Synthesis of phosphate-type fluorocarbon-hydrocarbon hybrid surfactants and their adsorption onto calcium hydroxyapatite

Article abstract of DOI:10.1016/j.jfluchem.2004.10.016

Five novel phosphate-type hybrid surfactants, C_mF _2m+1C₆H₄CH[OPO₂(OC₆H ₅)Na]C_nH_2n+1 (FmPHnPPhNa: m = 4, 6, 8; n = 3, 5; C₆H₄ = p-phenylene, C₆H₅ = phenyl), have been synthesized. When compared with sulfate-type hybrid surfactants, C_mF_2m+1C₆H₄CH(OSO ₃Na)C_nH_2n+1 (C₆H₄ = p-phenylene), the new hybrid surfactants are found to have comparable abilities to lower surface tension of water. The critical micelle concentrations of FmPHnPPhNa follow Klevens rule and their occupied areas per molecule increase with increasing m and n. Calcium hydroxyapatite (CaHAp) pellets modified with FmPH3PPhNa gives high hydrophobic and lipophobic surfaces. The hybrid surfactants are expected as new dental reagents for oral hygiene.

Full text of DOI:10.1016/j.jfluchem.2004.10.016

Journal of Fluorine Chemistry 126 (2005) 301–306
www.elsevier.com/locate/fluor
Synthesis of phosphate-type fluorocarbon–hydrocarbon hybrid
surfactants and their adsorption onto calcium hydroxyapatite
Haruhiko Miyazawaa, Hiroyuki Yokokuraa, Yuki Ohkuboa,
Yukishige Kondoa,b, Norio Yoshinoa,b,
*
aDepartment of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science,
1-3 Kagurazaka, Shinjuku, Tokyo 162-8601, Japan
bInstitute of Colloid and Interface Science, Tokyo University of Science, 1-3 Kagurazaka,
Shinjuku, Tokyo 162-8601, Japan
Received 30 March 2004; accepted 26 October 2004
Abstract
Five novel phosphate-type hybrid surfactants, CmF2m+1C6H4CH[OPO2(OC6H5)Na]CnH2n+1 (FmPHnPPhNa: m = 4, 6, 8; n = 3, 5;
C6H4 = p-phenylene, C6H5 = phenyl), have been synthesized. When compared with sulfate-type hybrid surfactants, CmF2m+1C6H4CH(O-
SO3Na)CnH2n+1 (C6H4 = p-phenylene), the new hybrid surfactants are found to have comparable abilities to lower surface tension of water.
The critical micelle concentrations of FmPHnPPhNa follow Klevens rule and their occupied areas per molecule increase with increasing m
and n. Calcium hydroxyapatite (CaHAp) pellets modified with FmPH3PPhNa gives high hydrophobic and lipophobic surfaces. The hybrid
surfactants are expected as new dental reagents for oral hygiene.
# 2004 Elsevier B.V. All rights reserved.
Keywords: Hybrid surfactant; Phosphate-type; Fluorocarbon; Calcium hydroxyapatite; Human teeth; Hydro- and lipophobic surface; Plaque-controlling
surface
1. Introduction
clean. We have also reported that hybrid surfactants can
solubilize hydrocarbon molecules in their micelles and thus
the hybrid surfactant micelles serve as drug carriers
[11,12]. On the other hand, phenyl-P is widely used as a
dental adhesive because its phenyl phosphate group
strongly adsorbs to human teeth [13–16]. Hybrid surfac-
tants having a phenyl phosphate group would be useful in
the field of dentistry. It is expected that not only the
surfactants adsorb on teeth to give hydrophobicity and
lipophobicity, but also the surfactant micelles solubilizing
dental drugs can penetrate into periodontal pockets to cure
periodontal disease.
Hybrid surfactants with a fluorocarbon chain and a
hydrocarbon chain in one molecule have unique properties
such as simultaneous emulsification of hydrocarbon oil/
fluorocarbon oil/water [1], the formation of small micelles
with unusually long lifetime [2], and very high viscosity of
the surfactant solution at body temperature [3–7]. These
properties cannot be showed by the mixture of fluorocarbon
surfactants and hydrocarbon surfactants.
The authors have so far synthesized fluorinated silane
coupling agents and modified bovine teeth using the silanes
[8–10]. The silanes gave hydrophobicity and lipophobicity
to the tooth surfaces and restrained dental plaque
formation. This result suggests that the fixation of
fluorocarbons onto teeth is effective to keep oral cavities
The present paper reports the synthesis of five novel
phenyl phosphate-type hybrid surfactants, CmF2m+1C6H4-
CH[OPO2(OC6H5)Na]CnH2n+1 (FmPHnPPhNa: m = 4, 6, 8;
n = 3, 5; C6H4 = p-phenylene, C6H5 = phenyl), the physi-
cochemical properties of their solutions and the adsorption
to calcium hydroxyapatite (CaHAp) pellet as a model of
human teeth.
