Hydroformylation of olefins catalyzed by rhodium complexes with phosphinitecalix[4]arenes

Article abstract of DOI:10.1134/S0965544107050052

Hydroformylation of alkenes with various carbon chain lengths and arylalkenes in the presence of the catalytic system consisting of Rh(acac)(CO)₂ and phosphinitecalix[4]arenes was studied. The influence of the P/Rh and substrate/catalyst ratios, temperature, and pressure on the process and the product composition was examined.

Full text of DOI:10.1134/S0965544107050052

ISSN 0965-5441, Petroleum Chemistry, 2007, Vol. 47, No. 5, pp. 340–344. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © E.A. Karakhanov, Yu.S. Kardasheva, E.A. Runova, M.V. Terenina, A.Yu. Shadrova, 2007, published in Neftekhimiya, 2007, Vol. 47, No. 5, pp. 371–375.
Hydroformylation of Olefins Catalyzed by Rhodium Complexes
with Phosphinitecalix[4]arenes
E. A. Karakhanov, Yu. S. Kardasheva, E. A. Runova, M. V. Terenina, and A. Yu. Shadrova
Moscow State University, Faculty of Chemistry, Leninskie gory, Moscow, 119899 Russia
e-mail: runova@petrol.chem.msu.ru
Received March 27, 2007
Abstract—Hydroformylation of alkenes with various carbon chain lengths and arylalkenes in the presence of
the catalytic system consisting of Rh(acac)(CO)2 and phosphinitecalix[4]arenes was studied. The influence of
the P/Rh and substrate/catalyst ratios, temperature, and pressure on the process and the product composition
was examined.
DOI: 10.1134/S0965544107050052
The hydroformylation of unsaturated hydrocarbons
is currently one of the leading and dynamically devel-
oping branches of petrochemical synthesis. Intensive
investigations into the use of compounds capable of
molecular recognition and formation of host–guest
inclusion complexes, such as calixarenes and cyclodex-
trins, in catalysis have been carried out in recent years.
Inspection of the literature on the chemistry of phos-
phorus-containing calixarenes showed that consider-
able attention has been given to the synthesis of new
cyclophanes and to the investigation of complexation of
these compounds with various metals [1–3], whereas
tBu
tBu
tBu
4
2
OPPh2
(I)
OPPh2
OCH3
(II)
EXPERIMENTAL
All operations were carried out in an argon atmo-
sphere with the use of the standard technique of work
their use as ligands in the hydroformylation reaction in an inert atmosphere [10].
has been poorly studied. The catalytic properties sub-
stantially depend on the nature of the organophospho- nylphosphinooxy)calix[4]arene (I) was synthesized
5,11,17,23-tetra (tert-butyl)-25,26,27,28-tetra (diphe-
with a yield of 67% from 5,11,17,23-tetra(tert-butyl)-
25,26,27,28-tetrahydroxycalix[4]arene via the succes-
sive reactions with butyllithium and diphenylchloro-
phosphine [11]. There is only one singlet signal at
δ 121.70ppm in the 31P NMR spectrum. (1H NMR
(CDCl3), ppm: 1.03 (s., 36ç, C(CH3)3), 2.13 (d, 4H,
Ar–CH2–Ar), 4.00 (d, 4H, Ar–CH2–Ar), 7.05 (s, 8H,
ArH), 7.07–7.44 (m, 40H, PPh2)). A signal at m/z =
rus ligand, with the influence of the structure on the
ratio and yield of reaction products being rather com-
plex in character and being determined, not only by
electronic, but also steric factors [4]. Some examples of
the use of phosphorus-containing calix[4,6]arenes in
hydroformylation of linear alkenes-1 and styrene have
been described in the literature [5–9].
1385 [å+] was observed in the AP-ESI mass spectrum.
The development of bifunctional catalysts that com-
bine the properties of a metal complex with the capabil-
ity of molecular recognition in one molecule is one of
the promising lines of work on the design of new cata-
lytic systems.
5,11,17,23-tetra(tert-butyl)-25,27-bis(diphenyl-
phosphinooxy)-26,28-dimetoxycalix[4]arene (II) was
obtained via a similar procedure from 5,11,17,23
tetra(tert-butyl)-25,27-dimetoxy-26,28-dihydroxy-
calix[4]arene with a yield of 81% [12.] (1H NMR
(CDCl3), ppm: 0.89 (s,18ç, C(CH3)3), 1.29 (s, 18H,
C(CH3)3), 3.56 (br. s, 6H, OCH3), 2.90 (br. d, 4H, Ar–
CH2–Ar), 3.88 (br. d, 4H, Ar–CH2–Ar), 6.45 (br. s, 4H,
m-H), 6.98 (s, 4H, m-H), 7.43–7.46 and 7.68–7.76 (m,
The objective of this study was to examine the cata-
lytic properties of systems based on phosphiniteca-
lix[4]arenes (I) and (II) in the hydroformylation reac-
tion of linear alkenes and alkenylarenes.
340

