Effect of solvent nature on the catalytic hydroformylation of 2,3-dihydrofuran

Article abstract of DOI:10.1134/S0965544113030134

The effect of the solvent nature on the process of hydroformylation of 2,3-dihydrofuran in the presence of the phosphine-containing, complex Rh catalyst HRh(CO)(PPh₃)₃ has been studied. The influence of solvent polarity and basicity on the conversion of 2,3-dihydrofuran has been revealed, and the composition of tetrahydrofuran aldehydes and the selectivity of their formation have been determined.

Full text of DOI:10.1134/S0965544113030134

ISSN 0965ꢀ5441, Petroleum Chemistry, 2013, Vol. 53, No. 3, pp. 194–196. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © E.Yu. Wol’f, M.M. Vartanyan, A.L. Lapidus, 2013, published in Neftekhimiya, 2013, Vol. 53, No. 3, pp. 218–220.
Effect of Solvent Nature on the Catalytic Hydroformylation
of 2,3ꢀDihydrofuran
E. Yu. Wol’f, M. M. Vartanyan, and A. L. Lapidus
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninskii pr. 47, Moscow, 119991 Russia
eꢀmail: ejwolf@rambler.ru
Received October 23, 2012
Abstract—The effect of the solvent nature on the process of hydroformylation of 2,3ꢀdihydrofuran in the
presence of the phosphineꢀcontaining, complex Rh catalyst HRh(CO)(PPh3)3 has been studied. The influꢀ
ence of solvent polarity and basicity on the conversion of 2,3ꢀdihydrofuran has been revealed, and the comꢀ
position of tetrahydrofuran aldehydes and the selectivity of their formation have been determined.
Keywords: hydroformylation, 2,3ꢀdihydrofuran, phosphineꢀcontaining complex, rhodium catalysts,
2ꢀformyltetrahydrofuran, 3ꢀformyltetrahydrofuran
DOI: 10.1134/S0965544113030134
Earlier [1] we have presented some results on the tris(triphenylphosphino)rhodium (HRh(CO)(PPh3)3
)
effect of a solvent nature, in particular benzene and triꢀ prepared according to the published procedure [10],
ethylamine, on the hydroformylation of 2,3ꢀdihyꢀ 5 mL of a solvent, and 0.013 mol of . The autoclave was
drofuran ( ) in the presence of the homogeneous filled with a mixture of CO and Н (СО : Н = 1 : 1) to
phosphineꢀcontaining Rh catalyst HRh(CO)(PPh3)3 the starting pressure of 10.0 MPa and placed into an
1
2
1
2
(
see Scheme 1).
electrically heated oven. The hydroformylation was run
at 90°С (see Table 1) and 60°С (see Table 2). The run
time was 90 min.
O
H
Testing the stability of a mixture of 2ꢀformyltetrahyꢀ
drofuran (2) and 3ꢀformyltetrahydrofuran (3) under
hydroformylation conditions. The autoclave was charged
with 0.043 mmol (0.0394 g) of HRh(CO)(PPh3)3, 5 mL
CO, H2
HRh(CO)(PPh3)3
O
+
O
O
O
3
H
1
2
of triethylamine (Et N), and 0.5 mL of a mixture conꢀ
3
taining
3 : 2 ratio = 1.6). The autoclave was filled with a mixꢀ
ture of CO and Н (СО : Н = 1 : 1) to a pressure of
2 and 3 in amounts of 38 and 62%, respectively
Scheme 1. Transformation of 2,3ꢀdihydrofuran under
(
catalytic hydroformylation conditions.
2
2
The possibility of a singleꢀstep selective synthesis of 10.0 MPa, placed in an electrically heated oven, and
tetrahydrofuran aldehydes, either in a mixture or 2ꢀ and held for 90 min at 90°С
.
3
ꢀformyltetrahydrofurans (
synthons for a number of biologically active compounds
2–5] and substances with other useful properties [6],
2) and (3) individually as
Analysis of the 2,3ꢀdihydrofuran (1) hydroformylaꢀ
tion product. The reaction products were determined on
a LKhMꢀ8MD chromatograph with a thermal conducꢀ
[
prompted us to continue the investigation. For this purꢀ
pose, we used a set of chemically different solvents to
have quite a broad range of polarity and basicity.
In this context, it is noteworthy that the recent studꢀ
tivity detector (column 2.5
× 3 mm with 5% SEꢀ30 silꢀ
icone on Chromaton NꢀAW; carrierꢀgas (helium) flow
rate of 20–30 mL/min, 50 to 120°С).
Solvent preparation. The solvents used in this were
commercial chemicals (see Table 1) dried according to
the conventional procedures.
ies of asymmetric hydroformylation of
out in the toluene medium [7–9].
1 were carried
EXPERIMENTAL
RESULTS AND DISCUSSION
General procedure for the hydroformylation of 2,3ꢀ
dihydrofuran (1). The hydroformylation was carried out
in a rotary autoclave made from Kh18N10T stainless selectivity for aldehydes 2 and 3 (S2 + 3) and the isomer
To reveal the effect of the solvent nature on the total
steel (0.15 L). The autoclave was charged with ratio (S3/S2), we chose the hydroformylation conditions
.043 mmol (0.0394 g) of the catalyst hydridocarbonylꢀ of in benzene, the solvent in which the main investiꢀ
0
1
194

