SYNTHESIS AND ANTIOXIDANT PROPERTIES OF UNSYMMETRICAL SULFIDES
1663
Butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)pro-
pyl sulfide IIe was prepared similarly to IIa from
5 g (17.8 mmol) of thiol Ib and 1.9 ml (18 mmol)
of 1-chlorobutane; yield 4.68 g (78%), bp 165 C
(1 mm Hg). 1H NMR spectrum (CDCl3), , ppm:
Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-
propyl sulfide IIh was prepared similarly to IIa from
5 g (17.8 mmol) of thiol Ib and 6.16 g (18.5 mmol)
of 1-bromooctadecane (synthesis time 8 h); yield
7.45 g (78%), mp 48 50 C. 1H NMR spectrum
0.89 0.92 t (3H, CH2 Me), 1.38 1.42 m (2H, (CDCl3), , ppm: 0.87 0.89 t (3H, (CH2)17 Me),
CH2Me), 1.43 s (18H, t-Bu), 1.53 1.59 m (2H,
CH2Et), 1.86 1.91 m (2H, ArCH2CH2), 2.50 2.52 t
(2H, SCH2Pr), 2.53 2.55 t (2H, CH2SBu), 2.61
2.64 t (2H, ArCH2), 5.03 s (1H, OH); 6.98 s (2H,
1.26 1.30 s [30H, (CH2)15 Me], 1.43 s (18H, t-Bu),
1.57 m (2H, CH2C16H33), 1.88 m (2H, ArCH2CH2),
2.50 2.56 m (4H, CH2SCH2), 2.61 2.69 t (2H,
ArCH2), 5.03 s (1H, OH), 6.98 s (2H, Ar H). IR
1
1
Ar H). IR spectrum (thin film), max, cm : 3646
spectrum (KBr), max, cm : 3645 (PhOH).
(PhOH).
Found, %: C 78.84, H 12.23, S 6.21.
C35H64OS.
Calculated, %: C 78.88, H 12.10, S 6.02.
Found, %: C 75.08, H 10.85, S 9.69.
C21H36OS.
Calculated, %: C 74.94, H 10.78, S 9.53.
Benzyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)pro-
pyl sulfide IIi was prepared similarly to IIa from 5 g
(17.8 mmol) of thiol Ib and 2.15 ml (18.7 mmol) of
benzyl chloride (synthesis time 0.5 h); yield 5.73 g
sec-Butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-
propyl sulfide IIf was prepared similarly to IIa from
5 g (17.8 mmol) of thiol Ib and 2 ml (18.3 mmol)
of 2-bromobutane; yield 4.33 g (72%), bp 151 C
(1 mm Hg). 1H NMR spectrum (CDCl3), , ppm:
1
(86%), mp 75 76 C. H NMR spectrum (CDCl3), ,
ppm: 1.42 s (18H, t-Bu), 1.85 m (2H, ArCH2CH2),
2.42 2.45 t (2H, CH2S), 2.57 2.60 t (2H, ArCH2),
3.69 s (2H, CH2Ph), 5.03 s (1H, OH); 6.94 s (2H,
Ar H); 7.26 7.28 m (5H, Ph). IR spectrum (KBr),
0.96 0.99
t (3H, CH2 Me), 1.24 1.26 d (3H,
SCHMe), 1.43 s (18H, t-Bu), 1.51 1.61 m (2H,
CH2Me), 1.87 1.89 m (2H, ArCH2CH2), 2.53 2.56 t
(2H, CH2S), 2.61 2.63 t (2H, ArCH2), 2.68 2.69 m
(1H, SCH), 5.03 s (1H, OH), 6.98 s (2H, Ar H). IR
1
max, cm : 3574 (PhOH).
1
spectrum (thin film), max, cm : 3647 (PhOH).
Found, %: C 77.91, H 9.19, S 8.79.
C24H34OS.
Found, %: C 74.98, H 10.89, S 9.72.
C21H36OS.
Calculated, %: C 77.78, H 9.25, S 8.65.
Calculated, %: C 74.94, H 10.78, S 9.53.
Butyl 4-(3,5-di-tert-butyl-4-hydroxyphenyl)butyl
sulfide IIj was prepared similarly to IIa from 5.7 g
(19.3 mmol) of thiol Ic and 2.2 ml (21.3 mmol) of
1-chlorobutane (synthesis time 4 h); yield 4.88 g
tert-Butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-
propyl sulfide IIg. A 120-ml ampule was charged with
5 g (17.8 mmol) of thiol Ib and 30 ml (270 mmol) of
2-bromo-2-methylpropane and kept at 150 C for 3 h
in a thermostat equipped with a shaker, after which it
was cooled. The reaction mixture was treated with
benzene. The extract was washed with water and dried
over Na2SO4; the solvent was distilled off. The prod-
uct was purified by column chromatography (silica
gel, hexane). Yield 2.60 g (43%), bp 157 160 C
1
(72%), bp 168 170 C (1 mm Hg). H NMR spectrum
(CDCl3), , ppm: 0.92 0.95 t (3H, CH2 Me), 1.42
1.42 m (2H, CH2Me), 1.46 s (18H, t-Bu), 1.56
1.62 m (2H, CH2Et), 1.71 m [4H, ArCH2(CH2)2],
2.55 2.56 m (4H, CH2SCH2), 2.64 t (2H, ArCH2),
5.03 s (1H, OH), 6.99 s (2H, Ar H). IR spectrum
1
(KBr), max, cm : 3645 (PhOH).
1
(1 mm Hg). H NMR spectrum (CDCl3), , ppm:
Found, %: C 75.61, H 11.09, S 9.32.
C22H38OS.
Calculated, %: C 75.36, H 10.92, S 9.15.
1.31 s (9H, S t-Bu), 1.43 s (18H, Ar t-Bu), 1.87 m
(2H, ArCH2CH2), 2.57 t (2H, CH2S), 2.66 t (2H,
ArCH2), 5.03 s (1H, OH), 6.98 s (2H, Ar H). IR
1
spectrum (KBr), max, cm : 3632 (PhOH).
Lard was oxidized at 130 C in an oxidation cell
with bubbling oxygen, as described in [14]. The
amount of lard placed in the cell was 50 g, and
the concentration of antioxidants, 1 mol per gram
of lard. The progress of oxidation was monitored
Found, %: C 74.87, H 10.91, S 9.94.
C21H36OS.
Calculated, %: C 74.94, H 10.78, S 9.53.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 10 2002