Synthesis of 8-acetoxytetracyclo[4.4.12.5.17.10.01.6]dodec-3-ene and diesters of C1-C5 acids on its basis

Article abstract of DOI:10.1134/S1070363214090035

Reaction of vinyl acetate with tricyclo[5.2.1^2.5.1.0^2.6]deca-3,8-diene in the presence of nano-TiO₂ (20 nm) catalyst was studied. 8-Acetoxytetracyclo[4.4.1^2.5.1^7.10.0^1.6]dodec-3-ene was obt

Full text of DOI:10.1134/S1070363214090035

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 9, pp. 1662–1666. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © M.K. Mamedov, E.G. Mahmudova, Ch.K. Salmanova, 2014, published in Zhurnal Obshchei Khimii, 2014, Vol. 84, No. 9,
pp. 1420–1424.
Synthesis of 8-Acetoxytetracyclo[4.4.12.5 .17.10 .0 1.6]dodec-3-ene
and Diesters of C1–C5 Acids on Its Basis
M. K. Mamedov, E. G. Mahmudova, and Ch. K. Salmanova
Mamedaliev Institute of Petrochemical Processes, Azerbaijan National Academy of Sciences,
Khodzhaly av. 30, Baku, 1025 Azerbaijan
e-mail: meh_nur@mail.ru
Received January 9, 2014
Abstract—Reaction of vinyl acetate with tricyclo[5.2.12.5.1.02.6]deca-3,8-diene in the presence of nano-TiO2
(20 nm) catalyst was studied. 8-Acetoxytetracyclo[4.4.12.5.17.10.01.6]dodec-3-ene was obtained in 88.5% yield.
Addition of saturated monobasic acids C1–C5 to the obtained unsaturated monoester in the presence of the
boron trifluoride etherate catalyst was investigated. Corresponding diesters were obtained in 68.1–93.0% yield.
They can be used as the additives to synthetic oils and as components of perfumes.
Keywords: nano-TiO2, dicyclopentadiene, condensation, vinyl acetate, tetracyclododecene, boron trifluoride
etherate
DOI: 10.1134/S1070363214090035
Diesters of polycyclic diols and hydroxy acids are
known to be successfully used as the plasticizers of
polymer materials significantly improving the
physicochemical properties [1].
bicyclo[2.2.1]hept-2-ene [6]. In this work it was also
shown that besides monoadduct insignificant amount
of bis-adduct, 8-acetoxytetracyclo[4.4.12.5.17.10.01.6]dodec-
3-ene I formed.
In this study with the purpose of the synthesis of
new diesters of tetracyclododecanediol we have studied
the reaction of vinyl acetate with tricyclo [5.2.1.02.6]-
deca-3,8-diene.
Diesters of saturated asids are also used to improve the
quality of mineral oils and their operating properties [2].
Diesters of polycyclic diols are utilized in the per-
fumery as components of synthetic aromatic sub-
stances as reported in scientific publications [3–5].
The depolymerization of tricyclo[5.2.1.02.6]deca-
3,8-diene to cyclopentadiene and its condensation with
vinyl acetate was carried out in the presence of
heterogenic nano-TiO2 catalyst (20 nm) (Scheme 1).
Recently we have studied cycloaddition of cyclo-
pentadiene with vinyl acetate affording and 5-acetoxy-
Scheme 1.
TiO2
TiO2
H
2
CH2
O
O
_
+ CH_O_C_CH3
CH3 C_O_
H
H
O
O
O
TiO2
_
_
_
CH3 C_O_
+
CH3 C_O
+
CH3 C_O
H
H
H
endo/endo-I
1662
exo/exo-I

