Products of direct hydroalkoxylation of norbornene with alcohols over H-beta zeolite catalyst

Article abstract of DOI:10.1134/S0965544115020164

The reaction of direct hydroalkoxylation of norbornene in the presence of H-beta zeolite catalyst has been studied. It has been found that the selectivity for exo-alkoxynorbornanes of the reaction of norbornene with monohydric alcohols (saturated, unsatur

Full text of DOI:10.1134/S0965544115020164

ISSN 0965ꢀ5441, Petroleum Chemistry, 2015, Vol. 55, No. 2, pp. 154–162. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © G.Z. Raskil’dina, A.M. Suleimanova, A.N. Kazakova, N.G. Grigor’eva, B.I. Kutepov, S.S. Zlotskii, 2015, published in Neftekhimiya, 2015, Vol. 55, No. 2,
pp. 162–170.
Products of Direct Hydroalkoxylation of Norbornene
with Alcohols over HꢀBeta Zeolite Catalyst
a
b
a
b
G. Z. Raskil’dina , A. M. Suleimanova , A. N. Kazakova , N. G. Grigor’eva ,
b
a
B. I. Kutepov , and S. S. Zlotskii
a
Ufa State Technological University of Petroleum, Ufa, Bashkortostan, Russia
b
Institute of Petroleum Chemistry and Catalysis, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
eꢀmail: nggꢀink@mail.ru
Received August 16, 2014
Abstract—The reaction of direct hydroalkoxylation of norbornene in the presence of Hꢀbeta zeolite catalyst
has been studied. It has been found that the selectivity for exoꢀalkoxynorbornanes of the reaction of norꢀ
bornene with monohydric alcohols (saturated, unsaturated, or aromatic) reaches 98% at a conversion of 78–
9
8% of the unsaturated compound. The reaction of norbornene with diols (ethylene glycol and 2ꢀbuteneꢀ1,4ꢀ
diol) in the presence of Hꢀbeta zeolite affords monoꢀ and diethers, whose yield and ratio can be controlled
by varying reaction parameters.
Keywords: hydroalkoxylation with alcohols, norbornene, zeolite catalyst
DOI: 10.1134/S0965544115020164
Norbornene derivatives are used in organic syntheꢀ and diols with norbornene in the presence of a comꢀ
sis and medicinal chemistry [1, 2] and in the perfume mercially available HꢀBeta zeolite catalyst.
industry [3, 4]. In addition to the first methods for the
synthesis of alkoxynorbornenes described in [5–9],
the direct addition of alcohols to the double bond of
EXPERIMENTAL
norbornene in the presence of sulfuric acid [10] or the
cationꢀexchange resin KUꢀ2ꢀ8 [11] was proposed.
Chromatographic analysis of the products was perꢀ
formed on a Carlo Erba HRGS 5300 Mega Series
New catalytic systems that can mediate the norꢀ chromatograph with a flameꢀionization detector using
bornene hydroalkoxylation reaction have been helium as the carrier gas at a flow rate of 30 mL/min,
reported recently. Most of them are based on trifluoꢀ a SEꢀ30ꢀcoated column of a 25 m length, and the colꢀ
romethanesulfonic acid (TfOH) [12, 13] and its salts, umn temperature programmed from 50 to 280°C at a
such as Cu(OTf) [14, 15], АuClPPh –AgOTf [16], rate of
8°C/min. Mass chromatograms were recorded
2
3
Cp*RuCl (PPh )–AgOTf [17], and AgOTf [18]. High on Fisons (50ꢀm fusedꢀsilica capillary column DB
2
3
yields (90–98%) of alkoxynorbornanes over these catꢀ 560) and Focus instruments with a Finingan DSQ II
alytic systems are obtained only in the reaction of norꢀ mass spectrometric detector (ion source temperature,
bornene with alcohols containing functional groups, 200
°
С
; onꢀcolumn injection temperature, 50–270
°С;
for example, Cl or OR. The addition of unsubstituted heating rate, 10°C/min; Thermo TRꢀ5MS column,
–4
aliphatic alcohols occurs less effectively: the yield of 50
×
2.5 10 m; helium flow rate, 0.7 mL/min). The
×
alkoxynorbornanes is 25–75% in this case [14]. The mass spectra of the compounds were obtained in the
exoꢀisomers dominate (>95%) in the product [14, 15]. electron ionization mode. NMR spectra were
The use of other heterogeneous catalysts, besides recorded on a Bruker AVANCEꢀ400 (1H 400.13 MHz)
the aforementioned sulfonated cationꢀexchange resin spectrometer in CDCl
, using benzeneꢀd and toluꢀ
6
KUꢀ2ꢀ8 [11], for the preparation of alkoxynorborꢀ eneꢀ as an internal standard. Oneꢀ and twoꢀdimenꢀ
3
d
8
nanes has not been described. At the same time, there sional NMR spectra were recorded using standard
are examples of the use of zeolite Beta in the pulse sequences. 2D homonuclear (COSY HH,
hydroalkoxylation of limonene and
ꢀpinene [19], as NOESY) and heteronuclear (HSQC, HMBS) correꢀ
α
well as hexene [20]. It has been shown that alkoxynorꢀ lation experiments were carried out using pulsed field
bornanes can be obtained through the addition of simꢀ gradient techniques.
