REDOX REACTION OF RED PHOSPHORUS
1817
NaS
NaS
NaS
NaS
MeS
MeS
MeS
MeS
SNa
O
SNa
S
SMe
O
SMe
S
MeI
P
P
P
P
+
+
I
II
III
IV
In some cases, ~3% of methylphosphonotrithioate
V was identified in the crude product (1Н and 31Р
NMR, GC–MS).
[CH2SP]+, 63 (100) [SP]+, 47 (29) [SMe]+, 45 (35)
[HCS]+. Found, %: С 18.96; Н 4.79; Р 15.32; S 57.32.
С3Н9OРS3 (III) : С3Н9РS4 (IV) = 1 : 1. Calculated, %:
С 18.35; Н 4.62; Р 15.78; S 57.17.
MeS
Me
Dimethyl methylphosphonotrithioate (V). 1Н
NMR spectrum (CDCl3), δ, ppm: 2.24 d (3Н, MeP,
P
MeS
S
3
3JНР 13.0 Hz), 2.35 d (6Н, MeS, JНР 15.9 Hz). 31Р
V
NMR spectrum (CDCl3), δР, ppm: 83.1. Mass
spectrum, m/z (Irel, %): 172 (68) [М]+·, 140 (8) [M – S]+·,
125 (76) [M –SMe]+, 111 (11) [MeSPSH]+, 93 (48)
[MeSPMe]+, 79 (51) [MeSPH]+, 78 (29) [MeSP]+, 77
(40) [CH2SP]+, 65 (42) [H2SP]+, 63 (100) [SP]+, 51
(15), 49 (64), 48 (21), 47 (44) [SMe]+, 46 (28), 45 (84)
[HCS]+, 44 (36) [CHP]+, 43 (8).
Thus, the discovered reaction contributes a prin-
cipally new basic knowledge into the chemistry of
phosphorus and sulfur and opens new possibilities for
synthesis of phosphorus- and sulfur-containing com-
pounds on the basis of elemental phosphorus in its
most stable and handy red modification.
1
The Н and 31Р NMR spectra were recorded on a
S,S,S-Trimethyl phosphorotrithioate (III) and
trimethyl phosphorotetrathioate (IV). To 63 ml of a
0.64 M solution of NaSH in DMSO, 0.77 g of red
phosphorus was added, the reaction mixture stirred at
100–116°С for 4.5 h, and cooled to 20–22°С. Methyl
iodide, 7.8 ml, was then added dropwise over the
course of 15 min (exothermic effect, self-heating to
45°С). The mixture was stirred at 50–55°С for another
2 h and then diluted by half with water and extracted
with ether (3×30 ml). The ethereal extract was washed
with water, dried over potassium carbonate, the ether
was removed, and the residue was dried in a vacuum to
Bruker DPX-400 spectrometer (400.13 and 161.98 MHz,
respectively), internal standard HMDS, external
standard 85% Н3РО4. The electron impact mass
spectra (70 eV) were obtained on a GCMS-QP5050A
instrument (quadrupole mass analyzer, mass range 34–
450, SPB–5 capillary column).
ACKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (project no. 08-03-
98012-r_sibir_a).
31
give 0.22 g of the product. According to the Р NMR
spectrum, it contained compounds III and IV in ~1:1
ratio (total yield 10% per taken NaSH).
REFERENCES
1
Compound III. Н NMR spectrum (CDCl3), δ,
3
ppm: 2.43 d (9Н, Me, JНР 15.9 Hz). 31Р NMR
1. Trofimov, B., Gusarova, N., and Brandsma, L., Main
Group Chem. News., 1996, vol. 4, no. 1, p. 18.
spectrum (CDCl3), δР, ppm: 69.8. Mass spectrum, m/z
(Irel, %): 188 (12) [М]+·, 142 (19) [M – CH2S]+·, 141
(53) [M –MeS]+, 95 (16) [MeSPOH]+, 94 (45)
[MeSPO]+·, 79 (17) [MeSPH]+, 77 (6) [CH2SP]+, 63
(8) [SP]+, 51 (25), 49 (75), 47 (100) [SMe]+, 46 (35)
[CH2S]+·, 45 (58) [HCS]+, 44 (22) [CHP]+, 43 (16).
2. Malysheva, S.F. and Arbuzova, S.N., Sovremennyi
organicheskii sintez (Modern Organic Synthesis),
Rakhmankulov, D.L., Ed., Moscow: Khimiya, 2003, p. 160.
3. Trofimov, B., Sukhov, B.G., Malysheva, S.F., and
Gusarova, N.K., Katal. Prom-sti, 2006, no. 4, p. 18.
1
Compound IV. Н NMR spectrum (CDCl3), δ,
4. Trofimov, B.A., Gusarova, N.K., Malysheva, S.F.,
Shaikhudinova, S.I., Belogorlova, N.A., Kazantseva, T.I.,
Sukhov, B.G., and Plotnikova, G.V., Russ. J. Gen.
Chem., 2005, vol. 75, no. 5, p. 684.
3
ppm: 2.42 d (9Н, Me, JНР 17.7 Hz). 31Р NMR
spectrum (CDCl3), δР, ppm: 100.2. Mass spectrum, m/z
(Irel, %): 204 (25) [M]+·, 157 (45) [M – MeS]+, 125 (26)
[(MeS)2P]+, 111 (11) [MeSPSH]+·, 110 (8) [MeSPS]+·,
94 (11), 79 (13) [MeSPH]+, 78 (5) [MeSP]+, 77 (11)
5. Trofimov, B.A., Gusarova, N.K., Malysheva, S.F.,
Kuimov, V.A., Sukhov, B.G., Shaikhudinova, S.I.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 9 2008