Synthesis of esters from cage-like unsaturated hydrocarbons, carboxylic acid anhydrides, and water

Article abstract of DOI:10.1007/s11178-005-0279-7

A convenient method for the preparation of esters was developed on the basis of reaction of cage-like polycyclic olefins with carboxylic acid anhydrides and water. Mixed anhydrides were found to give rise to the corresponding low-molecular acid esters. Among the obtained esters, acetates possess a pleasant odor, and they can be used as components of synthetic fragrant substances.

Full text of DOI:10.1007/s11178-005-0279-7

Russian Journal of Organic Chemistry, Vol. 41, No. 7, 2005, pp. 974–977. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 7, 2005,
pp. 995–998.
Original Russian Text Copyright © 2005 by Mamedov, Nabieva, Rasulova.
Synthesis of Esters from Cage-Like Unsaturated Hydrocarbons,
Carboxylic Acid Anhydrides, and Water
M. K. Mamedov, E. K. Nabieva, and R. A. Rasulova
Institute of Petrochemical Processes, National Academy of Sciences of Azerbaidjan,
pr. Khodzhaly 30, Baku, 370025 Azerbaidjan
Received August 2, 2004
Abstract—A convenient method for the preparation of esters was developed on the basis of reaction of cage-
like polycyclic olefins with carboxylic acid anhydrides and water. Mixed anhydrides were found to give rise to
the corresponding low-molecular acid esters. Among the obtained esters, acetates possess a pleasant odor, and
they can be used as components of synthetic fragrant substances.
Alicyclic esters derived from saturated monocar-
boxylic acids are successfully used in perfumery as
components of synthetic fragrant substances [1, 2].
These compounds are starting materials in the syn-
thesis of bicyclic ketones, such as camphor and nor-
camphor, which are used in medicine as antiseptics and
for the preparation of smokeless powder [3]. Bornyl
isovalerate and myrtenyl isovalerate are known as
sedative agents for treatment of nervous excitements
and cardiovascular neuroses accompanied by coronary
vasospasms and tachycardia [4]; these esters are also
used in the preparation of printer’s inks [5].
[6, 7] and of diesters by acylation and acetoxylation
of unsaturated bicyclic alcohols [8]. The present com-
munication reports on the synthesis of esters under
mild conditions by reactions of cyclic olefins with
saturated monocarboxylic acid anhydrides and water.
Cage-like cyclic olefins, bicyclo[2.2.1]hept-2-ene (I)
and its 5-methyl-substituted analog II reacted with
water and acetic, propionic, and mixed acetic pro-
pionic anhydrides at a ratio of 1:1:1 (140–160°C,
reaction time 4 h) to give the corresponding bicyclic
esters III–VI in 72–94% yield (Scheme 1). According
to the GLC data, bicyclo[2.2.1]hept-2-ene (I) gave rise
to stereoisomerically pure bicyclo[2.2.1]hept-exo-2-yl
acetate (III), while from exo-5-methylbicyclo[2.2.1]-
hept-2-ene (II) we obtained a mixture of two regio-
We previously developed procedures for the syn-
thesis of alicyclic esters by catalytic and thermal
addition of monocarboxylic acids to cyclic olefins
Scheme 1.
7
9
1
O
Me
8
2
6
10
MeC(O)OC(O)Me
R
3
+
MeCOOH
4
H
O
5
H
III, IV
MeC(O)OC(O)R'
R'C(O)OC(O)R'
+
H2O
III, IV
+
R'COOH
R
H
I, II
O
R'
R
+
R'COOH
H
O
H
V, VI
I, III, V, R = H; II, IV, VI, R = Me; R' = Et.
1070-4280/05/4107-0974 © 2005 Pleiades Publishing, Inc.

SYNTHESIS OF ESTERS FROM CAGE-LIKE UNSATURATED HYDROCARBONS
975
Scheme 2.
