SYNTHESIS OF NEW SULFANYL-, SULFINYL-, AND SULFONYL-...
901
(SO2), 1605, 1557 (C=C). UV spectrum (CHCl3):
λmax 251 nm (logε 4.24). H NMR spectrum, δ, ppm:
3.65 g (26.4 mmol) of 2,4-dimethylbenzenethiol in
30 mL of ethanol, and the mixture was stirred for 24 h
at room temperature. The mixture was treated with
~50 mL of water and extracted with chloroform (3×
40 mL), the combined extracts were dried over Na2SO4
and evaporated, and the residue was subjected to silica
gel column chromatography with n-hexane as eluent to
isolate compounds 8a and 9a.
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2.39 s (3H, CH3), 2.49 s (3H, CH3), 7.17 d (1H, Harom
,
J = 7.81 Hz), 7.31 d (1H, Harom, J = 7.81 Hz), 7.87 s
(1H, Harom). 13C NMR spectrum (APT), δC, ppm: 19.77
(CH3), 21.07 (CH3), 119.11, 124.19, 126.25, 131.09,
131.42, 132.87, 135.73, 135.91, 136.07, 136.79. Mass
spectrum (EI): m/z 393.8. Found, %: C 36.51; H 2.30;
S 8.11. C12H9Cl5O2S. Calculated, %: C 36.53; H 2.30;
S 8.13. M 394.53.
Compound 8a. Yield 1.87 g (40%), yellow oil,
Rf 0.8 (CHCl3–n-hexane, 1:2). IR spectrum, ν, cm–1:
1601, 1543 (C=C). UV spectrum, λmax, nm (logε): 244
(4.39), 321 (4.29). 13C NMR spectrum, δC, ppm: 19.12,
19.35, 19.66, 20.15 (CH3); 108.76, 119.48, 119.81,
126.00, 126.29, 126.39, 126.58, 130.15, 130.42,
130.52, 132.13, 133.86, 133.94, 134.08, 134.69,
134.88, 138.09, 138.83, 138.90, 140.51, 141.16. Mass
spectrum (+ESI): m/z 531.0 [M + H]+. Found, %:
C 63.24; H 5.30; S 18.08. C28H28Cl2S3. Calculated, %:
C 63.26; H 5.31; S 18.09. M + H 531.63.
1,1,2,3,4-Pentachloro-4-(heptane-1-sulfinyl)-
buta-1,3-diene (5d) and 1,1,2,3,4-pentachloro-4-
(heptane-1-sulfonyl)buta-1,3-diene (6d). A solution
of 0.2 g (0.56 mmol) of sulfide 3d in 10 mL of chloro-
form was added at 0°C to a solution of 0.19 g
(1.12 mmol) of m-chloroperoxybenzoic acid in 10 mL
of chloroform, and the mixture was stirred for 96 h at
0°C. The mixture was then treated as described above
for 5b and 6b to isolate sulfoxide 5d and sulfone 6d.
Compound 5d. Yield 136 mg (65%), light yellow
oil, Rf 0.5 (CHCl3). IR spectrum, ν, cm–1: 1077 (S=O),
1611, 1559 (C=C), 2856, 2926 (C–H). UV spectrum:
Compound 9a. Yield 0.23 g (8%), light yellow oil,
Rf 0.6 (n-hexane). IR spectrum, ν, cm–1: 1566, 1602
(C=C). UV spectrum, λmax, nm (logε): 268 (4.06), 239
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λmax 242 nm (logε 3.89). H NMR spectrum, δ, ppm:
(4.01). H NMR spectrum, δ, ppm: 2.24 s (3H, CH3),
0.82 t (3H, CH3), 1.16–1.32 m (6H, CH2), 1.33–1.48 m
(2H, CH2), 1.68 quint (2H, CH2), 2.76–3.00 m (2H,
CH2). 13C NMR spectrum, δC, ppm: 14.20 (CH3);
22.44, 22.70, 28.86, 28.98, 31.65, 52.99 (CH2); 123.21,
126.86, 131.06, 142.55 (C=C). Mass spectrum (+ESI):
m/z 372.8 [M + H]+. Found, %: C 35.44; H 4.06;
S 8.60. C11H15Cl5OS. Calculated, %: C 35.46; H 4.06;
S 8.61. M 372.57.
