Hydromenthoxycarbonylation of isobutylene in the presence of tetrakis(triphenylphosphine)palladium-based catalyst systems

Article abstract of DOI:10.1134/S0965544112060126

The catalytic activity of the Pd(PPh₃)₄-TsOH and Pd(PPh₃)₄-PPh₃-TsOH systems in the reaction of isobutylene hydromenthoxycarbonylation with carbon monoxide and l-menthol has been examined. It has been

Full text of DOI:10.1134/S0965544112060126

ISSN 0965ꢀ5441, Petroleum Chemistry, 2012, Vol. 52, No. 6, pp. 422–425. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © Kh.A. Suerbaev, E.G. Chepaikin, G.Zh. Zhaksylykova, 2012, published in Neftekhimiya, 2012, Vol. 52, No. 6, pp. 454–458.
Hydromenthoxycarbonylation of Isobutylene in the Presence
of Tetrakis(triphenylphosphine)palladiumꢀBased Catalyst Systems
a
b
a
Kh. A. Suerbaev , E. G. Chepaikin , and G. Zh. Zhaksylykova
a
AlꢀFarabi Kazakh National University, ul. AlꢀFarabi 71, Almaty, Kazakhstan
b
Institute of Structural Macrokinetics and Materials Science, Russian Academy of Sciences, Chernogolovka, Russia
eꢀmail: echep@ism.ac.ru; grig@ism.ac.ru
Received October 10, 2011
Abstract—The catalytic activity of the Pd(PPh ) –TsOH and Pd(PPh ) –PPh –TsOH systems in the reacꢀ
3
4
3 4
3
tion of isobutylene hydromenthoxycarbonylation with carbon monoxide and
It has been found that the reaction proceeds regioselectively yielding the linear product
Optimal conditions have been found for running the process. The spatial structure of
synthesized via the isobutylene hydromenthoxycarbonylation reaction has been established by H and
NMR techniques.
l
ꢀmenthol has been examined.
l
l
ꢀmenthyl isovalerate.
ꢀmenthyl isovalerate
1
13
C
DOI: 10.1134/S0965544112060126
Menthyl isovalerate (MIV) is an active ingredient
The experiments were carried out in the solventꢀ
of Validol, a pharmaceutical drug [1]. The industrial free mode in a laboratory stainless steel autoclave unit
MIV manufacturing process involving menthol esteriꢀ [9]. In a typical run, the 100ꢀmL autoclave equipped
fication with isovaleric acid has a number of serious with a stirrer and a carbon monoxide and isobutylene
–
4
disadvantages. The most convenient process is the feeding device was charged with 0.133 g (1.15
×
10 mol)
10 mol) of TsOH, and
.854 g (5.02 × 10 mol) of lꢀmenthol. The autoclave
–
3
oneꢀpot synthesis of MIV via the alkoxycarbonylation
reaction of isobutylene with carbon monoxide and
menthol. Isobutylene hydromenthoxycarbonylation
under the conditions of homogeneous catalysis by palꢀ
ladiumꢀbased metal complex systems was reported in
of Pd(PPh3)4, 0.263 g (1.38
7
×
–2
was sealed, purged with CO to remove air, and filled
with CO to a pressure of 1.0–1.1 MPa. Then, 2.565 g
6.35 × 10 mol) of isobutylene was introduced and
stirring and heating were switched on. The carbon
monoxide pressure was brought to 2.0 MPa, the temꢀ
–2
(
[
3–6]. An effective procedure for preparing MIV in
the presence of the PdCl –PPh –TsOH system was
2
3
developed [7, 8].
perature was elevated within 1 h to 100°С, and the
reaction mixture was agitated under these conditions
for 4 h. On completion, the autoclave was cooled to
room temperature and the reaction mixture was fracꢀ
tionated in a vacuum. We obtained 3.58 g (45.6% of
Earlier [9], we studied the hydromenthoxycarbonꢀ
ylation reaction of isobutylene in the presence of the
halogenꢀfree Pd(Асас) –PPh –TsOH catalyst sysꢀ
2
3
tem. In this work aiming at further development of the
MIV manufacturing process, we examined the cataꢀ
lytic activity of the Pd(PPh ) –TsOH and Pd(PPh ) –
the initial quantity) of unreacted
lꢀmenthol and 6.24 g
(
51.6%) (or 94.9% on converted menthol basis) of
3
4
3 4
20
PPh –TsOH systems in the isobutylene hydromenꢀ
3
lꢀmenthyl isovalerate. Bp 123
°
C/6 mmHg,
С/10 mmHg,
n
n
D
thoxycarbonylation reaction. These systems are more
promising, since they do not contain anionic ligands
20
1
.4480. Published data [11]: bp 129
°
D
(
halide ions, etc.), a circumstance that may appear 1.4486
.
important for meeting the drug safety standards.
RESULTS AND DISCUSSION
It was found that neither the Pd(PPh
nor the Pd(PPh ) –PPh system exhibits catalytic
EXPERIMENTAL
) complex
3 4
3
4
3
The complex Pd(PPh3)4 was obtained according to activity in the isobutylene hydromenthoxycarbonylaꢀ
the known procedure [10]. ꢀToluenesulfonic acid was tion reaction at low carbon monoxide pressures
recrystallized from 96% ethanol and dried until the
MPa). A catalytic activity in this reaction is disꢀ
TsOH H O composition. Triphenylphosphine was played by the binary Pd(PPh ) –TsOH or the ternary
recrystallized from an ether–ethanol mixture to a Pd(PPh ) –PPh –TsOH system. The stabilizing and
p
( 2
≤
⋅
2
3 4
3
4
3
constant melting point. Reagentꢀgrade
used without special purification.
l
ꢀmenthol was promoting role of PPh3 and TsOH in metal complexꢀ
catalyzed hydroesterification reactions of olefins was
422

