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

Article abstract of DOI:10.1016/j.jfluchem.2004.05.015

Five novel phosphate-type hybrid surfactants, C_m F_2m+1C₆H₄CH[OPO₂ (OC₆H₅)Na]C_nH_2n+1 (FmPHnPPhNa: m = 4, 6, 8; n = 3, 5), have been synthesized. When compared with sulfate-type hybrid surfactants, C_mF_2m+1C₆H₄ CH(OSO₃Na)C_nH_2n+1 (C₆H₄ = p-phenylene), the new hybrid surfactants were found to have comparable abilities to lower the surface tension of water. The critical micelle concentrations of F m PH n PPhNa followed Klevens' rule and their occupied areas per molecule increased with increasing m and n. Calcium hydroxyapatite (CaHAp) pellets modified with FmPH3PPhNa gave high hydro and lipophobic surfaces. The hybrid surfactants are expected to be useful as new dental reagents for oral hygiene.

Full text of DOI:10.1016/j.jfluchem.2004.05.015

Journal of Fluorine Chemistry 125 (2004) 1485–1490
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; received in revised form 14 May 2004; accepted 18 May 2004
Available online 20 July 2004
Abstract
Five novel phosphate-type hybrid surfactants, CmF2mþ1C6H4CH[OPO2(OC6H5)Na]CnH2nþ1 (FmPHnPPhNa: m ¼ 4, 6, 8; n ¼ 3, 5), have
been synthesized. When compared with sulfate-type hybrid surfactants, CmF2mþ1C6H4CH(OSO3Na)CnH2nþ1 (C6H4 ¼ p-phenylene), the new
hybrid surfactants were found to have comparable abilities to lower the surface tension of water. The critical micelle concentrations of
FmPHnPPhNa followed Klevens’ rule and their occupied areas per molecule increased with increasing m and n. Calcium hydroxyapatite
(CaHAp) pellets modified with FmPH3PPhNa gave high hydro and lipophobic surfaces. The hybrid surfactants are expected to be useful 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
widely used as a dental adhesive because its phenyl phos-
phate group strongly adsorbs to human teeth [13–16]. Then,
hybrid surfactants having a phenyl phosphate group, if
synthesized, would be useful in the field of dentistry. It is
expected that such surfactants adsorb on teeth to give
hydrophobicity and lipophobicity to the surface and their
micelles solubilizing dental drugs can penetrate into period-
ontal pockets to cure periodontal disease.
The present paper reports the synthesis of five novel
phenyl phosphate-type hybrid surfactants, CmF2mþ1C6H4CH-
[OPO2(OC6H5)Na]CnH2nþ1 (FmPHnPPhNa: m ¼ 4, 6, 8;
n ¼ 3, 5), the physicochemical properties of their solutions,
and their adsorption to calcium hydroxyapatite (CaHAp)
pellets as a model of human teeth.
Hybrid surfactants with a fluorocarbon chain and a hydro-
carbon chain in one molecule have unique properties such as
simultaneous emulsification of hydrocarbon oil/fluorocar-
bon oil/water [1], 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 shown by the mixture of fluorocarbon surfactants and
hydrocarbon surfactants.
Yoshino et al. 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 surface and restrained dental plaque formation.
This result suggests that the fixation of fluorocarbons onto
teeth is effective in keeping oral cavities clean. Hybrid
surfactants have also been reported to solubilize hydrocar-
bon molecules in their micelles, suggesting that they
can serve as a drug carrier [11,12]. On the other hand,
2-methacryloyloxyethyl hydrogen phenyl phosphate
(CH2¼C(CH3)COOC2H4[OPO2(OC6H5)H]: phenyl-P) is
2. Results and discussion
2.1. Synthesis of hybrid surfactants
Scheme 1 shows the synthetic route of the hybrid surfac-
tants. Hybrid alcohols, FmPHnA, were prepared according
to the previous paper [17]. The introduction of a phosphate
group to the hybrid alcohol was performed using diphenyl
* 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 # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2004.05.015

1486
H. Miyazawa et al. / Journal of Fluorine Chemistry 125 (2004) 1485–1490
Scheme 1. Synthesis of FmPHnPPhNa.
phosphorochloridate with dimethylaminopyridine (DMAP)
as catalyst at 35 8C. The obtained triesters, CmF2mþ1C6H4-
CH[OPO(OC6H5)2]CnH2nþ1 (FmPHnPPh2), were easily
alkalized with NaOH to give the desired phosphate-type
hybrid surfactants, FmPHnPPhNa, in a high yield (ca.
