A practical method for epoxidation of terminal olefins with 30% hydrogen peroxide under halide-free conditions

Full text of DOI:10.1021/jo961287e

8310
J . Org. Chem. 1996, 61, 8310-8311
Ta ble 1. Ep oxid a tion of Ter m in a l Olefin s w ith 30%
A P r a ctica l Meth od for Ep oxid a tion of
Ter m in a l Olefin s w ith 30% Hyd r ogen
P er oxid e u n d er Ha lid e-F r ee Con d ition s
Hyd r ogen P er oxid ea
Na2WO4, toluene, time, convn,b yield,b,c
entry
olefin
mmol
mmol
mL
h
%
%
1
2
3
4
5
6
7
8
9
1-octene
20
20
100
20
20
100
20
20
100
594
0.4
0.4
2
0.4
0.4
2
0.4
0.4
2
4
0
30
4
0
30
4
0
30
0
4
2
4
4
2
4
4
2
4
2
96
89
94
86
86d
99
Kazuhiko Sato, Masao Aoki, Masami Ogawa,
Tadashi Hashimoto, and Ryoji Noyori*
1-decene
99
94
93
91d
97
Department of Chemistry and Molecular Chirality Research
Unit, Nagoya University, Chikusa, Nagoya 464-01, J apan
1-dodecene
98
87
87
92d
87d
10
12
Received J uly 9, 1996
a
Reaction was run using 30% H2O2, olefin, Na2WO4‚2H2O,
NH2CH2PO3H2, and [CH3(n-C8H17)3N]HSO4 in a 150:100:2:1:1
Epoxidation of olefins is among the most important
reactions in organic synthesis,1 because epoxy compounds
are widely used as intermediates in the laboratory and
for chemical manufacturing.2 There is an ever increasing
demand for a practical efficient procedure. Epoxidation
of terminal olefins is the most important but difficult.
Industry in particular, requires high yield, high selectiv-
ity, sufficient productivity, low cost, safety, operational
simplicity, and environmental consciousness among other
technical factors. In this context, Venturello’s procedure
using aqueous H2O2 as the oxidant3 is appreciated,
because water is the sole expected side product.4 How-
ever, the original procedure for 1-octene epoxidation
using a Na2WO4-H3PO4-quaternary ammonium chlo-
ride combined catalyst was unsatisfactory, since the
reaction necessitated an excess of olefinic substrates in
a 1,2-dichloroethane-water biphasic system giving the
epoxy product in at most 53% yield. Since then a number
of modified procedures have appeared,5 and Ishii among
others made a great improvement by using a tungsten-
based heteropoly acid and N-cetylpyridinium chloride in
a chloroform-water mixture raising the yield up to 80%.6
Even the best procedure, however, requires toxic and
carcinogenic chlorinated hydrocarbon solvents7 to obtain
a high yield and high selectivity (yield was only 33% in
refluxing benzene6), defeating the environmental and
economic advantages of H2O2 as the oxidant.4,8,9 We now
b
molar ratio at 90 °C with stirring at 1000 rpm. Determined by
GC analysis. c Based on olefin charged. Isolated by distillation.
d
disclose a very practical method that overcomes this
serious problem (eq 1).
Our new catalytic system consists simply of Na2WO4
dihydrate, (aminomethyl)phosphonic acid, and methyltri-
n-octylammonium hydrogensulfate in a 2:1:1 molar ratio
and is free from any organic or inorganic chlorides.10 The
biphasic epoxidation of simple terminal olefins can be
carried out at 90 °C with 150 mol % of H2O2 and 0.2-2
mol % of the catalyst without organic solvents or alter-
natively by adding toluene. Terminal olefins, which are
normally least reactive, were epoxidized in 94-99% yield
with 2 mol % of the catalyst. Some examples are given
in Table 1. The turnover numbers of the epoxidation
were 150-200 per W atom. The reaction of 1-dodecene
when conducted on a 100 g scale without toluene, gave,
after simple distillation of the organic phase, 1,2-epoxy-
dodecane in 87% yield.
The use of ammonium hydrogensulfate, rather than
conventional chlorides,3,5a,c-f,6,7,11 as phase transfer cata-
lysts was crucial for the high reactivity; addition of NaCl
significantly retarded the reaction. Other trialkylmethy-
lammonium hydrogensulfates possessing C6 to C10 alkyl
chains were equally usable. The exact role of the
R-amino phosphonic acid in facilitating the epoxidation
remains unclear, since it is largely decomposed under the
reaction conditions (31P NMR). The reaction with â- or
γ-amino phosphonic acids was much slower.
(1) Rao, A. S. In Comprehensive Organic Synthesis; Trost, B. M.,
Fleming, I., Ley, S. V., Eds.; Pergamon: Oxford, 1991; Vol. 7, pp 357-
436.
(2) Gerhartz, W.; Yamamoto, Y. S.; Kaudy, L.; Rounsaville, J . F.;
Schulz, G., Eds. Ullmann’s Encyclopedia of Industrial Chemistry, 5th
ed.; Verlag Chemie: Weinheim, 1987; Vol. A9, pp 531-564.