HYDROMENTHOXYCARBONYLATION OF ISOBUTYLENE
Table 1. Hydromenthoxycarbonylation of isobutylene with carbon monoxide and
423
l
ꢀ
m4 enthol in the presence of the
–
Pd(PPh ) –TsOH catalytic system. Amount of Pd(PPh ) charged is 0.133 g (1.15
×
10 mol)
3
4
3 2
Molar ratio of reactants and catalyst
components
Yield of
isovalerate, wt %
lꢀmenthyl
Reaction conditions
l
ꢀMenthol
recovery, %
Run no.
(of mass
on fed
ꢀmenthol
basis
on reacted
fed)
l
l
ꢀmenthol
basis
Influence of reactants ratio
1
2
3
4
5
400
435
480
550
600
550
550
550
550
550
1
1
1
1
1
12
12
12
12
12
100
100
100
100
100
2
2
2
2
2
4
4
4
4
4
43.3
45.6
42.5
49.7
42.5
43.3
51.6
42.0
45.4
40.5
83.1
94.9
66.2
71.2
64.4
Influence of catalyst components ratio
6
7
8
9
435
435
435
435
550
550
550
550
1
1
1
1
8
10
13
14
100
100
100
100
2
2
2
2
4
4
4
4
71.7
49.6
49.7
73.7
27.4
49.4
42.3
20.3
96.9
97.9
83.9
77.3
Influence of reaction temperature
1
0
435
435
435
435
550
550
550
550
1
1
1
1
12
12
12
12
85
90
2
2
2
2
4
4
4
4
76.4
74.5
47.5
46.2
18.6
23.2
49.5
50.7
78.9
90.9
94.4
94.3
11
1
2
3
95
1
110
Influence of carbon monoxide pressure
14
15
16
17
435
435
435
435
550
550
550
550
1
1
1
1
12
12
12
12
100
100
100
100
1
4
4
4
4
72.5
46.7
46.3
73.2
23.6
49.7
50.6
21.8
86.5
93.3
94.2
81.2
1.5
2.5
3
Influence of reaction time
18
19
20
435
435
435
550
550
550
1
1
1
12
12
12
100
100
100
2
2
2
2
3
5
75.8
46.9
41.8
20.4
45.3
42.7
83.6
85.6
73.4
been repeatedly reported in the literature [3–5, 7, 9,
2]. Table 1 presents the results of study of the influꢀ product yield (
ence of different reaction conditions in the presence of [Pd] : [TsOH] = 1 : 12) (Table 1, entries 1–5). As the
the Pd(PPh ) –TsOH system on the yield of the ꢀС Н ]/[ ꢀmenthol] ratio increases from 0.92 to 1.26
The reactant ratio has a noticeable effect on the
о
1
Т
= 100 С, РСО = 2.0 MPa,
τ
= 4 h,
[
i
l
3
4
4
8
desired product. It is seen that in any run, the reaction (cf. runs 5 and 2), the product yield increases from
does not go to completion: the recovery of unconꢀ 40.5 to 51.6%. As the olefin excess is further increased
verted lꢀmenthol is 41.8–76.4% of the initial quantity. to 1.37, the yield decreases to 43.3% (run 1). The optiꢀ
PETROLEUM CHEMISTRY Vol. 52
No. 6
2012