ple alcohols 2–12 (see below) to norbornene on Hꢀ
Beta zeolite [21, 22].
The HꢀBeta zeolite catalyst was prepared by highꢀ
temperature treatment at 540 of NH4ꢀBeta zeolite
°C
These results have stimulated the development and with a SiO /Al О molar ratio of 18.0 for 4 h in an air
2
2
3
continuation of the study of the reaction of alcohols atmosphere.
154

PRODUCTS OF DIRECT HYDROALKOXYLATION OF NORBORNENE
155
Procedure for Norbornene Reaction
with Alcohols (2–10) and Diols (11 12
С –С7, allyl, and benzyl alcohols) gives corresponding
1
alkoxynorbornanes 13–21:
,
)
A mixture of alcohol and norbornene , taken in a
1
molar ratio of 1 : (1–3), and the HꢀBeta catalyst taken
in an amount of 20 wt % (based on a mixture of norꢀ
bornene : alcohol = 1 : 1 mol/mol) was heated at 50–
+ RꢀOH
O
R
80°C with vigorous stirring for 5 h. After completion
1
2–10
13–21
of the reaction, the catalyst was filtered off. To isolate
the products from the reaction mixture, the unreacted
alcohol was distilled off and ethers 13–21 and 22–25
were isolated by distillation under reduced pressure.
The reaction of norbornene with methanol or ethꢀ
anol at 80°C was carried out in a continuously rotating
thermostated autoclave. The norbornene conversion
was determined chromatographically.
R = Me (2, 13); Et (3, 14); nꢀPr (4, 15); nꢀBu (
Am (6, 17); nꢀHe (7, 18); nꢀHp (8, 19); Bn (9, 20);
All (10, 21).
5, 16);
The data presented in Table 2 show that at 80°С,
wt % catalyst, and a norbornene : alcohol molar
2
0
ratio of 1 : 3, the norbornene conversion reaches 98–
9% and the selectivity for alkoxynorbornanes is 84–
8%.
9
9
The structural characteristics of the synthesized
compounds are shown in Table 1.
Along with alkoxynorbornanes, the reaction mixꢀ
ture contained the following products of side reacꢀ
tions: nortricyclane (NTC), formed via the intramoꢀ
RESULTS AND DISCUSSION
The HꢀBeta zeoliteꢀcatalyzed reaction of norꢀ lecular cyclization of the reactant olefin, and norꢀ
bornene with various monohydric alcohols (aliphatic bornene dimers:
+
+
+
+
1
26a
26b
26c
26d
27
Using the reaction of norbornene with butanol as neous catalyst Cu(OTf)2, with the reaction being carꢀ
an example, we studied the influence of the temperaꢀ ried out in a dioxane medium for 18 h.
ture and the molar ratio of reactants on the norꢀ
bornene conversion and alkoxynorbornane selectivity
Norbornene reacts with allyl alcohol with a high
selectivity (90%) only at 50°С. As the temperature is
(
runs 4–6, Table 2). It was shown that the conversion
of norbornene increases as the temperature increases
from 50 to 80 , with the selectivity for butoxynorborꢀ
nane slightly (by 5%) decreasing as a result of an
increase in the amount of nortricyclane 27
elevated to 80 , oligomeric and polymeric comꢀ
°С
pounds become the main reaction products.
°С
As can be seen from the data in Table 2, by reacting
norbornene with aliphatic С –С4 alcohols and allyl or
1
.
benzyl alcohol, the ethers are formed in the exoꢀconꢀ
1
13
figuration. The analysis by H and C NMR techꢀ
niques of alkoxynorbornanes 17–19 obtained by
reacting norbornene with amyl, hexyl, and heptyl
alcohol, respectively, showed that two diastereomeric
products (exoꢀ and endoꢀisomers) were formed in all
The reactant molar ratio has the most significant
effect on the ether selectivity. For example, a reducꢀ
tion in the norbornene : butanol molar ratio from 1 : 3
to 1 : 1 leads to a significant decrease (by 21%) in the
selectivity for butoxynorbornane, although the conꢀ
version of the cycloalkene remains almost unchanged.
