H. Firouzabadi et al.
Bull. Chem. Soc. Jpn. Vol. 83, No. 6 (2010)
701
Finnigan Flash EA-1112 series. Thin-layer chromatography
was carried out on silica gel 254 analytical sheets obtained
from Fluka. Column chromatography was performed on Merck
Kieselgel (70-230 mesh).
raphy using light petroleum ether as an eluent to provide the
pure desired product in good to excellent yields (Table 2,
Entries 8-15).
Typical Physical Data for Some of the Reported Com-
pounds: Bis(4-methylbenzyl) Disulfide (7); Colorless oil;
1H NMR (250 MHz, CDCl3): ¤ 7.05 (s, 8H), 3.52 (s, 4H), 2.25
(s, 6H); 13C NMR (62.5 MHz, CDCl3): ¤ 137.2, 134.4, 129.4,
129.3, 42.7, 21.3; Anal. Calcd for C16H18S2: C, 70.02; H, 6.61;
S, 23.37%. Found: C, 70.09; H, 6.58; S, 23.33%.
General Procedure for One-Pot Preparation of Symmet-
ric Disulfides from Alkyl Halides in SDS Micellar Solution
at 80 °C. To a micellar solution of SDS (1.2 mL, 0.2 M), alkyl
halide (4 mmol), thiourea (6 mmol), MnO2 (4 mmol), and
NaHCO3 (6 mmol) were added. The resulting mixture was
stirred magnetically at 80 °C while being monitored by GC
until the alkyl halide was consumed. After completion of the
reaction, the mixture was directly extracted three times with
low-boiling petroleum ether (3 © 3 mL). The organic layer
extracts were combined and dried over Na2SO4, filtered and
concentrated to yield the crude product, which was further
purified by silica gel column chromatography, using petroleum
ether to provide the desired product in good to excellent yields
(Table 2, Entries 1-11).
Typical Physical Data for Some of the Reported Com-
pounds: Didecyl Disulfide (1); Colorless oil; 1H NMR
(250 MHz, CDCl3): ¤ 2.63 (t, J = 7.3 Hz, 4H), 1.76-1.61 (m,
4H), 1.21 (broad band, 28H), 0.84-0.79 (m, 6H); 13C NMR
(62.5 MHz, CDCl3): ¤ 39.2, 31.9, 29.6, 29.5, 29.3, 29.3, 29.2,
28.5, 22.7, 14.1; Anal. Calcd for C20H42S2: C, 69.29; H, 12.21;
S, 18.50%. Found: C, 69.20; H, 12.24; S, 18.56%.
Bis(4-bromobenzyl) Disulfide (8);30
Colorless oil;
1H NMR (250 MHz, CDCl3): ¤ 7.35 (d, J = 8.3 Hz, 4H),
7.00 (d, J = 8.3 Hz, 4H), 3.46 (s, 4H); 13C NMR (62.5 MHz,
CDCl3): ¤ 136.3, 131.7, 131.2, 121.5, 42.5; Anal. Calcd for
C14H12Br2S2: C, 41.60; H, 2.99; S, 15.87%. Found: C, 41.66;
H, 2.90; S, 15.93%.
Bis(2-methyl-2-propenyl) Disulfide (11); Colorless oil;
1H NMR (250 MHz, CDCl3): ¤ 4.89-4.80 (m, 4H), 3.22 (s, 4H),
1.76 (s, 6H); 13C NMR (62.5 MHz, CDCl3): ¤ 140.7, 114.9,
46.4, 20.9; Anal. Calcd for C8H14S2: C, 55.12; H, 8.09; S,
36.79%. Found: C, 55.16; H, 8.01; S, 36.83%.
We gratefully acknowledge the partial support of this study
by Shiraz University Research Council and also by TWAS
Chapter of Iran based at ISMO.
Dioctyl Disulfide (2);42 Colorless oil; 1H NMR (250 MHz,
CDCl3): ¤ 2.61 (t, J = 7.3 Hz, 4H), 1.66-1.54 (m, 4H), 1.30-
1.21 (broad band, 20H), 0.84-0.79 (m, 6H); 13C NMR (62.5
MHz, CDCl3): ¤ 39.2, 31.8, 29.2, 29.2, 29.1, 28.5, 22.6, 14.1;
Anal. Calcd for C16H34S2: C, 66.14; H, 11.79; S, 22.07%.
Found: C, 66.21; H, 11.71; S, 22.08%.
Typical Large-Scale Procedure for One-Pot Preparation
of Dibutyl Disulfide from n-Butyl Bromide in SDS Micellar
Solution at 80 °C (Table 2, Entry 5). To a micellar solution
of SDS (12 mL, 0.2 M), thiourea (60 mmol, 4.57 g), n-butyl
bromide (40 mmol, 5.48 g), MnO2 (40 mmol, 3.48 g), and
NaHCO3 (60 mmol, 5.04 g) were added. The mixture was
stirred magnetically at 80 °C and the progress of the reaction
was monitored by GC until n-butyl bromide was consumed.
After completion of the reaction (5 h), the mixture was
extracted with petroleum ether (3 © 10 mL). The organic layers
were combined together and dried over Na2SO4, filtered and
concentrated to yield the crude product. The resulting crude
product was further purified by silica gel column chromatog-
raphy eluted with low-boiling petroleum ether to provide the
desired product in 3.10 g (87% yield).
References
1
2
3
B. Schmidt, S. Lindman, W. Tong, G. Lindeberg, A.
Gogoll, Z. Lai, M. Thörnwall, B. Synnergren, A. Nilsson, C. J.
Welch, M. Sohtell, C. Westerlund, F. Nyberg, A. Karlén, A.
4
S. Uemura, in Comprehensive Organic Synthesis, ed. by
B. M. Trost, I. Fleming, Pergamon, Oxford, 1991, Vol. 7, pp. 757-
787.
5
6
7
8
M. D. Porter, T. B. Bright, D. L. Allara, C. E. D. Chidsey,
9
E. B. Troughton, C. D. Bain, G. M. Whitesides, R. G.
10 R. Sudharsanam, S. Chandrasekaran, P. K. Das, J. Mater.
General Procedure for One-Pot Preparation of Benzylic
and Allylic Disulfides from Their Corresponding Halides in
SDS Micellar Solution at Room Temperature. To a micellar
solution of SDS (2 mL, 0.2 M), thiourea (6 mmol), benzyl or an
allyl halide (4 mmol), MnO2 (4 mmol), and Na2CO3 (6 mmol)
were added. The mixture was stirred magnetically at room
temperature and the progress of the reaction was monitored by
TLC until the halide was consumed (10 h). After completion of
the reaction, the mixture was directly extracted with petroleum
ether (3 © 3 mL). The organic layers were decanted and
combined together, dried over Na2SO4, filtered and concen-
trated to yield the crude product. Further purification of the
crude product was performed by silica gel column chromatog-
12 S. Kodama, E. Nishinaka, A. Nomoto, M. Sonoda, A.
15 B. Movassagh, Y. Zakinezhad, Z. Naturforsch., B: Chem.
Sci. 2006, 61, 47.
17 A. Bartolozzi, H. M. Foudoulakis, B. M. Cole, Synthesis
18 K. R. Prabhu, P. S. Sivanand, S. Chandrasekaran, Angew.
19 B. Movassagh, S. Sobhani, F. Kheirdoush, Z. Fadaei, Synth.