2.31 s (3H, CH3), 6.42 s (1H, 2′-H), 6.92 d.d (1H,
3
4
H
arom, J = 7.80, J = 1.46 Hz), 6.99 s (1H, Harom),
7.27 d (1H, Harom, J = 7.81 Hz). 13C NMR spectrum
(APT), δC, ppm: 20.96, 21.45 (CH3); 123.88 (C2′);
127.72, 131.84, 135.52 (CHarom); 122.24, 124.79,
126.52, 138.57, 140.39, 142.04. Mass spectrum (EI),
m/z (Irel, %): 328.0 (50), 293.1 (38), 256.1 (100), 220.1
(30), 148.1 (40), 105.1 (55), 77.0 (69). Found, %:
C 43.92; H 3.06; S 9.75. C12H10Cl4S. Calculated, %:
C 43.93; H 3.07; S 9.77. M 328.09.
Compound 6d. Yield 20 mg (10%), light yellow oil,
Rf 0.8 (CHCl3). IR spectrum, ν, cm–1: 1341, 1143
(SO2), 1603 (C=C), 2857, 2926 (C–H). UV spectrum:
2,4-Dimethyl-1-(1,3,4,4-tetrachlorobuta-1,3-di-
ene-1-sulfinyl)benzene (11a). A solution of 70 mg
(0.21 mmol) of compound 9a in 10 mL of chloroform
was added at 0°C to a solution of 36 mg (0.21 mmol)
of m-chloroperoxybenzoic acid in 10 mL of chloro-
form, and the mixture was stirred for 48 h at 0°C. The
mixture was then treated with 2 N NaOH and washed
with water, the organic layer was separated, dried over
Na2SO4, and evaporated, and the residue was purified
by silica gel column chromatography with n-hexane as
eluent. Yield 60 mg (81%), yellow oil, Rf 0.6 (CHCl3).
IR spectrum, ν, cm–1: 1074 (S=O), 1603 (C=C).
1H NMR spectrum, δ, ppm: 2.30 s (3H, CH3), 2.48 s
(3H, CH3), 7.0 s (1H, 2′-H), 7.12 d (1H, Harom), 7.45 s
(1H, Harom), 7.53 d (1H, Harom). Mass spectrum (+ESI):
m/z 344.9 [M + H]+; calculated for C12H10Cl4OS:
M 344.1.
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λmax 250 nm (logε 4.05). H NMR spectrum, δ, ppm:
3.28 t (2H, CH2S, J = 7.81 Hz), 1.78 quint (2H, CH2,
J = 7.81 Hz), 1.39 quint (2H, CH2, J = 7.32 Hz),
1.23 m (6H, CH2), 0.82 t (3H, CH3, J = 6.83 Hz).
13C NMR spectrum (APT), δC 14.19 (CH3), 22.31,
22.68, 28.38, 28.83, 31.55, 54.29 (CH2); 124.00,
126.33, 132.69, 134.78 (C=C). Mass spectrum (EI):
m/z 388.0 [M]+. Found, %: C 34.01; H 3.87; S 8.23.
C11H15Cl5O2S. Calculated, %: C 34.00; H 3.89; S 8.25.
M 388.57.
1,1′,1″-[3,4-Dichlorobuta-1,3-diene-1,1,4-triyl-
tris(sulfanediyl)]tris(2,4-dimethylbenzene) (8a) and
2,4-dimethyl-1-(1,3,4,4-tetrachlorobuta-1,3-dien-1-
ylsulfanyl)benzene (9a). A solution of 1.4 g of sodi-
um hydroxide in 10 mL of water was added to a mix-
ture of 2.0 g (8.8 mmol) of pentachlorobutadiene 7 and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 6 2016