Synthesis of bi-and tricyclic monoesters of dicarboxylic acids

Article abstract of DOI:10.1134/S1070428006080057

A thermal addition of aliphatic dicarboxylic acids to bicyclo[2.2.1]- heptene hydrocarbons and to tricyclo[5.2.1.0^2,6]deca-3,8-diene was investigated and new samples of dicarboxylic acids alicyclic monoesters were synthesized. Some of monoesters synthesized have a pleasant fragrance and can find application as fragrance substances. They are also of interest as initial components for preparation of new organic compounds. Nauka/Interperiodica 2006.

Full text of DOI:10.1134/S1070428006080057

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 8, pp. 1137-1140. Ó Pleiades Publishing, Inc. 2006.
Original Russian Text Ó M.K. Mamedov, P.A. Rasulova, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No. 8, pp. 1159 -1162.
Synthesis of Bi- and Tricyclic Monoesters of Dicarboxylic Acids
M.K. Mamedov and P.A. Rasulova
Mamedaliev Institute of Pertochemical Processes, National Academy of Azerbaidzhan, Baku, 1025 Azerbaidzhan
Received February 11, 2005
Abstract—A thermal addition of aliphatic dicarboxylic acids to bicyclo[2.2.1]-heptene hydrocarbons and to
tricyclo[5.2.1.02,6]deca-3,8-diene was investigated and new samples of dicarboxylic acids alicyclic monoesters
were synthesized. Some of monoesters synthesized have a pleasant fragrance and can find application as fragrance
substances. They are also of interest as initial components for preparation of new organic compounds.
DOI: 10.1134/S1070428006080057
We formerly investigated a thermal addition reaction
of aliphatic saturated and unsaturated monocarboxylic
acid to bi-, tri-, and tetracyclic olefin hydrocarbons and
synthesized the corresponding esters [1–4]. The syn-
thesized 5-methylbicyclo[2.2.1]hept-2-yl, tricyclo-
[5.2.1.02.6]-dec-3-en-8(9)yl acetates have a pleasant
fragrance and are successfully employed in the fragrance
industry for preparation of various compositions [5, 6].
The synthesized unsaturated esters, acrylates, not only
have a pleasant odor, but are reactive monomers for
preparation of polymers [7].
The addition of acids to bicyclic olefins Ia and Ib
proceeded at heating, and the initial acids themselves
autocatalyzed the reaction.
Dicarboxylic acids in the same way as monocarboxylic
ones add stereo- and regiospecifically to bicyclo[2.2.1]-
hept-2-ene (Ia) forming exo-2-bicyclo[2.2.1]heptyl
monoesters [8]. Monoesters prepared from 5-methyl-
bicyclo[2.2.1]hept-2-ene (Ib) contain two regioisomers:
90–95% of exo-5- and 5–10% of methylbicyclo[2.2.1]-
hept-2-yl-exo-isomers.
The reaction of saturated and unsaturated, hydroxy-,
and dihydroxydicarboxylic acids with exo-tricyclo-
[5.2.1.02,6]deca-3,8-diene (X) was also studied. The initial
dicarboxylic acids added exclusively to the p-bond of the
In the present study we investigated the reaction of
dicarboxylic acids from the aliphatic series with bicyclic
olefin hydrocarbons and synthesized the corresponding
bicyclic monoesters in 70–90% yields.
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R = H (a), CH3 (b); R' = H (VIIIa, VIIIb), OH (IXa, IXb); n = 0, 1, 2, 3, 4.
1137