>70%).
m and n, and FmPHnPPhNa having long hydrophobic chains
(m þ n > 10) showed Kp values higher than room tempera-
ture. The Kp values of FmPHnPPhNa are higher than those of
the corresponding FmPHnOS. This is because phenyl phos-
phate group is less hydrophilic compared with sulfate
group. The cmcs of FmPHnPPhNa were lower than those
of FmPHnOS due to the higher hydrophobicity. Moreover,
2.2. Krafft point, cmc and surface tension of
FmPHnPPhNa
the gcmc values for FmPHnPPhNa were about 20 mN mÀ1
,
which are almost the same as those for the conventional
single-chain fluorinated surfactants [18].
Table 1 lists the Krafft points (Kp), cmcs, and surface
tension values at cmc (gcmc) of FmPHnPPhNa together
with the corresponding data of CmF2mþ1C6H4CH(OSO3Na)-
CnH2nþ1 (FmPHnOS: m ¼ 4, 6, 8; n ¼ 3, 5; C6H4 ¼ p-
phenylene) [17]. The value of Kp increased with increasing
Fig. 1 shows the relationship between surface tension and
concentration for FmPHnPPhNa aqueous solutions at 25 8C.
The occupied areas (AAir) per molecule of FmPHnPPhNa
were calculated from the surface excess concentration at air/
water interface (GAir). The value of GAir was calculated
Table 1
Krafft point (kp), cmc, and gcmc of FmPHnPPhNa at 258 C
a
Surfactant
Kp (8C)
Cmc (mM)
gcmc (mN/m)
F4PH3PPhNa <0
F6PH3PPhNa 13
F8PH3PPhNa 22
F4PH5PPhNa <0
F6PH5PPhNa 27
F8PH5PPhNac 37
(14 mM)
1.4
24
23
22
24
23b
–
(3.5 mM)
(0.74 mM)
(9.7 mM)
(2.1 mM)
(0.45 mM)
0.35
0.074
0.97
0.21b
–
F4PH3OSd
F6PH3OSd
F8PH3OSd
F4PH5OSd
F6PH5OSd
F8PH5OSd
<0
<0
16
<0
14
32
(35 mM)
(4.5 mM)
(0.4 mM)
(10 mM)
(1.5 mM)
(0.2 mM)
7.0
0.90
0.08
3.0
19
18
20
19
20
–
0.34
–
a Kp was measured in the concentration shown in parenthesis.
b 30 8C.
c The data were not obtained because of high Kp.
d From Ref. [17].
Fig. 1. Surface tension plot of FmPHnPPhNa aq. against surfactant
concentration at 25 8C.

H. Miyazawa et al. / Journal of Fluorine Chemistry 125 (2004) 1485–1490
1487
Table 2
where a and b are constants [18]. In the case of
FmPH3PPhNa, log(cmc) decreased linearly with increasing
m, obeying Klevens’ rule (4)
Adsorbed amount (GAir) and occupied area (AAir) per molecule at air/water
interface at 25 8C
Surfactant
GAir (mmol/m2)
AAir (nm2)
logðcmcÞ¼ À1:56À0:319 m ðcorrelation coefficient; 0:999Þ
(4)
F4PH3PPhNa
F6PH3PPhNa
F8PH3PPhNa
F4PH5PPhNa
F6PH5PPhNaa
F4PH3OSb
1.61
1.23
0.96
0.90
0.86
2.5
1.03
1.34
1.73
1.85
1.93
0.66
0.80
0.94
0.99
1.04
Eq. (4) suggests that the cmc decreases by 52% when the
number of CF2 group in the hydrophobic chain increases by
one. Moreover, the following three Eqs. (5)–(7) are obtained
assuming that Klevens’ rule holds for FmPH5PPhNa
(n ¼ 5), F4PHnPPhNa (m ¼ 4), and F6PHnPPhNa (m ¼ 6).
