Synthesis and solution properties of sulfate-type hybrid surfactants with a benzene ring

Article abstract of DOI:10.1016/j.jfluchem.2003.08.007

Nine novel sulfate-type hybrid surfactants, C_m F_2m+1C₆H₄CH(OSO₃Na) C_nH_2n+1 (FmPHnOS: m=4, 6, 8; n=3, 5, 7; C₆H₄: p-phenylene), with a benzene ring in their molecules were synthesized. Alkanoyl chlorides were allowed to react with iodobenzene in the presence of aluminum chloride to give the corresponding aromatic ketones. The reaction of the ketones with perfluoroalkyl iodides yielded 1-[4-(perfluoroalkyl)phenyl]-1-alkanones as intermediates. The intermediates were allowed to react with methanol in tetrahydrofuran in the presence of sodium borohydride to yield 1-[4-(perfluoroalkyl)phenyl]-1-alkanols. The desired hybrid surfactants were obtained by the reaction of 1-[4-(perfluoroalkyl)phenyl-1-alkanols with sulfur trioxide/pyridine complex in pyridine and by the subsequent neutralization of the products with sodium hydroxide solution. When compared with the conventional hybrid surfactants, C_m F_2m+1C₆H₄COCH(SO₃Na) C_nH_2n+1 (FmHnS: m=4, 6; n=2, 4, 6; C₆H₄: p-phenylene), the new hybrid surfactants thus synthesized were found to have a comparable ability to lower the surface tension of water and a high hydrophilicity. The cmc of FmPH n OS obeyed Kleven's rule and their occupied areas per molecule increased with increasing m and n with the values between 0.66 and 1.05 nm². The aggregation number for FmPHnOS micelles ranged from 6 to 45 and the hydrodynamic radius of the micelles was in the range of 1.4-3.1 nm.

Full text of DOI:10.1016/j.jfluchem.2003.08.007

Journal of Fluorine Chemistry 124 (2003) 189–196
Synthesis and solution properties of sulfate-type hybrid
surfactants with a benzene ring
Haruhiko Miyazawaa, Kanako Igawaa, Yukishige Kondoa,b, Norio Yoshinoa,b,*
aDepartment of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 1-3 Kagurazaka,
Shinjuku-ku, Tokyo 162-8601, Japan
bInstitute of Colloid and Interface Science, Tokyo University of Science, 1-3 Kagurazaka,
Shinjuku-ku, Tokyo 162-8601, Japan
Received 21 April 2003; received in revised form 13 August 2003; accepted 14 August 2003
Abstract
Nine novel sulfate-type hybrid surfactants, CmF2mþ1C6H4CH(OSO3Na)CnH2nþ1 (FmPHnOS: m ¼ 4, 6, 8; n ¼ 3, 5, 7; C6H4: p-phenylene),
with a benzene ring in their molecules were synthesized. Alkanoyl chlorides were allowed to react with iodobenzene in the presenceof aluminum
chloride to give the corresponding aromatic ketones. The reaction of the ketones with perfluoroalkyl iodides yielded 1-[4-(perfluoroalk-
yl)phenyl]-1-alkanones as intermediates. The intermediates were allowed to react with methanol in tetrahydrofuran in the presence of sodium
borohydride to yield 1-[4-(perfluoroalkyl)phenyl]-1-alkanols. The desired hybrid surfactants were obtained by the reaction of 1-[4-(perfluoro-
alkyl)phenyl-1-alkanols with sulfur trioxide/pyridine complex in pyridine and by the subsequent neutralization of the products with sodium
hydroxide solution. When compared with theconventionalhybrid surfactants, CmF2mþ1C6H4COCH(SO3Na)CnH2nþ1 (FmHnS: m ¼ 4, 6; n ¼ 2,
4, 6; C6H4: p-phenylene), the new hybrid surfactants thus synthesized were found to have a comparable ability to lower the surface tension of
water and a high hydrophilicity. The cmc of FmPHnOS obeyed Kleven’s rule and their occupied areas per molecule increased with increasing
m and n with the values between 0.66 and 1.05 nm2. The aggregation number for FmPHnOS micelles ranged from 6 to 45 and the hydrodynamic
radius of the micelles was in the range of 1.4–3.1 nm.
# 2003 Published by Elsevier B.V.
Keywords: Hybrid surfactant; Benzene ring; Sulfate; Critical micelle concentration; Surface tension at cmc; Krafft point; Occupied area per molecule;
Aggregation number; Hydrodynamic radius
1. Introduction
surfactants were easily hydrolyzed by moisture in the air,
making them practically useless. The present authors
synthesized six sulfonate-type hybrid surfactants with a
benzene ring in their molecule, CmF2mþ1C6H4COCH2-
(SO3Na)CnH2nþ1 (FmHnS: m ¼ 4, 6; n ¼ 2, 4, 6; C6H4:
p-phenylene), in 1995 [12], and have reported that the
surfactants are hardly hydrolyzable and are thermoresistant
up to 200 8C, and have an excellent surface tension lowering
ability, and 10 wt.% F6H4S aqueous solution exhibits a
very high visco elasticity at 37 8C [13–16]. Because of
low interfacial tension, FmHnS could emulsify mutually
immiscible ternary system, hydrocarbon/water/perfluoropo-
lyether, simultaneously [12,17]. In addition, intramicellar
phase separation has been observed to occur between fluoro-
carbon chains and hydrocarbon chains in aqueous solution
of FmHnS [18].
Fluorinated surfactants with a fluorocarbon chain as the
hydrophobic group exhibit characteristic properties includ-
ing thermal resistance, chemical resistance, high surface
activity, high surface modifying ability and low critical
micelle concentration [1–4]. Although mixing with fluori-
nated surfactants was attempted to give their characteristic
properties to hydrocarbon surfactants, the attempt failed
because no well-mixed surfactant micelle was formed
while fluorinated surfactant-rich and hydrocarbon surfac-
tant-rich micelles were found to form in the mixture [5–10].
