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KSENDZOVA et al.
4,6-Di-tert-butyl-3-(4-methylphenyliminomethyl)-
7.0 Hz), 7.60 d (2H, CHAr, 3JHH = 7.0 Hz), 9.39 s (1H,
CH=N). Mass spectrum, m/z (Irel, %): 403 (34) [М – H]+,
405 (34) [М + H]+. C21H26BrNO2.
1,2-dihydroxybenzene (8). A mixture of 2.5 g
(10 mmol) of 3,5-di-tert-butyl-2-hydroxybenzaldehyde
and 1.07 g (10 mmol) of para-toluidine in 30 mL of
anhydrous methanol was refluxed for 30 min and kept
overnight. The crystals were filtered off, washed with
light ligroin, and recrystallized from ethanol. Yield
4,6-Di-tert-butyl-3-(3-nitrophenyliminomethyl)-
1,2-dihydroxybenzene (12). A mixture of 0.25 g
(1 mmol) of 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde
and 0.14 g meta-nitroaniline in 20 mL of anhydrous
ethanol was refluxed for 3 h and then cooled down.
The precipitate was filtered off, washed with water,
dried, and recrystallized from a heptane–i-PrOH
mixture (10 : 1). Yield 0.25 g (68%), light-red needle-
1
3.30 g (96%), light-red powder, mp 186–187°С. H
NMR spectrum (CDCl3), δ, ppm: 1.48 s (9H, CH3),
1.55 s (9H, CH3), 2.23 s (3H, CH3), 6.84 s (1H, CHAr),
7.22–7.32 m (4H, CHAr), 9.39 s (1H, CH=N). Mass
spectrum, m/z (Irel, %): 339 (72) [М]+. С22H29NO2.
1
shaped crystals, mp 138–140°С. H NMR spectrum
(CDCl3), δ, ppm: 1.45 s (9Н, СН3), 1.55 s (9Н, СН3),
6.24 br. s (1Н, ОН), 6.92 s (1Н, СНAr), 7.58–7.66 m
(2Н, СНAr), 8.10–8.19 m (2Н, СНAr), 9.48 s (1Н,
CH=N). Mass spectrum, m/z (Irel, %): 370 (100) [М]+.
C21H26N2O4.
4,6-Di-tert-butyl-3-(2-sulfanylphenyliminomethyl)-
1,2-dihydroxybenzene (9). A mixture of 0.25 g
(1 mmol) of 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde
and 0.125 g (1 mmol) of aminothiophenol in 15 mL of
anhydrous ethanol was refluxed for 5 h. After removal
of the solvent, the residue was recrystallized from a
heptane–ethanol mixture. Yield 0.28 g (78%), light-
4,6-Di-tert-butyl-3-(1-adamantyliminomethyl)-
1,2-dihydroxybenzene (13). A mixture of 0.125 g
(0.5 mmol) of 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde,
0.075 g (0.5 mmol) of 1-adamantylamine, 15 mL of
toluene, and catalytic amount of TsOH was refluxed
for 15 h. After removal of toluene, the residue was
dissolved in 30 mL of Et2O. The obtained solution was
washed with dilute Н2SO4, NaHCO3 solution, and
water. The solvent was removed under vacuum, the
residue was recrystallized from toluene. Yield 0.12 g
(62%), orange crystalline powder, mp 263°С
(decomp.). 1H NMR spectrum (CDCl3), δ, ppm: 1.34 s
(9Н, СН3), 1.42 s (9Н, СН3), 1.65–2.34 m (15Н, 6СН2 +
3CH), 6.65 s (1Н, ОН), 7.29 s (1Н, СНAr), 8.92 s (1Н,
CH=N). Mass spectrum, m/z (Irel, %): 383 (39) [М]+.
C25H37NO2.
1
yellow powder, mp 112–114°С. H NMR spectrum
(CDCl3), δ, ppm: 1.43 s (9H, CH3), 1.53 s (9H, CH3),
3.67 br. s (1H, SH), 6.13 s (1H, OH), 6.85–7.48 m
(5H, CHAr), 9.43 s (1H, CH=N). Mass spectrum, m/z
(Irel, %): 357 (77) [М]+. С21H27NO2S.
4,6-Di-tert-butyl-3-(2-sulfanylethyliminomethyl)-
1,2-dihydroxybenzene (10). A solution containing
0.195 g (2 mmol) of cysteamine hydrochloride, 0.50 g
(2 mmol) of 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde,
and 0.20 g (2 mmol) of triethylamine in 10 mL of
anhydrous methanol was stirred at room temperature
for 6 h. The precipitate was filtered off, methanol was
evaporated under vacuum, the residue was washed
with cold ethanol and recrystallized from hexane.
Yield 0.44 g (72%), light-orange powder, mp 111–
10–3 М solutions of the investigated compounds in
n-hexane were used for the radiation-chemical experi-
ments. The solutions were irradiated in sealed glass
ampoules using an MPX-γ-25M unit with 60Co source.
The absorbed dose rate was 0.40±0.02 Gy/s. The used
dose range was 0.24–1.2 kGy.
1
112°С. H NMR spectrum (CDCl3), δ, ppm: 1.45 s
(9Н, СН3), 1.49 s (9Н, СН3), 2.92 br. s (2Н, СН2),
3.83 br. s (2Н, СН2), 6.71 br. s (1H, OH), 7.30 s (1Н,
СНAr), 9.04 s (1H, CH=N). Mass spectrum, m/z (Irel,
%): 309 (100) [М]+. С17H27NO2S.
4,6-Di-tert-butyl-3-(4-bromophenyliminomethyl)-
1,2-dihydroxybenzene (11). 0.17 g (1 mmol) of para-
bromoaniline was added to a solution of 0.25 g
(1 mmol) of 4,6-di-tert-butyl-2,3-dihydroxybenzaldehyde
in 10 mL of anhydrous methanol. After 0.5 h, the
solution was cooled down, the precipitate was filtered
off and washed with cold hexane. Yield 0.25 g (62%),
Analysis of products of free-radical oxidation of
n-hexane (hexan-2-ol, hexan-3-ol, hexan-2-one, and
hexan-3-one) was performed by gas chromatography
using a StabilWax-DA quartz capillary column (l =
30 m, 0.32 mm ID, 0.5 µm df) on a GC-17AAF/APC
Shimadzu chromatograph equipped with flame
ionization detector. Conditions: initial temperature 60°С,
heating to 180°С at 8 deg/min, evaporator temperature
250°С, detector temperature 220°С, flow rate of the
carrier gas (nitrogen) 30 cm/s.
1
red needle-shaped crystals, mp 195–196°С. H NMR
spectrum (CDCl3), δ, ppm: 1.45 s (9H, CH3), 1.52 s
(9H, CH3), 6.87 s (1H, CHAr), 7.18 d (2H, CHAr, 3JHH
=
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 3 2019