Synthesis of 4ꢀ(ωꢀchloroalkoxy)phenols
Russ.Chem.Bull., Int.Ed., Vol. 66, No. 2, February, 2017
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(tt ~ quint, CH2, J = 6.1 Hz, partially overlapping with the
signal of the CH2O group of compound 1b). These data are in
a good agreement with both the published values44 and an inꢀ
creased integral intensity of the remaining 1H NMR signals.
Replacement of bromine by chlorine in the mixture of comꢀ
pounds 1b and 10. To a solution of the mixture of 1b and 10
(23.44 g; molar ratio 92 : 8, 0.123 mol) in anhydrous DMF
(150 mL), anhydrous LiCl (23.44 g, 0.553 mol) was added. The
reaction mixture was stirred at 70 °C for 20 h under argon and
DMF was distilled off under vacuum. The residue was partiꢀ
tioned between ButOMe (300 mL) and water (700 mL),
the organic layer was washed with water (3×300 mL), dried
with Na2SO4, and concentrated under reduced pressure. The
residue was crystallized from light petroleum ether—chloroform
(7 : 3; room temperature→–18 °C) to give pure 1b (18.93 g, 54%
(based on 6)).
7. N. N. Kondakov, T. M. Melnikova, A. I. Zinin, V. I. Torꢀ
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ov, Carbohydr. Res., 2016, 431, 25.
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Synthesis of 4ꢀ(3ꢀchloropropoxy)phenol (1b) from 1,4ꢀbenzoꢀ
quinone (3) (Scheme 1, route A). A mixture of 3 (0.324 g, 3 mmol),
Amberlyst 15 cationꢀexchange resin (H+, 0.120 g), and 3ꢀchloroꢀ
propanꢀ1ꢀol (12 mL, 13.6 g, 0.144 mol) was heated at 100 °C
until 3 was consumed (8 h). The reaction mixture was cooled to
room temperature, filtered, and the solids were washed with
ethyl acetate (2×10 mL). Water (40 mL) was added to the comꢀ
bined filtrate and the aqueous layer was extracted with ethyl
acetate (2×40 mL). The combined organic extracts were dried
with Na2SO4, ethyl acetate was distilled off on a rotary evaporator,
and the excess of 3ꢀchloropropanꢀ1ꢀol was removed from the
residue by distillation under oil pump vacuum (5 Torr). The
residue (0.856 g, a complex mixture according to TLC) was subꢀ
jected to silica gel column chromatography (gradient 0→20%
ethyl acetate in toluene) to give crude 1b. Pure 1b (0.170 g, 30%)
was obtained after an additional column chromatography (graꢀ
dient 0→20% ethyl acetate in light petroleum ether).
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This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 10ꢀ03ꢀ01019,
13ꢀ03ꢀ00666, 14ꢀ33ꢀ50103, 16ꢀ03ꢀ00755, and 16ꢀ33ꢀ
50034).
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