F6PH3OSb
2.1
F8PH3OSb
1.8
1.7
F4PH5OSb
F6PH5OSb
1.6
FmPH5PPhNa : logðcmcÞ ¼ À1:68À0:333 m
F4PHnPPhNa : logðcmcÞ ¼ À2:62À0:080 n
F6PHnPPhNa : logðcmcÞ ¼ À3:12À0:111 n
(5)
(6)
(7)
a 308C.
b From Ref. [17].
using the Gibbs adsorption isotherm (1) [18],
ꢁ
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 and CH2 groups 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 the hydrophobic interaction between
hydrophobic chains to become weaker than that in
FmPHnOS.
ꢀ
4:606RT @ log C
1
@g
GAir ¼ À
(1)
Here, g is the surface tension of water, C is the concentration
of FmPHnPPhNa aqueous solution, R is the gas constant, and
T is the absolute temperature. The value of 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 values of
GAir and AAir. The AAir increased with increasing m and n.
FmPHnPPhNa had a large AAir value compared with the
corresponding FmPHnOS. Phenyl phosphate group is struc-
turally larger than sulfate group. This would be the reason
for the larger AAir values for FmPHnPPhNa.
Fig. 2 shows the logarithmic plots of the cmc determined
by surface tension measurements against m and n. Klevens
found that log(cmc) was empirically related to the hydro-
phobic chain length N in Eq. (3),
2.3. Modification of CaHAp pellets with FmPHnPPhNa
Table 3 gives the contact angles of water and oleic acid on
the modified pellet after being dipped in water for 12 h. The
contact angle of water increased with increasing m and n,
while the contact angle of oleic acid increased with increas-
ing m and decreased with increasing n. The pellet surface
modified with FmPH3PPhNa was highly hydrophobic and
oil-repellent. In contrast, whereas the pellets modified with
FmPH5PPhNa were highly hydrophobic, they were lipophi-
lic compared to those pellets modified with FmPH3PPhNa.
logðcmcÞ ¼ a À bN
(3)
Fig. 2. Log(cmc) plots of FmPHnPPhNa aq. against hydrophobic chain length m or n.

1488
H. Miyazawa et al. / Journal of Fluorine Chemistry 125 (2004) 1485–1490
Table 3
conductivity meter CM-60S and the temperature at which
the conductivity abruptly changes was defined as the Kp
value of the surfactant.
Contact angles of CaHAp pellets modified by FmPHnPPhNa at 25 8C
Compound
Water (8)
Oleic acid (8)
F4PH3PPhNa
F6PH3PPhNa
F8PH3PPhNa
F4PH5PPhNa
F6PH5PPhNa
70 ꢀ 5
77 ꢀ 4
91 ꢀ 5
80 ꢀ 2
92 ꢀ 2
48 ꢀ 3
74 ꢀ 4
82 ꢀ 2
44 ꢀ 3
48 ꢀ 3
3.2.3. Contact angle of water on CaHAp pellet modified
with FmPHnPPhNa
A 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 in the solution
for 6 h at 25 8C, the modified pellet was taken out and dried
for 30 min at room temperature in vacuo. Only with
F6PH5PPhNa, the pellet was dipped in 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 (for F6PH5PPhNa). The contact angles of
water and oleic acid were measured using 0.9 mm3 droplets
of the liquids after the washed pellet was dried for 30 min in
vacuo.
Unmodified
55 ꢀ 4
24 ꢀ 4
We previously reported that the hydrophobic and lipophobic
tooth surface markedly inhibits plaque formation on it. In
particular, CaHAp pellets modified with FmPH3PPhNa
remained highly hydro and lipophobic even after being
dipped in water for 12 h. FmPH3PPhNa are thus expected
to be a useful dental reagent from a viewpoint of oral
hygiene.
3. Experimental section
3.3. Synthesis of FmPHnPPh2
3.1. Materials
3.3.1. Synthesis of diphenyl 1-[(4-perfluorobutyl)phenyl]-
1-butylphosphate (F4PH3PPh2)
IC6H4COCnH2nþ1 (n ¼ 3, 5), CmF2mþ1C6H4COCnH2nþ1
(m ¼ 4, 6, 8; n ¼ 3, 5), and CmF2mþ1C6H4CH(OH)CnH2nþ1
(FmPHnA: m ¼ 4, 6, 8; n ¼ 3, 5) were synthesized as
reported previously [17]. DMAP (TCI) and diphenyl phos-
phorochloridate (Kanto Chemical) were used without
further purification. Dichloromethane (bp 40 8C), 1,4-diox-
ane (bp 101 8C), and pyridine (bp 83 8C) were purified
before use by distillation after being dehydrated with cal-
cium hydride.