10
3
O
1
4
MeC(O)OC(O)Me
MeC(O)OC(O)Et
EtC(O)OC(O)Et
2
9
12
Me
+
MeCOOH
11
O
5
7
6
8
VIII
+
H2O
VIII
+
EtCOOH
VII
O
+
EtCOOH
O
Et
IX
(VII). The reactions of VII with acetic, acetic pro-
pionic, and propionic anhydrides involved the double
bond in the norbornene fragment, and the products
were tricyclo[5.2.1.02,6]dec-3-en-8(9)-yl esters VIII
and IX (yield 72–91%; Scheme 2). Likewise, exo,exo-
tetracyclo[4.4.12,5.17,10.01,6]dodec-3-ene (X) and its
8-methyl-substituted analog XI reacted with the same
anhydrides in the presence of water to afford the cor-
responding tetracyclic esters XII–XV in 61–85% yield
(Scheme 3).
isomers: 97.0% of exo-5-methylbicyclo[2.2.1]hept-
exo-2-yl acetate (IV) and 3.0% of exo-6-methylbicy-
clo[2.2.1]hept-exo-2-yl acetate.
The reaction of I and II with acetic propionic
anhydride at 150°C afforded only the corresponding
acetates III and IV in 83–85% yield. Here, the regio-
selectivity was higher than in the reaction with acetic
anhydride. From 5-methylbicyclo[2.2.1]hept-2-ene,
acetic propionic anhydride, and water we obtained
99.5% of exo-5-methylbicyclo[2.2.1]hept-exo-2-yl
acetate (IV), while the fraction of the exo-6-methyl
isomer was as small as 0.5%. The reactions of bicyclic
olefins I and II with propionic anhydride required
a higher temperature (by 10°C), as compared to acetic
propionic anhydride. The products were propionic acid
esters V and VI which were formed in 72–77% yield.
In order to elucidate how the nature of the cage-like
skeleton affects the process, we examined analogous
reactions of exo-tricyclo[5.2.1.02,6]deca-3,8-diene
The structure of the products was additionally con-
firmed by independent syntheses, i.e., by acylation of
the corresponding alcohols according to the procedure
described in [9]. The purity of the isolated products
was 99.7–99.9%. In the IR spectra of these compounds
we observed strong absorption bands in the regions
1730–1740 and 1200–1250 cm–1, which are typical of
1
ester groups. Their H NMR spectra contained signals
at δ 4.60–4.80 ppm due to exo-protons. The ester
Scheme 3.
14
13 Me
3
11
7
O
4
1
2
10
6
9
15
R
MeC(O)OC(O)Me
5
O
+
MeCOOH
12
8
H
XII, XIII
MeC(O)OC(O)R'
R'C(O)OC(O)R'
+
H2O
XII, XIII
+
R'COOH
O
R
H
H
H
R'
X, XI
O
R
+
R'COOH
H
XIV, XV
X, XII, XIV, R = H; XI, XIII, XV, R = Me; R' = Et.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005

MAMEDOV et al.
976
(C7), 35.92 (C4), 40.04 (C3), 41.98 (C1), 77.42 (C2),
169.7 (CO). Found, %: C 70.05; H 9.10. C9H14O2.
Calculated, %: C 70.08; H 9.14.
b. Ester III was synthesized in a similar way from
47 g of compound I, 58 g of acetic propionic anhy-
dride, and 9 g of water; the mixture was stirred for 4 h
at 150°C. Yield 63.4 g (83%), bp 100–102°C (30 mm),
d420 = 1.0302, nD20 = 1.4588.
carbonyl carbon atoms give signals at δC 160.98–
169.7 ppm in the 13C NMR spectra.
The esters were isolated as colorless transparent
liquids possessing a grass, flower, or fruit odor, and
they may be recommended for use as components of
fragrant substances.
EXPERIMENTAL
exo-5-Methylbicyclo[2.2.1]hept-exo-2-yl acetate
(IV). a. A mixture of 54 g of compound II, 51 g of
acetic anhydride, and 9 g of water was heated for 4 h at
140°C. Acetic acid was distilled off, and fractional
distillation under reduced pressure gave 75.6 g (90%)
of ester IV with bp 106–107°C (30 mm), d420 = 1.0035,
nD20 = 1.4612. IR spectrum, ν, cm–1: 1730 (C=O), 1220
The IR spectra were recorded on a UR 20 instru-
ment. The H NMR spectra were measured on a Tesla
1
BS-487 instrument (80 MHz) using carbon tetrachlo-
ride as solvent and hexamethyldisiloxane as internal
reference. The 13C NMR spectra were obtained on
a Varian spectrometer at 80 MHz from solutions in
dioxane. The initial compound and reaction products
were analyzed by GLC on an LKhM-8MD chroma-
tograph (1.5-m column, stationary phase 10% of
polyethylene glycol succinate on Sferokhrom; injector
temperature 200–250°C, oven temperature 120–150°C;
carrier gas helium, flow rate 45 ml/min)..