(3) (a) Venturello, C.; Alneri, E.; Ricci, M. J . Org. Chem. 1983, 48,
3831-3833. (b) Venturello, C.; D’Aloisio, R. J . Org. Chem. 1988, 53,
1553-1557.
(4) Strukul, G., Ed. Catalytic Oxidations with Hydrogen Peroxide
as Oxidant, Kluwer: Dordrecht, The Netherlands, 1992.
(5) (a) Prandi, J .; Kagan, H. B.; Mimoun, H. Tetrahedron Lett. 1986,
27, 2617-2620. (b) Anelli, P. L.; Banfi, S.; Montanari, F.; Quici, S. J .
Chem. Soc., Chem. Commun. 1989, 779-780. (c) Aubry, C.; Chottard,
G.; Platzer, N.; Bre´geault, J . M.; Thouvenot, R.; Chauveau, F.; Huet,
C.; Ledon, H. Inorg. Chem. 1991, 30, 4409-4415. (d) Dengel, A. C.;
Griffith, W. P.; Parkin, B. C. J . Chem. Soc., Dalton Trans. 1993, 2683-
2688. (e) Neumann, R.; Gara, M. J . Am. Chem. Soc. 1994, 116, 5509-
5510. (f) Neumann, R.; Gara, M. J . Am. Chem. Soc. 1995, 117, 5066-
5074.
One drawback of this method is the difficulty encoun-
tered in the epoxidation of styrene (eq 1, R ) C6H5) and
its simple derivatives. Styrene was converted to the
epoxide but the latter was very sensitive to hydrolytic
decomposition that probably occurs at the aqueous/
organic interface. Yield of the epoxide remained less
than 23%.
Exp er im en ta l Section
(6) Ishii, Y.; Yamawaki, K.; Ura, T.; Yamada, H.; Yoshida, T.;
Ogawa, M. J . Org. Chem. 1988, 53, 3587-3593.
Gen er a l a n d Ma ter ia ls. 1H NMR spectra were recorded on
(7) Duncan, D. C.; Chambers, R. C.; Hecht, E.; Hill, C. L. J . Am.
Chem. Soc. 1995, 117, 681-691.
a
J EOL J NM-A400 NMR spectrometer at 400 MHz with
(8) Hileman, B.; Long, J . R.; Kirschner, E. M. Chem. Eng. News
1994, 72 (47), 12-22.
tetramethylsilane used as an internal standard. The chemical
shifts are reported in ppm on δ scale downfield from tetram-
(9) For expoxidation in tert-butyl alcohol using H2O2 dried over Mg2-
SO4 see: (a) Herrmann, W. A.; Fischer, R. W.; Marz, D. W. Angew.
Chem., Int. Ed. Engl. 1991, 30, 1638-1641. (b) Herrmann, W. A.;
Fischer, R. W.; Rauch, M. U.; Scherer, W. J . Mol. Catal. 1994, 86, 243-
266. In methanol: (c) Clerici, M. G.; Ingallina, P. J . Catal. 1993, 140,
71-83.
(10) For example, epoxy resin encapsulants for semiconductors are
required to be entirely free from chlorides.
(11) Dehmlow, E. V.; Dehmlow, S. S. Phase Transfer Catalysis, 3rd
ed.; Verlag Chemie: Weinheim, 1993.
S0022-3263(96)01287-X CCC: $12.00 © 1996 American Chemical Society

Notes
J . Org. Chem., Vol. 61, No. 23, 1996 8311
ethylsilane, and signal patterns are indicated as follows: s,
singlet; d, doublet; t, triplet; m, multiplet; br, broad peak. 13C
NMR spectra were measured on a J EOL J NM-A400 NMR
spectrometer at 100 MHz. The chemical shifts are reported in
ppm with chloroform-d (77.0 ppm) as an internal standard. Gas
chromatographic analyses were performed on a Shimadzu GC-
14A gas chromatograph.
Sodium tungstate dihydrate, aqueous 30% hydrogen peroxide,
tri-n-octylamine, dimethyl sulfate, and toluene were obtained
from Nacalai Tesque, Inc., and used as received. 1-Octene and
1-dodecene were purchased from Tokyo Kasei Kogyo Co., Ltd.,
and were distilled before use. 1-Decene was purchased from
Aldrich Chemical Co. and purified by distillation before use.
(Aminomethyl)phosphonic acid12 was synthesized according to
the literatures.