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
chloroform:acetone ¼ 90:1) performed on silica gel (Wako-
gel C-300, Wako pure chemical industries) gave
F4PH3PPh2 as a white solid. Yield 6.2 g (81%); IR
(cmÀ1): 1089 (nP–O), 1132 (nP¼O), 1264 (nC–F), 1488
3.2. Measurements and instruments
1
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
(nPh–O); H-NMR (CDCl3): d 0.78 (3H, t, J ¼ 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 –OPO(O–)2), 6.97 (2H, t, J ¼ 7.3 Hz, p-
proton from –OPO(O–)2), 7.18 (4H, m, m-proton from –
OPO3–), 7.30 (2H, d, J ¼ 8.2 Hz, m-proton from C4F9–),
7.40 (2H, d, J ¼ 8.2 Hz, o-proton from C4F9–) for
1
DPX-400 spectrometer was used to measure 400 MHz H-
NMR spectrum at 30 8C in CDCl3 and CD3OD (with tetra-
methylsilane (TMS) as internal standard). The same spectro-
meter was also used to measure 376 MHz 19F-NMR
spectrum at 30 8C in CDCl3 and CD3OD (with trifluoroa-
cetic acid as external standard). GC–mass spectrum (GC–
MS) was measured with a Hewlett Packard HP6890 series
GC System (Hewlett Packard 5973 Mass Selective Detec-
tor). MS measurement (FABMS) using the fast atom bom-
bardment (FAB) method was performed with a JEOL JMS
SX102A.
a
b
c
CH3 CH2 CH2 CHd[OPO3(C6H5)2]C6H4C4F9; 19F-NMR
(CDCl3): d À85.8 (3F, s, a), À129.9 (2F, s, b), À126.9
a
b
c
d
(2F, s, c), À114.7 (2F, s, d) for CF3 CF2 CF2 CF2 C6H4-
CH[OPO(OC6H5)2]C3H7; GC–MS 70 eV, m/z (rel. int.): 600
[M]þ (12), 557 [MÀC3H7]þ (5), 350 [MÀOPO(OC6H5)2]þ
(25), 309 [C4F9C6H4CH2]þ (30), 251 [OPO(OC6H5)2]þ
(100).
3.3.2. Synthesis of diphenyl 1-[(4-perfluorohexyl)phenyl]-
1-butylphosphate (F6PH3PPh2) etc.
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
The methods of synthesis and purification were the same
as those in Section 3.3.1.
F6PH3PPh2: white solid, yield 77%; IR (cmÀ1): 1089
(nP–O), 1143 (nP¼O),1241 (nC–F), 1488 (nPh–O), 2960(nC–H);

H. Miyazawa et al. / Journal of Fluorine Chemistry 125 (2004) 1485–1490
1489
1H-NMR (CDCl3): d 0.81 (3H, t, J ¼ 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 –OPO(O–)2), 7.01 (2H, t, J ¼ 7.3 Hz, p-proton
from –OPO(O–)2), 7.22 (4H, m, m-proton from –OPO3–),
7.33 (2H, d, J ¼ 8.2 Hz, m-proton from C4F9–), 7.43 (2H, d,
CH[OPO(OC6H5)2]C5H11; GC–MS 70 eV, m/z (rel. int.):
728 [M]þ (20), 657 [MÀC5H11]þ (5), 478 [MÀOPO-
(OC6H5)2]þ (25), 409 [MÀOPO(OC6H5)2]þ (30), 251
[OPO(OC6H5)2]þ (100).