1
(C–O–C), 1380 (CH3), 1375 (CH3). H NMR spec-
trum, δ, ppm: 1.24 s (3H, CH3), 1.30–1.90 d (8H,
CH2), 2.20 s (3H, CH3), 2.24 s (3H, CH3), 2.45 m (2H,
13
CH), 4.75 d (2H, CH). C NMR spectrum, δC, ppm:
17.10 (CH3), 20.95 (COCH3), 32.62 (C5), 33.44
(C6), 37.10 (C7), 37.44 (C4), 39.64 (C3), 42.42 (C1),
74.22 (C2), 166.36 (CO). Found, %: C 71.38; H 9.49.
C10H16O2. Calculated, %: C 71.42; H 9.52.
Initial cyclic olefins, bicyclo[2.2.1]hept-2-ene (I)
and 5-methylbicyclo[2.2.1]hept-2-ene (II), were syn-
thesized by Diels–Alder reaction of cyclopentadiene
with ethylene and propylene, respectively; tetracyclo-
[4.4.12,5.17,10.01,6]dodec-3-ene (X) and 8-methyltetra-
cyclo[4.4.12,5.17,10.01,6]dodec-3-ene (XI) were prepared
by the procedures reported in [10, 11]. The initial
cyclic olefins were preliminarily converted into exo
isomers by treatment with AlCl3 in methylene chloride
according to [12]: exo-5-methylbicyclo[2.2.1]hept-2-
ene (II), bp 116°C, d420 = 0.8602, n2D0 = 1.4599; exo-
tricyclo[5.2.1.02,6]deca-3,8-diene (VII), mp 19.5°C;
exo,exo-tetracyclo[4.4.12,5.17,10.01,6]dodec-3-ene (X),
bp 94–95°C (11 mm), d420 = 1.0002, nD20 = 1.5168;
exo,exo-8-methyltetracyclo[4.4.12,5.17,10.01,6]dodec-3-
ene (XI), bp 128–129°C (28 mm), d240 = 1.0012,
nD20 = 1.5190.
b. Likewise, from 54 g of compound II, 58 g of
acetic propionic anhydride, and 9 g of water (150°C,
4 h) we obtained 71.4 g (85%) of ester IV, bp 106–
107°C (30 mm), d420 = 1.0045, nD20 = 1.4622.
Bicyclo[2.2.1]hept-exo-2-yl propionate (V).
A mixture of 47 g of compound I, 65 g of propionic
anhydride, and 9 g of water was heated for 4 h at
160°C. Vacuum fractionation gave 63.7 g (76.6%) of
ester V, bp 100–101°C (25 mm), d420 = 0.9998, nD20 =
1.4592. IR spectrum, ν, cm–1: 1730 (C=O), 1220
(C–O–C), 1380 (CH3). Found, %: C 71.10; H 9.32.
C10H16O2. Calculated, %: C 71.42; H 9.52.
exo-5-Methylbicyclo[2.2.1]hept-exo-2-yl pro-
pionate (VI). A mixture of 54 g of compound II, 65 g
of propionic anhydride, and 9 g of water was heated
for 4 h at 160°C. Yield 65.5 g (72%), bp 119–120°C
(4 mm), d420 = 0.9891, nD20 = 1.4616. IR spectrum, ν,
cm–1: 1730 (C=O), 1220 (C–O–C), 1380 (CH3), 1375
(CH3). Found, %: C 72.39; H 9.70. C11H18O2. Calcu-
lated, %: C 72.53; H 9.89.
exo-Tricyclo[5.2.1.02,6]dec-3-en-exo-8(9)-yl
acetate (VIII). a. A mixture of 66 g of compound VII,
51 g of acetic anhydride, and 9 g of water was heated
for 4 h at 140°C. Yield 87 g (90.6%), bp 130–131°C
(10 mm), d420 = 1.0620, nD20 = 1.5038. IR spectrum, ν,
cm–1: 1730 (C=O), 1220 (C–O–C), 1380 (CH3).
1H NMR spectrum, δ, ppm: 1.36 m (2H, CH2), 2.00 d
(2H, CH), 2.26 m (4H, CH2), 2.52–2.62 m (2H, CH),
The reactions were performed in a stainless steel
high-pressure reactor.
