1
344
LEVANOVA et al.
+
(
26), 109 (100) (PhS ), 91 (8), 77 (18), 75 (19), 65 (19).
complete (see above), the mixture was cooled to 25°C,
3.56 g (0.03 mol) of 2,3-dichloroprop-1-ene (I) was
added, and the mixture was stirred for 19 h at 60°C,
cooled, and extracted with methylene chloride. Eva-
poration of the extract gave 4.7 g of bis(phenyl-
sulfanyl)propene V. The aqueous hydrazine layer was
treated with 4.4 g (0.03 mol) of methyl iodide, the
mixture was stirred for 4 h at 25–30°C and extracted
with diethyl ether (3×50 ml), and the extract was dried
Found, %: C 58.33; H 4.73; S 17.11; Cl 19.13. C H SCl.
9
9
Calculated, %: C 58.53; H 4.91; S 17.36; Cl 19.20.
-Phenylsulfanylpropadiene (III). IR spectrum: ν
1
–
1
1
1
941 cm (C=C=C). H NMR spectrum, δ, ppm: 5.00
4
d (2H, CH =), 5.96 t (1H, =CHS, J = 6.2 Hz), 7.32 m
2
1
3
(
7
5H, C H ) (cf. [7]). C NMR spectrum, δ , ppm:
6
5
C
8.65 (CH =), 85.94 (=CHS), 209.32 (=C=). The mass
2
spectrum of III is given in text.
over MgSO and evaporated to obtain 2.2 g (28%) of
4
1
-Phenylsulfanylprop-1-yne (IV) was isolated in
2% yield in the reaction of 2,3-dichloroprop-1-ene (I)
7.13 g, 0.06 mol) with Ph S (7.0 g, 0.03 mol) at 60°C.
thioanisole (VI). bp 76–78°C (15 mm); published data
2
(
1
[
12]: bp 78–79°C (15 mm). H NMR spectrum, δ,
13
2
2
ppm: 2.42 s (CH ), 7.22 s (H ). C NMR spectrum,
3
arom
After extraction and removal of the solvent, the residue
p
δ , ppm: 15.83 (CH ), 125.02 (C ), 126.73 and 128.79
C
3
(
5.45 g) contained ~2.1 g of sulfide IV, traces of III,
o
m
i
+
(
C , C ), 138.50 (C ). Mass spectrum: m/z 124 [M] .
and 3.35 g of bis(phenylsulfanyl)propene V. Pure
sulfide IV was isolated by distillation; yield 1.2 g, bp
REFERENCES
7
[
5–76°C (1.5 mm); published data: bp 83°C (2 mm)
–1
1. Levanova, E.P., Grabel’nykh, V.A., Russavskaya, N.V.,
Klyba, L.V., Zhanchipova, E.R., Albanov, A.I.,
Tarasova, O.A., and Korchevin, N.A., Russ. J. Gen.
Chem., 2009, vol. 79, no. 6, p. 1097.
10], 78–81°C (0.75 mm) [11]. IR spectrum: ν 2203 cm ,
1
w (C≡C). H NMR spectrum, δ, ppm: 2.07 s (3H,
1
3
CH ), 7.29 m (5H, C H ), (cf. [7, 10]). C NMR
3
6
5
spectrum, δ , ppm: 5.18 (CH ), 63.85 (≡C–S), 95.33
C
3
2
3
4
. Levanova, E.P., Grabel’nykh, V.A., Russavskaya, N.V.,
Albanov, A.I., Elaev, A.V., Tarasova, O.A., and Kor-
chevin, N.A., Russ. J. Gen. Chem., 2011, vol. 81, no. 7,
p. 1560.
. Levanova, E.P., Vshivtsev, V.Yu., Grabel’nykh, V.A.,
Sukhomazova, E.N., Russavskaya, N.V., Albanov, A.I.,
Tarasova, O.A., and Korchevin, N.A., Russ. J. Gen.
Chem., 2008, vol. 78, no. 10, p. 1980.