F8PH5PPh2: white solid, yield 74%; IR (cmÀ1): 1089
(nP–O), 1147 (nP¼O), 1241 (nC–F), 1483 (nPh–O), 2963 (nC–H);
1H-NMR (CDCl3): d 0.82 (3H, t, J ¼ 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 –OPO(O–)2), 7.11 (2H, t, J ¼ 7.3 Hz, p-
proton from –OPO(O–)2), 7.31 (4H, m, m-proton from –
OPO3–), 7.40 (2H, d, J ¼ 8.2 Hz, m-proton from C4F9–),
7.50(2H, d, J ¼ 8.2 Hz, o-proton from C4F9–) for
a
b
c
J ¼ 8.2 Hz, o-proton from C4F9–) for CH3 CH2 CH2 -
CHd[OPO(OC6H5)2]C6H4C6F13; 19F-NMR (CDCl3):
d
À85.6 (3F, s, a), À130.4 (2F, s, b), À127.0 (2F, s, c),
À126.0 (2F, s, d), À125.6 (2F, s, e), À114.5 (2F, s, f) for
a
b
c
d
e
f
CF3 CF2 CF2 CF2 CF2 CF2 C6H4CH[OPO(OC6H5)2]C3H7;
GC–MS 70 eV, m/z (rel. int.): 700 [M]þ (20), 657
[MÀC3H7]þ (5), 450 [MÀOPO(OC6H5)2]þ (25), 409
[C6F13C6H4CH2]þ (30), 251 [OPO(OC6H5)2]þ (100).
CH3 CH2 CH2 CH2 CH2 CHf[OPO(OC6H5)2]C6H4C8F17;
19F-NMR (CDCl3): d À85.5 (3F, s, a), À130.4 (2F, s, b),
À126.8 (2F, s, c), À126.0 (6F, s, d, e and f), À125.3 (2F, s, g),
a
b
c
d
e
F8PH3PPh2: white solid, yield 78%; IR (cmÀ1): 1092
(nP–O), 1147 (nP¼O), 1247 (nC–F), 1484 (nPh–O), 2959 (nC–H);
1H-NMR (CDCl3): d 0.81 (3H, t, J ¼ 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 –OPO(O–)2), 7.09 (2H, t, J ¼ 7.3 Hz, p-proton
from –OPO(O–)2), 7.22 (4H, m, m-proton from –OPO3–),
7.33 (2H, d, J ¼ 8.2 Hz, m-proton from C4F9–), 7.43 (2H, d,
a
b
c
d
e
f
g
À114.5 (2F, s, h) for CF3 CF2 CF2 CF2 CF2 CF2 CF2 -
h
CF2 C6H4CH[OPO(OC6H5)2]C5H11; GC–MS 70 eV, m/z
(rel. int.): 828 [M]þ (20), 757 [MÀC5H11]þ (5), 578
[MÀOPO(OC6H5)2]þ (25), 509 [MÀOPO(OC6H5)2]þ
(30), 251 [OPO(OC6H5)2]þ (100).
a
b
c
J ¼ 8.2 Hz, o-proton from C4F9–) for CH3 CH2 CH2 -
CHd[OPO(OC6H5)2]C6H4C8F17; 19F-NMR (CDCl3)
d
3.4. Synthesis of FmPHnPPhNa
À85.5 (3F, s, a), À130.4 (2F, s, b), À126.8 (2F, s, c),
À126.0 (6F, s, d, e and f), À125.3 (2F, s, g), À114.5 (2F,
3.4.1. Synthesis of sodium phenyl 1-[(4-
a
b
c
d
e
f
g
h
s, h) for CF3 CF2 CF2 CF2 CF2 CF2 CF2 CF2 C6H4CH[O-
PO(OC6H5)2]C3H7; GC–MS 70 eV, m/z (rel. int.): 800 [M]þ
(20), 757 [MÀC3H7]þ (5), 550 [MÀOPO(OC6H5)2]þ
(30), 509 [C8F17C6H4CH2]þ (30), 251 [OPO(OC6H5)2]þ
(100).
perfluorobutyl)phenyl]-1-butylphosphate (F4PH3PPhNa)
F4PH3PPh2 (7.6 g, 12.6 mmol), 1,4-dioxane (50 cm3),
4N-sodium hydroxide aqueous solution (25 cm3) were
mixed and the mixture was heated for 2 h at 50 8C. After
1N-hydrochloric acid was added to the mixture until the
value of pH attained 4, the precipitate formed was filtrated.