Guo et al. synthesized hybrid surfactants with a fluoro-
carbon chain and a hydrocarbon chain in one molecule,
CmF2mþ1CH(OSO3Na)CnH2nþ1 (FmHn: m ¼ 6, 7, 8, 9;
n ¼ 1, 2, 3, 4, 5, 6, 7, 8, 9), in 1992 [11]. However, these
The present paper reports the synthesis of nine novel
sulfate-type hybrid surfactants, CmF2mþ1C6H4CH(OSO3Na)-
CnH2nþ1 (FmPHnOS: m ¼ 4, 6, 8; n ¼ 3, 5, 7; C6H4:
* Corresponding author. Tel.: þ81-3-5228-8319; fax: þ81-3-3260-4281.
E-mail address: yoshino@ci.kagu.tus.ac.jp (N. Yoshino).
0022-1139/$ – see front matter # 2003 Published by Elsevier B.V.
doi:10.1016/j.jfluchem.2003.08.007

190
H. Miyazawa et al. / Journal of Fluorine Chemistry 124 (2003) 189–196
Table 1
p-phenylene) and the physicochemical properties of their
solutions.
Cmc, surface tension at cmc (gcmc), and Krafft point (Kp) for FmPHnOS
c
Surfactant
cmc
gcmc
(mN/m)
Kp (8C)
Surface tensiona 1H NMRb
2. Result and discussion
(mM)
(mM)
F4PH3OS
F6PH3OS
F8PH3OS
F4PH5OS
F6PH5OS
F8PH5OSe
F4PH7OS
F6PH7OSe
F8PH7OSe
7.0
0.90
0.08
3.0
0.34
–
7.0
0.81
19
18
20
19
20
–
<0 (35 mM)
<0 (4.5 mM)
16 (0.4 mM)
<0 (10 mM)
14 (1.5 mM)
32 (0.2 mM)
8 (6.5 mM)
43 (0.5 mM)
76(0.01 mM)
2.1. Synthesis of hybrid surfactants
d
–
Scheme 1 is the route of synthesis of the hybrid surfac-
tants.
3.6
0.30
–
All reactions proceeded in mild conditions. The yield of
FmPHnA was higher than 80%. An attempt failed to sulfate
FmPHnA with concentrated sulfuric acid and fuming sulfu-
ric acid to obtain FmPHnOS. However, SO3/pyridine com-
plex with a lower SO3 activity was found to give FmPHnOS
in a high yield. Only 2.0 mg of water was absorbed when
F6PH5OS (104.0 mg) was exposed to the air for 10 days.
After F6PH5OS with absorbed water was dried for 3 h under
1.3
–
1.3
–
20
–
–
–
–
a 27 8C.
b 30 8C.
c Kp was measured in the concentration shown in parenthesis.
d Accurate cmc of FBPH3OS was not obtained because of low 1H
NMR signal intensities.
e These data except for Kp were not obtained because of high Kp.
1
reduced pressure 20 Pa, H NMR and FT-IR spectra of the
dried surfactant were measured. The spectra obtained were
the same as those of pure F6PH5OS. FmHn [11] are easily
hydrolyzed since a strongly electron attracting fluorocarbon
group and a sulfate ester group bind to the same carbon atom
in their molecules, whereas the hybrid surfactants synthe-
sized in the present work are hardly susceptible to hydrolysis
because of the presence of a benzene ring between the
fluorocarbon and sulfate ester groups in their molecules.
The occupied area per molecule for FmPHnOS was
calculated from the surface excess concentration at air/water
interface (G). G was calculated using the Gibbs adsorption
isotherm (1) [20].
ꢀ
4:606RT @ logC
ꢁ
1
@g
G ¼ À
(1)
Here, R is the gas constant and T is the absolute temperature.
The occupied area (A) per molecule for FmPHnOS relates to
the adsorption amount G via the following Eq. (2).
2.2. Krafft point, cmc, and surface tension
of FmPHnOS
1
A ¼
(2)
Table 1 lists the cmc, surface tension at cmc (gcmc), and
Krafft point (Kp) for FmPHnOS.
The cmc was determined using surface tension and H
GNA
1
where NA is Avogadro’s number.
Table 2 shows the surface excess concentration G and A
for FmPHnOS.
The value A increased with increasing m and n. The value
of A was 0.66–1.04 nm2/molecule, while for sodium alkyl
NMR measurements. No big difference was found between
the cmc determined by two methods. The gcmc for FmPHnOS
was around 20 mN/m which was almost same as that for
FmHnS [19] or the conventional single-chain fluorinated
surfactant [20]. The hydrophilicity of FmPHnOS was
slightly higher than that of FmHnS [19]. Fig. 1 shows the
relationship between surface tension and concentration for
FmPHnOS aqueous solution.
Scheme 1. Synthesis of FmPHnOS.
Fig. 1. Surface tension plots of FmPHnOS against concentration at 27 8C.

H. Miyazawa et al. / Journal of Fluorine Chemistry 124 (2003) 189–196
191
Table 2
available for the surfactants, the following two Eqs. (5)
and (6) are obtained.
Surface excess concentration G and occupied area A per molecular at 27 8C
Surfactant
G (mmol/m2)
A (nm2)
FmPH5OS : logðcmcÞ ¼ À0:633 À 0:473m
F6PHnOS : logðcmcÞ ¼ À2:41 À 0:211n
(5)
(6)
F4PH3OS
F6PH3OS
F8PH3OS
F4PH5OS
F6PH5OS
F4PH7OS
2.5
2.1
1.8
1.7
1.6
1.6
0.66
0.80
0.94
0.99
1.04
1.04
These equations give the rates of cmc decrease of 38%
per CH2 group and 66% per CF2 group for F6PHnOS and
FmPH5OS, respectively. With FmHn, cmc decreases by 35
and 75% when the number of CH2 group and CF2 group,
respectively, increase by one [11]. A comparison of the
contribution to cmc of CH2 group or CF2 group between
FmPHnOS and FmHn reveals that the contribution of CF2
group is smaller for FmPHnOS than for FmHn while that of
CH2 group is almost the same for both types of surfactants.