MAMEDOV, RASULOVA
1138
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bicycloheptene ring in the molecule of tricyclic hydro-
EXPERIMENTAL
carbon X.
IR spectra were recorded on a spectrophotometer
UR-20, 1H MNR spectra were registered on a spectrom-
eter BS-487C (Czechia), operating frequency 80 MHz,
internal reference HMDS, solvent CCl4.
The analysis revealed that the dicarboxylic acids
stereoselectively added to the tricyclo[5.2.1.02,6]-deca-
3,8-diene giving rise to a mixture of two exo-exo-regio-
mers: tricyclo[5.2.1.02,6]dec-3-en-8- and tricyclo-
[5.2.1.02,6]dec-3-en-9-yl monoesters with the prevalence
of the first isomer (92–97%).
The composition and purity of compounds synthesized
and also of initial reagents was analyzed by GLC on
a chromatograph LKhM-8MD, column 1500mm long,
stationary phase 10 wt% of poly(ethylenglycol succinate)
on sferokhrom, carrier gas helium.
By the reaction of maleic, malic, and d-tartaric acids
with tricyclo[5.2.1.02,6]deca-3,8-diene the corresponding
monoesters were obtained in a 83.9–89.0% yield.
The following compounds were used as intial stuff:
bicyclo[2.2.1]hept-2-ene (Ia), bp 96°C, mp 46°C, purity
99.8% by GLC data; exo-5-methylbicyclo[2.2.1]hept-2-
ene (Ib), bp 115.5°C, d240 0.8605, nD20 1.4600, purity 99%
by GLC data; the compounds were prepared by the
condensation of cyclopentadiene with ethylene and
propylene [11, 12]; exo-tricyclo[5.2.1.02,6]deca-3,8-diene
(X), bp 170°C (decomp.), mp 19.5°C, d240 0.9760, nD20
1.5051 [13].
The structure of the obtained bicyclic and tricyclic
dicarboxylic acids monoesters was confirmed by
an independent synthesis from the corresponding alcohols
by their esterification with dicarboxylic acids in the
presence of sulfuric acid [9, 10].
The structure of the synthesized monoesters was also
proved by the IR and 1H NMR spectra. The IR spectra
contained the characteristic absorption bands of aliphatic
dicarboxylic and oxydicarboxylic acids monoesters: 3000–
2800 (C–H), 1645 (C=C), 1740 (C=O), 1200–1250
Initial dicarboxylic acids were chemically pure
substances, and their physical constants were consistent
with the published data [14].
–1
(–O–), and 3500 cm (–OH).
In all 1H NMR spectra the signal of the exo-proton at
the C2 atom of the bicyclic monoesters appeared in the
region 4.6 ppm, the signals of the carboxy group protons
at 10.0–11.0 ppm, of the hydroxy group in the spectra if
oxyacids monoesters at 2.28 ppm. The protons of the
double bond in the spectrum of the maleic acid exo-ester
gave rise to a multiplet at 6.10–6.25 ppm
The addition of dicarboxylic acids to bicyclic and
tricyclic olefins was carried out in a pressure reactor of
stainless steel. For homogenization of the initial
compounds CCl4 (38.5 g) was used as solvent, reaction
time was 4 h.
Oxalic acid exo-bicyclo[2.2.1]hept-2-yl mono-
ester (IIa). A mixture of 47 g of compound Ia, 22.5 g of
oxalic acid and of solvent was heated at 150°C. The
unreacted compound Ia and solvent were distilled off in
a vacuum, and from the condensate was isolated 41.4 g
Compounds IIb and XIIa possess a fine pleasant
fragrance with a verdure tint and can be used as
components for preparation of fragrant compositions.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