* Corresponding author. Tel.: +81 3 5228 8319; fax: +81 3 3260 4281.
E-mail address: yoshino@ci.kagu.tus.ac.jp (N. Yoshino).
0022-1139/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2004.10.016

302
H. Miyazawa et al. / Journal of Fluorine Chemistry 126 (2005) 301–306
Table 1
2. Results and discussion
2.1. Synthesis of hybrid surfactants
Krafft point (Kp), cmc, and gcmc of FmPHnPPhNa at 25 8C
Surfactant
Cmc (mM)
gcmc (mN mꢀ1
)
a
Kp (8C)
F4PH3PPhNa
F6PH3PPhNa
F8PH3PPHNa
F4PH5PPhNa
F6PH5PPhNa
F8PH5PPhNac
<0 (14 mM)
13 (3.5 mM)
22 (0.74 mM)
<0 (9.7 mM)
27 (2.1 mM)
37 (0.45 mM)
1.4
24
23
22
24
23b
–
0.35
0.074
0.97
0.21b
–
Scheme 1 shows the synthetic route of the hybrid
surfactants. The alcohol, FmPHnA, was prepared according
to the previous paper [17]. The introduction of a phosphate
group to hybrid alcohol FmPHnA was performed using
diphenyl phosphorochloridate under the catalyst of dimethy-
laminopyridine (DMAP) at 35 8C. The obtained triester,
CmF2m+1C6H4CH[OPO(OC6H5)2]CnH2n+1 (FmPHnPPh2),
was easily alkalized with NaOH to give the phosphate-
type hybrid surfactant FmPHnPPhNa in a high yield (ca.
>70%).
F4PH3OSd
F6PH3OSd
F8PH3OSd
F4PH5OSd
F6PH5OSd
F8PH5OSd
a
<0 (3.5 mM)
<0 (4.5 mM)
16 (0.4 mM)
<0 (10 mM)
14 (1.5 mM)
32 (0.2 mM)
7.0
0.90
0.08
3.0
0.34
–
19
18
20
19
20
–
Kp was measured in concentration shown in parenthesis.
b
c
d
30 8C.
The data were not obtained because of high Kp.
2.2. Krafft point, cmc and surface tension of
FmPHnPPhNa
From Ref. [17].
Table 1 shows Krafft point (Kp), cmc, and surface tension
at cmc (gcmc) of FmPHnPPhNa aqueous solutions together
with the corresponding data of CmF2m+1C6H4CH(OSO3-
Na)CnH2n+1 (FmPHnOS: m = 4, 6, 8, n = 3, 5; C6H4 = p-
phenylene) [17]. The value Kp increased with increasing m
and n, and FmPHnPPhNa having long hydrophobic chains
(m + n > 10) showed Kp values higher than room tempera-
ture. The Kp of FmPHnPPhNa is higher than that of the
corresponding FmPHnOS. This is because phenyl phosphate
group was less hydrophilic compared with sulfate group. By
the hydrophobicity of FmPHnPPhNa, the cmc was lower than
that of FmPHnOS. Moreover the gcmc for FmPHnPPhNa was
about 20 mN mꢀ1, almost same as that for the conventional
single-chain fluorinated surfactants [18].
Fig. 1 shows the relationship between surface tension and
concentration for FmPHnPPhNa aqueous solutions at 25 8C.
Fig. 1. Surface tension plots of FmPHnPPhNa aq. against surfactant con-
centration at 25 8C.
Scheme 1. Synthesis of FmPHnPPhNa.

H. Miyazawa et al. / Journal of Fluorine Chemistry 126 (2005) 301–306
303
Table 2
has found that log(cmc) was empirically related to a
hydrophobic chain length N in Eq. (3),
Adsorbed amount (GAir) and occupied area (AAir) per molecule at air/water
interface at 25 8C
logðcmcÞ ¼ a ꢀ bN
(3)
Surfactant
GAir (mmol mꢀ2
)
AAir (nm2)
where a and b are constants [18]. In the case of
FmPH3PPhNa, log(cmc) decreased linearly with increasing
m, obeying Klevens rule (4),
F4PH3PPhNa
F6PH3PPhNa
F8PH3PPHNa
F4PH5PPhNa
F6PH5PPhNaa
1.61
1.23
0.96
0.90
0.86
1.03
1.34
1.73
1.85
1.93
logðcmcÞ ¼ ꢀ1:56 ꢀ 0:319m
ðcorrelation coefficient : 0:999Þ
Eq. (4) suggests that when the number of CF2 group in the
hydrophobic chain increases by one, the cmc decreases by
52%. Moreover, assuming that Klevens rule hold for
FmPH5PPhNa (n = 5), F4PHnPPhNa (m = 4), and
F6PHnPPhNa (m = 6), the following three Eqs. (5)–(7)
are obtained.
F4PH3OSb
F6PH3OSb
F8PH3OSb
F4PH5OSb
F6PH5OSb
2.5
2.1
1.8
1.7
1.6
0.66
0.80
0.94
0.99
1.04
(4)
a
30 8C.