The smaller contribution of CF2 group for FmPHnOS
would be brought about by the introduction of a spatially
large benzene ring between the fluorocarbon chain and the
hydrophilic group, thereby causing weakened hydrophobic
interaction between fluorocarbon chains as compared with
that for FmHn.
sulfates having two alkyl chains such as (C10H21)(C7H15)-
CHOSO3Na it was 0.50–0.60 nm2/molecule [20]. The
values A for FmPHnOS were smaller than those for FmHnS
(0.81 and 1.06 nm2 for F4H2S and F4H6S, respectively
[19]) when the lengths of hydrocarbon chain n and fluoro-
carbon chain m are respectively about the same for both
types of hybrid surfactants. The A value depends on the
species of hydrophilic group rather than those of hydro-
phobic group [20]. Since FmHnS has a hydrophilic carbonyl
group that can form hydrogen bond with water molecule,
this surfactant has two hydrophilic groups. This would make
the value A of the surfactant larger than that of FmPHnOS.
Fig. 2 shows the logarithmic plots of the cmc determined by
surface tension measurement against m and n.
2.3. Aggregation number and diameter of
FmPHnOS micelles
In the case of FmPH3OS, log(cmc) decreased linearly
with increasing m, obeying Kleven’s rule (3).
Fig. 3 shows the relationship between the 1H NMR
chemical shift dobs for o-CH3 group and the reciprocal
concentration for F4PH3OS.
The dobs at concentrations lower than cmc are for the
chemical shift for monomer dmon while those at concen-
trations higher than cmc are the weight average of the
chemical shift for monomer and that for micelle dmic [21].
logðcmcÞ ¼ À0:186 À 0:486m
ðcorrelation coefficient; 0:998Þ (3)
This rule also holds for F4PHnOS with respect to n,
Eq. (4).
The following relation (7) then holds among dobs, dmon
and dmic
,
logðcmcÞ ¼ À1:61À0:183n
:
ðcorrelation coefficient; 0:999Þ
(4)
dobs ¼ pmondmon þ ð1 À pmonÞdmic
Cmon
(7)
Eqs. (3) and (4) suggest that when the number of CH2 or
CF2 group in the hydrophobic chain increases by one, the
cmc decreases by 34 or 67%, respectively.
pmon
¼
C
(8)
where Cmon and pmon are the concentration and mole fraction
of monomer. Since changes in the monomer concentration
If Kleven’s rule is assumed to hold for FmPH5OS (n ¼ 5)
and F6PHnOS (m ¼ 6), even though only two cmc are
Fig. 2. Plots of log(cmc) for FmPHnOS against m and n.

192
H. Miyazawa et al. / Journal of Fluorine Chemistry 124 (2003) 189–196
Table 3
Diffusion coefficient of the surfactants (Dobs), micelle (Dmic), monomer
(Dmon), and hydrodynamic radius (RH) for FmPHnOS in D2O at 30 8C
Surfactant
N
Dobs
(10 nm2/s)
Dmic
(10 nm2/s)
Dmon
(10 nm2/s)
RH
(nm)
F4PH3OS
F6PH3OS
F4PH5OS
F6PH5OSa
F4PH7OS
6
0.32
0.22
0.21
0.21
0.38
0.17
0.75
0.57
0.65
0.39
0.54
1.4
1.8
2.2
1.1
3.1
–
15
–
0.095
0.10
0.17
0.074
45
a Data from [21].
Table 3 shows the aggregation numbers N for FmPHnOS.
The numbers for F6PH3OS and F6PH5OS could not
be determined because the hydrodynamic radius of their
micelles changed at concentrations above the cmc [21]. The
value N was found to increase exponentially with increasing
length of hydrocarbon chain n.
The diffusion coefficient of FmPHnOS micelles was
determined by the pulsed-gradient spin echo (PGSE) method.
The diffusion coefficient Dobs for FmPHnOS at concen-
trations higher than cmc is the weight average of those for
monomer Dmon and micelle Dmic as is given by Eq. (17) [21].
Fig. 3. Chemical shift plot for o-CH3 group in F4PH3OS against recipro-
cal concentration.
can be neglected above cmc, dobs is linearly related with 1/C
as in (9).
ðdmon À dmicÞcmc
dobs ¼ dmic
þ
(9)
C
The concentration at the intersection of the two lines in
Fig. 3 gives cmc [11], and the dobs at 1=C ! 0 correspond-
Dobs ¼ pmonDmon þ ð1 À pmonÞDmic
(17)
ing to dmic
.
On the other hand, the mass action model for micelle
formation is given by Eq. (10), assuming no effect from the
counterion and also assuming one single micelle size with a
well-defined aggregation number [22,23]:
If the monomer concentration is assumed to be constant at
concentrations above cmc, that is, Cmon ꢁ cmc, then Eq. (17)
is written simply as:
ꢀ
ꢁ
cmc
C À cmc
Dobs
¼
Dmon
þ
Dmic
(18)
N S?SN
(10)
C
C
where N is the aggregation number and S and SN denote
respectively monomer and micelle. The equilibrium con-
stant K for micelle formation according to Eq. (10) can be
written in the form (11):
Thus, Dmic can be obtained from the Dobs measured at
concentrations below cmc, which is equal to Dmon
Table 3 shows the values of Dobs, Dmic and Dmon at a con-
centration four times higher than cmc, and hydrodynamic
radius of micelle RH. The hydrodynamic micelle radius was
calculated using the Stokes–Einstein equation:
.
½SNꢀ
K ¼
(11)
N
½Sꢀ
kT
½Sꢀ ¼ Cmon
Cmic
½SNꢀ ¼
N
(12)
(13)
RH ¼
(19)
6pZ0D
where k is the Boltzmann constant and Z0 is the viscosity of
solvent. The hydrodynamic radius of F6PH5OS micelle was
smaller than that of F4PH3OS micelle, though the radius of
surfactant micelle generally increases with increasing length
of the hydrophobic chain. This would presumably be due to
an interdigitated structure of F6PH5OS micelle [21].
where Cmic is the concentration of FmPHnOS forming
micelles. Substituting Eqs. (12) and (13) into Eq. (11)
and taking the logarithms of both sides the resulting equation
yield Eq. (14).
log Cmic À N log Cmon ¼ log NK ¼ constant
(14)
Then, the plot of log Cmic against log Cmon gives a straight
line, the slope of which allows to determine the aggregation
number N. Cmon and Cmic can be calculated using the
3. Conclusion
Novel sulfate-type hybrid surfactants, CmF2mþ1C6H4CH-
(OSO3Na)CnH2nþ1 (FmPHnOS: m ¼ 4, 6, 8; n ¼ 3, 5, 7),
were synthesized in a relatively high yield. These surfactants
were stable and hardly hydrolyzed and had surface activity
as high as that of the conventional surfactants, while they
showed a lower Krafft point.
following equations with the dobs
.
dobs À dmic
Cmon ¼ pmonC ¼
C
(15)
(16)
dmon À dmic
dmon À dobs
Cmic ¼ ð1 À pmonÞC ¼
C
dmon À dmic

H. Miyazawa et al. / Journal of Fluorine Chemistry 124 (2003) 189–196
193
The cmc for FmPHnOS obeyed Kleven’s rule and the
decreasing rates of their cmc with increasing hydrophobic
chain length were 34–38% per CH2 group and 66–67% per
CF2 group, respectively. The occupied area per molecule for
FmPHnOS increased with increasing length of fluorocarbon
chain or hydrocarbon chain, and the area ranged from 0.66 to
1.04 nm2.
