixture crystallized. Phos-
phate IV, 1.7 g (55%), was isolated. The melting
point and spectral characteristics of this sample were
similar to those of the sample prepared by procedure a.
Reaction of white phosphorus with thiophenol
and diethylamine. To a mixture of 0.5 g of P4, 4.5 g
of thiophenol, and 4 ml of acetonitrile, 1.6 g of di-
ethylamine was added dropwise. The reaction mixture
was heated for 18 h at 80 90 C and then for 6 h at
95 100 C. The solvent was removed in a vacuum
to give a viscous yellow liquid that crystallized on
cooling. It was thrice crystallized from acetone to ob-
tain 2.8 g (43.8%) of salt II, mp 149 150 C. IR spec-
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project nos. 03-03-
33076 and 02-03-32280).
REFERENCES
1
trum, , cm : 1640 (C=N), 1580 (C6H5), 1250 (P=O).
31P NMR spectrum:
25 ppm. Found, %: C 55.0; H
1. Badeeva, E.K., Batyeva, E.S., and Sinyashin, O.G.,
6.2; N 6.71; P 7.95;P S 16.5. C18H25N2O2PS2. Cal-
culated, %: C 54.5; H 6.3; N 7.07; P 7.83; S 16.16.
Zh. Obshch. Khim., 2001, vol. 71, no. 2, p. 344.
2. Burdford, N., Royan, B.W., and White, P.S., Acta
Crystallogr., 1990, vol. 46, no. 1, p. 274.
Reaction of triphenyl phosphorotrithioite with
thiophenol and diethylamine. To a mixture of 2.5 g
of triphenyl phosphorotrithioite, 1.14 g of thiophenol,
and 2 ml of acetonitrile, 0.76 g of diethylamine was
added dropwise. The reaction mixture was heated for
6 h at 70-80 C and then for 10 h at 95 C. After cool-
ing, 1.1 g (42%) of salt II was obtained. Their
constants and physicochemical characteristics agree
with those of the sample obtained by scheme (2).
3. Al’fonsov, V.A., Litvinov, I.A., Kataeva, O.N.,
Pudovik, D.A., and Catsyuba, S.A., Zh. Obshch.
Khim., 1995, vol. 65, no. 7, p. 1129.
4. Shibao, R.K., Keder, N.L., and Eckert, H., Acta Crys-
tallogr., 1992, vol. 48, no. 11, p. 1525.
5. Stumpf, K., Blachnik, R., Roth, G., and Kastner, G.,
Z. Kristallogr.-New Crystal Struct., 1999, vol. 214,
p. 399.
6. Comprehensive Organic Chemistry, Barton, D. and
Synthesis of S,S,S-triphenyl phosphotrithioate
(IV). a. Reaction of white phosphorus with thiophenol
in the presence of triethylamine. To a mixture of 1 g
of P4, 11 g of thiophenol, and 5 ml of acetonitrile,
0.5 g of triethylamine was added dropwise. The result-
ing mixture was heated for 15 h at 70 90 C. The
solvent was removed, and the reaction mixture was
cooled to isolate 6.7 g (56%) of compound IV, mp
116 117 C. IR spectrum, , cm : 1220 (P=O). H
NMR spectrum, , ppm: 7.3 s (C6H5S). 31P NMR
spectrum, P 54.7 ppm. Found, %: C 57.61; H 4.02; P
8.04; S 26.0. C18H15OPS3. Calculated, %: C 57.7; H
4.01; P 8.29; S 25.6.
Ollis, W.D., Eds., Oxford: Pergamon, 1982, vol. 2.
7. Granik, V.G., Usp. Khim., 1983, vol. LII, no. 4,
p. 669.
8. Schnur, R.S., J. Org. Chem., 1979, vol. 44, no. 21,
p. 3726.
9. The Chemistry of the Thiol Group, Patai, S., Ed.,
London: Wiley, 1974, part 2.
1
1
10. Pudovik, A.N., Batyeva, E.S., and Sinyashin, O.G.,
Tioproizvodnye kislot trehvalentnogo fosfora (Thio
Derivatives of Trivalent Phosphorus Acids), Moscow:
Nauka, 1990.
11. Altomare, A., Cascarano, G., Giacovazzo, C., and
Viterbo, D., Acta Crystallogr., Sect. A, 1991, vol. 47,
p. 744.
In a similar way, from 0.5 g of P4, 5.5 g of thio-
phenol, and 6 ml of acetonitrile in the presence of
0.78 g of dimethylaniline we obtained 2.1 g (35%)
of compound IV.
12. Straver, L.H. and Schierbeek, A.J., MolEN. Structure
Determination System, vol. 1, Program Description,
Nonius, B.V., 1994.
b. Reaction of white phosphorus with thiophenol
in the presence of diphenyl disulfide. To a mixture of
0.26 g of P4, 2.76 g of thiophenol, and 5 ml of aceto-
nitrile, 0.36 g of diphenyl disulfide prepared by the
procedure in[14] were added. The reaction mixture
13. Speck, A.L., Acta Crystallogr., 1990, vol. 46, p. 34.
14. Juaristi, M., Aizpurua, J.M., Lecea, B., and Palomo, C.,
Can. J. Chem., 1984, vol. 62, no. 12, p. 2941.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005