From Ref. [17].
b
The occupied area (AAir) per molecule of FmPHnPPhNa was
calculated from the surface excess concentration at air/water
interface (GAir). The value GAir was calculated using the
Gibbs adsorption isotherm (1) [18],
FmPH5PPhNa : logðcmcÞ ¼ ꢀ1:68 ꢀ 0:333m
F4PHnPPhNa : logðcmcÞ ¼ ꢀ2:62 ꢀ 0:080n
F6PHnPPhNa : logðcmcÞ ¼ ꢀ3:12 ꢀ 0:111n
(5)
(6)
(7)
ꢀ
ꢁ
1
@g
These equations give the rates of cmc decrease of 54%/CF2
group, 17%/CH2 group, and 23%/CH2 group for
FmPH5PPhNa, F4PHnPPhNa and F6PHnPPhNa, respec-
tively. For FmPHnOS, the cmc decreases by 66–67%/CF2
group and 34–38%/CH2 group. The contribution to cmc of
both CF2 group and CH2 group in FmPHnPPhNa is smaller
than that in FmPHnOS. This result would be brought about
by the introduction of a spatially large phenyl group into
phosphate group, thereby causing weakened hydrophobic
interaction between hydrophobic chains as compared with
that for FmPHnOS.
GAir ¼ ꢀ
(1)
4:606RT @ log C
Here, g is the surface tension of water, C the concentration of
FmPHnPPhNa aqueous solutions, R the gas constant and T
the absolute temperature. The value AAir relates to the
adsorption amount GAir via the following Eq. (2) [18],
1
AAir
¼
(2)
G
AirNA
where NA is Avogadro’s number. Table 2 shows the value of
GAir and AAir. The AAir increased with increasing m and n.
FmPHnPPhNa has a large AAir value compared with the
corresponding FmPHnOS. Phenyl phosphate group is struc-
turally larger than sulfate group. This will be the reason for
the larger AAir values of FmPHnPPhNa.
2.3. Modification of CaHAp pellets with FmPHnPPhNa
Table 3 shows the contact angles of water and oleic acid
on the modified pellet after being dipped in water for 12 h.
The contact angles of water increased with increasing value
Fig. 2 shows the logarithmic plots of the cmc determined
by surface tension measurement against m and n. Klevens
Fig. 2. Log(cmc) plots of FmPHnPPhNa aq. against hydrophobic chain length m or n.

304
H. Miyazawa et al. / Journal of Fluorine Chemistry 126 (2005) 301–306
Table 3
3.2.2. Measurement of cmc, surface tension, and Kp
Surface tension was measured at 25 8C by the Wilhelmy
method using a Kru¨ss Model K12 surface tensiometer.
Electroconductivity measurement was conducted on surfac-
tant solution as a function of temperature with a DKK-TOA
conductivity meter CM-60S and the temperature at which
the conductivity abruptly changes was defined as the Kp
value of the surfactant.
Contact angles on modified surface of CaHAp pellets modified by
FmPHnPPhNa at 25 8C
Compound
Water (8)
Oleic acid (8)
F4PH3PPhNa
F6PH3PPhNa
F8PH3PPhNa
F4PH5PPhNa
F6PH5PPhNa
Unmodified
70 ꢁ 5
77 ꢁ 4
91 ꢁ 5
80 ꢁ 2
92 ꢁ 2
55 ꢁ 4
48 ꢁ 3
74 ꢁ 4
82 ꢁ 2
44 ꢁ 3
48 ꢁ 3
24 ꢁ 4
3.2.3. Contact angles of water and oleic acid on the
CaHAp pellet modified by FmPHnPPhNa
The CaHAp pellet (Cellyard pellet, Pentax) with a
diameter of 13 mm and a height of 2 mm was introduced
in 10 cm3 of FmPHnPPhNa aqueous solution whose
concentration was twice as high as the cmc. After being
dipped for 6 h at 25 8C, the pellets were dried for 30 min at
room temperature invacuo. Only for F6PH5PPhNa, the pellet
was dipped in the surfactant solution at 30 8C because the Kp
of the surfactant was 27 8C. The modified pellet was soaked in
10 cm3 of pure water for 12 h at 25 or 30 8C (the case of
F6PH5PPhNa). The contact angles of water and oleic acid
were measured using 0.9 mm3 of droplets after the pellets
were dried for 30 min in vacuo.
of m and n, and the contact angles of oleic acid increased by
increasing m, while decreased as value n increased. The
modified pellet surface with FmPH3PPhNa was highly
hydrophobic and oil-repellent. In contrast, although the
pellets modified by FmPH5PPhNa are highly hydrophobic,
those showed lipophilicy compared to pellets modified by
FmPH3PPhNa. We previously reported that the hydro- and
lipophobic tooth surface markedly inhibits plaque formation
on it. In particular, the CaHAp pellets modified by
FmPH3PPhNa remained highly hydro- and lipophobic even
after being dipped in water for 12 h. FmPH3PPhNa is
expected to be a useful dental reagent from the viewpoint of
oral hygiene.