SYNTHESIS OF 8-ACETOXYTETRACYCLO[4.4.12.5.17.10.01.6]DODEC-3-ENE
1663
Scheme 2.
O
3
3
O_C_R
11
7
11
7
15
4
1
O
O
4
2H
2
10
10
6
1
9
9
cat
_
_
CH3 C_O
+
R_COOH
CH3 C_O
12
12
5
13
14
5
13
14
8
H
8
6
H
I
II_VII
VIII_XIII
R = H (II), CH3 (III), CH3CH2 (IV), (CH3)2CH (V), CH3(CH2)2 (VI), C4H9 (VII).
All three stages of the reaction simultaneously
proceed in a pressure reactor. The effect of tem-
perature, of molar ratio of components, of the reaction
time, and of the amount of nano-TiO2 catalyst on the
yield of compound I was studied, and optimal param-
eters of synthetic procedure for the target product were
evaluated. It was shown that optimum parameters of
synthesis areas follows: tricyclo[5.2.1.02.6]deca-3,8-
diene : vinyl acetate molar ratio 1 : 1–1.25 wt % of
nano-TiO2 catalyst, 0.2 mass % of hydroquinone with
respect to tricyclo[5.2.1.02.6]deca-3,8-diene, tempera-
ture 190°C, and the reaction time 4 h. After filtering of
the heterogenic catalyst and distillation in a vacuum
the target product I was obtained in 88.5% yield.
90°C the yield of tetracyclododecan-3,8-diol diacetate
IX increases from 52.5 to 70.0%. Further increase in
temperature to 120°C causes the decrease in the yield
of compound IX to 50.0% due to the formation of side
products of dimerization and oligomerization of the
starting substance I. Therefore 90°C was accepted as
the optimum reaction temperature (see Fig. 1a).
The dependence of the target product yield on the
I : III reagent ratio was studied in the range 1 : (1–1.5)
(see Fig. 1b). Experiments were carried out at 90°C for
3 h using 0.2 wt % of catalyst. The yield of diester IX
grows from 45.5 to 76.0% at the increase of reagent
ratio from 1 : 1 to 1 : 1.3. Further increase to 1.5 mol
decreases the yield of the target product to 73.2%.
The composition and purity of the synthesized
unsaturated tetracyclic monoesters were evaluated by
means of GLC. It was shown that monoester is a
mixture of 28.0% of endo-endo- and 72% of exo-exo-
steric isomers.
The influence of the catalyst amount was studied at
the above-established optimum values of the
temperature and reagent ratio and the reaction time 3 h
(see Fig. 1c). Amount of catalyst was varied in the
range 0.4–0.6 wt %. The use of 0.5 wt % of catalyst
was optimal, because the yield increased from 60% to
79%. Using larger amount of the boron trifluoride
etherate decreased the target product yield to 56.5%.
The product obtained was heated at 200°C for 1 h
to carry out isomerization of the mixture to most stable
exo-exo-isomer [7]. This process resulted in the
formation of monoester containing 99.9% of exo-exo-
and 0.1% of endo-endo- isomer.
Yield of compound IX depends also significantly
on the reaction time (see Fig. 1d). Its increase from
1 to 4 h permits to achieve 90% yield of diacetate, but
more prolonged heating decreases the yield of
compound IX to 85%.
In the second step of our work the synthesis of
diesters by catalytic addition of saturated C1-C5
monobasic acids to cycloalkene I was investigated.
Boron trifluoride etherate as catalyst was used. The
reaction can be described by the Scheme 2.
Hence, optimal parameters of diacetate IX forma-
tion in the reaction of compound I with the acetic acid
III in the presence of boron trifluoride etherate are as
follows: reaction temperature 90°C, molar ratio of com-
pounds I and III 1 : 1.3, amount of the catalyst 0.5 wt %
with respect to substance I, reaction time 4 h. Under
optimum conditions yield of product IX reaches 90%.
Addition of formic II, propionic IV, butyric V,
isobutyric VI, and n-valeric VII acids was carried out
analogously. Yields of the products, their physico-
chemical characteristic, and elemental analysis data are
listed in Table 1.
By an example of acetic acid the effect of
temperature, of molar ratio of the reaction components,
of the amount of catalyst, and of the reaction time on
the yield of tetracyclo[4.4.12.5.17.10.01.6]dodecan-3.8-
diol diacetate IX was studied.
I : III molar ratio 1 : 1, 0.2 wt % of catalyst and the
reaction time 3 h were used as starting conditions. The
temperature of the reaction was varied with in the limits
70–120°C. At the increase in temperature from 70 to
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 9 2014

1664
MAMEDOV et al.
Yield, %
(a)
(b)
Yield, %
1 : 1 1 : 1.1
1 : 1.3 1 : 1.5
Т, °С
I : III molar ratio
(c)
(d)
Yield, %
Yield, %
Time, h
Amount of BF3O·(Et)2, %
Fig. 1. (a) Dependence of the diacetate IX yield on temperature, (b) molar ratio of reagents I : III, (c) amount of the boron
trifluoride etherate catalyst, (d) and the reaction time.
Table 1. Yields, physicochemical constants, and elemental analysis data of the synthesized diesters of tetracyclododecan-3,8-
diol and saturated acids
Physicochemical constants
Found, %
Calculated, %
Acid
С1–С5
Yield,
%
Diester
Formula
bp, °С
d420
nD20
С
Н
С
Н
(1 mmHg)
148–151
162–165
171–174
186–188
170–173
193–195
II
VIII
IX
93.0
90.0
84.9
76.5
70.4
68.1
1.1821
1.1204
1.1108
1.1088
1.1015
1.1001
1.5006
1.5038
1.5049
1.5068
1.5038
1.5011
68.02
68.91
69.71
70.44
70.39
71.18
7.52
7.87
8.19
8.50
8.45
8.70
С15Н20О4
С16Н22О4
С17Н24О4
С18Н26О4
С18Н26О4
С19Н28О4
68.16
69.05
69.84
70.56
70.56
71.32
7.63
7.97
8.27
8.55
8.55
8.81
III
IV
V
X
XI
VI
VII
XII
XIII
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 9 2014

