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M. Clericuzio et al.
PAPER
2.38–2.58 (m, 4 H, 2 SCH2), 2.84 (t, J = 7.2 Hz, 2 H, COSCH2),
7.23–7.43 and 7.61–7.66 (2 m, 4:1, 5 H, Ar).
and CHCH2), 2.85 (t, J = 7.2 Hz, 2 H, COSCH2), 7.10 and 7.38 (2
d, 1:1, J = 8.2 Hz, 4 H, Ar).
MS: m/z = 384 (M+).
MS: m/z = 249 (M+ – COSBu).
Anal. Calcd for C20H32OS3 (384.65): C, 62.45; H, 8.39; S, 25.00.
Found: C, 62.39; H, 8.30; S, 25.10.
Anal. Calcd for C21H34OS2 (366.62): C, 68.80; H, 9.35; S, 17.49.
Found: C, 68.72; H, 9.40; S, 17.55.
S-Butyl Bis(butylsulfanyl)(3-benzoylphenyl)thioacetate (9h)
2,2,2-Tris(butylsulfanyl)-1-(3-benzoylphenyl)ethanone (6h; 4.88 g,
10 mmol); PE-Et2O (9.5:0.5); Procedure A, yield: 67% (3.27 g),
Procedure B, yield: 92% (4.49 g); bp 212-213 °C/0.2 mbar.
S-Butyl -(3-Benzoylphenyl)- -(butylsulfanyl)thiopropionate
(12h)
S-Butyl bis(butylsulfanyl)(3-benzoylphenyl)thioacetate (9h; 4.88 g,
10 mmol); PE–Et2O (9.5:0.5); yield: 74% (3.06 g); bp 194–195 °C/
0.1 mbar.
IR (CCl4): 1659.7, 1668.1 (2 CO) cm–1.
1H NMR (200 Hz, CDCl3): = 0.82 (t, J = 6.7 Hz, 3 H, Me), 0.89
(t, J = 7.0 Hz, 3 H, Me), 1.25–1.61 (m, 8 H, 2 CH2CH2Me), 1.90
(s, 3 H, Me), 2.37–2.55 (m, 2 H, SCH2), 2.86 (t, J = 7.2 Hz, 2 H,
COSCH2), 7.41–7.61, 7.69–7.81 and 7.92 (3 m, 4:4:1, 9 H, Ar).
IR (CCl4): 1660.4, 1666.3 (2 CO) cm–1.
1H NMR (200 MHz, CDCl3): = 0.87 (t, J = 7.0 Hz, 6 H, 2 Me),
0.89 (t, J = 6.9 Hz, 3 H, Me), 1.27–1.57 (m, 12 H, 3 CH2CH2Me),
2.43–2.55 (m, 4 H, 2 SCH2), 2.86 (t, J = 7.0 Hz, 2 H, COSCH2),
7.45–7.61, 7.75–7.91 and 8.04–8.06 (3 m, 4:4:1, 9 H, Ar).
MS: m/z = 399 (M+ – SBu).
MS: m/z = 297 (M+ – COSBu).
Anal. Calcd for C27H36O2S3 (488.76): C, 66.35; H, 7.42; S, 19.68.
Found: C, 66.40; H, 7.49; S, 19.64.
Anal. Calcd for C24H30O2S2 (414.62): C, 69.52; H, 7.29; S, 15.46.
Found: C, 69.60; H, 7.35; S, 15.44.
S-Ethyl -(4-Isobutylphenyl)- -(ethylsulfanyl)thiopropionate
(11b)
S-Ethyl -(4-Isobutylphenyl)thiopropionate (14b)
Prepared according to the general procedure for S-methyl -aryl- -
(methylsulfanyl)thiopropionates 10, starting from the above pre-
pared S-ethyl bis(ethylsulfanyl)(4-isobutylphenyl)thioacetate (8b;
3.56 g, 10 mmol). Chromatographic solvent: PE–Et2O (9.8:0.2);
yield: 81% (2.39 g); bp 149–150 °C/0.3 mbar.
Prepared according to the general procedure for S-methyl -arylth-
iopropionates 13, starting from the above prepared S-ethyl -(4-
isobutylphenyl)- -(ethylsulfanyl)thiopropionate (11b; 3.10 g, 10
mmol) and sodium ethanethiolate (1.01 g, 12 mmol) in anhyd
MeCN (20 mL). The reaction was complete after 60 min at r.t. GC–
MS analysis of the reaction mixture revealed the presence of the by-
product diethyl disulfide, MS: m/z = 122 (M+). The crude residue,
obtained after the usual work up, was the virtually pure (GC, TLC,
1H NMR) title compound 14b. No device was adopted to avoid the
loss of diethyl disulfide during the evaporation of the solvent. Yield
of 14b was 82% (2.05 g); bp 121–122 °C/0.3 mbar.
IR (CCl4): 1665.7 (CO) cm–1.
