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TROFIMOV et al.
85% ç3êé4 as internal and external reference, respec-
tively. IR spectra were recorded on a Bruker ISF-25
spectrophotometer. Mass spectra with electronic ion-
ization (70 eV) were obtained on a Shimadzu GCMS-
Potassium S,S-dibutyl trithiophosphate (IIa) was
obtained similarly to salt IIb. Yield 0.42 g (13%,
butanethiol conversion is 87%), white crystals, mp 98–
100°C. For C8H18KOPS3 anal. calcd. (%): C, 32.41; H,
QP5050A instrument (quadrupole mass analyzer, 6.12; P, 10.45; S, 32.44. Found (%): C, 32.90; H, 5.94;
1
detected mass range 34–450, capillary column, SPB-5
phase). X-ray diffraction study of crystals of IIa was
performed at 123 K on a Bruker SMART APEX2 CCD
diffractometer (MoKα radiation). GLC analysis was
carried out on a LKhM-8MD chromatograph (column
1.2 m × 3 mm), 1% of PEG 20000 on NaCl, column
temperature 100°C, injector temperature 250°ë,
helium carrier gas, flow rate 2 L/h).
P, 9.97; S, 32.47. H NMR (CDCl3, δê, ppm): 0.92 (t,
6H, Me, 3JHH = 7.29 Hz), 1.42 (m, 4H, CH2Me), 1.67
(m, 4H, CH2CH2S), 2.90 (m, 4H, CH2S). 13C NMR
(CDCl3, δê, ppm): 13.42 (Me), 21.85 (CH2), 31.69 (d,
CH2, JCP = 5.53), 35.24 (d, CH2, JCP = 2.58). 31ê NMR
(CDCl3, δê, ppm): 85.6. IR (KBr, ν, cm–1): 645 (P=S).
The conversion of red phosphorus was 85%, the yield
of dibutyl disulfide was 50%. The main crystallo-
graphic and experimental data for IIa: C8H18KOPS3,
M = 296.47, orthorhombic, space group Iba2, a =
16.772(4), b = 24.884(7), c = 6.872(2) Å, U =
2867.8(1) Å3, Z = 8, Dcalcd =1.37 g m–3, µ = 0.890 mm–1,
2θmax = 49.42°, 6618 total reflections, 2296 reflections
measured, 127 refined parameters, R = 0.089 for
1422 reflections with F0 > 4σ(F0).
General procedure for the synthesis of trithio-
phosphates IV–VI.A solution of organyl halide (CH3I,
CH2=CHCH2Br, 2.0 mmol) in 1 mL of tetrahydrofuran
(THF) was added to a solution of potassium S,S-dialkyl
trithiophosphate (1.0 mmol) in 4 mL of THF. The reac-
tion mixture was stirred at ambient temperature for 1 h,
the resulting precipitate was filtered off, the THF was
removed from the filtrate at reduced pressure, and the
residue was dried in vacuum.
General procedure for the synthesis of salts IIa
and IIb. A mixture of 2.38 g (36.6 mmol) of pulverized
KOH · 0.5ç2é and 4.84 g (36.6 mmol) of C7H15SH in
50 mL of DMSO was heated with stirring at 60°ë until
complete homogenization. Red phosphorus (0.71 g,
22.9 mmol) was added to the obtained potassium thi-
olate solution and the reaction mixture was stirred at
125–128°ë for 4 h, evolution of êç3 is observed (qual-
itative reaction with aqueous solution of CuSO4). The
reaction mixture was cooled and filtered, the precipitate
was washed on filter with DMSO (10 mL), H2O
(10 mL), acetone (10 mL), ether (10 mL), dried in vac-
uum to give 0.16 g of red phosphorus (conversion is
78%). The filtrate was combined with DMSO and H2O
washings and analyzed by NMR and GLC. 31P NMR
1
spectrum showed signals at (δ, ppm) 3.4 (t, JPH
=
464 Hz), 73.6, 98.1, and 118.5 in 70 : 26 : 3 : 1 ratio
related to KH2PO2, (C7H15S)2P(S)OK (IIb),
(C7H15S)3P(S) (IIIb), and (C7H15S)3P (Ib), respec-
tively. According to GLC data, the filtrate contains also
0.45 g of Me2S, 0.45 g of C7H15SH (conversion is
91%), and 0.57 g (12%, hereinafter the yield is calcu-
lated with an allowance for the conversion of the thiol)
of C7H15SMe (as a result of the known reaction of thiols
with KOH–DMSO system [15], identified by compari-
son with authentic sample by GLC and GC–MS). The
filtrate was diluted with water (1 : 1), treated with 5%
aqueous solution of hydrochloric acid to pH 4,
extracted with ether (5 × 30 mL), the extract was
washed with water (5 × 30 mL) and dried with K2CO3.