Bicyclo[2.2.1]hept-exo-2-yl acetate (III). a. A mix-
ture of 27 g of compound I, 51 g of acetic anhydride,
and 9 g of water was heated for 4 h at 140°C. Acetic
acid was distilled off, and fractional distillation under
reduced pressure gave 72 g (94%) of compound III
with bp 100–101°C (30 mm), d420 = 1.0268, nD20
=
1.4565. IR spectrum, ν, cm–1: 1730 (C=O), 1220
1
(C–O–C), 1380 (CH3). H NMR spectrum, δ, ppm:
1.30–1.90 d (8H, CH2), 2.20 s (3H, CH3), 2.50–2.55 m
(2H, CH), 4.75 d (2H, CH). 13C NMR spectrum, δC,
ppm: 20.94 (COCH3), 24.74 (C6), 28.62 (C5), 35.57
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005

SYNTHESIS OF ESTERS FROM CAGE-LIKE UNSATURATED HYDROCARBONS
977
4.81–4.88 d (2H, CH), 5.75–5.90 q (2H, CH=).
13C NMR spectrum, δC, ppm: 17.62 (COCH3), 26.00
(C10), 35.53 (C5), 36.02 (C9), 37.88 (C7), 38.93 (C1),
41.92 (C6), 45.72 (C2), 73.90 (C8), 121.69 (C3), 128.55
(C4), 166.2 (CO). Found, %: C 74.62; H 8.26.
C12H16O2. Calculated, %: C 74.91; H 8.35.
b. A mixture of 66 g of compound VII, 58 g of
acetic propionic anhydride, and 9 g of water was
heated for 4 h at 150°C. Yield 78.2 g (81.5%), bp 130–
132°C (10 mm), d420 = 1.0602, nD20 = 1.5033.
b. A mixture of 87 g of compound XI, 58 g of
acetic propionic anhydride, and 9 g of water was
heated for 4 h at 150°C. Yield 73 g (62.3%), bp 151–
153°C (2 mm), d420 = 1.0111, n2D0 = 1.5200.
exo,exo-Tetracyclo[4.4.12,5.17,10.01,6]dodec-exo-3-
yl propionate (XIV). A mixture of 80 g of compound
X, 65 g of propionic anhydride, and 9 g of water was
heated for 4 h at 160°C. Yield 82 g (70%), bp 132–
136°C (2 mm), d420 = 1.0708, nD20 = 1.5168. IR spec-
trum, ν, cm–1: 1730 (C=O), 1220 (C–O–C), 1380
(CH3). Found, %: C 78.71; H 9.31. C15H22O2. Calculat-
ed, %: C 78.88; H 9.45.
exo,exo-8-Methyltetracyclo[4.4.12,5.17,10.01,6]-
dodec-exo-3(4)-yl propionate (XV). A mixture of
87 g of compound XI, 65 g of propionic anhydride,
and 9 g of water was heated for 4 h at 160°C. Yield
75 g (60%), bp 150–152°C (2 mm), d420 = 1.0109, nD20 =
1.52018. IR spectrum, ν, cm–1: 1730 (C=O), 1220
(C–O–C), 1380 (CH3), 1375 (CH3). Found, %: C 77.18;
H 9.60. C16H24O2. Calculated, %: C 77.42; H 9.67.
exo-Tricyclo[5.2.1.02,6]dec-3-en-exo-8(9)-yl pro-
pionate (IX). A mixture of 66 g of compound VII,
65 g of propionic anhydride, and 9 g of water was
heated for 4 h at 160°C. Yield 73.7 g (71.6%), bp 108–
110°C (2 mm), d420 = 1.0546, nD20 = 1.5059. IR spec-
trum, ν, cm–1: 1730 (C=O), 1220 (C–O–C), 1380
(CH3). Found, %: C 75.42; H 8.50. C13H18O2. Calcu-
lated, %: C 75.67; H 8.78.
exo,exo-Tetracyclo[4.4.12,5.17,10.01,6]dodec-exo-3-
yl acetate (XII). a. A mixture of 80 g of compound X,
51 g of acetic anhydride, and 9 g of water was heated
for 4 h at 140°C. Yield 93 g (84.6%), bp 155–156°C
(10 mm), d420 = 1.0963, nD20 = 1.5060. IR spectrum, ν,
cm–1: 1730 (C=O), 1220 (C–O–C), 1380 (CH3).
