MAMEDBEILI et al.
324
Prop-2-yn-1-yl 4-chlorobenzoate (IIIe) was pre-
bp 198–200°C (1 mm), nD20 = 1.5880, d420 = 1.5658. IR
spectrum, ν, cm–1: 3600 (=C–H), 3050 (OH), 1740
(C=O), 1500, 1280 (C–O), 700 (C–Cl). 1H NMR spec-
trum, δ, ppm: 3.92 m and 4.30 m (1H each, 2-CH2),
5.4 s (1H, OH), 6.40 s (1H, 3-H), 7.5–8.0 d.d (4H,
Harom). Found, %: C 41.4; H 2.4; Cl 48.9. C15H8Cl6O3.
Calculated, %: C 40.09; H 1.178; Cl 47.04.
pared from 15.6 g of 4-chlorobenzoate (IIe). Yield
9.31 g (48%), bp 95–96°C (1 mm), nD20 = 1.5444, d420
=
1.1482. IR spectrum, ν, cm–1: 3100 (≡C–H), 2200
(C≡C), 1740 (C=O), 1450 (C–Carom), 1150 (C–O).
Found, %: C 62.15; H 3.79; Cl 19.01. C10H7ClO2. Cal-
culated, %: C 61.86; H 3.61; Cl 18.30.
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hepta-2,5-di-
en-2-ylmethyl 4-methoxybenzoate (Vd) was synthe-
sized from 1.9 g of ester IIId. Yield 4.15 g (89%),
bp 201–203°C (2 mm), nD20 = 1.6030, d240 = 1.5670. IR
spectrum, ν, cm–1: 3050 (=C–H), 1740 (C=O), 1500
Prop-2-yn-1-yl 4-bromobenzoate (IIIf) was pre-
pared from 20.1 g of 4-bromobenzoic acid (IIf). Yield
15.42 g (60%), mp 35°C (from heptane). IR spectrum,
ν, cm–1: 3100 (≡C–H), 2250 (C≡C), 1730 (C=O), 1450
(C–Carom), 1050 (C–O), 500 (C–Br). Found, %:
C 50.35; H 2.75; Br 33.01. C10H7BrO2. Calculated, %:
C 50.21; H 2.93; Br 33.47.
1
(C–O), 650 (C–Cl). H NMR spectrum, δ, ppm: 3.3 s
(3H, OCH3), 3.92 m and 4.30 m (1H each, 2-CH2),
6.40 s (1H, 3-H), 7.0–8.0 d.d (4H, Harom). Found, %:
C 42.5; H 1.6; Cl 45.2. C16H10Cl6O3. Calculated, %:
C 41.46; H 1.16; Cl 46.0.
Prop-2-yn-1-yl 4-nitrobenzoate (IIIg) was pre-
pared from 16.7 g of 4-nitrobenzoate (IIg). Yield
12.26 g (55%), mp 33°C (from octane). IR spectrum,
ν, cm–1: 3020 (≡C–H), 2200 (C≡C), 1740 (C=O), 1450
(C–Carom). 1050 (C–O). Found, %: C 57.91; H 3.39;
N 7.11. C10H7NO4. Calculated, %: C 58.54; H 3.41;
N 6.83.
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hepta-2,5-di-
en-2-ylmethyl 4-chlorobenzoate (Ve) was synthesized
from 1.94 g of ester IIIe. Yield 3.69 g (89%), mp 98°C
(from isooctane). IR spectrum, ν, cm–1: 3100 (=C–H),
1
1730 (C=O), 1500 (C–O), 700 (C–Cl). H NMR spec-
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hepta-2,5-di-
en-2-ylmethyl benzoates Va–Vg (general procedure).