424
SUERBAEV et al.
Table 2. Hydromenthoxycarbonylation of isobutylene with carbon monoxide and
l
ꢀmenthol in the presence of the
–4
Pd(PPh ) –PPh –TsOH catalytic system. Amount of Pd(PPh ) charged is 0.133 g (1.15
×
10 mol)
3
4
3
3 4
Yield of
isovalerate, wt %
l
ꢀmenthyl
Molar ratio of reactants and catalyst
components
Reaction conditions
l
ꢀMenthol
recovery,
% (of mass
fed)
Run no.
on fed on reacted
l
ꢀmenthol
basis
l
ꢀmenthol
basis
Influence of reactants ratio
1
2
3
4
5
400
435
480
550
600
550
550
550
550
550
1
1
1
1
1
3
3
3
3
3
12
12
12
12
12
100
100
100
100
100
2
2
2
2
2
4
4
4
4
4
14.7
16.4
30.3
59.3
62.0
75.6
77.6
65.4
48.8
36.3
96.3
92.9
85.1
79.6
88.0
Influence of catalyst components ratio
6
7
8
9
435
435
435
435
435
435
550
550
550
550
550
550
1
1
1
1
1
1
2
5
7
3
3
3
12
12
12
8
100
100
100
100
100
100
2
2
2
2
2
2
4
4
4
4
4
4
24.2
38.3
46.9
54.5
38.2
38.8
66.4
57.8
50.3
44.3
56.5
60.1
87.5
93.7
94.9
97.3
91.4
98.2
1
0
1
10
13
1
Influence of reaction temperature
12
13
14
15
435
435
435
435
550
550
550
550
1
1
1
1
3
3
3
3
12
12
12
12
85
90
2
2
2
2
4
4
4
4
56.8
56.6
36.3
56.7
35.9
37.8
59.8
36.9
83.3
86.9
93.9
85.3
95
110
Influence of carbon monoxide pressure
16
17
18
435
435
435
550
550
550
1
1
1
3
3
3
12
12
12
100
100
100
1
4
4
4
32.7
26.9
41.6
62.5
67.3
48.6
92.9
91.9
83.2
1.5
2.5
Influence of reaction time
19
20
21
22
435
435
435
435
550
550
550
550
1
1
1
1
3
3
3
3
12
12
12
12
100
100
100
100
2
2
2
2
2
39.2
35.6
28.5
32.9
57.8
58.4
65.1
66.1
95.0
90.5
91.0
98.4
3
3.5
5
mal reactant ratio is [
i
ꢀС Н ]/[lꢀmenthol] = 1.26 a reduction in the yield to 42.3%. The optimal ratio of
4
8
(
run 2). All the subsequent experiments were conꢀ the components of the catalytic system is [Pd(PPh3)4]
ducted at this ratio of the reactants.
: [TsOH] = 1 : 12.
The ratio of the components of the catalytic system
The influence of the process conditions (temperaꢀ
has a considerable effect on the yield of the product. ture, CO pressure, reaction time) on the yield of the
This dependence is nonmonotonic in character desired product was determined. As the temperature
о
(
Table 1, runs 2, 6–9): as the [TsOH]/[Pd] ratio increases from 85 to 100 С, the product yield abruptly
increases from 8 to 12, the product yield dramatically increase from 18.6 to 51.6%, but the further elevation
о
increases from 27.4 to 51.6%; however, the further of the temperature to 110 С decrease the yield to
increase in the promoter (TsOH) excess to 13 results in 50.7% (Table 1, runs 2, 10–13). The dependence of
PETROLEUM CHEMISTRY Vol. 52
No. 6
2012