The aggregation number of FmPHnOS molecules forming
a micelle increased abruptly with increasing n and the
hydrodynamic radius of FmPHnOS micelle was in a range
1.4–3.1 nm.
intensity was calibrated before measurement using the
diffusion coefficient of H2O (Dobs ¼ 2:3 ꢂ 10À9 m2/s
[25]).
4.3. Synthesis of hybrid alcohols
4.3.1. Synthesis of 1-[4-(perfluorobutyl)phenyl]-1-butanol
(F4PH3A)
C4F9C6H4COC3H7 (22.3 g, 60.8 mmol) [12], sodium boro-
hydride (0.689 g, 18.2 mmol), and THF (50 cm3) were
placed in a 300 ml eggplant-shaped flask equipped with
an isobaric dropping funnel, through which methanol
(30.1 g, 939 mmol) was then slowly added dropwise under
ice-cooling. After the reaction mixture was stirred for 5 h at
room temperature, THF and methanol were removed by
distillation under reduced pressure. The ether-soluble part of
the residue was washed with water and dehydrated with
magnesium sulfate. Removal of diethyl ether by distillation
under reduced pressure from this part gave F4PH3A as a
colorless transparent viscous liquid. IR (cmÀ1): 3130–3337
(nO–H), 2880–2957 (nC–H), 1243 (nC–F); 1H NMR (CDCl3): d
0.93 (3H, t, J ¼ 7:3 Hz, a), 1.27 (2H, m, b), 1.58 (2H, dd, c),
4.61 (1H, t, J ¼ 7:1 Hz, d), 2.34 (1H, s, e), 7.36 (2H, d,
J ¼ 8:2 Hz, m-protons from C4F9), 7.46 (2H, d, J ¼ 8:2 Hz,
4. Experimental
4.1. Materials
IC6H4COCnH2nþ1 (n ¼ 3, 5, 7) and CmF2mþ1C6H4-
COCnH2nþ1 (m ¼ 4, 6, 8; n ¼ 3, 5, 7) were synthesized
as reported previously [12]. Sulfur trioxide/pyridine com-
plex, sodium hydroxide (all from Kanto Kagaku), and
sodium borohydride (Nacalai Tesque) were used as sup-
plied. Tetrahydrofuran (THF: bp 65 8C) used as a solvent
was purified by distillation after being dehydrated with
calcium hydride. The other commercially available solvents
(diethyl ether, hexane, methanol, and pyridine) were used
without further purification.
o-protons from C4F9) for CH3 CH2 CH2 CHd(OH)eC6H4-
C4F9; 19F NMR (CDCl3): d À81.3 (3F, s, a), À126.6
(2F, s, b), À122.3 (2F, s, c), À111.4 (2F, s, d) for
a
b
c
a
b
c
d
CF3 CF2 CF2 CF2 C6H4CH(OH)C3H7; GC–MS 70 eV,
m/z (rel. int.): 368 [M]þ (1.2), 325 [M–C3H7]þ (100), 277
[C4F8C6H5]þ (33), 156 [CF2C6H4CH(OH)]þ (15), 127
[CF2C6H5]þ (25).
4.2. Measurements and instruments
A Nicolet Avatar 360-FT-IR spectrometer was used to
measure FT-IR spectrum with the ATR method. A Bruker
1
DPX-400 spectrometer was used to measure 400 MHz H
4.3.2. Synthesis of 1-[4-(perfluorohexyl)phenyl]-
1-butanol (F6PH3A), etc.
NMR spectrum at 30 8C in CDCl3, CD3OD (with tetra-
methylsilane (TMS) as the internal standard), or D2O. The
same spectrometer was also used to measure 376 MHz
19F NMR spectrum at 30 8C in CDCl3 or CD3OD (with
trifluoroacetic acid as external standard). GC–mass spec-
trum (GC–MS) was measured with a Hewlett-Packard
HP6890 series GC System (Hewlett-Packard 5973 Mass
Selective Detector). MS measurement (FABMS) using the
Fast Atom Bombardment (FAB) method was performed
with a JEOL JMS SX102A. Surface tension was measured
at 27 8C by the Wilhelmy method using a Kru¨ss Model
K12 surface tensiometer. Electroconductivity measurement
was conducted on surfactant solution as a function of tem-
perature with a DKK-TOA conductivity meter CM-60S
and the temperature at which the conductivity abruptly
changes was defined as the Krafft point of the surfactant.
The cmc and the aggregation number of FmPHnOS
were determined for their D2O solution by plotting the
1H NMR chemical shift of o-CH3 against the reciprocal
concentration according to the method previously repor-
ted [11]. The diffusion coefficient of FmPHnOS was
The methods of synthesis and purification were the same
as those used in Section 4.3.1.