SYNTHESIS OF 8-ACETOXYTETRACYCLO[4.4.12.5.17.10.01.6]DODEC-3-ENE
Table 2. Parameters of the IR and 13C NMR spectra of compounds I and IX
1665
Structure
ν, cm–1
δС, ppm
2800–3000 (СН, СН2), 3100, 1645 165.81 (С13), 136.40 (С3), 135.85 (С4), 59.61
(НС=СН), 1730 (С=О), 1380 (СН3) (С8), 53.44 (С2), 50.20 (С5), 48.50 (С6), 47.12
3
11
10
4
O
2
(С1), 47.05 (С7), 43.60 (С10), 40.56 (С9), 36.71
(С11), 34.46 (С12), 17.88 (С14)
1
9
1100–1250 (С–О–С)
_
CH3 C_O
12
5
14
13
7
8
6
H
705, 1440, 1366, 2938 (СН2, СН3); 163.75 (С13), 164.52 (С15), 78.12 (С3), 77.45
1017, 1056, 1233, 1292 (С–О–С), (С8), 35.91 (С4), 32.45 (С9), 52.45 (С2), 49.82
O
3
O_C_CH3
11
7
2 H 15
16
(С5), 40.05 (С1), 38.91 (С6), 35.6 (С7), 34.55
(С10), 28.01 (С11), 27.85 (С12), 18.92 (С14),
19.62 (С15)
4
1730 (С=О)
O
10
1
9
_
CH3 C_O
12
14
13
5
8
6
H
From the presented data it is seen that the yield
exo-exo ones, at 6.1–6.3 ppm. After the isomerization
the signals of endo-endo isomer are absent.
diesters of tetracyclododecan-3,8-diol decreases from
93.0 to 68.1% at the increase in molecular mass of the
acid from formic to n-valeric one. Hence, the activity
of the acids in the addition to the double bond of
cycloalkene I decreases with the increase in the length
of the saturated residue.
Considering these data the following mechanism of
formation diesters on the basis of unsaturated
tetracyclic monoesters and monobasic saturated acids
in the presence of boron trifluoride etherate catalyst
(Scheme 3) have been suggested.
The structure of the synthesized esters I and IX was es-
tablished by the IR and the 13C NMR spectra (see Table 2).
The diesters obtained are colorless viscous oils.
They may be used as additives to synthetic oils and the
aromatic substances in the perfumeric industry.
1
In the H NMR spectra of esters signals of endo-
endo- isomers are observed at 4.2–4.6 ppm, and of
Scheme 3.
_
O
BF3 OEt2 + R_COOH
H+ R_C_O
+ OEt2
BF3
+
+
_
_
O
O
O
H
R_C_O
CH3 C_O
CH3 C_O
H+
_
_
+
.
BF3
H
H
H
H
H
H
O
O
O_C_R
BF3
O_C_R
H
.
O
BF3
.
O
O
R_C_O_
+
CH3 C_O
CH3 C_O
_
_
H
_BF3
H
H
H
H
H
H
.
BF3 OEt2
BF3 + OEt2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 9 2014

1666
MAMEDOV et al.
procedure). The mixture of 1 mol of compound I,
EXPERIMENTAL
0.3 mol of the acid, and 1.0 g of boron trifluoride
etherate was heated for 4 h at 90°C. After the
completion of the reaction the obtained mixture was
washed with distilled water and dried over sodium
sulfate. Then it was distilled in a vacuum. Yields of the
products, their physicochemical characteristics and
elemental analysis data are presented in Table 1.
IR spectra were obtained on a Bruker Alpha
spectrometer (Germany) in the range 600–4000 cm–1.
NMR spectra were taken on a Bruker AV-300
spectrometer (300 MHz) in acetone-d6.
The composition and purity of starting substances
and the diesters synthesized was evaluated by GLC on
an LKhM-8MD chromatograph, stationary phase 10%
of polyethyleneglycol disuccinate on spherochrom,
column 1.5 m, carrier gas helium, flow rate 50 mL/min,
temperatures of evaporator, column, and detector 250,
190, and 150°C respectively, detector current 120 mA.
Tricyclo[5.2.1.02.6]deca-3,8-diene, vinyl acetate,
and starting saturated acids were freshly distilled.
Their physicochemical properties were in agreement
with the reported data [8–10].
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 9 2014