EFFECT OF SOLVENT NATURE ON THE CATALYTIC HYDROFORMYLATION
Table 1. Effect of solvent polarity and basicity on the hydroformylation of 2,3ꢀdihydrofuran, = 90
195
T
°C
µ
, D
pKa
Conversion
S2 + 3
,
Solvent
(in C H )
S3/S2
6
6
(
in H O)
K , %
%
2
1
[14]
Tetramethylene sulfone
4.81
4.09
3.86
3.47
–
65
92
54
62
56
54
0.8
1.1
0.8
1.1
N
N
N
ꢀMethylpyrrolidoneꢀ2
–0.92 [16]
0.18 [17]
2.00 [18]
,
,
N
N
ꢀDimethylformamide
', 'ꢀTetramethylcarꢀ
100
100
,
N N
bonyldiamide
3.40*
N
,
N
ꢀDiethylbenzylamine
2.64* [15]
9.48 [19]
100
97
3.0
7.00**
Tetrahydrofuran
Triethylamine
1.75
1.20
–
100
96
67
51
0.9
4.2
10.74 [20]
8.12**
0.81*
o
ꢀXylene
Toluene
ꢀHexane
Benzene
0.54
0.37
0.05
0.00
–
–
–
–
100
100
100
100
86
79
97
52
0.6
1.0
0.7
0.8
n
0.08*
*
In cyclohexane. ** In EtOH [21].
gations were performed, to medium values of S2 + 3 and medium under hydroformylation conditions showed
S3/S2 at a high conversion of (К1) [1]. that the more reactive compound is amenable to the
1
2
secondary processes to a greater extent: the liquid prodꢀ
ucts contained up to 36% THFS along with the reactant
aldehydes. It is likely for this reason that S3/S increased
We took the solvents that are used for the hydroꢀ
formylation of vinyl ethers [11–13], which linear anaꢀ
logs of
descending order of polarity characterized by the dipole
moment ( , D). There is no correlation between the
1
. In Table 1, the solvents are listed in the
2
to 4.2.
µ
To obtain another piece of evidence that the basicity
of the medium has an effect on hydroformylation of 1,
we chose conditions at which К1 is far from 100%, takꢀ
ing a mixture of benzene and Et N in different volume
solvent polarity, S2 + 3, and S3/S2. The application of
N,Nꢀdiethylbenzylamine having a medium polarity
2.64 D) provides for the maximal values of S2 + 3 (97%)
and considerable regioselectivity for (S /S = 3.0). A
similar value of S2 + 3 (95%) is observed in the medium
(
3
3
3
2
ratios as a solvent (Table 2).
It was found that a decrease in the basicity of the
medium facilitates an increase in К1 and S2 + 3 to the
detriment of regioselectivity, a development that agree
with the published data [25]. Triethylamine, possessing
the highest nucleophilicity among the amines used, disꢀ
places РРh3 to yield more stable catalytic complexes.
This leads to the reduction in the rate of hydroformylaꢀ
of lowꢀpolarity (0.05 D)
in this case.
A direct relationship between the solvent polarity
and S2 + 3 was revealed in the medium of aromatic
hydrocarbon solvents. In the benzene, toluene, and оꢀ
xylene series, S2 + 3 increases as the solvent polarity
increases, with S3/S2 changing within the range of 0.6–
nꢀhexane, however, S3/S2 = 0.7
tion of
1 and, as a consequence, to a decrease in the
1
.0.
In [22–24], it was shown that catalytic complexes of
the HRh(CO) (NR ) type are formed in situ during
value of К1 when the reaction is conducted in the presꢀ
m
3 n
the hydroformylation reaction in the presence of
amines. Based on this finding, we chose as solvents a position on the of hydroformylation of 2,3ꢀdihydrofuran,
Table 2. Effect of Et N : benzene ratio in the solvent comꢀ
3
series of amines differing in basicity (Table 1 lists their
T = 60°C
рКа values).
Et N : benꢀ
zene (vol)
3
The highest regioselectivity for
most basic solvents, such as ꢀdiethylbenzylamine
and Et N. The decrease in S2 + 3 to 51% in Et N is preꢀ
3
is observed in the
K , %
S2 + 3, % S3/S2 STHFS, %
1
N,N
1 : 0 [1]
50
73
92
52
64
74
1.5
11
6
3
3
sumably due to the secondary processes of aldehyde
transformation, in particular, hydrogenation of to tetꢀ
rahydrofurfuryl alcohol (11%, run 7, Table 1). Testing
for the stability of a mixture of and in the Et N
1
0
: 1
1.2
2
: 1 [1]
0.83
–
2
3
STHFS is the selectivity for THFS.
3
PETROLEUM CHEMISTRY Vol. 53
No. 3
2013