3.3. Synthesis of FmPHnPPh2
3.3.1. Synthesis of diphenyl 1-[(4-perfluorobutyl)phenyl]-
1-butylphosphate (F4PH3PPh2)
3. Experimental section
F4PH3A (4.7 g, 12.7 mmol), dichloromethane (50 cm3),
pyridine (1.51 cm3, 19.1 mmol), and DMAP (2.3 g,
19.1 mmol) were placed in a 100 ml eggplant-shaped
flask equipped with an isobaric dropping funnel under
nitrogen atmosphere. Diphenyl phosphorochloridate (5.1 g,
19.1 mmol) was then slowly added through the funnel. The
reaction mixture was stirred for 10 h at 35 8C, and flash
column chromatography (eluent is mixture (v/v) of chlor-
oform:acetone = 90:1) performed on silica gel (Wakogel C-
300, Wako pure chemical industries) gave F4PH3PPh2 as
white solid. Yield 6.2 g (81%); IR (cmꢀ1): 1089 (nP–O), 1132
(nP=O), 1264 (nC–F), 1488 (nPh–O); 1H-NMR (CDCl3): d 0.78
(3H, t, J = 7.4 Hz, a), 1.18 (2H, m, b), 1.77 (2H, dd, c), 5.44
(1H, m, d), 6.85 (4H, m, o-proton from –OPO3–), 6.97 (2H, t,
J = 7.3 Hz, p-proton from –OPO3–), 7.18 (4H, m, m-proton
from –OPO3–), 7.30 (2H, d, J = 8.2 Hz, m-proton from
C4F9–), 7.40 (2H, d, J = 8.2 Hz, o-proton from C4F9–)
3.1. Materials
IC6H4COCnH2n+1 (n = 3, 5), CmF2m+1C6H4COCnH2n+1
(m = 4, 6, 8, n = 3, 5), and CmF2m+1C6H4CH(OH)CnH2n+1
(m = 4, 6, 8, n = 3, 5: FmPHnA) were synthesized as
reported previously [15]. DMAP (TCI) and diphenyl
phosphorochloridate (Kanto Chemical) were used without
further purification. Dichloromethane (bp 40 8C), 1,4-
dioxane (bp 101 8C), and pyridine (bp 83 8C) were purified
by distillation after being dehydrated with calcium hydride.
3.2. Measurements and instruments
3.2.1. Characterization of FmPHnPPhNa
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-
for CH3 CH2 CH2 CHd[OPO3(C6H5)2]C6H4C4F9; 19F-NMR
a
b
c
NMR spectrum at 30 8C in CDCl3 and CD3OD (with
tetramethylsilane (TMS) as the internal standard). The same
spectrometer was also used to measure 376 MHz 19F-NMR
spectrum at 30 8C in CDCl3 and CD3OD (with trifluor-
oacetic acid as external standard). GC–mass spectrum (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.
(CDCl3): d ꢀ85.8 (3F, s, a), ꢀ129.9 (2F, s, b), ꢀ126.9 (2F, s,
a
b
c
d
c), ꢀ114.7 (2F, s, d) for CF3 CF2 CF2 CF2 C6H4CH[O-
PO3(C6H5)2]C3H7; GC–MS 70 eV, m/z (rel. int.): 600 [M]+
(12), 557 [M–C3H7]+ (5), 350 [M–OPO3(C6H5)2]+ (25), 309
[C4F9C6H4CH2]+ (30), 251 [OPO3(C6H5)2]+ (100).
3.3.2. Synthesis of diphenyl 1-[(4-perfluorohexyl)phenyl]-
1-butylphosphate (F6PH3PPh2) and others
The methods of synthesis and purification were the same
as those in Section 3.3.1.

H. Miyazawa et al. / Journal of Fluorine Chemistry 126 (2005) 301–306
305
F6PH3PPh2: white solid, yield 77%; IR (cmꢀ1): 1089
(nP–O), 1143 (nP=O), 1241 (nC–F), 1488 (nPh–O), 2960 (nC–H);
1H-NMR (CDCl3): d 0.81 (3H, t, J = 7.4 Hz, a), 1.28(2H, m,
b), 1.81 (2H, dd, c), 5.49(1H, m, d), 6.89 (4H, m, o-proton
from –OPO3–), 7.01 (2H, t, J = 7.3 Hz, p-proton from –
OPO3–), 7.22 (4H, m, m-proton from –OPO3–), 7.33 (2H,
d, J = 8.2 Hz, m-proton from C4F9–), 7.43 (2H, d,
(rel. int.): 728 [M]+ (20), 657 [M–C5H11]+ (5), 478 [M–
OPO3(C6H5)2]+ (25), 409 [M–OPO3(C6H5)2]+ (30), 251
[OPO3(C6H5)2]+ (100).