. Deryagina, E.N., Russavskaya, N.V., Papernaya, L.K.,
Levanova, E.P., Sukhomazova, E.N., and Korchevin, N.A.,
Izv. Akad. Nauk, Ser. Khim., 2005, no. 11, p. 2395.
. Deryagina, E.N., Korchevin, N.A., and Papernaya, L.K.,
Russ. J. Gen. Chem., 1997, vol. 67, no. 5, p. 812.
. Acetylenes, Viehe, H.G., Ed., New York: Marcel
Dekker, 1969.
m
p
o
(
(
CH C≡), 125.81 (C ), 126.08 (C ), 129.00 (C ), 133.54
3
i
C ). Signals from the triple-bonded carbon atoms were
13
assigned on the basis of the C NMR spectrum recorded
without decoupling from protons but with NOE: the
3
signal at δ 63.85 ppm was a quartet with J = 5.2 Hz,
C
CH
2
and the signal at δ 95.33 ppm was a quartet with J
=
C
CH
1
0.6 Hz. The mass spectrum of IV is given in text.
(
Z)-1,2-Bis(phenylsulfanyl)prop-1-ene (V) was
isolated by distillation of the still residue after
distillation of sulfide IV, bp 184–185°C (2 mm). IR
5
6
7
–1
spectrum, ν, cm : 3073, 3058, 3019, 2970, 2950, 2912,
2
868, 2849, 1583, 1478, 1439, 1374, 1321, 1306, 1257,
1
178, 1157, 1105, 1090, 1069, 1024, 1008, 906, 740, 690,
1
6
29, 590, 564, 532, 487, 470. H NMR spectrum, δ,
. Brownbridge, P., Hunt, P.G., and Warren, S., J. Chem.
Soc. Perkin Trans. 1, 1986, no. 9, p. 1695.
4
ppm: 1.89 d (3H, CH , J = 1.3 Hz), 6.36 q (1H, HC=,
3
4
13
J = 1.3 Hz), 7.22 m (10H, C H ). C NMR spectrum,
6
5
8. Polyakova, A.A. and Khmel’nitskii, R.A., Mass-
spektrometriya v organicheskoi khimii (Mass Spectro-
metry in Organic Chemistry), Leningrad: Khimiya, 1972.
9. Lebedev, A.T., Mass-spektrometriya v organicheskoi
khimii (Mass Spectrometry in Organic Chemistry),
Moscow: BINOM, 2003.
δ , ppm: 24.00 (CH ), 126.20 (HC=), 131.63 (CH C=);
C
3
3
p
m
1
1
26.71 and 127.30 (C ), 128.97 and 131.75 (C ),
o
i
29.46 and 129.07 (C ), 133.17 and 135.92 (C ) (the
first value refers to the PhS group located near the CH
3
+
group). Mass spectrum, m/z (I , %): 258 (100) [M] ,
rel
1
0. Filippova, A.Kh., Lyashenko, G.S., Kalikhman, I.D.,
Pestunovich, V.A., Nikol’skaya, S.A., and Voronkov,
M.G., Zh. Org. Khim., 1976, vol. 12, no. 4, p. 756.
1
1
7
99 (8), 186 (7), 167 (43), 149 (60), 148 (23), 147 (33),
34 (55), 121 (9), 115 (23), 109 (29), 105 (16), 91 (7),
7 (16), 65 (19). Found, %: C 69.46; H 5.68; S 24.56.
11. Parham, W.E. and Stright, P.L., J. Am. Chem. Soc.,
C H S . Calculated, %: C 69.72; H 5.46; S 24.81.
1
5
14 2
1
956, vol. 78, no. 18, p. 4783.
Methylsulfanylbenzene (VI). Diphenyl disulfide,
.0 g (0.03 mol), was added to a solution of 9.0 g
0.16 mol) of potassium hydroxide in 40 ml of
hydrazine hydrate. After the reduction of Ph S was
1
2. Aivazov, B.V., Petrov, S.M., Khairullina, V.R., and
Yapryntseva, V.G., Fiziko-khimicheskie konstanty seraor-
ganicheskikh soedinenii (Physicochemical Constants of
Organosulfur Compounds), Moscow: Khimiya, 1964.
7
(
2
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 7 2013