SYNTHESIS OF SATURATED BICYCLIC DIESTERS
1135
1
3
11
12
1
20°С, carrier gas (helium) flow rate 60 mL/min. The
С NMR spectrum, δ , ppm: 20.7 (С ), 21.1 (С ),
С
6
7
4
5
3
IR spectra were measured on a UR-20 spectropho-
tometer. The NMR spectra were run on a Bruker AV-
28.4 (С ), 30.4 (С ), 37.5 (С ), 39.3 (С ), 39.4 (С ),
41.9 (С ), 64.8 (С ), 76.8 (С ), 170.2 (С ), 170.2 (С ).
1
9
2
8
10
1
13
300 spectrometer and 300 ( Н) and 75 MHz ( С) in
acetone-d6.
5-(Methoxycarbonyl)bicyclo[2.2.1]hept-2-yl
formate (19) was prepared in a similar way. Yield
–
1
(
Bicyclo[2.2.1]hept-2-ene-5-yl) acetate (1) [99.8%,
92%. IR spectrum, ν, cm : 2885 (СН), 1735 (С=О),
1200–1240 (С–О–С), 1460 (СН ), 1380 (СН ). ¹Н
2
0
20
bp 60–61°С (10 mmHg), d4 1.070 g/mL, nD 1.4570]
and (bicyclo[2.2.1]hept-2-ene-5-yl)methyl acetate (2)
99.8%, bp 78–79°С (10 mmHg), d 1.0558 g/mL, n
.4768] were synthesized by the [4+2]-cycloaddition
of cyclopentadiene to vinyl acetate and allyl acetate,
respectively [7, 8]. Methyl bicyclo[2.2.1]hept-2-ene-5-
2
3
NMR spectrum, δ, ppm: 1.63–1.95 m (6Н, 3СН ),
2
2
0
20
[
1
4 D
2.07–2.54 m (2Н, 2СН), 2.26 m (1Н, СН), 3.68 s (3Н,
СН ), 3.90 d (1Н, СН, J = 7.5 Hz), 8.04 s (1Н, НСОО,
3
1
3
7
J = 8.5 Hz). С NMR spectrum, δ , ppm: 28.2 (С ),
0.1 (С ), 32.3 (С ), 36.1 (С ), 38.4 (С ), 46.2 (С ),
0.5 (С
С
3
6
4
1
5
3
5
2
0
10
2
8
9
carboxylate (3) [bp 78–79°С (17 mmHg), d 1.0516 g/mL,
4
), 81.3 (С ), 158.0 (С ), 175.8 (С ).
2
0
nD 1.4761], methyl 5-methyl-bicyclo[2.2.1]hept-2-
2
4
0
ene-5-carboxylate (4) [bp 105–106°С (17 mmHg), d
.0309 g/mL, nD 1.4712], ethyl bicyclo[2.2.1]hept-2-
ene-5-carboxylate (5) [bp 90–91°С (17 mmHg), d4
.0208 g/mL, v 1.4686], and ethyl 5-methylbicyclo-
2.2.1]hept-2-ene-5-carboxylate (6) [bp 112–113°С
17 mmHg), d4 1.0361 g/mL, nD 1.4785] were
synthesized by the condensation of cyclopenta-diene
with methyl and ethyl acrylate and methacrylate in the
5-(Methoxycarbonyl)bicyclo[2.2.1]hept-2-yl
acetate (20) was prepared in a similar way. Yield
20
1
2
0
–
1
8
1
8%. IR spectrum, ν, cm : 2800 (СН), 1740 (С=О),
1
[
(
1
200–1250 (С–О–С), 1460 (СН ), 1380 (СН ). Н
2
3
NMR spectrum, δ, ppm: 1.63–1.95 m (6Н, 3СН ), 2.07–
2
2
0
20
2
.54 m (2Н, 2СН), 2.21 d (3Н, СН , J = 8.3 Hz), 2.26
3
m (1Н, СН), 3.68 s (3Н, СН ), 3.90 d (1 Н, СН, J =
3
13
8
8
1
3
.3 Hz). С NMR spectrum, δ , ppm: 170.2 (С ),
75.8 (С ), 76.5 (С ), 46.2 (С ), 38.3 (С ), 36.2 (С ),
2.3 (С ), 37.2 (С ), 28.2 (С ), 50.4 (С ), 21.6 (С ).