F8PH5PPh2: white solid, yield 74%; IR (cmꢀ1): 1089
(nP–O), 1147 (nP=O), 1241 (nC–F), 1483 (nPh–O), 2963 (nC–H);
1H-NMR (CDCl3): d 0.82 (3H, t, J = 7.4 Hz, a), 1.22 (6H, m,
b, c, and d), 1.90 (2H, dd, e), 5.53 (1H, m, f), 6.94 (4H, m, o-
proton from –OPO3–), 7.11 (2H, t, J = 7.3 Hz, p-proton from
–OPO3–), 7.31 (4H, m, m-proton from –OPO3–), 7.40 (2H,
d, J = 8.2 Hz, m-proton from C4F9–), 7.50(2H, d, J = 8.2 Hz,
a
b
c
J = 8.2 Hz, o-proton from C4F9–) for CH3 CH2 CH2 CH-
d
[OPO3(C6H5)2]C6H4C6F13; 19F-NMR (CDCl3): d ꢀ85.6 (3F,
s, a), ꢀ130.4 (2F, s, b), ꢀ127.0 (2F, s, c), ꢀ126.0 (2F, s, d),
ꢀ125.6 (2F, s, e), ꢀ114.5 (2F, s, f) for CF3 CF2 CF2 CF2 C-
o-proton from C4F9–) for CH3 CH2 CH2 CH2 CH2 CHf[O-
PO3(C6H5)2]C6H4C8F17; 19F-NMR (CDCl3): d ꢀ85.5 (3F,
s, a), ꢀ130.4 (2F, s, b), ꢀ126.8 (2F, s, c), ꢀ126.0 (6F, s, d,
e, and f), ꢀ125.3 (2F, s, g), ꢀ114.5 (2F, s, h) for
a
b
c
d
a
b
c
d
e
e
f
F2 CF2 C6H4CH[OPO3(C6H5)2]C3H7; GC–MS 70 eV, m/z
(rel. int.): 700 [M]+ (20), 657 [M–C3H7]+ (5), 450
[M–OPO3(C6H5)2]+ (25), 409 [C6F13C6H4CH2]+ (30), 251
[OPO3(C6H5)2]+ (100).
a
b
c
d
e
f
g
h
CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 C6H4CH[OPO3(C6-
H5)2]C5H11; GC–MS 70 eV, m/z (rel. int.): 828 [M]+ (20),
757 [M–C5H11]+ (5), 578 [M–OPO3(C6H5)2]+ (25), 509 [M–
OPO3(C6H5)2]+ (30), 251 [OPO3(C6H5)2]+ (100).
F8PH3PPh2: white solid, yield 78%; IR (cmꢀ1): 1092
(nP–O), 1147 (nP=O), 1247 (nC–F), 1484 (nPh–O), 2959 (nC–H);
1H-NMR (CDCl3): d 0.81 (3H, t, J = 7.4 Hz, a), 1.26 (2H, m,
b), 1.80 (2H, dd, c), 5.48 (1H, m, d), 6.87 (4H, m, o-proton
from –OPO3–), 7.09 (2H, t, J = 7.3 Hz, p-proton from –
OPO3–), 7.22 (4H, m, m-proton from –OPO3–), 7.33 (2H, d,
J = 8.2 Hz, m-proton from C4F9–), 7.43 (2H, d, J = 8.2 Hz,
3.4. Synthesis of FmPHnPPhNa
3.4.1. Synthesis of sodium phenyl 1-[(4-
o-proton from C4F9–) for CH3 CH2 CH2 CHd[O-
PO3(C6H5)2]C6H4C8F17; 19F-NMR (CDCl3) d ꢀ85.5 (3F,
s, a), ꢀ130.4 (2F, s, b), ꢀ126.8 (2F, s, c), ꢀ126.0 (6F, s, d, e,
and f), ꢀ125.3 (2F, s, g), ꢀ114.5 (2F, s, h) for
perfluorobutyl)phenyl]-1-butylphosphate (F4PH3PPhNa)
F4PH3PPh2 (3.0 g, 5.0 mmol), 1,4-dioxane (50 cm3), 4N-
sodium hydroxide aqueous solution (25 cm3) was heated for
2 h at 50 8C. After 1N-hydrochloric acid was added to the
mixture by pH = 4, the precipitation was filtrated. The sodium
hydrogencarbonate (1.0 g) in water (10 cm3) was introduced
to aqueous solution dispersed the precipitation (5.2 g). The
precipitation of methanol-soluble part from hexane was
preformed to give F4PH3PPhNa as white solid. Yield 5.40 g
(78%); IR (cmꢀ1): 1089 (nP–O), 1132 (nP=O), 1264 (nC–F),
1488 (nPh–O); 1H-NMR (CD3OD): d 0.87 (3H, t, J = 7.4 Hz,
a), 1.32 (2H, m, b), 1.80 (2H, dd, c), 5.30 (1H, m, d), 7.11
(2H, t, J = 8.2 Hz, m-proton from –OPO3–), 6.92 (2H,
d, J = 8.2 Hz, o-proton from –OPO3–), 6.98 (1H, J = 7.3 Hz,
t, p-proton from –OPO3–), 7.50 (4H, m, e) for
a
b
c
a
c
e
f
CF3 CF2bCF2 CF2dCF2 CF2 CF2gCF2hC6H4CH[OPO3-
(C6H5)2]C3H7; GC–MS 70 eV, m/z (rel. int.): 800 [M]+ (20),
757 [M–C3H7]+ (5), 550 [M–OPO3(C6H5)2]+ (30), 509
[C8F17C6H4CH2]+ (30), 251 [OPO3(C6H5)2]+ (100).