HYDROFORMYLATION OF OLEFINS
341
%
100
(‡)
(b)
Isomeric
alkenes
80
60
40
20
0
Aldehydes
1
2
4
6
8
1
2
P/Rh
Fig. 1. Hydroformylation of nonene-1 at various P/Rh ratios. Toluene, 1.5 ml; 50°C; (a) Ligand I: nonene-1, 1.5 mmol;
Rh(acac)(CO) , 0.01 mmol; 0.5 MPa; 2 h. (b) Ligand II: nonene-1, 0.75 mmol; Rh(acac)(CO) , 0.005 mmol; 1.0 MPa; 6 h.
2
2
20H, PPh2)). (31P NMR (CDCl3), ppm: 120.3). The
AP-ESI mass spectrum: m/z = 1045 [M+].
RESULTS AND DISCUSSION
Rhodium complexes with phosphorus-containing
ligands were obtained in situ from Rh(acac)(CO)2 and
corresponding calixarene. In the products of the reac-
tion of alkenes-1 with synthesis gas, corresponding
aldehydes with both normal and branched carbon
chains, as well as isomeric alkenes, were detected.
The purity of the products was monitored by means
1
of H and 31P NMR spectroscopy and ESI-MS mass
spectrometry.
Rhodium acetylacetonate dicarbonyl was
obtained via a procedure described in [13].
An analysis of published data on hydroformylation
has shown that the maximal transformation of substrate
is reached at the P/Rh ratio of its own for each organo-
phosphorus ligand. With the use of nonene-1 as an
example, it was found that the maximum value of the
yield of aldehydes for ligand I is reached at a phospho-
rus : rhodium ratio of 4 : 1 (Fig. 1). Ligand II has a
much lower solubility in most organic solvents; for this
reason, all catalytic experiments with its participation
were carried out at P : Rh = 2.
The general procedure of hydroformylation is
described in [14].
The reaction mixture was analyzed by means of
gas–liquid chromatography on a Chrom-5 chromato-
graph with a flame ionization detector, a fused-silica
capillary column 30 m × 0.5 mm coated with the XE-60
phase, and temperature programming in the range
30−220°ë.
ESI-MS spectra were obtained on an Agilent
LC/MS 1100 SL instrument using atmospheric-pres-
sure electrospray ionization (AP-ESI) in the positive-
ion detection mode.
1H and 31P NMR spectra were recorded in the sta-
tionary mode on a Bruker Avance 400 spectrometer
It was found that the conversion and the aldehyde
yield substantially depend on temperature; a tempera-
ture of 50°ë turned out to be the optimal value for both
ligands. When the process is conducted at 70°ë, an
increase in the rate of isomerization reaction is
with working frequencies of 400.13 and 161.9 MHz, observed and the yield of byproducts noticeably
respectively.
increases. The further elevation of temperature results
%
80
Isomeric
alkenes
60
40
20
0
Aldehydes
1
2
4
6
Time, h
Fig. 2. Hydroformylation of octene-1 in the presence of ligand (I). Rh(acac)(CO) , 0.01 mmol; P/Rh = 4; octene-1, 1.5 mmol; 50°C;
2
0.5 MPa.
PETROLEUM CHEMISTRY Vol. 47 No. 5 2007