Sodium hydrogencarbonate solution (1.0 g in 10 cm3 water)
was introduced to an aqueous suspension of the precipitate
(5.2 g) to make an aqueous solution. After a stirring for
20 min at 25 8C, the solution was evaporated to dryness at
120 8C and obtained a white solid. The methanol soluble
components of this white solid were extracted with metha-
nol. The pure white solid, F4PH3PPhNa, was obtained as
reprecipitation product by adding 500 cm3 of hexane to
5 cm3 of the methanol solution. Yield 5.40 g (78%); IR
(cmÀ1): 1089 (nP–O), 1132 (nP¼O), 1264 (nC–F), 1488
F4PH5PPh2: white solid, yield 76%; IR (cmÀ1): 1090
(nP–O), 1147 (nP¼O), 1240 (nC–F), 1483 (nPh–O), 2967 (nC–H);
1H-NMR (CDCl3): d 0.74 (3H, t, J ¼ 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 –OPO(O–)2), 6.99 (2H, t, J ¼ 7.3 Hz, p-
proton from –OPO(O–)2), 7.21 (4H, m, m-proton from –
OPO3–), 7.31 (2H, d, J ¼ 8.2 Hz, m-proton from C4F9–),
7.41 (2H, d, J ¼ 8.2 Hz, o-proton from C4F9–) for
CH3 CH2 CH2 CH2 CH2 CHf[OPO(OC6H5)2]C6H4C4F9;
a
b
c
d
e
19F-NMR (CDCl3): d À85.9 (2F, s, a), À130.0 (2F, s, b),
a
b
À126.9 (2F, s, c), À114.7 (3F, s, d) for CF3 CF2 -
c
d
1
CF2 CF2 C6H4CH[OPO(OC6H5)2]C5H11; GC–MS 70 eV,
m/z (rel. int.): 628 [M]þ (15), 557 [MÀC5H11]þ (5), 378
[MÀOPO(OC6H5)2]þ (25), 309 [MÀOPO(OC6H5)2]þ (30),
251 [OPO(OC6H5)2]þ (100).
(nPh–O); H-NMR (CD3OD): d 0.87 (3H, t, J ¼ 7.4 Hz, a),
1.32 (2H, m, b), 1.80 (2H, dd, c), 5.30 (1H, m, d), 7.11 (2H, t,
J ¼ 8.2 Hz, m-proton from –OPO2(O–)), 6.92 (2H, d,
J ¼ 8.2 Hz, o-proton from –OPO2(O–)), 6.98 (1H, J ¼
7.3 Hz, t, p-proton from –OPO2(O–)), 7.50 (4H, m, e)
F6PH5PPh2: white solid, yield 78%; IR (cmÀ1): 1093
(nP–O), 1147 (nP¼O), 1237 (nC–F), 1492 (nPh–O), 2959 (nC–H);
1H-NMR (CDCl3): d 0.75 (3H, t, J ¼ 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 –OPO(O–)2), 7.02 (2H, t, J ¼ 7.3 Hz, p-
proton from –OPO(O–)2), 7.18 (4H, m, m-proton from –
OPO3–), 7.33 (2H, d, J ¼ 8.2 Hz, m-proton from C4F9–),
7.43 (2H, d, J ¼ 8.2 Hz, o-proton from C4F9–) for
for CH3 CH2 CH2 CHd[OPO2(OC6H5)Na]C6H4 C4F9;
a
b
c
e
19F-NMR (CD3OD): d À85.8 (2F, s, a), À129.9 (2F, s, b),
a
b
c
À126.9 (2F, s, c), À114.7 (2F, s, d) for CF3 CF2 CF2 -
d
CF2 C6H4CH[OPO2(OC6H5)Na]C3H7; FABMS m/z (rel.
int.): 1069 [2MÀNa]À (18), 523 [MÀNa]À (100), 79
[PO3]À (26).
CH3 CH2 CH2 CH2 CH2 CHf[OPO(OC6H5)2]C6H4C6F13;
19F-NMR (CDCl3): d À85.4 (3F, s, a), À130.4 (2F, s, b),
À127.0 (2F, s, c), À126.0 (2F, s, d), À125.6 (2F, s, e),
a
b
c
d
e
3.4.2. Synthesis of sodium phenyl 1-[(4-perfluorohexyl)-
phenyl]-1-butylphosphate (F6PH3PPhNa) etc.