F4PH5PPh2: white solid, yield 76%; IR (cmꢀ1): 1090
(nP–O), 1147 (nP=O), 1240 (nC–F), 1483 (nPh–O), 2967 (nC–H);
1H-NMR (CDCl3): d 0.74 (3H, t, J = 7.4 Hz, a), 1.13 (6H, m,
b, c, and d), 1.79 (2H, dd, e), 6.14 (1H, m, f), 6.87 (4H, m,
o-proton from –OPO3–), 6.99 (2H, t, J = 7.3 Hz, p-proton
from –OPO3–), 7.21 (4H, m, m-proton from –OPO3–), 7.31
(2H, d, J = 8.2 Hz, m-proton from C4F9–), 7.41 (2H, d,
J = 8.2 Hz, o-proton from C4F9–) for CH3 CH2 CH2 CH2 -
CH2 CHf[OPO3(C6H5)2]C6H4C4F9; 19F-NMR (CDCl3): d
CH3 CH2 CH2 CHd[OPO2(OC6H5)Na]C6H4 C4F9; 19F-NM
a
b
c
d
a
b
c
e
e
R (CD3OD): d ꢀ85.8 (3F, s, a), ꢀ129.9 (2F, s, b), ꢀ126.9
a
b
c
d
ꢀ85.9 (3F, s, a), ꢀ130.0 (2F, s, b), ꢀ126.9 (2F, s, c), ꢀ114.7
(2F, s, c), ꢀ114.7 (2F, s, d) for CF3 CF2 CF2 CF2 C6H4-
CH[OPO2(OC6H5)Na]C3H7; FABMS m/z (rel. int.): 1069
[2M–Na]ꢀ (18), 523 [M–Na]ꢀ (100), 79 [PO3]ꢀ (26).
a
b
c
d
(2F, s, d) for CF3 CF2 CF2 CF2 C6H4CH[OPO3(C6H5)2]-
C5H11; GC–MS 70 eV, m/z (rel. int.): 628 [M]+ (15),
557 [M–C5H11]+ (5), 378 [M–OPO3(C6H5)2]+ (25), 309
[M–OPO3(C6H5)2]+ (30), 251 [OPO3(C6H5)2]+ (100).
F6PH5PPh2: white solid, yield78%; IR (cmꢀ1):1093 (nP–
O), 1147 (nP=O), 1237 (nC–F), 1492 (nPh–O), 2959 (nC–H); 1H-
NMR (CDCl3): d 0.75 (3H, t, J = 7.4 Hz, a), 1.16 (6H, m, b, c,
and d), 1.82 (2H, dd, e), 5.46 (1H, m, f), 6.87 (4H, m, o-proton
from –OPO3–), 7.02 (2H, t, J = 7.3 Hz, p-proton from –
OPO3–), 7.18 (4H, m, m-proton from –OPO3–), 7.33 (2H, d,
J = 8.2 Hz, m-proton from C4F9–), 7.43 (2H, d, J = 8.2 Hz,
3.4.2. Synthesis of sodium phenyl 1-[(4-
perfluorohexyl)phenyl]-1-butylphosphate (F6PH3PPhNa)
and others
The methods of synthesis and purification were the same
as those in Section 3.4.1.