F6PH3A: white solid; IR (cmÀ1): 3149–3350 (nO–H),
2844–2963 (nC–H), 1240 (nC–F); 1H NMR (CDCl3): d
0.96 (3H, t, J ¼ 7:4 Hz, a), 1.36 (2H, m, b), 1.74 (2H,
dd, c), 4.78 (1H, t, J ¼ 5:2 Hz, d), 1.91 (1H, s, e), 7.49 (2H,
d, J ¼ 8:2 Hz, m-protons from C6F13), 7.58 (2H, d,
J ¼ 8:2 Hz, o-protons from C6F13) for CH3 CH2 CH2 CHd-
(OH)eC6H4C6F13; 19F NMR (CDCl3): d À81.5 (3F, s, a),
À126.2 (2F, s, b), À123.4 (2F, s, c), À122.3 (2F, s, d), À122.0
a
b
c
a
b
c
d
e
(2F, s, e), À111.3 (2F, s, f) for CF3 CF2 CF2 CF2 CF2 -
f
CF2 C6H4CH(OH)C3H7; GC–MS 70 eV, m/z (rel. int.):
468 [M]þ (1.4), 425 [M–C3H7]þ (100), 377 [C6F12C6H5]þ
(43), 156 [CF2C6H4CH(OH)]þ (32), 127 [CF2C6H5]þ
(41).
F8PH3A: white solid; IR (cmÀ1): 3131–3550 (nO–H),
2810–2998 (nC–H), 1233 (nC–F); 1H NMR (CDCl3): d
0.96 (3H, t, J ¼ 7:4 Hz, a), 1.36 (2H, m, b), 1.74 (2H,
dd, c), 4.78 (1H, t, J ¼ 5:2 Hz, d), 1.91 (1H, s, e), 7.49 (2H,
d, J ¼ 8:2 Hz, m-protons from C8F17), 7.58 (2H, d,
a
b
c
d
1
measured on the H NMR chemical shift for o-CH3 by the
pulsed-gradient spin echo (PGSE) method [24]. The gradient
J ¼8:2 Hz, o-protons from C8F17) for CH3 CH2 CH2 CH2 -
(OH)eC6H4C8F17; 19F NMR (CDCl3): d À81.3 (3F, s, a),

194
H. Miyazawa et al. / Journal of Fluorine Chemistry 124 (2003) 189–196
À126.6 (2F, s, b), À123.3 (2F, s, c), À122.3 (6F, s, d, e and f ),
F6PH7A: white solid; IR (cmÀ1): 3136–3565 (nO–H),
2816–3024 (nC–H), 1245 (nC–F); 1H NMR (CDCl3): d
0.80 (3H, t, J ¼ 6:6 Hz, a), 1.20 (10H, m, b, c, d, e
and f ), 1.65 (2H, m, g), 4.67 (1H, t, J ¼ 5:9 Hz, h), 1.86
(1H, s, i), 7.40 (2H, d, J ¼ 8:1 Hz, m-protons from C6F13),
7.49 (2H, d, J ¼ 8:2 Hz, o-protons from C6F13) for
a
b
c
d
À121.7 (2F, s, g), À111.0 (2F, s, h) for CF3 CF2 CF2 CF2 -
e
f
g
h
CF2 CF2 CF2 CF2 C6H4CH(OH)C3H7; GC–MS 70 eV, m/z
(rel. int.): 468 [M]þ (1.4), 425 [M–C3H7]þ (100), 377
[C6F12C6H5]þ (43), 156 [CF2C6H4CH(OH)]þ (32), 127
[CF2C6H5]þ (41).
F4PH5A: colorless liquid; IR (cmÀ1): 3165–3343 (nO–H),
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CHh(OH)iC6H4C6F13;
19F NMR (CDCl3): d À81.5 (3F, s, a), À126.2 (2F, s, b),
À123.4 (2F, s, c), À122.3 (2F, s, d), À122.0 (2F, s, e),
a
b
c
d
e
f
g
1
2845–2961 (nC–H), 1236 (nC–F); H NMR (CDCl3): d 0.88
(3H, t, J ¼ 7:3 Hz, a), 1.31 (6H, m, b, c and d), 1.72 (2H, m,
e), 4.72 (1H, t, J ¼ 5:8 Hz, f), 1.92 (1H, s, g), 7.47 (2H, d,
J ¼ 8:1 Hz, m-protons from C4F9), 7.54 (2H, d, J ¼ 8:2 Hz,
a
b
c
d
e
f
À111.0 (2F, s, f ) for CF3 CF2 CF2 CF2 CF2 CF2 C6H4-
CH(OH)C7H15; GC–MS 70 eV, m/z (rel. int.): 524 [M]þ
(1.4), 425 [M–C7H15]þ (100), 377 [C4F8C6H5]þ (35), 156
[CF2C6H4CH(OH)]þ (6.7), 127 [CF2C6H5]þ (25).
o-protons from C4F9) for CH3 CH2 CH2 CH2 CH2 CHf-
(OH)gC6H4C4F9; 19F NMR (CDCl3): d À81.3 (3F, s, a),
À126.6 (2F, s, b), À122.3 (2F, s, c), À111.2 (2F, s, d) for
a
b
c
d
e
F8PH7A: white solid; IR (cmÀ1): 3124–3560 (nO–H),
2826–2995 (nC–H), 1240 (nC–F); 1H NMR (CDCl3):
d 0.85 (3H, t, J ¼ 6:6 Hz, a), 1.29 (10H, m, b, c, d, e
and f ), 1.75 (2H, m, g), 4.75 (1H, t, J ¼ 5:8 Hz, h), 1.95
(1H, s, i), 7.47 (2H, d, J ¼ 8:1 Hz, m-protons from C8F17),
7.56 (2H, d, J ¼ 8:2 Hz, o-protons from C8F17) for
a
b
c
d
CF3 CF2 CF2 CF2 C6H4CH(OH)C5H11; GC–MS 70 eV,
m/z (rel. int.): 396 [M]þ (1.3), 325 [M–C5H11]þ (100),
277 [C4F8C6H5]þ (34), 156 [CF2C6H4CH(OH)]þ (14),
127 [CF2C6H5]þ (25).