The methods of synthesis and purification were the same
as those in Section 3.4.1.
a
b
c
d
e
f
À114.5 (2F, s, f) for CF3 CF2 CF2 CF2 CF2 CF2 C6H4-

1490
H. Miyazawa et al. / Journal of Fluorine Chemistry 125 (2004) 1485–1490
F6PH3PPhNa: white solid, yield 72%; IR (cmÀ1): 1089
CH[OPO2(OC6H5)Na]C5H11; FABMS m/z (rel. int.): 1325
[2MÀNa]À (16), 651 [MÀNa]À (100), 79 [PO3]À (25).
F8PH5PPhNa: white solid, yield 80%; IR (cmÀ1): 1089
(nP–O), 1147 (nP¼O), 1241 (nC–F), 1483 (nPh–O), 2963 (nC–H);
1H-NMR (CD3OD): d 0.83 (3H, t, J ¼ 7.3 Hz, a), 1.28 (6H,
m, b, c and d), 1.87 (2H, dd, e), 5.34 (1H, m, f), 7.12 (2H, t,
J ¼ 8.2 Hz, m-proton from –OPO2(O–)), 6.93 (2H, d,
J ¼ 8.2 Hz, o-proton from –OPO2(O–)), 6.99 (1H, J ¼
7.3 Hz, t, p-proton from –OPO2(O–)), 7.52 (4H, m, g)
(nP–O), 1143 (nP¼O),1241 (nC–F), 1488 (nPh–O), 2960(nC–H);
1H-NMR (CD3OD): d 0.85 (3H, t, J ¼ 7.4 Hz, a), 1.33 (2H,
m, b), 1.80 (2H, dd, c), 5.34 (1H, m, d), 7.13 (2H, t,
J ¼ 8.2 Hz, m-proton from –OPO2(O–)), 6.92 (2H, d, J ¼
8.2 Hz, o-proton from –OPO2(O–)), 6.97 (1H, J ¼ 7.3 Hz, t,
p-proton from –OPO2(O–)), 7.50 (4H, m, e) for
a
b
c
e
CH3 CH2 CH2 CHd[OPO2(OC6H5)Na]C6H4 C6F13; 19F-
NMR (CD3OD): d À85.6 (3F, s, a), À130.4 (2F, s, b),
À127.0 (2F, s, c), À126.0 (2F, s, d), À125.6 (2F, s, e),
a
b
c
e
g
for CH3 CH2 CH2 CHdCH2 CHf[OPO2(OC6H5)Na]C6H4 -
C8F17; 19F-NMR (CD3OD) d À85.5 (3F, s, a), À130.4 (2F, s,
b), À126.8 (2F, s, c), À126.0 (6F, s, d, e and f), À125.3 (2F, s,
a
b
c
d
e
f
À114.5 (2F, s, f) for CF3 CF2 CF2 CF2 CF2 CF2 C6H4-
CH[OPO2(OC6H5)Na]C3H7; FABMS m/z (rel. int.): 1269
[2MÀNa]À (7.5), 563 [MÀNa]À (100), 79 [PO3]À (44).
F8PH3PPhNa: white solid, yield 75%; IR (cmÀ1): 1092
(nP–O), 1147 (nP¼O), 1247 (nC–F), 1484 (nPh–O), 2959 (nC–H);
1H-NMR (CD3OD): d 0.87 (3H, t, J ¼ 7.4 Hz, a), 1.31 (2H,
m, b), 1.82 (2H, dd, c), 5.32 (1H, m, d), 7.12 (2H, t,
J ¼ 8.2 Hz, m-proton from –OPO2(O–)), 6.93 (2H, d, J ¼
8.2 Hz, o-proton from –OPO2(O–)), 6.96 (1H, J ¼ 7.3 Hz, t,
p-proton from –OPO2(O–)), 7.50 (4H, m, e) for
a
b
c
d
e
f
g
g), À114.5 (2F, s, h) for CF3 CF2 CF2 CF2 CF2 CF2 CF2 -
h
CF2 C6H4CH[OPO2(OC6H5)Na]C5H11; FABMS m/z (rel.
int.): 1525 [2MÀNa]À (12), 751 [MÀNa]À (100), 79
[PO3]À (32).
References
CH3 CH2 CH2 CHd[OPO2(OC6H5)Na]C6H4 C8F17; 19F-
NMR (CD3OD) d À85.5 (3F, s, a), À130.4 (2F, s, b),
À126.8 (2F, s, c), À126.0 (6F, s, d, e and f), À125.3 (2F,
a
b
c
e
[1] N. Yoshino, K. Hamano, Y. Omiya, Y. Kondo, A. Ito, M. Abe,
Langmuir 11 (1995) 466–469.