342
KARAKHANOV et al.
Table 1. Hydroformylation of octene-1 and decene-1 at various temperatures in the presence of ligand I
Substrate
Pressure
Octene-1
Decene-1
0.5 MPa
0.5 MPa
2.5 MPa
Tempera- Conver- Yield of al- Regioselec- Conver- Yield of al- Regioselec- Conver- Yield of al- Regioselec-
ture, °C
sion, % dehydes, % tivity, %
sion, % dehydes, % tivity, %
sion, % dehydes, % tivity, %
25
50
–
–
–
8
99
98
5
94
92
60
57
65
8
62
88
53
5
51
49
29
60
65
65
66
62
79
59
49
48
22
63
70
68
70
100
Reaction conditions: Rh(acac)(CO) , 0.01 mmol; P/Rh = 4; substrate, 1.5 mmol; 2 h; 0.5 MPa; regioselectivity is (the yield of n-alde-
2
hyde/total aldehyde yield)100%.
in a significant decrease in both olefin conversion and evident from the data presented in Table 3, the conver-
the yield of aldehydes.
sion for 2 h was 60–80% for all investigated olefins and
the yield of aldehydes was 50–60%. The ratio of the
normal- to branched-chain aldehyde yields remained
practically unchanged.
An increase in a gas pressure from 0.5 to 2.5 MPa
resulted, not only in substantial acceleration of the cat-
alytic reaction, but also in a sharp growth of chemose-
lectivity of the process even at a temperature of 70°ë
(Table 1).
As the synthesis gas pressure was increased, the ole-
fin conversion became quantitative already at a gas
pressure of 2.5 MPa, with the practically entire amount
of the reactant alkene converting into aldehydes within
2 h (Table 2).
By the example of octene-1, it was shown that an
increase in the reaction time leads to an insignificant
growth of conversion (Fig. 2) and the yield of aldehydes
remains practically constant with time.
The catalytic systems based on phosphinite ligands
I and II have displayed a high activity in the hydro-
formylation of a number of linear alkenes ë7–ë12. As is
The substrate : catalyst ratio in the reaction mixture
has an effect on the proceeding of the hydroformylation
reaction. An increase in this ratio promotes the isomer-
ization reaction, a result that may be caused by the hin-
dered access of carbon monoxide molecules to the
rhodium coordination sphere because of the growth in
olefin concentration. We carried out the hydroformyla-
tion of linear substrates at a pressure of 2.5 MPa and
ratios of 150 and 500. As is seen from the results pre-
sented in Table 4, practically complete conversion is
observed for all alkenes at a substrate : catalyst ratio of
150, whereas the yield of aldehydes sharply decreases
at a 500-fold excess of alkene.
Under the optimal conditions for the hydroformyla-
tion of linear alkenes, we studied the reaction of some
alkenylarenes and cycloalkenes with synthesis gas. The
data are presented in Table 5; it can be seen from these
data that all of the substrates easily enter into the hydro-
formylation reaction and corresponding aldehydes are
the main products of the reaction.
Table 2. Hydroformylation of nonene-1 at various pressures
in the presence of ligand I
Regioselectivity
Conversion, Yield of alde-
P, MPa
(decanal yield/total
aldehyde yield)100%
%
hydes, %
In the case of styrene and allyl phenyl ether, the pre-
vailing formation of iso-aldehyde is observed. For allyl
phenyl ether, its formation can be associated with the
influence of the lone electron pair on the oxygen atom
in the β-position to the double bond, and the prevalence
of 2-phenylpropanal in the styrene hydroformylation
products can be explained by the preferable formation
in the catalytic cycle of the iso-acyl intermediate stabi-
lized by conjugation of the double bond with the π-sys-
tem of the aromatic ring.
0.5
1.0
2.5
5.0
69
91
99
98
56
82
98
98
64
65
60
61
Reaction conditions: Rh(acac)(CO) , 0.01 mmol; P/Rh = 4; nonene-1,
1.5 mmol; toluene, 1.5 ml; 50°C; 2 h.
2
PETROLEUM CHEMISTRY Vol. 47 No. 5 2007