P r ep a r a tion of Meth yltr i-n -octyla m m on iu m Hyd r ogen -
su lfa te. A 100-mL, round-bottomed flask equipped with a
magnetic stirring bar was charged with 17.7 g (50.0 mmol) of
tri-n-octylamine and 20 mL of toluene. Under stirring, 6.50 g
(51.5 mmol) of dimethyl sulfate was added in portions at room
temperature, and then the mixture was heated at 140 °C for 17
h. The dark red solution was mixed with 1.0 mL of water and
heated at 90 °C for 12 h. The mixture was cooled to room
temperature, 20 mL of 49% sulfuric acid was added, and the
biphasic mixture was vigorously stirred for 12 h. Removal of
volatile material in vacuo gave 23.4 g (99%) of methyltri-n-
octylammonium hydrogensulfate.13 1H NMR (400 MHz, CDCl3)
δ 0.88 (t, 9H, J ) 7.0 Hz), 1.27-1.35 (m, 30H), 1.66 (br, 6H),
3.19 (s, 3H), 3.25 (t, 6H, J ) 8.0 Hz). 13C NMR (100 MHz, CDCl3)
δ 14.0, 22.2, 22.5, 26.1, 28.9, 29.0, 31.6, 61.4.
P r oced u r e for Hectogr a m -Sca le Ep oxid a tion of 1-Dod e-
cen e. A 1-L, round-bottomed flask equipped with a reflux
condenser and a magnetic stirring bar was charged with 3.919
g (11.9 mmol) of Na2WO4‚2H2O, 101.0 g (891 mmol) of aqueous
30% H2O2, 0.660 g (5.94 mmol) of NH2CH2PO3H2, and 2.767 g
(5.94 mmol) of [CH3(n-C8H17)3N]HSO4, and the biphasic mixture
was vigorously stirred at room temperature for 15 min. To this
was added 100.0 g (594 mmol) of 1-dodecene, and the mixture
was heated at 90 °C for 2 h with stirring at 1000 rpm and cooled
to room temperature. The organic phase was separated, washed
with 150 mL of saturated aqueous Na2S2O3, and distilled
through a short column under vacuum to give 96.20 g (87.2%)
of 1,2-epoxydodecane as a colorless liquid, bp 73.5-77.0 °C/0.3
mmHg.14,15 GC (column, OV-1, 0.25 mm x 50 m, GL Sciences
Inc.); carrier gas, helium (1.2 kg/cm2); initial column temp, 70
°C; final column temp, 280 °C; progress rate, 9 °C/min; injection
temp, 280 °C; split ratio, 100:1; retention time (tR) of 1-dodecene,
12.4 min; tR of 1,2-epoxydodecane, 16.5 min. 1H NMR (400 MHz,
CDCl3) δ 0.88 (t, 3H, J ) 6.7 Hz), 1.27-1.54 (m, 18H), 2.46 (dd,
1H, J ) 2.9, 4.9 Hz), 2.74 (dd, 1H, J ) 3.9, 4.9 Hz), 2.89 (br,
1H). 13C NMR (100 MHz, CDCl3) δ 14.1, 22.7, 26.0, 29.4, 29.5,
29.6, 29.7, 32.0, 32.6, 47.1, 52.4.
1,2-Ep oxyocta n e.16 GC (column, OV-1, 0.25 mm x 50 m, GL
Sciences Inc.); carrier gas, helium (1.2 kg/cm2); initial column
temp, 70 °C; final column temp, 280 °C; progress rate, 5 °C/
min; injection temp, 280 °C; split ratio, 100:1; tR of 1-octene, 6.4
min; tR of 1,2-epoxyoctane, 10.7 min. 1H NMR (400 MHz, CDCl3)
δ 0.89 (t, 3H, J ) 6.8 Hz), 1.29-1.55 (m, 10H), 2.46 (dd, 1H, J
) 2.9, 4.9 Hz), 2.74 (dd, 1H, J ) 3.9, 4.9 Hz), 2.89 (br, 1H). 13C
NMR (100 MHz, CDCl3) δ 14.1, 22.6, 26.0, 29.1, 31.8, 32.5, 47.1,
52.4.
1,2-Ep oxyd eca n e.17 GC (column, OV-1, 0.25 mm x 50 m,
GL Sciences Inc.); carrier gas, helium (1.2 kg/cm2); initial column
temp, 70 °C; final column temp, 280 °C; progress rate, 9 °C/
min; injection temp, 280 °C; split ratio, 100:1; tR of 1-decene,
8.8 min; tR of 1,2-epoxydecane, 14.4 min. 1H NMR (400 MHz,
CDCl3) δ 0.88 (t, 3H, J ) 6.8 Hz), 1.27-1.55 (m, 14H), 2.46 (dd,
1H, J ) 3.0, 5.0 Hz), 2.74 (dd, 1H, J ) 3.9, 5.0 Hz), 2.90 (br,
1H). 13C NMR (100 MHz, CDCl3) δ 14.0, 22.6, 25.9, 29.2, 29.4,
29.5, 31.8, 32.4, 47.0, 52.3.
J O961287E
(14) Davies, S. G.; Whitham, G. H. J . Chem. Soc., Perkin Trans. 2,
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(15) The cost of the reagents used for the oxidation of 1 mol of olefin
(12) Available from Aldrich. It can be prepared inexpensively
according to the literature method: (a) Tracy, D. J . Synthesis 1976,
467-469. (b) Soroka, M. Synthesis 1989, 547-548.
(13) Feldman, D.; Rabinovitz, M. J . Org. Chem. 1988, 53, 3779-
3784.
is only $3.30.
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493-499.
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2828.