SYNTHESIS AND ANTIOXIDATIVE PROPERTIES
1901
30 ml of 1-butanol was refluxed for 5 h, after which 3650 (OH). UV spectrum (EtOH),
, nm (log ):
max
207 (3.88), 278 (3.28).
the solvent was distilled off, and the product was
washed with warm pentane, filtered off, and dried.
Found, %: C 73.09, H 10.13, S 11.20.
C17H28OS.
Calculated, %: C 72.80, H 10.06, S 11.43.
Yield of V 4.13 g (92%); colorless crystalline sub-
1
stance, mp 165 C. H NMR spectrum (CDCl ),
,
3
ppm: 1.430 s (18H, t-Bu), 2.048 m (2H, ArCH CH ),
2
2
2.726 t (2H, ArCH ), 3.123 t (2H, CH S), 7.146 s
2
2
S-[3-(3,5-Di-tert-butyl-4-hydroxyphenyl)propyl]
ethanethioate VIII. To a mixture of 5 g (17.8 mmol)
of I, 5 ml (35.6 mmol) of triethylamine, and 20 ml of
benzene, we added dropwise 1.3 ml (18.2 mmol) of
acetyl chloride. The mixture was refluxed for 2 h,
cooled, and treated with toluene. The extract was
washed with water and dried over Na SO , the solvent
1
(2H, H
). IR spectrum (KBr), , cm : 3644 (OH),
3263 and 3062 (NH ), 1650 (NH ). UV spectrum
arom
+
+
2
2
(EtOH),
, nm (log ): 209 (1.84), 276 (0.16).
max
Found, %: C 59.89, H 8.92, Cl 9.74, N 7.52, S 8.71.
C18H31ClN2OS.
Calculated, %: C 60.22, H 8.70, Cl 9.88, N 7.80, S 8.93.
2
4
was distilled off, and the reaction product was recrys-
tallized from ethanol. Yield of VIII 5.12 g (89%),
Butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)prop-
yl sulfide VI. A mixture of 7 g (19.5 mmol) of iso-
thiuronium chloride V, 1.72 g (43 mmol) of NaOH,
3.04 ml (29.3 mmol) of 1-chlorobutane, and 20 ml of
ethanol was stirred for 1 h at 20 C under argon and
then heated at 50 60 C for 2 h. The mixture was
treated with toluene. The extract was washed with
water and dried over Na SO , the solvent was distilled
1
mp 57 58 C. H NMR spectrum (CDCl ), , ppm:
3
1.428 1.446 s (18H, t-Bu), 1.851 1.881 m (2H,
ArCH CH ), 2.328 s (3H, COMe), 2.580 2.611 t (2H,
2
2
ArCH ), 2.893 2.921 t (2H, CH S), 5.040 s (1H,
2
2
OH), 6.952 s (2H, H
). IR spectrum (CCl ),
,
arom
4
1
cm : 3647 (OH), 1695 (C=O). UV spectrum (EtOH),
, nm (log ): 206 (2.18), 229 (0.94), 221 (0.92),
277 (0.18).
max
2
4
off, and the product was vacuum-distilled. Yield of VI
1
4.59 g (70%); bp 165 C (1 mm Hg). H NMR spec-
Found, %: C 70.82, H 9.36, S 9.77.
C19H30O2S.
Calculated, %: C 70.76, H 9.38, S 9.94.
trum (CDCl ), , ppm: 0.892 0.921 t (3H, CH Me),
3
2
1.380 1.416 m (2H, CH Me), 1.430 s (18H, t-Bu),
2
1.532 1.591 m (2H, CH Et), 1.862 1.908 m (2H,
ArCH CH ), 2.498 2.524 t (2H, SCH Pr), 2.528
2.553 t (2H, CH SBu), 2.610 2.641 t (2H, ArCH ),
5.030 s (1H, OH), 6.977 s (2H, H
2
2
2
2
1,4-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)
propylthio]butane IX. A mixture of 5.05 g (18 mmol)
od I and 1.3 g (19.7 mmol) of KOH was dissolved in
30 ml of ethanol, and 1.14 g (9 mmol) of 1,4-dichlo-
robutane was added. The mixture was refluxed for
2.5 h, cooled, and treated with toluene. The extract
was washed with water and dried over Na SO , the
2
2
). IR spectrum
arom
1
(CCl ), , cm : 3646 (OH). UV spectrum (EtOH),
4
max
, nm (log ): 208 (1.56), 277 (0.19).
Found, %: C 75.13, H 10.62, S 9.50.
C21H36OS.
Calculated, %: C 74.94, H 10.78, S 9.53.
2
4
solvent was distilled off, and the product was recrys-
tallized from ethanol. Yield of IX 4.0 g (72%), mp
1
64 65 C. H NMR spectrum (CDCl ), , ppm:
3
3-(3,5-Di-tert-butyl-4-hydroxyphenyl)-1-prop-
anethiol VII. A mixture of 30 g (106 mmol) of I,
9.7 g (127 mmol) of thiourea, and 100 ml of DMF
was heated at 130 C for 2 h. After cooling to 50 C,
a solution of 0.92 g (23 mmol) of NaOH in 3 ml of
water was added, and the mixture was stirred for 2 h
at 50 C, acidified with HCl, and treated with toluene.
The extract was washed with water and dried over
Na SO , the solvent was distilled off, and the reaction
1.430 s (36H, t-Bu), 1.691 m [4H, SCH (CH ) CH S],
1.871 m (4H, ArCH CH ), 2.526 2.556 m (8H,
SCH ), 2.603 2.635 t (4H, ArCH ), 5.030 s (2H,
OH), 6.970 s (4H, H
cm : 3643 (OH). UV spectrum (EtOH),
(log ): 210 (1.84), 277 (0.36).
2
2 2
2
2
2
2
2
). IR spectrum (KBr),
,
arom
1
, nm
max
Found, %: C 74.47, H 10.31, S 10.65.
C38H62O2S2.
Calculated, %: C 74.21, H 10.16, S 10.43.
2
4
product was vacuum-distilled. Yield of VII 25.3 g
1
(85%); mp 48, bp 138 145 C (1 2 mm Hg). H NMR
spectrum (CDCl ), , ppm: 1.132 s (1H, SH), 1.430 s
Oxidation of lard (50 g, Novosibirsk Meat Packing
and Canning Plant) was performed at 130 C in an
oxygen flow in an oxidation cell similar to that de-
scribed in [17]. In the course of oxidation, 1-g sam-
3
(18H, t-Bu), 1.912 m (2H, ArCH CH ); 2.257
2
2
2.756 m (4H, ArCH , CH S), 4.852 s (1H, OH),
2
2
1
6.871 s (2H, H
). IR spectrum (KBr), , cm :
arom
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 74 No. 11 2001