1
96
WOL’F et al.
ence of Et N. It is likely that the lower conversion of
in the more basic medium is also due to the deactivation
1
12. R. Lassaroni, S. Bertozzi, P. Pocai, et al., J. Organomet.
3
Chem. 295 (3), 371 (1985).
of the catalyst by the products of transformation of aldeꢀ 13. US Patent No. 4533756 (1985); Chem. Abstrs 104
,
69238c (1986).
hydes
2
and
3
under the hydroformylation conditions.
1
4. O. A. Osipov, V. I. Minkin, and A. D. Garnovskii, Handꢀ
book of Dipole Moments (Vysshaya Shkola, Moscow,
1971) [in Russian].
REFERENCES
1
5. L. A. Kudryavtseva, A. B. Teitel’baum, N. A. Shishkina,
et al., Izv. Akad. Nauk SSSR, Ser. Khim., No. 6, 1302
1
2
3
4
5
6
7
8
9
. E. Yu. Vol’f, T. Yu. Solov’eva, M. M. Vartanyan, et al.,
Izv. Akad. Nauk SSSR, Ser. Khim., No. 11, 2569 (1989).
(
1979).
6. P. Virtanen, I. Olavi, and T. Sodervall, Suomen Kem. 40
37 (1967).
7. G. Wada and T. Takenaka, Bull. Chem. Soc. Jpn. 44
877 (1971).
8. A. Luttringhaus and H. W. Dirksen, Angew. Chem., Int.
Ed. Engl. , 260 (1964).
. US Patent No. 932079 (1979); Chem. Abstr. 91, 15182p
1
1
1
1
,
,
(1979).
3
. R. E. Doolittle, J. H. Tumlinson, A. T. Proveaux, and
R. R. Heath, J. Chem. Ecol. , 473 (1980).
6
2
. M. Zhang, J. Tamiya, L. Nguyen, et al., Bioorg. Med.
Chem. Lett. 17, 2535 (2007).
. G.ꢀD. Zhu, V. B. Gandhi, J. Gong, et al., Bioorg. Med.
Chem. Lett. 18, 3955 (2008).
3
9. M. G. Voronkov, T. V. Kashik, and E. S. Deriglazova,
Zh. Obshch. Khim. 51, 1602 (1981).
. Ger. Offen. No. 2645277 (1978); Chem. Abstr. 89
,
20. H. K. Hall, J. Am. Chem. Soc. 79, 5444 (1957).
112227y (1978).
21. V. E. Bel’skii, L. A. Kudryavtseva, K. A. Derstuganova,
et al., Izv. Akad. Nauk SSSR, Ser. Khim., No. 5, 966
. M. Dieguez, O. Pamies, and C. Claver, Chem. Comꢀ
mun., 1221 (2005).
. J. Mazuela, M. Coll, and O. Pamies, J. Org. Chem.,
No. 74, 5440 (2009).
. A. Gual, C. Godard, S. Castillon, and C. Claver, Adv.
Synth. Catal. 352, 463 (2010).
(1981).
22. G. HenriciꢀOlive and S. Olive, Coordination and Catalyꢀ
sis (Chemie, Weinheim, 1977).
23. B. Fell and E. Muller, Monatsh. Chem. 103, 1222
(1972).
1
0. Handbuch der präporativen anorganischen Chemie, Ed. 24. E. Mieczynska, A. M. Trzeciak, and J. J. Ziolkowski,
by G. Brauer, (Ferdinand Enke, Stuttgart, 1975–1981),
vol. 6.
J. Mol. Catal. 73, 1 (1992).
2
5. G. V. Lisichkin and A. Ya. Yuffa, Heterogeneous Metal
Complex Catalysts (Khimiya, Moscow, 1981) [in Rusꢀ
sian].
11. R. Lassaroni, S. Pucci, S. Bertozzi, and D. Pini, J. Orgaꢀ
nomet. Chem. 247 (3), 56 (1983).
PETROLEUM CHEMISTRY Vol. 53
No. 3
2013