F6PH5A: colorless liquid; IR (cmÀ1): 3153–3340 (nO–H),
2847–2960 (nC–H), 1240 (nC–F); H NMR (CDCl3): d 0.89
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CHh(OH)iC6H4C8F17;
19F NMR (CDCl3): d À81.3 (3F, s, a), À126.6 (2F, s, b),
À123.3 (2F, s, c), À122.3 (6F, s, d, e and f), À121.7 (2F, s, g),
a
b
c
d
e
f
g
1
(3H, t, J ¼ 7:2 Hz, a), 1.30 (6H, m, b, c and d), 1.72 (2H, m,
e), 4.74 (1H, t, J ¼ 5:7 Hz, f ), 1.93 (1H, s, g), 7.48 (2H, d,
J ¼ 8:1 Hz, m-protons from C6F13), 7.56 (2H, d, J ¼
a
b
c
d
e
f
g
À111.3 (2F, s, h) for CF3 CF2 CF2 CF2 CF2 CF2 CF2 -
a
b
c
h
CF2 C6H4CH(OH)C7H15; GC–MS 70 eV, m/z (rel. int.):
8:2 Hz, o-protons from C6F13) for CH3 CH2 CH2 CH2-
e
dCH2 CHf(OH)gC6H4C6F13; 19F NMR (CDCl3): d À81.5
624 [M]þ (0.9), 525 [M–C7H15]þ (100), 477 [C8F16C6H5]þ
(3F, s, a), À126.2 (2F, s, b), À123.4 (2F, s, c), À122.3
(2F, s, d), À122.0 (2F, s, e), À111.4 (2F, s, f ) for
(37), 156 [CF2C6H4CH(OH)]þ (10), 127 [CF2C6H5]þ (30).
a
b
c
d
e
f
CF3 CF2 CF2 CF2 CF2 CF2 C6H4CH(OH)C5H11; GC–MS
70 eV, m/z (rel. int.): 496 [M]þ (0.66), 425 [M–C5H11]þ
(100), 377 [C6F12C6H5]þ (19), 156 [CF2C6H4CH(OH)]þ
(15), 127 [CF2C6H5]þ (24).
4.4. Synthesis of hybrid surfactants
4.4.1. Synthesis of sodium 1-[4-(perfluorobutyl)phenyl]-
1-butylsulfate (F4PH3OS)
F8PH5A: white solid; IR (cmÀ1): 3124–3560 (nO–H),
2816–3000 (nC–H), 1240 (nC–F); 1H NMR (CDCl3): d
0.88 (3H, t, J ¼ 7:4 Hz, a), 1.30 (6H, m, b, c and d),
1.73 (2H, m, e), 4.73 (1H, t, J ¼ 5:7 Hz, f), 1.93 (1H, s,
g), 7.49 (2H, d, J ¼ 8:1 Hz, m-protons from C8F17),
7.55 (2H, d, J ¼ 8:2 Hz, o-protons from C8F17) for
A mixture of F4PH3A (5.00 g, 13.6 mmol), sulfur triox-
ide/pyridine complex (2.38 g, 15.0 mmol), and pyridine
(20 cm3) were stirred at 50 8C for 24 h. An aqueous solution
containing sodium hydroxide (1.2 g, 30.0 mmol) in water
(10 cm3) was added to the reaction mixture and the resultant
aqueous mixture was stirred for 10 min. After pyridine and
water were removed by distillation under reduced pressure,
the methanol-soluble part of the residue was precipitated
from hexane to give a white solid as F4PH3OS. Yield 5.31 g
CH3 CH2 CH2 CH2 CH2 CHf(OH)gC6H4C8F17; 19F NMR
(CDCl3):dÀ81.3(3F,s,a),À126.6(2F,s,b),À123.3(2F,s,c),
À122.3 (6F, s, d, e and f), À121.7 (2F, s, g), À111.4 (2F, s, h)
a
b
c
d
e
for CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 C6H4CH(OH)C5-
H11; GC–MS 70 eV, m/z (rel. int.): 596 [M]þ (0.41), 525
[M–C5H11]þ (100), 477 [C8F16C6H5]þ (8.5), 156 [CF2C6-
H4CH(OH)]þ (6.1), 127 [CF2C6H5]þ (11).
(83.0%); IR (cmÀ1): 2806–3064 (nC–H), 1225 (nC–F); H
a
b
c
d
e
f
g
h
1
NMR(CD3OD):d0.83(3H, t, J ¼ 7:1 Hz, a), 1.39(2H, m, b),
1.73 (2H, dd, c), 5.27 (1H, t, J ¼ 5:7 Hz, d), 7.51 (4H, s, e)
a
b
c
e
for CH3 CH2 CH2 CHd(OSO3Na)C6H4 C4F9; 19F NMR
F4PH7A: colorless liquid; IR (cmÀ1): 3125–3561 (nO–H),
(CD3OD): d À81.3 (3F, s, a), À127.3 (2F, s, b), À122.7
a
b
c
d
1
2816–3002 (nC–H), 1235 (nC–F); H NMR (CDCl3): d 0.87
(2F, s, c), À111.2 (2F, s, d) for CF3 CF2 CF2 CF2 C6H4-
CH(OSO3Na)C3H7; FABMS m/z (rel. int.): 917 [2M–Na]À
(8.8), 447[M–Na]À (100), 97[OSO3H]À (19),80[SO3]À (15).
(3H, t, J ¼ 5:8 Hz, a), 1.20 (10H, m, b, c, d, e and f), 1.71
(2H, m, g), 4.76 (1H, t, J ¼ 5:8 Hz, h), 2.03 (1H, s, i), 7.46
(2H, d, J ¼ 8:1 Hz, m-protons from C4F9), 7.56 (2H, d,
a
b
c
d
J ¼ 8:2 Hz, o-protons from C4F9) for CH3 CH2 CH2 CH2 -
4.4.2. Synthesis of sodium 1-[4-(perfluorohexyl)phenyl]-
1-butylsulfate (F6PH3OS), etc.
CH2 CH2 CH2 CHh(OH)iC6H4C4F9; 19F NMR (CDCl3): d
À81.3 (3F, s, a), À126.6 (2F, s, b), À122.3 (2F, s, c), À111.2
e
f
g
The methods of synthesis and purification were the same
as those in Section 4.4.1.
F6PH3OS: white solid; yield 79.0%; IR (cmÀ1): 2812–
3065 (nC–H), 1227 (nC–F); 1H NMR (CD3OD): d 0.92 (3H, t,
J ¼ 8:0 Hz, a), 1.39 (2H, m, b), 1.83 (2H, dd, c), 5.33 (1H, t,
a
b
c
d
(2F, s, d) for CF3 CF2 CF2 CF2 C6H4CH(OH)C7H15; GC–
MS 70 eV, m/z (rel. int.): 424 [M]þ (1.2), 325 [M–C7H15]þ
(100), 277 [C4F8C6H5]þ (33), 156 [CF2C6H4CH(OH)]þ
(5.4), 127 [CF2C6H5]þ (23).