1H NMR (CDCl3): = 0.88 (d, J = 6.4 Hz, 6 H, 2 Me), 1.18 (t,
J = 7.1 Hz, 3 H, Me), 1.22 (t, J = 7.1 Hz, 3 H, Me), 1.40–2.05 (m, 1
H, CH), 1.90 (s, 3 H, Me), 2.46 (d, J = 6.6 Hz, 2 H, CH2), 2.50 (q,
J = 7.0 Hz, 2 H, SCH2), 2.95 (q, J = 7.1 Hz, 2 H, COSCH2), 7.05
and 7.35 (2 d, 1:1, J = 8.1 Hz, 4 H, Ar).
IR (CCl4): 1671.7 (CO) cm–1.
MS: m/z = 310 (M+).
1H NMR (CDCl3): = 0.98 (d, J = 6.4 Hz, 6 H, 2 Me), 1.15–1.70
(m, 6 H, 2 Me), 1.70–2.20 (m, 1 H, CH), 2.55 (d, J = 6.4 Hz, 2 H,
CH2), 2.94 (q, J = 7.0 Hz, 2 H, SCH2), 3.95 (q, J = 7.0 Hz, 1 H, CH),
7.05–7.40 (m, 4 H, Ar).
Anal. Calcd for C17H26OS2 (310.51): C, 65.76; H, 8.44; S, 20.65.
Found: C, 65.85; H, 8.50; S, 20.73.
According to the same procedure compounds 12a,b,h were also
prepared. Starting compounds, chromatographic solvents, yields,
physical, spectral and analytical data are given below.
MS: m/z = 250 (M+).
Anal. Calcd for C15H22OS (250.39): C, 71.95; H, 8.86; S, 12.80.
Found: C, 72.04; H, 8.93; S, 12.88.
S-Butyl -(Phenyl)- -(butylsulfanyl)thiopropionate (12a)
S-butyl bis(butylsulfanyl)(phenyl)thioacetate (9a; 3.84 g, 10
mmol); PE–Et2O (9.8:0.2); yield: quantitative (3.10 g); bp 160–
161 °C/0.3 mbar.
S-Butyl -(Phenyl)thiopropionate (15a)
Prepared according to the general procedure for S-methyl -arylth-
iopropionates 13, starting from the above prepared S-butyl -(phe-
nyl)- -(butylsulfanyl)thiopropionate (12b; 3.10 g, 10 mmol) and
sodium butanethiolate (1.34 g, 12 mmol) in anhyd MeCN (20 mL).
The reaction was complete after 60 min at r.t. GC–MS analysis of
the reaction mixture revealed the presence of the by-product dibutyl
disulfide, MS: m/z = 178 (M+). The crude residue, obtained after the
usual work up, was column chromatographed, using PE–Et2O
(9.8:0.2), as eluent. The pure title compound 14b was obtained in
93% yield (2.06 g); bp 116–117 °C/0.35 mbar.
IR (CCl4): 1662.1 (CO) cm–1.
1H NMR (200 MHz, CDCl3): = 0.88 (t, J = 7.1 Hz, 3 H, Me), 0.92
(t, J = 7.1 Hz, 3 H, Me), 1.30–1.64 (m, 8 H, 2 CH2CH2Me), 1.89
(s, 3 H, Me), 2.38–2.56 (m, 2 H, SCH2), 2.87 (t, J = 7.2 Hz, 2 H,
COSCH2), 7.24–7.39 and 7.46–7.52 (2 m, 3:2, 5 H, Ar).
MS: m/z = 310 (M+).
Anal. Calcd for C17H26OS2 (310.51): C, 65.76; H, 8.44; S, 20.65.
Found: C, 65.68; H, 8.40; S, 20.68.
IR (CCl4): 1684.0 (CO) cm–1.
1H NMR (200 MHz, CDCl3): = 0.89 (t, J = 7.2 Hz, 3 H, Me),
1.29–1.59 (m, 4 H, CH2CH2Me), 1.54 (d, J = 7.1 Hz, 3 H, Me),
2.79–2.88 (m, 2 H, SCH2), 3.89 (q, J = 7.1 Hz, 1 H, CH), 7.27–7.35
(m, 5 H, Ar).
S-Butyl -(4-Isobutylphenyl)- -(butylsulfanyl)thiopropionate
(12b)
S-Butyl bis(butylsulfanyl)(4-isobutylphenyl)thioacetate (9b; 4.40
g, 10 mmol); PE–CH2Cl2 (4:1); yield: 94% (3.44 g); bp 163–
164 °C/0.5 mbar.
MS: m/z = 222 (M+).
IR (CCl4): 1668.1 (CO) cm–1.
Anal. Calcd for C13H18OS (222.34): C, 70.23; H, 8.16; S, 14.42.
Found: C, 70.30; H, 8.22; S, 14.42.
1H NMR (200 MHz, CDCl3): = 0.81–0.94 (m, 6 H, 2 Me), 0.89
(d, J = 6.5 Hz, 6 H, 2 Me), 1.26–1.59 (m, 8 H, 2 CH2CH2Me),
1.76–1.96 (m, 1 H, CH), 1.88 (s, 3 H, Me), 2.40–2.55 (m, 4 H, SCH2
In a collateral proof, compound 12b (3.10 g, 10 mmol) was treated,
in the above conditions, with sodium methanethiolate (0.84 g, 12
Synthesis 2002, No. 7, 921–927 ISSN 0039-7881 © Thieme Stuttgart · New York