SYNTHESIS OF ALKYL BIPHENYL-4-CARBOXYLATES
361
biphenyl (1), 0.31 mL (3.2 mmol) of carbon tetra-
chloride, and 3.2 mmol of the corresponding alcohol
(0.13 mL of methanol, 0.19 mL of ethanol, or 0.24 mL
of propan-1-ol). The ampule was sealed and placed in
the reactor which was hermetically closed and heated
for 8 h at 130°C. When the reaction was complete, the
reactor was cooled to room temperature, the ampule
was opened, and the mixture was neutralized with
sodium carbonate and filtered through a filter paper.
The solvent was distilled off, and the residue was dis-
tilled under reduced pressure. Esters 2–4 were isolated
by chromatography in a 1.2×21-cm column charged
with silica gel (60–200 nm, 60 Å) using petroleum
ether as eluent. Analytical samples of esters 3 and 4
were obtained by recrystallization from ethanol.
(Irel, %): 212 (78) [M]+, 181 (100), 152 (60), 90 (17),
76 (35), 51 (7).
Ethyl [1,1′-biphenyl]-4-carboxylate (4). Yield
14%, off-white crystals, mp 46–46.5°C (from EtOH);
1
published data [7]: mp 46°C. H NMR spectrum, δ,
ppm: 1.55 t (2H, CH3, J = 7.2 Hz), 4.55 q (2H, OCH2,
J = 7.2 Hz), 7.48 t (1H, 4′-H, J = 8 Hz), 7.58 d (2H,
3′-H, 5′-H, J = 7.2 Hz), 7.74 d (2H, 2′-H, 6′-H, J =
7.6 Hz), 7.78 d (2H, 2-H, 6-H, J = 8.4 Hz), 8.29 d (2H,
3-H, 5-H, J = 8.4 Hz). 13C NMR spectrum, δC, ppm:
14.52 (CH3), 61.11 (OCH2), 127.13 (C2, C6), 127.28
(C2′, C6′), 128.26 (C4′), 129.06 (C3′, C5′), 129.40 (C4),
130.24 (C3, C5), 140.13 (C1′), 145.64 (C1). Mass
spectrum, m/z (Irel, %): 226 (70) [M]+, 198 (30), 181
(100), 152 (56), 90 (12), 76 (23), 51 (5).
Propyl [1,1′-biphenyl]-4-carboxylate (2). Yield
90%, yellowish oily liquid, bp 114–115°C (0.2 mm);
published data [6]: mp 53–54°C, bp 345–348°C.
1H NMR spectrum, δ, ppm: 1.08 t (3H, CH3, J =
7.2 Hz), 1.84 m (2H, CH2CH3), 4.33 t (2H, OCH2, J =
6.8 Hz), 7.42 m (1H, 4′-H), 7.49 d (2H, 3′-H, 5′-H, J =
7.2 Hz), 7.65 d (2H, 2′-H, 6′-H, J = 7.6 Hz), 7.67 d
(2H, 2-H, 6-H, J = 8.4 Hz), 8.14 d (2H, 3-H, 5-H, J =
8.4 Hz). 13C NMR spectrum, δC, ppm: 10.55 (CH3),
22.16 (CH2CH3), 66.57 (OCH2), 128.11 (C4′), 128.93
(C3′, C5′), 127.03 (C2, C6), 127.29 (C2′, C6′), 129.28
(C4), 130.07 (C3, C5), 140.08 (C1′), 145.55 (C1). Mass
spectrum, m/z (Irel, %): 240 (55) [M]+, 211 (42), 198
(100), 181 (87), 152 (68), 76 (27), 40 (65).
The structural studies were performed at the Agidel
Collective Usage Center (Institute of Petrochemistry
and Catalysis, Russian Academy of Sciences).
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Methyl [1,1′-biphenyl]-4-carboxylate (3). Yield
45%, off-white crystals, mp 117–118°C (from EtOH);
published data [7]: mp 117–118°C. 1H NMR spectrum,
δ, ppm: 4.04 s (3H, CH3), 7.48 m (1H, 4′-H), 7.56 d
(2H, 3′-H, 5′-H, J = 7.2 Hz), 7.73 d (2H, 2′-H, 6′-H,
J = 7.6 Hz), 7.77 d (2H, 2-H, 6-H, J = 8.4 Hz), 8.25 d
(2H, 3-H, 5-H, J = 8.4 Hz). 13C NMR spectrum, δC,
ppm: 53.56 (CH3), 127.16 (C2, C6), 127.28 (C2′, C6′),
128.26 (C4′), 128.89 (C4), 129.05 (C3′, C5′), 130.24 (C3,
C5), 140.09 (C1′), 145.72 (C1). Mass spectrum, m/z
Recl. Trav. Chim. Pays–Bas, 1953, vol. 72, p. 774.
7. Dictionary of Organic Compounds, Heilbron, J. and
Bunbury, H.M., Eds., London: Eyre and Spottswoode,
1953, vol. 1.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 3 2017