The ether was distilled off at atmospheric pressure,
C7H15SH and C7H15SMe were distilled in a vacuum.
The residue was washed with hexane (5 × 5 mL) and
dried in vacuum to give 0.63 g (15%) of potassium
diheptyl trithiophosphate (IIb) as white crystals, mp
114–116°C. For C14H30KOPS3 anal. calcd. (%): C,
44.17; H, 7.94; P, 8.14; S, 25.27. Found (%): C, 43.77;
H, 7.65; P, 7.72; S, 24.79. 1H NMR (CDCl3, δê, ppm):
S,S-Dibutyl S-methyl trithiophosphate (IV).
Yield 0.26 g (95%), yellow oil. For ë9ç21OêS3 anal.
calcd. (%): C, 39.68; H, 7.77; P, 11.37; S, 35.31. Found
1
(%): C, 39.55; H, 7.40; P, 10.89; S, 34.97. H NMR
3
(CDCl3, δê, ppm): 0.93 (t, 6H, Me, JHH = 7.29 Hz),
1.43 (m, 4H, CH2Me), 1.73 (m, 4H, CH2CH2S), 2.41
(d, 3H, MeS, 3JPH = 15.87 Hz), 2.98 (m, 4H, CH2S). 31ê
NMR (CDCl3, δê, ppm): 61.9. IR (KBr, ν, cm–1): 1202
(P=O). MS (m/z): 272 [å]+•.
S-Allyl S,S-dibutyl trithiophosphate (V). Yield
0.29 g (97%), light yellow liquid. For C11H23OPS3 anal.
calcd. (%): C, 44.26; H, 7.77; P, 10.38; S, 32.23. Found
1
(%): C, 44.45; H, 8.01; P, 10.78; S, 32.69. H NMR
3
(CDCl3, δê, ppm): 0.93 (t, 6H, Me, JHH = 7.29 Hz),
1.44 (m, 4H, CH2Me), 1.73 (m, 4H, CH2CH2S), 2.99
(m, 4H, CH2CH2S), 3.62 (m, 2H, CH2=CHCH2S),
3
5.17 (d, 1H, Hcis, =CH2, JHH = 9.86 Hz), 5.29 (d, 1H,
3
H
trans, =CH2, JHH = 16.77 Hz), 5.94 (m, 1H, =CH).
31ê NMR (CDCl3, δê, ppm): 64.9. IR (film, ν, cm–1):
1201 (P=O).
3
0.89 (t, 6H, Me, JHH = 6.72 Hz), 1.20–1.45 (m, 16H,
S,S-Diheptyl S-methyl trithiophosphate (VI).
Yield 0.22 g (62%), yellow oil. For C15H33OPS3 anal.
calcd. (%): C, 50.52; H, 9.33; P, 8.69; S, 26.98. Found
CH2), 1.68 (m, 4H, CH2CH2S), 2.88 (m, 4H, CH2S).
31ê NMR (CDCl3, δê, ppm): 86.5. IR (KBr, ν, cm–1):
635 (P=S). The hexane was distilled off, and the residue
was dried in a vacuum to give 2.44 g (56%) of diheptyl
disulfide.
1
(%): C, 45.01; H, 7.93; P, 6.31; S, 30.76. H NMR
3
(CDCl3, δ, ppm): 0.88 (t, 6H, Me, JHH = 6.68 Hz),
DOKLADY CHEMISTRY Vol. 427 Part 1 2009