In this case (norbornene : butanol = 1 : 1), the contriꢀ
bution of both the cyclization reaction of norbornene
and its dimerization increases.
13
cases. The C NMR technique proved to be most
informative for the rigorous quantitative determinaꢀ
tion of the isomeric ratio. According to our data, the
exo : endo ratios for ethers 17–19 are 8.5, 4.1, and 2.3,
respectively.
The HꢀBeta zeolite catalyst exhibits a high effiꢀ
ciency not only in the norbornene reaction with aliꢀ
phatic alcohols. Benzyloxynorbornane is produced
The structure of all alkoxynorbornanes synthesized
in this study was proved by oneꢀdimensional and twoꢀ
dimensional homonuclear (SOSY, NOESY) and hetꢀ
1
13
with a selectivity of 95% and an almost complete conꢀ eronuclear (HSQC, HMBC) Н, С NMR spectrosꢀ
13
version of the olefin. Note that these results are similar copy. In the C NMR spectrum, signals of the Cꢀ7
to those obtained by Taylor et al. [14], who prepared atom of alkoxynorbornenes 13–21 appear in the
benzyloxynorbornane in the presence of the homogeꢀ region of 34.7–35.1 ppm, suggesting the exoꢀconfiguꢀ
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RASKIL’DINA et al.
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PRODUCTS OF DIRECT HYDROALKOXYLATION OF NORBORNENE
161
Table 2. Reaction of norbornene
alyst, 5 h)
1
with monohydric alcohols
2–10 in the presence of HꢀBeta zeolite (20 wt % HꢀBeta catꢀ
Selectivity, %
ether
Run
no.
1
: ROH molar
ratio
Conversion
of , %
ROH
T
, °C
1
NTC
dimers 1
exoꢀ
endoꢀ
1
2
3
4
5
6
7
8
9
MeOH
EtOH
80
80
80
50
80
80
80
80
80
80
50
1 : 3
1 : 3
1 : 3
1 : 3
1 : 3
1 : 3
1 : 3
1 : 3
1 : 3
1 : 3
1 : 3
96
93
88
70
96
98
93
95
99
99
78
84
92
87
98
93
77
77
74
63
95
90
–
–
–
–
–
–
9
18
27
–
–
12
8
13
2
4
–
–
–
–
6
–
–
–
–
2
n
n
n
n
n
n
n
n
ꢀPrOH
ꢀBuOH
ꢀBuOH
ꢀBuOH
ꢀAmOH
ꢀHeOH
ꢀHpOH
ꢀBnOH
7
17
14
8
10
5
1
1
0
1
AllOH
8
Table 3. Reaction of norbornene with diols in the presence of HꢀBeta zeolite (of norbornene : diol molar ratio = A : B,
20 wt % catalyst, 5 h)
Selectivity, %
Conversion
of , %
Diol
A : B
T
, °C
1
monoether
diether
NTC
dimers
1
: 3
50
60
80
80
88
92
92
84
58
4
12
32
68
2
1
3
2
2
3
7
5
HO
OH
11
25
3
1
: 1
: 1
80
78*
90
HO
OH
46
60
41
30
5
8
12
1 : 3
91
2.5
7.5
*
Diol conversion.
ration of the ethers, since the signals of the endoꢀisoꢀ amiloxyꢀ, hexoxyꢀ, and heptoxynorbornanes, which
mers are in a weaker field (~40 ppm) [23].
are mixtures of the exoꢀ and endoꢀisomers, display
As direct evidence for the stereo configuration of proton coupling of the Cꢀ2 and Cꢀ7 atoms in addition
alkoxynorbornanes, we used NOESY data. For examꢀ
ple, the NOESY spectrum of exoꢀmethoxynorbornane
to these cross peaks for the exoꢀisomers.
The reaction of norbornene with diol (ethylene
glycol 11 or 2ꢀbuteneꢀ1,4ꢀdiol 12) mediated by the Hꢀ
1
3
exhibits cross peaks between the protons of the Cꢀ6
and Cꢀ2 atoms. These protons cannot approach each
other in space unless the substituent is in the exoꢀposiꢀ Beta zeolite catalyst sequentially gives monoether 22
tion on the norbornene cage. The NOESY spectra of or 24 and diether 23 or 25, respectively:
HO
OH
1
1
O
O
+
+
OH
O
2
2
23
HꢀBeta
1
HO
OH
1
2
O
OH
O
O
2
4
25
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62
RASKIL’DINA et al.