HYDROMENTHOXYCARBONYLATION OF ISOBUTYLENE
425
1
13
the product yield on the CO pressure is also nonꢀ
H and C NMR spectra, the 1e, 2e, and 5e conforꢀ
monotonic (Table 1; runs 2, 14–17): pressure elevaꢀ mation of the substituents on the cyclohexane ring can
tion from 1.0 to 2.0 MPa increases the product yield be unequivocally attributed to the synthesis product
from 23.6 to 51.6% and the further elevation to (MIV).
3
.0 MPa dramatically reduces the yield to 21.8%. This
Thus, a moderate catalytic activity of the
behavior is obviously due to the competition of CO
and isobutylene in the Pd coordination sphere. The
optimal reaction time at a temperature of 100 С is 4 h
Pd(PPh ) –TsOH system and a higher catalytic activꢀ
3
4
ity of the Pd(PPh ) –PPh –TsOH system in the
3
4
3
о
isobutylene hydromenthoxycarbonylation reaction
have been revealed. This fact is explained in terms of
(
runs 18–20).
As has been noted above, triphenylphosphine staꢀ the stabilizing effect of triphenylphosphine. The proꢀ
bilizes catalytic systems. In this context, we examined moting action of
ꢀtoluenesulfonic acid is supposed to
p
the effect of its excess on the reaction in question. be due to the intermediate formation of catalytically
Table 2 presents the results of study of the isobutylene active hydride complexes of palladium. Optimal conꢀ
hydromenthoxycarbonylation reaction in the ditions of running the process have been determined.
Pd(PPh ) –PPh –system. Both the reactants and catꢀ The reaction proceeds regioselectively at the terminal
3
4
3
alyst components ratios have a considerable effect on carbon atom yielding the linear product (
1ꢀmenthyl
1
13
the yield of the product. The reaction is facilitated by isovalerate) only. By H and C NMR spectroscopy,
a small excess of isobutylene (Table 2, runs 1–5). As the spatial structure of the product has been estabꢀ
the [iꢀC H ]/[lꢀmenthol] ratio increases from 0.92 to lished: the 1e, 2e, and 5e conformations of the substitꢀ
4 8
1
3
.26 (entries 1, 5), the product yield increases from uents on the cyclohexane ring. The test catalytic sysꢀ
6.3 to 77.6%, although the further increase in olefin tems do not contain halide ions and are more promisꢀ
excess leads to a decrease in the yield to 75.6%. The ing as compared with the systems studied earlier.
optimal reactant ratio is [ ꢀС Н ]/[ ꢀmenthol] = 1.26
run 2). All the subsequent runs were conducted at this
optimal ratio between the reactants.
i
l
4
8
(
REFERENCES
The dependence of the product yield on the ratio
between the components of the catalytic system is
nonmonotonic in character (Table 2; runs 2, 6–11).
The optimal ratio of the catalyst components is
1. M. D. Mashkovskii, Medicines, 10th Ed. (Meditsina,
Moscow, 1987), vol. 1 [in Russian].
2. D. S. Yaskina, V. I. Trubnikov, L. A. Kheifets, et al.,
Khim.ꢀFarm. Zh., No. 4, 51 (1974).
[
Pd(PPh ) ] : [PPh3] : [TsOH] = 1 : 3 : 12.
3 4
3. A. R. El’man, V. M. Matveev, E. V. Slivinskii, and
S. M. Loktev, Khim.ꢀFarm. Zh., No. 3, 47 (1990).
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reaction and the yield of the desired products was
4. Kh. A. Suerbaev, I. A. Tsukanov, A. R. El’man, and
K. A. Zhubanov, Zh. Obshch. Khim. 64, 1189 (1994).
determined. As the temperature increases from 90 to
5
. Kh. A. Suerbaev, A. R. El’man, I. A. Tsukanov, et al.,
RU Patent No. 2036897; Otkr. Izobret., No. 16, 135
(1995).
. A. R. El’man, Kh. A. Suerbaev, I. A. Tsukanov, et al.,
RU Patent No. 2059605, Otkr. Izobret., No. 13, 176
(1995).
о
100 С, the product yield increases from 37.8 to 77.6%
(
Table 2; runs 2, 12–15). However, upon the further
increase in temperature, a decrease in the yield to
6.9% takes place because of catalyst deactivation
appearance of palladium black). The dependence of
6
3
(
the product yield on the CO pressure is also nonꢀ
monotonic: pressure elevation from 1.0 to 2.0 MPa
increases the product yield from 67.3 to 77.6%
7
. Kh. A. Suerbaev, K. M. Shalmagambetov, and
K. A. Zhubanov, Zh. Obshch. Khim. 70, 1575 (2000).
8
. Kh. A. Suerbaev, I. A. Tsukanov, and K. A. Zhubanov,
KZ Patent No. 757; Prom. Sobstv.: Ofitsial. Byull.,
No. 2, 128 (1996).
(
2
Table 2; runs 2, 16–18) and the further elevation to
.5 MPa strongly reduces the yield to 48.6%. As in the
case of the former system, the optimal reaction time is
h (Table 2; runs 2, 19–22). Under the optimal conꢀ
ditions, the yield of MIV in the presence of
Pd(PPh ) –PPh –TsOH is substantially higher than
9. Kh. A. Suerbaev, E. G. Chepaikin, G. Zh. Zhaksylykꢀ
4
ova, et al., Pet. Chem. 48, 206 (2008).
1
0. U. M. Dzhemilev, N. R. Popod’ko, and E. V. Kozlova,
Metal Complex Catalysis in Organic Synthesis: Alicyclic
Compounds (Khimiya, Moscow, 1999) [in Russian].
3
4
3
in the presence of Pd(PPh ) –TsOH (cf. entries 2 in
3
4
Tables 1 and 2).
The spatial structure of
study via isobutylene hydromenthoxycarbonylation
with carbon monoxide and ꢀmenthol has been estabꢀ
lished by NMR spectroscopy. Based on analysis of the
1
1. V. I. Isagulyants, Synthetic Fragrances (Izd. AN
l
ꢀMIV obtained in this
ArmSSR, Yerevan, 1946) [in Russian].
1
2. F. J. Waler, in Proceeding of Symposium on Catalytic
Conversions of Synthesis Gas and Alcohols to Chemicals
(Amsterdam, 1983), p. 193.
l
PETROLEUM CHEMISTRY Vol. 52
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2012