[2] Y. Kondo, H. Miyazawa, H. Sakai, M. Abe, N. Yoshino, J. Am.
Chem. Soc. 124 (2002) 6516–6517.
a
b
c
d
e
f
s, g), À114.5 (2F, s, h) for CF3 CF2 CF2 CF2 CF2 CF2 -
[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.
g
h
CF2 CF2 C6H4CH[OPO2(OC6H5)Na]C3H7; FABMS m/z
(rel. int.): 1469 [2MÀNa]À (18), 763 [MÀNa]À (100), 79
[PO3]À (30).
[4] K. Tobita, H. Sakai, Y. Kondo, N. Yoshino, M. Iwahashi, N.
Momozawa, 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, Colloids Surf. A: Physicochem. Eng. Aspects
167 (2000) 47–60.
F4PH5PPhNa: white solid, yield 72%; IR (cmÀ1): 1090
(nP–O), 1147 (nP¼O), 1240 (nC–F), 1483 (nPh–O), 2967 (nC–H);
1H-NMR (CD3OD): d 0.81 (3H, t, J ¼ 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 ¼ 8.2 Hz, m-proton from –OPO2(O–)), 6.94 (2H, d, J ¼
8.2 Hz, o-proton from –OPO2(O–)), 6.99 (1H, J ¼ 7.3 Hz, t,
¨
[7] D. Danino, D. Weihs, R. Zana, G. Oradd, G. Lindblom, M. Abe, Y.
Talmon, J. Colloid 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
p-proton from –OPO2(O–)), 7.50 (4H, m, g) for CH3 CH2 -
CH2 CHdCH2 CHf[OPO2(OC6H5)Na]C6H4 C4F9; 19F-NMR
c
e
g
(CD3OD):dÀ85.9(2F,s,a),À130.0(2F,s,b),À126.9(2F,s,c),
a
b
c
d
[10] N. Yoshino, T. Yamauchi, Y. Kondo, T. Kawase, T. Teranaka, React.
Funct. Polym. 37 (1–3) (1998) 271–282.
À114.7 (2F, s, d) for CF3 CF2 CF2 CF2 C6H4CH[O-
PO2(OC6H5)Na]C5H11; FABMS m/z (rel. int.): 1125
[2MÀNa]À (5), 551 [MÀNa]À (100), 79 [PO3]À (78).
[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.
[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.
F6PH5PPhNa: white solid, yield 73%; IR (cmÀ1): 1093
(nP–O), 1147 (nP¼O), 1237 (nC–F), 1492 (nPh–O), 2959 (nC–H);
1H-NMR (CD3OD): d 0.82 (3H, t, J ¼ 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 ¼ 8.2 Hz, m-proton from –OPO2(O–)), 6.92 (2H, d,
J ¼ 8.2 Hz, o-proton from –OPO2(O–)), 6.98 (1H, J ¼
7.3 Hz, t, p-proton from –OPO2(O–)), 7.50 (4H, m, g)
[14] I. Watanabe, N. Nakabayashi, D.H. Pashley, J. Dent. Res. 73 (6)
(1994) 1212–1220.
[15] N. Nakabayashi, Y. Saimi, J. Dent. Res. 75 (9) (1996) 1706–1715.
[16] K. Miyasaka, N. Nakabayashi, Dent. Mater. 17 (2001) 499–503.
[17] H. Miyazawa, K. Igawa, Y. Kondo, N. Yoshino, J. Fluorine Chem.
124 (2003) 189–196.
for CH3 CH2 CH2 CHdCH2 CHf[OPO2(OC6H5)Na]C6H4 -
C6F13; 19F-NMR (CD3OD) d À85.4 (3F, s, a), À130.4 (2F, s,
b), À127.0 (2F, s, c), À126.0 (2F, s, d), À125.6 (2F, s, e),
a
b
c
e
g
[18] M.J. Rosen, Surfactants and Interfacial Phenomena, 2nd ed., Wiley,
New York, 1989, Chapters 2 and 3.
a
b
c
d
e
f
À114.5 (2F, s, f) for CF3 CF2 CF2 CF2 CF2 CF2 C6H4-