F6PH3PPhNa: white solid, yield 72%; IR (cmꢀ1): 1089
(nP–O), 1143 (nP=O), 1241 (nC–F), 1488 (nPh–O), 2960(nC–H);
1H-NMR (CD3OD): d 0.85 (3H, t, J = 7.4 Hz, a), 1.33 (2H, m,
b), 1.80 (2H, dd, c), 5.34 (1H, m, d), 7.13 (2H, t, J = 8.2 Hz, m-
proton from –OPO3–), 6.92 (2H, d, J = 8.2 Hz, o-proton from
–OPO3–), 6.97 (1H, J = 7.3 Hz, t, p-proton from –OPO3–),
o-proton from C4F9–) for CH3 CH2 CH2 CH2 CH2 CHf[O-
PO3(C6H5)2]C6H4C6F13; 19F-NMR (CDCl3): d ꢀ85.4 (3F, s,
a), ꢀ130.4 (2F, s, b), ꢀ127.0 (2F, s, c), ꢀ126.0 (2F, s, d),
a
b
c
d
e
ꢀ125.6 (2F, s, e), ꢀ114.5 (2F, s, f) for CF3 CF2 CF2 CF2 C-
7.50 (4H, m, e) for CH3 CH2 CH2 CHd[OPO2(OC6H5)Na]-
a
b
c
d
a
b
c
e
F2 CF2 C6H4CH[OPO3(C6H5)2]C5H11;GC–MS 70 eV, m/z
f
e
C6H4 C6F13; 19F-NMR (CD3OD): d ꢀ85.6 (3F, s, a), ꢀ130.4

306
H. Miyazawa et al. / Journal of Fluorine Chemistry 126 (2005) 301–306
(2F, s, b), ꢀ127.0(2F, s, c), ꢀ126.0(2F, s, d), ꢀ125.6(2F, s, e),
b, c, and d), 1.87 (2H, dd, e), 5.34 (1H, m, f), 7.12 (2H, t,
J = 8.2 Hz, m-proton from –OPO3–), 6.93 (2H, d, J = 8.2 Hz,
o-proton from –OPO3–), 6.99 (1H, J = 7.3 Hz, t, p-proton
a
b
c
d
e
f
ꢀ114.5 (2F, s, f) for CF3 CF2 CF2 CF2 CF2 CF2 C6H4-
CH[OPO2(OC6H5)Na]C3H7; FABMS m/z (rel. int.): 1269
[2M–Na]ꢀ (7.5), 563 [M–Na]ꢀ (100), 79 [PO3]ꢀ (44).
F8PH3PPhNa: white solid, yield 75%; IR (cmꢀ1): 1092
(nP–O), 1147 (nP=O), 1247 (nC–F), 1484 (nPh–O), 2959 (nC–H);
1H-NMR (CD3OD): d 0.87 (3H, t, J = 7.4 Hz, a), 1.31 (2H, m,
b), 1.82 (2H, dd, c), 5.32 (1H, m, d), 7.12 (2H, t, J = 8.2 Hz, m-
proton from –OPO3–), 6.93 (2H, d, J = 8.2 Hz, o-proton from
–OPO3–), 6.96 (1H, J = 7.3 Hz, t, p-proton from –OPO3–),
from –OPO3–), 7.52 (4H, m, g) for CH3 CH2 CH2 CHd-
a
b
c
CH2 CHf[OPO2(OC6H5)Na]C6H4 C8F17; 19F-NMR (CD3
OD) d ꢀ85.5 (3F, s, a), ꢀ130.4 (2F, s, b), ꢀ126.8 (2F, s,
c), ꢀ126.0 (6F, s, d, e, and f), ꢀ125.3 (2F, s, g), ꢀ114.5 (2F, s,
e
g
a
b
c
d
e
f
g
h
h) for CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 C6H4CH[O-
PO2(OC6H5)Na]C5H11; FABMS m/z (rel. int.): 1525 [2M–
Na]ꢀ (12), 751 [M–Na]ꢀ (100), 79 [PO3]ꢀ (32).
7.50 (4H, m, e) for CH3 CH2 CH2 CHd[OPO2(OC6H5)Na]-
a
b
c
C6H4 C8F17; 19F-NMR (CD3OD) d ꢀ85.5 (3F, s, a), ꢀ130.4
e
(2F, s, b), ꢀ126.8 (2F, s, c), ꢀ126.0 (6F, s, d, e, and f), ꢀ125.3
References
a
b
c
d
(2F, s, g), ꢀ114.5 (2F, s, h) for CF3 CF2 CF2 CF2 C-
e
f
g
h
[1] N. Yoshino, K. Hamano, Y. Omiya, Y. Kondo, A. Ito, M. Abe,
Langmuir 11 (1995) 466–469.
F2 CF2 CF2 CF2 C6H4CH[OPO2(OC6H5)Na]C3H7; FABMS
m/z (rel. int.): 1469 [2M–Na]ꢀ (18), 763 [M–Na]ꢀ (100), 79
[PO3]ꢀ (30).
[2] Y. Kondo, H. Miyazawa, H. Sakai, M. Abe, N. Yoshino, J. Am. Chem.
Soc. 124 (2002) 6516–6517.
F4PH5PPhNa: white solid, yield 72%; IR (cmꢀ1): 1090
(nP–O), 1147 (nP=O), 1240 (nC–F), 1483 (nPh–O), 2967 (nC–H);
1H-NMR (CD3OD): d 0.81 (3H, t, J = 7.3 Hz, a), 1.28 (6H, m,
b, c, and d), 1.86 (2H, dd, e), 5.31 (1H, m, f), 7.11 (2H, t,
J = 8.2 Hz, m-proton from –OPO3–), 6.94 (2H, d, J = 8.2 Hz,
o-proton from –OPO3–), 6.99 (1H, J = 7.3 Hz, t, p-proton
[3] 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.