1H NMR spectrum, δ, ppm: 1.75–1.81 m (4H, CH2),
2.15 s (3H, CH3), 2.11–2.35 m (2H, CH), 2.41–2.65 d
(2H, CH), 4.78 m (1H, CH). 13C NMR spectrum, δC,
ppm: 14.48 (COCH3), 24.93 (C9), 28.51 (C8), 29.52
(C11), 32.71 (C12), 33.85 (C10), 33.93 (C7), 34.04
(C6), 35.09 (C1), 40.30 (C5), 42.62 (C4), 42.87 (C2),
70.96 (C3), 162.72 (CO). Found, %: C 76.20; H 9.11.
C14H20O2. Calculated, %: C 76.32; H 9.14.
REFERENCES
1. Kustova, S.D., Titova, N.B., and Duchinskaya, Yu.I.,
Maslo-zhir. Promst., 1965, no. 7, p. 45.
2. JPN Patent no. 2000-131177; Ref. Zh., Khim., 2003,
no. 4N189P.
3. Kheifits, L.A. and Dashunin, V.M., Dushistye veshche-
stva i drugie produkty parfyumerii (Fragrant Substances
and Other Perfume Products), Moscow: Khimiya, 1994,
p. 73.
4. Murav’eva, D.A., Farmakognoziya (Pharmacognosy),
Moscow: Meditsina, 1978, p. 224.
5. Chem. News, 2002, vol. 77, p. 17; Ref. Zh., Khim., 2003,
no. 15N17.
6. Mamedov, M.K. and Suleimanova, E.T., Zh. Org.
Khim., 1993, vol. 29, p. 1138.
7. Mamedov, M.K., Nabieva, E.K., and Dzhafarova, E.N.,
Russ. J. Org. Chem., 2001, vol. 37, p. 1700.
8. Mamedov, M.K., Russ. J. Org. Chem., 2000, vol. 36,
p. 203.
9. Weygand–Hilgetag organisch-chemische Experimen-
tierkunst, Hilgetag, G. and Martini, A., Eds., Leipzig:
Johann Ambrosius Barth, 1964, 3rd ed. Translated
under the title Metody eksperimenta v organicheskoi
khimii, Moscow: Khimiya, 1968, p. 351.
b. Ester XII was obtained from 80 g of compound
X, 58 g of acetic propionic anhydride, and 9 g of water
(150°C, 4 h). Yield 86 g (78.5%), bp 155–156°C
(10 mm), d420 = 1.0972, nD20 = 1.5041.
exo,exo-8-Methyltetracyclo[4.4.12,5.17,10.01,6]-
dodec-exo-3(4)-yl acetate (XIII). a. A mixture of 87 g
of compound XI, 51 g of acetic anhydride, and 9 g of
water was heated for 4 h at 140°C. Yield 80 g (68.5%),
bp 190–192°C (10 mm), d420 = 1.0651, nD20 = 1.5156.
IR spectrum, ν, cm–1: 1730 (C=O), 1220 (C–O–C),
1
1380 (CH3), 1375 (CH3). H NMR spectrum, δ, ppm:
1.28 s (3H, CH3), 1.78–1.95 m (2H, CH), 2.15 s (3H,
CH3), 2.21 m (2H, CH2), 2.40–2.65 m (2H, CH), 2.55–
2.62 m (2H, CH), 3.80 d (1H, CH), 4.80 d (1H, CH).
13C NMR spectrum, δC, ppm: 13.81 (CH3), 14.42
(COCH3), 24.91 (C9), 28.51 (C8), 29.52 (C11), 32.70
(C12), 33.80 (C10), 33.90 (C7), 34.04 (C6), 35.08 (C1),
40.62 (C4), 42.31 (C5), 42.85 (C2), 70.95 (C3), 161.98
(CO). Found, %: C 78.74; H 9.40. C15H22O2. Calculat-
ed, %: C 78.88; H 9.45.
10. Mamedov, M.K. and Suleimanova, E.T., Neftekhimiya,
1991, vol. 31, no. 3, p. 350.
11. Mamedov, M.K. and Suleimanova, E.T., Zh. Org.
Khim., 1993, vol. 29, p. 1143.
12. US Patent no. 4107223, 1979; Ref. Zh., Khim., 1980,
no. 10N108P.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 7 2005