H. Miyazawa et al. / Journal of Fluorine Chemistry 124 (2003) 189–196
195
a
b
c
J ¼ 4:7 Hz, d), 7.59 (4H, s, e) for CH3 CH2 CH2 CHd-
(rel. int.): 1029 [2M–Na]À (10), 503 [M–Na]À (100), 97
[OSO3H]À (20), 80 [SO3]À (15).
e
(OSO3Na)C6H4 C6F13; 19F NMR (CD3OD): d À82.3 (3F,
s, a ), À127.1 (2F, s, b), À123.7 (2F, s, c), À122.7 (2F, s, d),
F6PH7OS: white solid; yield 70.4%; IR (cmÀ1): 2811–
3090 (nC–H), 1245 (nC–F); 1H NMR (CD3OD): d 0.64
(3H, t, J ¼ 4:6 Hz, a), 1.18 (10H, m, b, c, d, e and f ),
1.60 (2H, dd, g), 5.26 (1H, t, J ¼ 6:4 Hz, h), 7.49 (4H, s, i)
a
b
c
d
À122.2 (2F, s, e), À111.2 (2F, s, f) for CF3 CF2 CF2 CF2 -
e
f
CF2 CF2 C6H4CH(OSO3Na)C3H7; FABMS m/z (rel. int.):
1117 [2M–Na]À (10), 547 [M–Na]À (100), 97 [OSO3H]À
(6.2), 80 [SO3]À (6.2).
for CH3 CH2 CH2 CH2 CH2 CH2 CH2 CHh (OSO3Na)-
a
b
c
d
e
f
g
i
F8PH3OS: white solid; yield 88.3%; IR (cmÀ1): 2806–
3064 (nC–H), 1225 (nC–F); 1H NMR (CD3OD): d 0.84 (3H, t,
J ¼ 7:3 Hz, a), 1.32 (2H, m, b), 1.69 (2H, dd, c), 5.27 (1H, t,
C6H4 C6F13; 19F NMR (CD3OD): d À82.1 (3F, s, a),
À127.1 (2F, s, b), À123.7 (2F, s, c), À122.7 (2F, s, d),
a
b
c
d
À122.2 (2F, s, e), À111.1 (2F, s, f) for CF3 CF2 CF2 CF2 -
J ¼ 5:5 Hz, d), 7.45 (4H, s, e) for CH3 CH2 CH2 CHd-
CF2 CF2 C6H4CH(OSO3Na)C7H15; FABMS m/z (rel. int.):
1429 [2M–Na]À (11), 703 [M–Na]À (100), 97 [OSO3H]À
(25), 80 [SO3]À (20).
a
b
c
e
f
e
(OSO3Na)C6H4 C8F17; 19F NMR (CD3OD): d À82.1 (3F,
s, a), À127.3 (2F, s, b), À123.5 (2F, s, c), À122.6 (6F, s,
d, e and f ), À122.2 (2F, s, g), À111.2 (2F, s, h) for
F8PH7OS: white solid; yield 69.3%; IR (cmÀ1): 2812–
3067 (nC–H), 1230 (nC–F); 1H NMR (CD3OD): d 0.77 (3H, t,
J ¼ 4:2 Hz, a), 1.16 (10H, m, b, c, d, e and f), 1.71 (2H,
dd, g), 5.25 (1H, t, J ¼ 6:4 Hz, h), 7.53 (4H, s, i) for
a
b
c
d
e
f
g
h
CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 C6H4CH(OSO3Na)-
C3H7; FABMS m/z (rel. int.): 1317 [2M–Na]À (16), 647
[M–Na]À (100), 97 [OSO3H]À (13), 80 [SO3]À (6.8).
F4PH5OS: white solid; yield 78.8%; IR (cmÀ1): 2804–
3073 (nC–H), 1228 (nC–F); 1H NMR (CD3OD): d 0.76 (3H, t,
J ¼ 5:4 Hz, a), 1.22 (6H, m, b, c and d), 1.69 (2H, dd, e),
5.25 (1H, t, J ¼ 6:4 Hz, f), 7.49 (4H, s, g) for CH3-
a
b
c
d
e
f
g
i
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CHh(OSO3Na)C6H4 -
C8F17;19FNMR(CD3OD):dÀ82.2(3F,s,a),À127.3(2F,s,b),
À123.5 (2F, s, c), À122.6 (6F, s, d, e and f), À122.2 (2F, s, g),
a
b
c
d
e
f
g
À111.2 (2F, s, h) for CF3 CF2 CF2 CF2 CF2 CF2 CF2 -
aCH2 CH2 CH2 CH2 CHf(OSO3Na)C6H4 C4F9; 19F NMR
CF2 C6H4CH(OSO3Na)C7H15; FABMS m/z (rel. int.):
b
c
d
e
g
h
(CD3OD): d À82.1 (3F, s, a), À127.3 (2F, s, b), À122.7
1029 [2M–Na]À (10), 503 [M–Na]À (100), 97 [OSO3H]À
a
b
c
d
(2F, s, c), À111.2 (2F, s, d) for CF3 CF2 CF2 CF2 C6H4-
CH(OSO3Na)C5H11; FABMS m/z (rel. int.): 973 [2M–Na]À
(26),475[M–Na]À (100),97[OSO3H]À (6.2),80[SO3]À (6.2).
F6PH5OS: white solid; yield 70.4%; IR (cmÀ1): 2806–
3080 (nC–H), 1230 (nC–F); 1H NMR (CD3OD): d 0.80 (3H, t,
J ¼ 4:7 Hz, a), 1.18 (6H, m, b, c and d), 1.75 (2H, dd, e),
5.28 (1H, t, J ¼ 6:4 Hz, f), 7.53 (4H, s, g) for
(20), 80 [SO3]À (15).
References
[1] H.G. Bryce, in: J.H. Simons (Ed.), Fluorine Chemistry, vol. 5,
Academic Press, New York, 1950, p. 370.
CH3 CH2 CH2 CH2 CH2 CHf(OSO3Na)C6H4 C6F13; 19F
NMR (CD3OD): d À82.1 (3F, s, a), À127.1 (2F, s, b),
À123.7 (2F, s, c), À122.7 (2F, s, d), À122.2 (2F, s, e),
a
b
c
d
e
g
[2] H. Liebig, K. Ulm, Chem. Zeit. 100 (1976) 3–14.