HYDROFORMYLATION OF OLEFINS
343
Table 3. Hydroformylation of linear alkenes
Ligand I, S : Cat = 150*
Conver- Yield of al- Regioselec- Conver- Yield of al- Regioselec- Conver- Yield of al- Regioselec-
Ligand I, S : Cat = 500*
Ligand II, S : Cat = 150**
Alkene
sion, % dehydes, % tivity, % sion, % dehydes, % tivity, % sion, % dehydes, % tivity, %
Heptene-1
Octene-1
Nonene-1
Decene-1
Dodecene-1
68
62
69
62
74
50
49
56
51
57
66
63
64
65
68
27
33
23
32
36
13
25
12
12
14
62
68
67
67
64
75
70
67
59
87
57
60
48
41
67
63
63
62
61
66
Reaction conditions: *-Rh(acac)(CO) , 0.01 mmol; 2 h; 50°C; 0.5 MPa; P : Rh = 4.
2
**-Rh(acac)(CO) , 0.005 mmol; 2 h; 50°C; 1.0 MPa; P : Rh = 2.
2
Table 4. Hydroformylation of linear alkenes in the presence of ligand I
S : Cat = 150
S : Cat = 500
Alkene
Conversion,
%
Yield
of aldehydes, %
Regioselectivity, Conversion, Yield of aldehydes, Regioselectivity,
%
%
%
%
Hexene-1
Heptene-1
Octene-1
Nonene-1
Decene-1
Dodecene-1
99
96
95
99
92
94
83
78
93
98
83
84
61
63
59
60
58
58
55
71
82
76
66
68
38
52
74
61
52
49
66
65
61
64
65
65
Reaction conditions: Rh(acac)(CO) , 0.01 mmol; P/Rh = 4; substrate, 1.5 mmol; toluene, 1.5 ml; 50°C; 2 h; 2.5 MPa.
2
Table 5. Hydroformylation of alkenylarenes and cycloalkenes
Ligand
Pressure
Substrate
Ligand I
Ligand II
0.5 MPa
TOF, h–1
2.5 MPa
TOF, h–1
2.5 MPa
TOF, h–1
n/i
n/i
n/i
22
27
24
0.3
42
74
0.1
44
32
75
0.1
0.9
0.4
1.2
0.6
1
O
105
0.5
35
1.2
138
1.1
90
1.1
OH
35
41
3.6
2.1
86
57
2.8
2.4
81
18
2.9
1.4
Reaction conditions: *-Rh(acac)(CO) , 0.01 mmol; 50°C; P : Rh = 4; 1 h.
2
**-Rh(acac)(CO) , 0.005 mmol; 50°C; P : Rh = 2; 1 h.
2
–1
TOF, h is the number of moles of the product per mole of catalyst per unit time.
PETROLEUM CHEMISTRY Vol. 47 No. 5 2007

344
KARAKHANOV et al.
6. Z. Csok, G. Szalontai, G. Czira, and L. Kollar, J. Orga-
ACKNOWLEDGEMENTS
nometal. Chem. 570, 23 (1998).
This work was supported by the Russian Foundation
for Basic Research, project no. 06-03-32889a.
7. R. Paciello, L. Siggel, and M. Roper, Angew. Chem., Int.
Ed. Engl. 38, 1920 (1999).
8. Y. Obora, Y. K. Liu, S. Kubouchi, et. al., Eur. J. Inorg.
Chem., 222 (2006).
REFERENCES
9. C. Kunz, D. Selent, I. Neda, et al., Z. Anorg. Allg. Chem.
628, 779 (2002).
1. I. S. Antipin, E. Kh. Kazakova, V. D. Khabikher, and
A. I. Konovalov, Usp. Khim. 67, 995 (1998).
10. D. F. Shriver, Manipulation with Air-Sensitive Com-
pounds (McGraw-Hill, New York, 1969), p. 36.
2. B. R. Cameron, F. C. J. M. van Veggel, and D. N. Rein-
11. C. Floriani, D. Jacoby, A. Chiesi-Villa, and C. Guastini,
houdt, J. Org. Chem. 60, 2802 (1995).
Angew. Chem., Int. Ed. Engl. 28, 1376 (1989).
3. C. Loeber, C. Wieser, D. Matt, et al., Bull. Soc. Chim. Fr.
12. C. Loeber, D. Matt, P. Briard, and D. Grandjean, J.
Chem. Soc., Dalton Trans., No. 4, 513 (1996).
132, 166 (1995).
4. P. W. N. M. van Leeuwen and C. Claver, Comprehensive
13. Yu. S. Varshavskii and T. G. Cherkasov, Zh. Neorg.
Coord. Chem. II 9, 141.
Khim. 12, 1709 (1967).
5. S. Steyer, C. Jeunesse, J. Harrowfield, and D. Matt, J. 14. E. A. Karakhanov, Yu. S. Kardasheva, E. A. Runova, et al.,
Chem. Soc., Dalton Trans., 1301 (2005).
Neftekhimiya 46, 290 (2006) [Pet. Chem. 46, 264 (2006)].
PETROLEUM CHEMISTRY Vol. 47 No. 5 2007