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KRYSIN et al.
mixture was introduced 12 ml (0.103 mol) of SnCl4
and 18 ml (0.23 mol) of epichlorohydrin. The mixture
was stirred at a temperature of 10–15°C for 20 min. To
the reactor was added 20 ml of cold water in small
portions maintaining room temperature of the reaction
mixture. The organic layer was separated, washed with
water to neutral reaction, and the solvent was
evaporated. The obtained oil was distilled in a vacuum,
and 4.6 g (0.022 mol) of 2,6-di-tert-butyl-phenol was
isolated. The oily residue, 20 g, was dissolved in 10 ml
of petroleum ether and the resulting solution was left
overnight at –15°C. The precipitate was filtered off
and washed with 10 ml of cold petroleum ether. 13.9 g
of 3-(3,5-di-tert-butyl-4-hyd-roxyphenyl)-2-hydroxy-
1-chloropropane XXI was obtained. Combined filtrates
were evaporated and distilled in a vacuum, 3.7 g
fraction with bp 160°C at 1 mm Hg was isolated. It
was crystallized from an equal amount of hexane, and
thus an additional 2.1 g portion of compound XXI was
obtained, mp 97–98°C. The total yield of compound
XXI 16 g (53%). Found, %: C 68. 56; H 9.34, Cl
11.90. C17H27ClO2. Calculated, %: C 68.32, H 9.10, Cl
and 2.66), 3.04–3.08 m (1H, C2'H), 5.02 s (1H, OH),
6.96 s (2H, ArH). The 13C NMR spectrum (CCl4), δC,
ppm: C8, 30.37; C7, 34.27, C1', 38.83; C3', 46.69; C2',
52.65; C2 and C6, 125.33; C1, 127.83; C3 and C5,
135.80; C4, 152.43.
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1
11.86. H NMR spectrum (in CDCl3), δ, ppm: 1.45 s
(18 H, C4H9-tert) 2.31 s (1H, CHOH), 2.81 d (2H, J =
7.0, PhCH2), 3.5–3.7 m (2H, CH2C1), 4.02 m (1H,
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2-(3,5-Di-tert-butyl-4-hydroxybenzyl)oxirane
XXII. To a solution of 2 g (0.0066 mol) of compound
IX in 2 ml of DMF was added a solution of 0.4 g
(0.01 mol) of NaOH in 0.5 ml of water. The reaction
mixture was stirred for 2 h in a nitrogen atmosphere at
room temperature. A solution of compound X in DMF
was thus obtained, containing according to GLC no
more than 3% of the initial compound IX. For isolation
of pure compound XXII this solution was poured on
the snow to obtain an oil, which solidified at
introducing a seed. The solid product was filtered off,
washed with water, dried, the obtained oxirane XXII
(1.64 g) was distilled in a vacuum, bp 160–165°C at
2 mm Hg, mp 83.2°C. Found: M+ 262.19330 (mass
spectrometry). Calculated: M+ 262.19327; C17H26O2.
1H NMR spectrum in CCl4, δ, ppm: 1.41 s (18H, C4H9-
tert), two groups of proton signals from C1'H2: 2.48–
2.51 d.d (1H, J = 0.55, 2.490 and 2,497 ) and 2.71–
2.74 d.d (1H, J = 0.55, 2.725 and 2.732), two groups of
proton signals C3'H2: 2.62–2.67 d.d (1H, J = 0.55,
2.630 and 2.660) and 2.75–2.80 d.d (1H, J = 0.55, 2.63
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 2 2011