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J Surfact Deterg (2010) 13:41–49
instrument. Chemical shifts are reported in ppm downfield
The other homologues containing the oxyethylene group
were obtained in a similar manner from the corresponding
alkyl polyoxyethylene glycol ether 2m,n.
(d) from an internal standard (TMS in CDCl3 and CD3OD).
Preparation of Raw Materials
Their b.p. and yield were as follows: 410,0: 104–110 °C/
3 mmHg, 67%. 412,0: 110–115 °C/1.5 mmHg, 85%. 412,2
:
In this study, we prepared two kinds of oxirane derivatives,
1m and 4m,n, as raw materials. As Scheme 1 shows, one is
a normal a-olefin oxide, 1,2-epoxyalkane 1m, where, m is
the number of carbons of the corresponding olefin. These
epoxy compounds, a-olefin oxide 1m, [dodecene, tetrade-
cene, hexadecene and octadecene oxide] were obtained
from the ADEKA Co., Ltd., and were used without further
purification. Another homologue 4m,n contains an ether
group and oxyethylene group in addition to the epoxide
group, where m and n indicate the number of carbon atoms
in the alkyl group and the number of oxyethylene groups,
respectively. We solely synthesized these raw materials
4m,n. The synthetic procedure is described in the next
section. The phosphorylating agent composed of a mixture
of diethyl phosphate 48 mol%, ethyl phosphate 49 mol%,
and H3PO4 3 mol% was also obtained from the ADEKA
Co., Ltd.
198–205 °C/1.5 mmHg. 82%, 412,3: 226–232 °C/2 mmHg,
71%. 412,4: 220–226 °C/1 mmHg, 60%, and the representa-
tive 1H-NMR spectra are summarized in Table 1. The spectra
of other homologues containing various alkyl chain lengths
and oxyethylene groups were also in fair agreement with their
d values and integration with the theoretical values.
Synthesis of Phosphate Surfactants (6m, 7m,n)
Scheme 2 summarizes the preparation of the phosphate
surfactants 6m and 7m,n. The preparation of the 2-hydroxy
tetradecyl phosphate homologue 614 is described here as an
example. 1,2-Epoxytetradecane (6.37 g, 30 mmol, 114) was
reacted with phosphorylation agent (48 mol% diethyl
phosphate (DEP), 4.58 g, 33 mmol) at 60–70 °C. After a
2-h reaction, 5.4 ml (0.3 mol) of water was added with
stirring in order to hydrolyze the diethyl phosphate ester
514, which was not isolated. The solution was diluted with
toluene, and the toluene layer was washed with water.
After drying and evaporation of the toluene, the crude
product was purified by recrystallization from ethyl acetate
and hexane 1:1 [v/v] as a white solid powder, 3.92 g, yield
42%, m.p. of 614 was 88–92 °C. The m.p. of the other
homologues were as follows: 612 68–74 °C, 616 99–
101 °C, 618 101–104 °C. The structure of the product was
Preparation of epoxide derivatives (4m,n)
Scheme 1 illustrates an outline of the preparation proce-
dure. n-Alkyl glycidyl ether was prepared according to the
published method [16]. The synthesis of n-octyl glycidyl
ether 48,0 is described here as an example. To a solution of
70.1 g (0.54 mol) of n-octanol and 0.85 g of SnCl4 was
slowly added 54.9 g (0.60 mol) of epichlorohydrin. The
mixture was well stirred and maintained at 80 °C during
the addition, and then the contents were heated at 110 °C
for 2 h. The epoxide was produced by the dehydrochlori-
nation of the crude chlorohydrin 3m,n, which was not
isolated, in a strong alkaline solution (45 g of 48% NaOH
aqueous solution) as described by Sandler and Karo [16].
The crude epoxide ether was purified by distillation under
reduced pressure to yield n-octyl glycidyl ether 48,0 as a
colorless liquid, b.p. 94–97 °C/6 mmHg. 75.9 g yield 74%.
1
1
determined by H NMR. The representative H-NMR data
are summarized in Table 1. The other phosphate surfactant
homologues of 7m,n were also prepared from the corre-
sponding epoxides 4m,n in a similar manner as already
described. Due to the ether linkage, all of these phosphates
7m,n were very viscous, therefore, they did not exhibit a
clear melting points.
In order to prepare some specimens with different neu-
tralization degree, the product was neutralized with the
prescribed amount of 0.5 M NaOH aqueous solution in
Scheme 1 Normal
O
CH3
Normal epoxyalkanes (1m)
m= 10,12,14, 16
epoxyalkanes (1m) and
preparation of epoxide
homologues containing
oxyethylene and ether linkage
m-3
O
Cl
Epoxides containing oxyethylene
and ether linkage (4m,n
CH3
O
(4m,n)
O
H
n
)
m-2
SnCl4, 100-110oC, 3h
(2m,n
)
OH
O
NaOH
60-70oC, 6h
CH3
O
Cl
CH3
O
O
O
m-2
n
n
m-2
(3m,n
)
(4m,n) m=8,10,12 n= 0,2,3,4
123