SYNTHESIS OF BI-ANDTRICYCLIC MONOESTERS OF DICARBOXYLICACIDS
1139
(90%) of compound IIa, bp 99–100°C (10 mm Hg), d420
1.0415, nD20 1.4690. 1H NMR spectrum, d, ppm: 1.0–1.41
d (8H, 4CH2), 2.20–2.22 m (2H, 2CH), 4.60 d (1H, CH),
10.20 s (1H, COOH). Found, %: C 58.67; H 6.57.
C9H12O4. Calculated, %: C 58.69; H 6.57.
Adipic acid exo-bicyclo[2.2.1]hept-2-yl mono-
ester (VIa). A mixture 47 g of compound Ia, 36.5 g of
adipic acid and of solvent was heated at 160°C. We
obtained 42 g (70%) of compound VIa, bp 142–143°C
(10 mm Hg), d240 1.02091, nD20 1.4728. Found, %: C 64.97;
H 8.36. C13H20O4. Calculated, %: C 64.98; H 8.38.
Oxalic acid exo-5-methylbicyclo[2.2.1]hept-2-
exo-yl monoester (IIb). Amixture of 54 g of compound
Ib, of oxalic acid and of solvent was heated at 150°C.
From the condensate we isolated 44.3 g (89.5%) of
compound IIb, bp 109–110°C (10 mm Hg), d240 1.0186,
nD20 1.4720. Found, %: C 60.58; H 7.11. C10H14O4.
Calculated, %: C 60.60; H 7.12.
Adipic acid exo-5-methylbicyclo[2.2.1]hept-2-
exo-yl monoester (VIb). From 54 g of compound Ib
and 36.5 g of adipic acid at 160°C was obtained 44.4 g
(70%) of compound VIb, bp 145–147°C (5 mm Hg), d420
1.0052, nD20 1.4822. Found, %: C 66.11; H 8.71. C14H22O4.
Calculated, %: C 66.12; H 8.72.
Maleic acid exo-bicyclo[2.2.1]hept-2-yl mono-
ester (VIIa). From 47 g of compound Ia and 29 g of
maleic acid at 130°C we obtained 48.3 g (92%) of
compound VIIa, bp 121–122°C (5 mm Hg), d240 1.0191,
nD20 1.4798. 1H NMR spectrum, d, ppm: 1.1–1.41 d (8H,
4CH2), 2.20–2.21 m (2H, 2CH), 4.60 d (1H, CH), 6.0–
6.2 m (2H, 2CH=), 10.10 s (1H, COOH). Found, %:
C 62.83; H 6.70. C11H14O4. Calculated, %: C 62.85;
H 6.71.
Malonic acid exo-bicyclo[2.2.1]hept-2-yl
monoester (IIIa). From 47 g of compound Ia and 26 g
of malonic acid at 150°C was obtained 40.6 g (82%) of
compound IIIa, bp 107–108°C (10 mm Hg), d240 1.0315,
nD20 1.4705. 1H NMR spectrum, d, ppm: 1.0–1.41 d (8H,
4CH2), 1.25 t (2H, CH2), 2.20–2.22 m (2H, 2CH), 4.60 d
(1H, CH), 10.0 s (1H, COOH). Found, %: C 60.59;
H 7.11. C10H14O4. Calculated, %: C 60.60; H 7.12.
Malonic acid exo-5-methylbicyclo[2.2.1]hept-2-
exo-yl monoester (IIIb). Amixture of 54 g of compound
Ib and 26 g of malonic acid was heated at 150°C to
obtain 42.9 g (81%) of compound IIIb, bp 120–122°C
(10 mm Hg), d240 1.0170, nD20 1.4731. Found, %: C 62.25;
H 7.58. C11H16O4. Calculated, %: C 62.26; H 7.59.
Maleic acid exo-5-methylbicyclo[2.2.1]hept-2-
exo-yl monoester (VIIb). From 54 g of compound Ib
and 29 g of maleic acid at 130°C we obtained 49.2 g
(88%) of compound VIIb, bp 132–135°C (5 mm Hg),
d420 1.0102, nD20 1.4858. Found, %: C 64.26; H 7.18.
C12H16O4. Calculated, %: C 64.28; H 7.19.
Succinic acid exo-bicyclo[2.2.1]hept-2-yl mono-
ester (IVa). From 47 g of compound Ia and 29.5 g of
succinic acid at 150°C was obtained 40.3 g (76.6%) of
compound IVa, bp 122–123°C (10 mm Hg), d240 1.0223,
nD20 1.4760. Found, %: C 62.27; H 7.57. C11H16O4.
Calculated, %: C 62.25; H 7.59.
3-Hydroxysuccinic acid exo-bicyclo[2.2.1]hept-
2-yl monoester (VIIIa). From 47 g of compound Ia
and 33.5 g of malic acid at 150°C we obtained 54.1 g
(95%) of compound VIIIa, bp 123–124°C (5 mm Hg),
d420 1.0101, nD20 1.4690. Found, %: C 57.86; H 7.05.
C11H16O5. Calculated, %: C 57.89; H 7.06.
Succinic acid exo-5-methylbicyclo[2.2.1]hept-2-
exo-yl monoester (IVb). From 54 g of compound Ib
and 29.5 g of succinic acid at 150°C was obtained 41.5 g
(73.4%) of compound IVb, bp 133–135°C (10 mm Hg),
d420 1.0105, nD20 1.4805. Found, %: C 63.71; H 8.01.
C12H18O4. Calculated, %: C 63.70; H 8.02.
3-Hydroxysuccinic acid exo-5-methylbicyclo-
[2.2.1]hept-2-exo-yl monoester (VIIIb). From 54 g of
compound Ib and 33.5 g of malic acid at 150°C we
obtained 55.9 g (92.5%) of compound VIIIb, bp 132–
135°C (5 mm Hg), d420 1.1065, nD20 1.4635. Found, %:
C 59.47; H 7.47. C12H18O5. Calculated, %: C 59.48;
H 7.48.
Glutaric acid exo-bicyclo[2.2.1]hept-2-yl
monoester (Va). From 47 g of compound Ia and 33 g of
glutaric acid at 150°C was obtained 40.4 g (71.5%) of
compound Va, bp 133–134°C (10 mm Hg), d240 1.02001,
nD20 1.4718. Found, %: C 63.70; H 8.01. C12H18O4.
Calculated, %: C 63.71; H 8.02.
d-Tartaric acid exo-bicyclo[2.2.1]hept-2-yl
monoester (IXa). From 47 g of compound Ia and 37.5
g of d-tartaric acid at 150°C we obtained 58.2 g (93.5%)
of compound IXa, bp 131–132°C (5 mm Hg), d240 1.0305,
nD20 1.4695. Found, %: C 54.07; H 6.58. C11H16O6.
Calculated, %: C 54.09; H 6.60.
Glutaric acid exo-5-methylbicyclo[2.2.1]hept-2-
exo-yl monoester (Vb). From 54 g of compound Ib
and 33 g of glutaric acid at 150°C we obtained 43.2 g
72%) of compound Vb, bp 130–132°C (5 mm
Hg), d240 1.0095, nD20 1.4810. Found, %: C 64.97; H 8.36.
C13H20O4. Calculated, %: C 64.98; H 8.39.
d-Tartaric acid exo-5-methylbicyclo[2.2.1]hept-
2-exo-yl monoester (IXb). From 54 g of compound Ib
and 37.5 g of d-tartaric acid at 150°C we obtained 58 g
(90%) of compound IXb, bp 148–150°C (5 mm Hg), d420
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006