A mixture of 8.19 g (0.03 mol) of hexachlorocyclo-
pentadiene (IV) and 0.01 mol of ester IIIa–IIIg was
heated for 13 h at 160°C in a sealed ampule. The
ampule was cooled and opened, and the mixture was
distilled under reduced pressure.
trum, δ, ppm: 7.1–7.9 d.d (4H, Harom), 6.40 s (1H,
3-H), 4.29 m and 3.90 m (1H each, 2-CH2). Found, %:
C 37.3; H 2.1; Cl 52.2. C15H7Cl7O2. Calculated, %:
C 38.5; H 1.9; Cl 53.1.
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hepta-2,5-di-
en-2-ylmethyl 4-bromobenzoate (Vf) was synthe-
sized from 3.39 g of ester IIIf. Yield 2.33 g (65%),
mp 115°C (from isooctane). IR spectrum, ν, cm–1:
3050 (=C–H), 1740 (C=O), 1550 (C–O), 700 (C–Cl),
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hepta-2,5-di-
en-2-ylmethyl benzoate (Va) was synthesized from
1.6 g of ester IIIa. Yield 3.54 g (82%), bp 195–196°C
(2 mm), nD20 = 1.5820, d420 = 1.5760. IR spectrum, ν,
cm–1: 3050 (=C–H), 1730 (C=O), 1450 (C=C), 1100
(C–O), 600 (C–Cl). 1H NMR spectrum, δ, ppm: 3.94 m
and 4.20 m (1H each, 2-CH2), 6.45 s (1H, 3-H), 7.1–
8.0 d.d (5H, Harom). Found, %: C 40.7; H 2.28; Cl 50.8.
C15H8Cl6O2. Calculated, %: C 41.6; H 1.85; Cl 49.2.
1
600 (C–Br). H NMR spectrum, δ, ppm: 3.90 m and
4.30 m (1H each, 2-CH2), 6.40 s (1H, 3-H), 7.1–8.0 d.d
(4H, Harom). Found, %: C 34.4; H 2.0; Hlg 58.2.
C15H7BrCl6O2. Calculated, %: C 35.15; N 1.38;
Hlg 57.3.
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hepta-2,5-di-
en-2-ylmethyl 4-nitrobenzoate (Vg) was synthesized
from 2.05 g (0.01 mol) of ester IIIg. Yield 3.95 g
(83%), mp 137°C (from isooctane). IR spectrum, ν,
cm–1: 3100 (=C–H), 1740 (C=O), 1550 (C–O), 1230
(C–N), 700 (C–Cl). 1H NMR spectrum, δ, ppm: 3.91 m
and 4.30 m (1H each, 2-CH2), 6.4 s (1H, 3-H), 7.1–
8.0 d.d (4H, Harom). Found, %: C 37.1; H 1.9; Cl 43.6.
C15H7Cl6NO4. Calculated, %: C 37.6; H 1.46; Cl 44.5.
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hepta-2,5-di-
en-2-ylmethyl 4-methylbenzoate (Vb) was synthe-
sized from 1.74 g of ester IIIc. Yield 3.91 g (83%),
bp 205–206°C (2 mm), nD20 = 1.6050, d240 = 1.5010. IR
spectrum, ν, cm–1: 3100 (=C–H), 1740 (C=O), 1460
1
(C=C), 1150 (C=O), 700 (C–O). H NMR spectrum,
δ, ppm: 2.2 s (3H, CH3), 3.93 m and 4.25 m (1H each,
2-CH2), 6.40 s (1H, 3-H), 7.0–8.0 d.d (4H, Harom).
Found, %: C 42.1; H 1.8; Cl 48.3. C16H10Cl6O2. Calcu-
lated, %: C 42.9; H 2.24; Cl 47.6.
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hepta-2,5-di-
en-2-ylmethanol (VI) was synthesized as described in
[9] by condensation of hexachlorocyclopentadiene
(IV) with prop-2-yn-1-ol (I). Compounds Va–Vg were
also obtained by esterification of bicyclic alcohol VI
with the corresponding para-substituted benzoic acids
1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hepta-2,5-di-
en-2-ylmethyl 4-hydroxybenzoate (Vc) was synthe-
sized from 1.9 g of ester IIIc. Yield 3.76 g (90%),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010