-Methyl-5-(methoxycarbonyl)bicyclo[2.2.1]hept-
С
presence of a nano-ТiO catalyst (20–22 nm) be the
9
2
5
1
4
2
procedures in [9, 10]. According to the GLC data,
unsaturated bicyclic monoesters 1–6 were mixtures of
the exo and endo isomers (55–60 and 40–45%,
respectively). According to [11], on heating, the endo
isomers transform into thermodynamically more stable
exo isomers. Therefore, we heated the resulting isomer
mixtures to obtain the exo isomer (by GLC, 99.0%).
6
3
7
10
12
5
2
8
-yl formate (25) was prepared in a similar way. Yield
7%. IR spectrum, ν, cm : 1200–1250 (С–О–С), 1380
–1
(
(
СН ), 1460 (СН ), 1730–1740 (С=О), 3000–2800
3 2
1
СН). Н NMR spectrum, δ, ppm: 1.38 m (3Н, СН ),
3
1
.63–1.95 m (6Н, 3СН ), 2.26 m (1Н, СН), 3.68 s (3Н,
2
5
-Acetoxybicyclo[2.2.1]hept-2-yl acetate (8). A
СН ), 3.90 d (1 Н, СН, J = 8.3 Hz), 8.04 d (1Н,
НСОО, J = 8.3 Hz). С NMR spectrum, δ , ppm:
2
46.1 (С ), 46.2 (С ), 52.5 (С ), 81.6 (С ), 160.7 (С ),
1
3
mixture of 152 g of compound 1, 100 g of acetic acid,
and 0.1 g of BF ·OEt was heated at 80°С for 3 h.
Vacuum distillation gave 175.7 g (87%) of compound
1
3
С
3
2
1
3
7
6
3
1
7.4 (С ), 30.9 (С ), 33.3 (С ), 34.4 (С ), 38.6 (С ),
5
4
10
2
8
–
1
8
(
. IR spectrum, ν, cm : 1200–1210 (С–О–С), 1380
9
77.8 (С ).
СН ), 1460 (СН ), 1730 (С=О), 3000 (СН). ¹Н NMR
3
2
spectrum, δ, ppm: 1.70–1.90 m (6Н, 3СН ), 2.21–2.35
2
5
-Ethyl-5-(methoxycarbonyl)bicyclo[2.2.1]hept-2-
s (6Н, 2СН ), 2.40–2.60 m (2Н, 2СН), 4.10–4.20 m
3
13
11
yl formate (31) was prepared in a similar way. Yield
2%. IR spectrum, ν, cm : 1200–1250 (С=О), 1380
(
2
4
2Н, 2СН), С NMR spectrum, δ , ppm: 19.0 (С ),
1.0 (С ), 29.0 (С ), 35.0 (С ), 38.0 (С ), 44.0 (С ),
8.0 (С ), 78.5 (С ), 79.0 (С ), 169.3 (С ), 170.2 (С ).
С
–
1
1
0
7
6
3
4
8
(
(
1
2
5
9
8
СН ), 1460 (СН ), 1730–1740 (С=О), 3000–2800
3
2
1
СН). Н NMR spectrum, δ, ppm: 1.29 m (3Н, СН ),
3
5
-(Acetoxymethyl)bicyclo[2.2.1]hept-2-yl acetate
1.63–1.95 m (6Н, 3СН
2
), 2.07–2.54 m (2Н, 2СН),
2
.26 m (1Н, СН), 3.90 d (1Н, СН, J = 7.5 Hz), 4.21 t
(
(
(
¹
2
8
14) was prepared in a similar way. Yield 191 g
84.5%). IR spectrum, ν, cm : 2800 (СН), 1740
С=О), 1200–1230 (С–О–С), 1460 (СН ), 1380 (СН ).
Н NMR spectrum, δ, ppm: 1.60–2.00 m (6H, 3CH ),
.20 d (6H, 2CH , J = 8.0 Hz), 2.60 d (2H, 2CH, J =
–
1
(2Н, СН , J = 8.5 Hz), 8.04 d (1Н, НСОО, J =
2
1
3
11
8.3 Hz). С NMR spectrum, δ , ppm: 14.1 (С ), 27.4
С
2
3
1
3
7
6
3
1
(С ), 30.9 (С ), 33.2 (С ), 34.4 (С ), 38.4 (С ), 46.1
2
5
4
10
2
8
(С ), 46.2 (С ), 61.9 (С ), 81.6 (С ), 160.7 (С ), 177.8
3
9
.3 Hz), 4.2 m (1H, CH), 4.8 d (1H, CH, J = 8.0 Hz).
(С ).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 6 2017