MAMEDOV, RASULOVA
1140
1.1025, nD20 1.4790. Found, %: C 55.78; H 7.01. C12H18O6.
Calculated, %: C 55.80; H 7.02.
3-Hydroxysuccinic acid exo-tricyclo[5.2.1.02,6]-
dec-3-en-8(9)-exo-yl monoester (XVII). From 66 g
of compound X and 33.5 g of malic acid at 140°C we ob-
tained 55.8 g (83.9%) of compound XVII, bp 119–121°C
(2 mm Hg), d240 1.2015, nD20 1.5201. Found, %: C 63.01;
H 6.66. C14H18O5. Calculated, %: C 63.15; H 6.81.
d-Tartaric acid exo-tricyclo[5.2.1.02,6]dec-3-en-
8(9)-exo-yl monoester (XVIII). From 66 g of
compound X and 37.5 g of d-tartaric acid at 140°C we
obtained 62 g (88%) of compound XVIII, bp 145–147°C
(2 mm Hg), d240 1.2111, nD20 1.5107. Found, %: C 59.48;
H 6.25. C14H18O6. Calculated, %: C 59.56; H 6.43.
Oxalic acid exo-tricyclo[5.2.1.02,6]dec-3-en-8(9)-
exo-yl monoester (XI). From 66 g of compound X and
22.5 g of oxalic acid at 140°C we obtained 53.8 g (97%)
of compound XI, bp 68–69°C (2 mm Hg), d240 1.0262,
nD20 1.5109. Found, %: C 64.73; H 6.22. C12H14O4.
Calculated, %: C 64.86; H 6.35.
Malonic acid exo-tricyclo[5.2.1.02,6]dec-3-en-
8(9)-exo-yl monoester (XII). From 66 g of compound
X and 26 g of malonic acid at 140°C we obtained 47.8 g
(81%) of compound XII, bp 78–80°C (2 mm Hg), d420
1.0181, nD20 1.5208. Found, %: C 66.00; H 6.61. C13H16O4.
Calculated, %: C 66.08; H 6.82.
REFERENCES
Succinic acid exo-tricyclo[5.2.1.02,6]dec-3-en-
8(9)-exo-yl monoester (XIII). From 66 g of compound
X and 29.5 g of succinic acid at 140°C we obtained
48.9 g (78.3%) of compound XIII, bp 86–87°C
(2 mm Hg), d240 1.0113, nD20 1.5261. Found, %: C 67.10;
H 7.09. C14H18O4. Calculated, %: C 67.18; H 7.25.
Glutaric acid exo-tricyclo[5.2.1.02,6]dec-3-en-
8(9)-exo-yl monoester (XIV). From 66 g of compound
X and 33 g of glutaric acid at 140°C we obtained 50.3 g
(76.2%) of compound XIV, bp 97–100°C (2 mm Hg),
d240 1.0080, nD20 1.5282. Found, %: C 68.05; H 7.46.
C15H20O4. Calculated, %: C 68.17; H 7.62.
Adipic acid exo-tricyclo[5.2.1.02,6]dec-3-en-8(9)-
exo-yl monoester (XV). From 66 g of compound X and
36.5 g of adipic acid at 140°C we obtained 50.1 g (72.1%)
of compound XV, bp 105–108°C (2 mm Hg), d240 1.0075,
nD20 1.5298. Found, %: C 68.89; H 7.85. C16H22O4.
Calculated, %: C 69.05; H 7.97.
Maleic acid exo-tricyclo[5.2.1.02,6]dec-3-en-8(9)-
exo-yl monoester (XVI). From 66 g of compound X
and 29 g of maleic acid at 130°C we obtained 55.9 g
(90.2%) of compound XVI, bp 85–88°C (2 mm Hg), d420
1.1122, nD20 1.5185. 1H NMR spectrum, d, ppm: 1.45 m
(2H, CH2), 2.0–2.25 m (4H, 2CH2), 2.25–2.30 d (2H,
2CH), 2.50–2.60 m (2H, 2CH), 4.80–4.88 q (2H, 2CH=),
5.90 d (1H, CH), 6.10–6.25 m (2H, 2CH=), 10.12 s (1H,
COOH). Found, %: C 67.64; H 6.36. C14H16O4.
Calculated, %: C 67.72; H 6.49.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 8 2006