5. A. F. Plate and T. A. Meerovich, Izv. Akad. Nauk SSSR,
The reactions proceed to a high conversion of norꢀ
No. 2, 219 (1947).
bornene and quite selectively (Table 3).
The reaction of norbornene with ethylene glycol as
an example in the presence of HꢀBeta zeolite showed
that the yield of the diether increases with the increasꢀ
ing temperature. Thus, the amount of diether 23 in the
products of the reaction at 50
whereas it is formed in an amount comparable to that
of monoether 22 at 80 . The total selectivity for
6. H. C. Brown and M.ꢀH. Reie, J. Am. Chem. Soc. 24,
5646 (1969).
7. S. A. Shackelford, J. Org. Chem. 44, 3485 (1979).
8. D. F. Shellhamer, C. M. Curtis, R. H. Dunham, et al.,
°
С
is about 5% (Table 3),
J. Org. Chem. 50, 2751 (1985).
9. D. F. Shellhamer, R. D. Chapman, S. A. Shackelford,
et al., J. Chem. Soc., Perkin Trans. 2, No. 2, 787 (1997).
°
С
ethers 23 and 25 decreases with the increasing temperꢀ
ature, since the amount of the byproducts nortricyꢀ
clane (NTC) and norbornene dimers grows.
1
0. M. J.ꢀL. Tschan, C. M. Thomas, H. Strub, and J.ꢀF. Carꢀ
pentier, Adv. Synth. Catal. 351, 2496 (2009).
11. A. G. Gasanov and A. V. Nagiev, Zh. Org. Khim. 30
,
Variation of the norbornene : diol molar ratio from
707 (1994).
1
: 3 to 3 : 1 in the reaction of norbornene with 2ꢀ 12. D. C. Rosenfeld, S. Shekhar, A. Takemiya, et al., Org.
buteneꢀ1,4ꢀdiol results in an increase in the proporꢀ
tion of diether 25 in the products (Table 3).
Lett. 8, 4179 (2006).
13. R. T. Mathers, C. LeBlond, K. Damodaran, et al.,
In summary, the data obtained in the study show a
Macromolecules 41, 524 (2008).
high efficiency of the HꢀBeta zeolite catalyst in reacꢀ 14. J. G. Taylor, N. Whittall, and K. K. (Mimi) Hii, Chem.
tions of the direct hydroalkoxylation of norbornene.
Commun., Issue 40, 5103 (2005).
In the reaction of norbornene with monohydric 15. M. J.ꢀL. Tschan, C. M. Thomas, H. Strub, and
alcohols, HꢀBeta zeolite does not rank below homoꢀ
J.ꢀF. Carpentier, Adv. Synth. Catal. 351, 2496 (2009).
geneous catalytic systems based on trifluoromethaneꢀ 16. Т. Hirai, А. Hamasaki, А. Nakamura, and
sulfonic acid in activity and selectivity and is even М. Tokunaga, Org. Lett. 11, 5510 (2009).
superior to them in the case of saturated aliphatic 17. Y. Oe, T. Ohta, and Y. Ito, Synlett, No. 1, 179 (2005).
alcohols. The conversion of norbornene in the reacꢀ
tion with saturated and unsaturated aliphatic and aroꢀ
matic monohydric alcohols is 78–98%, and the selecꢀ
tivity for alkoxynorbornanes reaches 98%.
The products of the norbornene reactions with
diols in the presence of HꢀBeta zeolite are monoꢀ and
diethers, whose yield and ratio can be controlled by
varying the reaction parameters.
1
1
2
2
8. T. T. Dang, F. Boeck, and L. Hintermann, J. Org.
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1. G. Z. Raskil’dina, A. M. Suleimanova, A. N. Kazakꢀ
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Tekhnol. 56 (10), 29 (2013).
2
2. G. Z. Raskil’dina, Yu. G. Borisova, E. A. Mustafina,
and N. G. Grigor’eva, in LowꢀWaste, ResourceꢀSaving
Chemical Technologies and Environmental Safety: Proꢀ
ceedings of AllꢀRussia Scientific–Practical Conference
with International Participation (Fobos, Sterlitamak,
2013), p. 29 [in Russian].
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Translated by S. Zatonsky
(
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