[3] E. Schuierer, Tenside 13 (1976) 1–5.
[4] K. Shinoda, M. Hato, T. Hayashi, J. Phys. Chem. 76 (1972) 909–914.
[5] Y. Muto, K. Esumi, K. Meguro, R. Zana, J. Colloid Interface Sci. 120
(1987) 162–171.
a
b
c
d
e
f
À111.1 (2F, s, f) for CF3 CF2 CF2 CF2 CF2 CF2 C6H4-
CH(OSO3Na)C5H11; FABMS m/z (rel. int.): 1173 [2M–
Na]À (1.0), 575 [M–Na]À (100), 97 [OSO3H]À (4.9), 80
[SO3]À (4.9).
[6] S.J. Burkitt, B.T. Ingram, R.H. Ottewill, Prog. Colloid Polym. Sci. 76
(1988) 247–250.
[7] K. Kalyanasundaram, Langmuir 4 (1988) 942–945.
[8] H. Matsuki, N. Ikeda, M. Aratono, S. Kaneshina, K. Motomura, J.
Colloid Interface Sci. 150 (1992) 331–337.
F8PH5OS: white solid; yield 75.4%; IR (cmÀ1): 2810–
3070 (nC–H), 1227 (nC–F); 1H NMR (CD3OD): d 0.82
(3H, t, J ¼ 5:4 Hz, a), 1.20 (6H, m, b, c and d), 1.69
(2H, dd, e), 5.26 (1H, t, J ¼ 6:1 Hz, f), 7.56 (4H, s, g)
[9] M. Abe, T. Yamaguchi, Y. Shibata, H. Uchiyama, K. Ogino, N.
Yoshino, S.D. Christian, Colloids Surf. 67 (1992) 29–35.
[10] K. Kamogawa, K. Tajima, J. Phys. Chem. 97 (1993) 9506–9512.
[11] W. Guo, Z. Li, B.M. Fung, E.A. O’Rear, J.H. Harwell, J. Phys.
Chem. 96 (1992) 6738–6742.
a
b
c
d
e
g
for CH3 CH2 CH2 CH2 CH2 CHf(OSO3Na)C6H4 C8F17;
19F NMR (CD3OD): d À82.1 (3F, s, a), À127.1 (2F, s,
b), À123.5 (2F, s, c), À122.7 (6F, s, d, e and f), À122.2 (2F, s,
[12] N. Yoshino, K. Hamano, Y. Omiya, Y. Kondo, A. Ito, M. Abe,
Langmuir 11 (1995) 466–469.
a
b
c
d
e
f
g
g), À111.2 (2F, s, h) for CF3 CF2 CF2 CF2 CF2 CF2 CF2 -
[13] M. Abe, K. Tobita, H. Sakai, Y. Kondo, N. Yoshino, Y. Kasahara, H.
Matsuzawa, M. Iwahashi, N. Momozawa, K. Nishiyama, Langmuir
13 (1997) 2932–2934.
h
CF2 C6H4CH(OSO3Na)C5H11; FABMS m/z (rel. int.): 1373
[2M–Na]À (16), 675 [M–Na]À (100), 97 [OSO3H]À (19), 80
[SO3]À (13).
[14] K. Tobita, H. Sakai, Y. Kondo, N. Yoshino, M. Iwahashi, N.
Momozawa, M. Abe, Langmuir 13 (1997) 5054–5055.
[15] K. Tobita, H. Sakai, Y. Kondo, N. Yoshino, K. Kamogawa, N.
Momozawa, M. Abe, Langmuir 14 (1998) 4753–4757.
[16] M. Abe, K. Tobita, H. Sakai, K. Kamogawa, N. Momozawa,
Y. Kondo, N. Yoshino, Colloids Surf. A Physicochem. Eng. Aspects
167 (2000) 47–60.
F4PH7OS: white solid; yield 69.3%; IR (cmÀ1): 2812–
1
3067 (nC–H), 1230 (nC–F); H NMR (CD3OD): d 0.77 (3H,
t, J ¼ 4:2 Hz, a), 1.16 (10H, m, b, c, d, e and f), 1.71
(2H, dd, g), 5.25 (1H, t, J ¼ 6:4 Hz, h), 7.53 (4H, s, i)
for CH3 CH2 CH2 CH2 CH2 CH2 CH2 CHh (OSO3Na)-
a
b
c
d
e
f
g
[17] M. Abe, N. Yoshino, J. Jpn. Oil. Chem. 45 (1996) 991–999.
[18] M. Abe, A. Saeki, K. Kamogawa, H. Sakai, Y. Kondo, N. Yoshino,
H. Uchiyama, J.H. Harwell, Ind. Eng. Chem. Res. 39 (2000) 2697–
2703.
i
C6H4 C4F9; 19F NMR (CD3OD): d À82.2 (3F, s, a),
À127.3 (2F, s, b), À122.6 (2F, s, c), À111.2 (2F, s, d) for
a
b
c
CF3 CF2 CF2 CF2 C6H4CH(OSO3Na)C7H15; FABMS m/z
d

196
H. Miyazawa et al. / Journal of Fluorine Chemistry 124 (2003) 189–196
[19] A. Ito, H. Sakai, Y. Kondo, N. Yoshino, M. Abe, Langmuir 12 (1996)
5768–5772.
[22] N. Muller, E.F. Platko, J. Phys. Chem. 75 (1971) 547–553.
[23] B.-O. Persson, T. Drakenberg, B. Lindman, J. Phys. Chem. 83 (1979)
3011–3015.
[20] M.J. Rosen, Surfactants and Interfacial Phenomena, second ed.,
Wiley, New York, 1989 (Chapters 2 and 3).
[24] S. Braun, H.-O. Kalinowski, S. Berger, 150 and More Basic NMR
Experiments, Wiley-VCH, Weinheim, 1998, p. 442.
¨
[25] M. Holz, H. Weingartner, J. Magn. Reson. 92 (1991) 115–125.
[21] Y. Kondo, H. Miyazawa, H. Sakai, M. Abe, N. Yoshino, J. Am.
Chem. Soc. 124 (2002) 6516–6517.