698
PONOMAREV et al.
purity was 95% according to GLC; n = 1.4991, d 42 0
0
2
0
=
accordance with the procedure described in [14].
D
–
3
.9733 g cm .
Mass spectrum of butyl 3-{endo-(1,7,7-trimethyl-
bicyclo[2.2.1]hept-2-yl)}propanoate, m/z (I , %): 266
Methyl 3-{endo-(1,7,7-trimethylbicyclo[2.2.1]hept-
2
-yl)}propanoate 1. A500-ml flask calcined and purged
with argon was charged with CuI (4.8 g, 25 mmol). The
flask was quickly heated again on an alcohol burner
and cooled. To the cooled flask, 150 ml of diethyl ether
was added, and the contents were cooled with strirring
to –78°C. After that, bornyl lithium (160 ml, 50 mmol)
was added dropwise. The mixture was quickly warmed
to –20°C and kept at this temperature for 5 min. Then
the mixture was again cooled to –78°C, and methyl
propenoate (methyl acrylate) diluted with diethyl ether
rel
+
(
2) [M] , 251 (4), 193 (5), 167 (5), 150 (16), 159 (16),
1
1
8
37 (4), 123 (13), 12 (9), 110 (11),109 (13), 107 (22),
05 (8), 96 (7), 95 (74), 94 (7), 93 (18), 91 (11), 82 (84),
1 (27), 79 (20), 77 (10), 69 (20), 68 (12), 67 (35), 57
(
23), 56 (22), 55 (53), 53 (14), 43 (31), 41 (100).
1H NMR spectrum, δ, ppm: 0.76 s (3H), 0.82 s (3H),
0
1
2
.84 s (3H), 0.92 t (3H, J = 7.3 Hz), 0.95–1.08 m (1H),
.22–1.80 m (12H), 1.91 m (1H), 2.17–2.26 m (1H),
.31–2.37 m (1H), 4.06 t (2H, J = 6.7 Hz).
(volume ratio ~1 : 1) was added dropwise. The mixture
was warmed to –30°C and stirred at this temperature
for 30–40 min. Then the mixture was decomposed with
Ethyl 3-{endo-(1,7,7-trimethylbicyclo[2.2.1]
hept-2-yl)}propenoate 3 was prepared from 160 ml
(50 mmol) of bornyllithium, 1.5 g (12.5 mmol) of ethyl
propynoate, and 4.8 g (25 mmol) of CuI similarly to
methyl 3-{endo-(1,7,7-trimethylbicyclo[2.2.1]hept-2-
yl)}propanoate. The reaction was performed at –50°C.
The product (yield 7 g, 92%) was a viscous reddish oily
liquid with the Z : E isomer ratio of 1 : 49. The isomers
were separated on an adsorption column (adsorbent
silica gel, eluent petroleum ether–diethyl ether, 95/5%).
a saturated NH Cl solution, which was added quickly
4
with vigorous stirring. Then the mixture was warmed to
room temperature with stirring, and the aqueous layer
was separated and extracted with two portions of diethyl
ether. The organic layer was combined with the ether
extracts, washed with a saturated NaCl solution, and
dried overMgSO , after which the solvent was distilled
4
off. The bottoms were passed through an adsorption
column packed with silica gel, eluent hexane–diethyl
ether (the fraction of ether was gradually increased from
E Isomer: bp 96°C/0.1 mm Hg, purity 94% (GLC
analysis); n D2 0 = 1.4991, d 42 0 = 0.9733 g cm–3.
1
to 5%). The resulting product (2.66 g) was a viscous
yellowish oily liquid, bp 77–78°C/0.1 mm Hg. The
Mass spectrum of ethyl Z-3-{endo-(1,7,7-trimethyl-
2
0
substance purity was 96% according to GLC data; n
=
D
bicyclo[2.2.1]hept-2-yl)}propenoate, m/z (I , %): 236
rel
20
–3
1
.4710, d4 = 0.9536 g cm . Yield 95%.
+
[
(
M] (2), 235 (3), 221 (3), 191 (3),161 (3), 147 (6), 146
5), 133 (3), 132 (4), 126 (30), 121 (6), 119 (8), 118 (4),
Mass spectrum of methyl 3-{endo-(1,7,7-trimethyl-
bicyclo[2.2.1]hept-2-yl)}propanoate, m/z (I , %): 224
rel
1
8
5
09 (17), 108 (17), 105 (17), 97 (20), 94 (100), 91 (15),
0 (6), 79 (30), 77 (22), 71 (4), 67 (16), 65 (16), 53 (26),
1 (15), 42 (16), 40 (43), 39 (45).
+
(
5) [M] , 209 (20), 182 (8), 181 (63), 150 (24), 149 (39),
1
(
7
(
37 (8), 135 (11), 123 (17), 110 (13.5), 109 (16), 107
35), 105 (14), 96 (9), 95 (100), 94 (10),82 (81), 81 (38),
9 (32), 77 (19), 69 (19), 68 (14), 67 (47), 55 (51),41
69).
1H NMR spectrum, δ, ppm: 0.77 s (3H), 0.83 s (3H),
.84 s (3H), 0.99–1.08 m (2H), 1.17–1.31 m (2H), 1.40–
1H NMR spectrum: 0.76 s (3H), 0.86 s (3H), 0.93 s
(3H), 1.28 t (3H, J = 7.1 Hz), 1.53–1.85 m (6H), 2.13–
2
5
.18 m (1H), 2.24–2.27 m (1H), 4.14 t (2H, J = 7.1 Hz),
.8 d (1H, J = 11.7 Hz), 6.26 dd (1H, J = 11.5, 10.4 Hz).
0
1
3
Mass spectrum of ethyl E-3-{endo-(1,7,7-trimethyl-
.77 m (5H), 1.90–1.98 m (1H), 2.18–2.39 m (2H),
.66 s (3H).
bicyclo[2.2.1]hept-2-yl)}propenoate, m/z (I , %): 236
rel
+
[
(
(
(
M] (2), 221 (3), 191 (3), 147 (4), 133 (2), 128 (4), 127
4), 121 (3), 119 (3),110 (13),107 (5),105 (4), 99 (7), 96
8), 95 (100), 93 (6), 91 (8), 81 (12), 79 (11), 77 (8), 69
4), 67 (11), 55 (12), 41 (17).
Butyl 3-{endo-(1,7,7-trimethylbicyclo[2.2.1]
hept-2-yl)}propanoate 2 was prepared from 1.6 g
12.5 mmol) of butyl propenoate (butyl acrylate),
60 ml (50 mmol) of bornyllithium solution, and 4.8 g
25 mmol) of CuI similarly to methyl 3-{endo-(1,7,7-
(
1
(
1H NMR spectrum: 0.77 s (3H), 0.84 s (3H), 0.86 s
trimethylbicyclo[2.2.1]hept-2-yl)}propanoate. The
product (yield 3.16 g, 95%) was a viscous yellowish
oily liquid, bp 104–105°C/0.1 mm Hg. The substance
(3H), 1.06–1.16 m (2H), 1.25 t (3H, J = 7.1 Hz), 1.40–
1.47 m (1H), 1.61–1.65 m (1H, J = 4.4 Hz), 1.65–1.73 m
(2H), 1.93–2.02 m (1H), 2.39–2.46 m (1H), 4.15 q (2H,
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 4 2010