[4] K. Tobita, H. Sakai, Y. Kondo, N. Yoshino, M. Iwahashi, N. Momo-
zawa, M. Abe, Langmuir 13 (1997) 5054–5055.
[5] K. Tobita, H. Sakai, Y. Kondo, N. Yoshino, K. Kamogawa, N.
Momozawa, M. Abe, Langmuir 14 (1998) 4753–4757.
[6] M. Abe, K. Tobita, H. Sakai, K. Kamogawa, N. Momozawa, Y. Kondo,
N. Yoshino, Coll. Surf. A: Physicochem. Eng. Asp. 167 (2000) 47–60.
a
b
from –OPO3–), 7.50 (4H, m, g) for CH3 CH2
g
c
e
CH2 CHdCH2 CHf[OPO2(OC6H5)Na]C6H4 C4F9; 19F-NMR
¨
[7] D. Danino, D. Weihs, R. Zana, G. Oradd, G. Lindblom, M. Abe, Y.
(CD3OD): d ꢀ85.9 (3F, s, a), ꢀ130.0 (2F, s, b), ꢀ126.9 (2F, s,
Talmon, J. Coll. Interf. Sci. 259 (2003) 382–390.
[8] N. Yoshino, T. Teranaka, Chem. Lett. 5 (1993) 821–824.
[9] N. Yoshino, T. Teranaka, J. Biomater. Sci. Polym. Edn. 8 (1997) 623–
653.
a
b
c
d
c), ꢀ114.7 (2F, s, d) for CF3 CF2 CF2 CF2 C6H4CH[O-
PO2(OC6H5)Na]C5H11; FABMS m/z (rel. int.): 1125 [2M–
Na]ꢀ (5), 551 [M–Na]ꢀ (100), 79 [PO3]ꢀ (78).
F6PH5PPhNa: white solid, yield 73%; IR (cmꢀ1): 1093
(nP–O), 1147 (nP=O), 1237 (nC–F), 1492 (nPh–O), 2959 (nC–H);
1H-NMR (CD3OD): d 0.82 (3H, t, J = 7.3 Hz, a), 1.28 (6H, m,
b, c, and d), 1.87 (2H, dd, e), 5.31 (1H, m, f), 7.12 (2H, t,
J = 8.2 Hz, m-proton from –OPO3–), 6.92 (2H, d, J = 8.2 Hz,
o-proton from –OPO3–), 6.98 (1H, J = 7.3 Hz, t, p-proton
[10] N. Yoshino, T. Yamauchi, Y. Kondo, T. Kawase, T. Teranaka, React.
Funct. Polym. 37 (1–3) (1998) 271–282.
[11] 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.
[12] A. Saeki, H. Sakai, K. Kamogawa, Y. Kondo, N. Yoshino,
H. Uchiyama, J.H. Harwell, M. Abe, Langmuir 16 (2000) 9991–
9995.
from –OPO3–), 7.50 (4H, m, g) for CH3 CH2 CH2 CHd-
a
b
c
[13] H. Chigira, W. Yukitani, T. Hasegawa, A. Manabe, K. Itoh, T.
Hayakawa, K. Debari, S. Wakumoto, H. Hisamitsu, J. Dent. Res.
73 (5) (1994) 1088–1095.
CH2 CHf[OPO2(OC6H5)Na]C6H4 C6F13; 19F-NMR (CD3
OD) d ꢀ85.4 (3F, s, a), ꢀ130.4 (2F, s, b), ꢀ127.0 (2F, s,
c), ꢀ126.0 (2F, s, d), ꢀ125.6 (2F, s, e), ꢀ114.5 (2F, s, f)
e
g
[14] I. Watanabe, N. Nakabayashi, D.H. Pashley, J. Dent. Res. 73 (6) (1994)
1212–1220.
a
b
c
d
e
f
for CF3 CF2 CF2 CF2 CF2 CF2 C6H4CH[OPO2(OC6H5)-
Na]C5H11; FABMS m/z (rel. int.): 1325 [2M–Na]ꢀ (16), 651
[M–Na]ꢀ (100), 79 [PO3]ꢀ (25).
[15] N. Nakabayashi, Y. Saimi, J. Dent. Res. 75 (9) (1996) 1706–1715.
[16] K. Miyasaka, N. Nakabayashi, Dental Mater. 17 (2001) 499–503.
[17] H. Miyazawa, K. Igawa, Y. Kondo, N. Yoshino, J. Fluorine Chem. 124
(2003) 189–196.
F8PH5PPhNa: white solid, yield 80%; IR (cmꢀ1): 1089
(nP–O), 1147 (nP=O), 1241 (nC–F), 1483 (nPh–O), 2963 (nC–H);
1H-NMR (CD3OD): d 0.83 (3H, t, J = 7.3 Hz, a), 1.28 (6H, m,
[18] M.J. Rosen, Surfactants and Interfacial Phenomena, 2nd ed. Wiley,
New York, 1989, chapter 2, 3.