Synthesis of new aromatic perfluorovinyl ether monomers containing phosphonic acid functionality

Article abstract of DOI:10.1016/j.jfluchem.2004.03.010

The synthesis of a new perfluorovinyl ether monomer containing phosphonic acid functionality is reported. It started from 4-[(α,β,β-trifluorovinyl)oxy]bromo benzene prepared in two steps from the nucleophilic substitution of 4-bromophenate to 1,2-dibromot

Full text of DOI:10.1016/j.jfluchem.2004.03.010

Journal of Fluorine Chemistry 125 (2004) 1317–1324
Synthesis of new aromatic perfluorovinyl ether monomers
containing phosphonic acid functionality
Renaud Souzya, Bruno Ameduria,*, Bernard Boutevina, David Virieuxb
a
´
Laboratory of Macromolecular Chemistry, UMR (CNRS) 5076, Ecole Nationale Superieure de Chimie de Montpellier,
8 Rue Ecole Normale, 34296 Montpellier Cedex 5, France
b
´
Laboratory of Organic Chemistry, UMR (CNRS) 5076, Ecole Nationale Superieure de Chimie de Montpellier,
8 Rue Ecole Normale, 34296 Montpellier Cedex 5, France
Received 17 February 2004; received in revised form 18 March 2004; accepted 25 March 2004
Available online 17 June 2004
Abstract
The synthesis of a new perfluorovinyl ether monomer containing phosphonic acid functionality is reported. It started from 4-[(a,b,b-
trifluorovinyl)oxy]bromo benzene prepared in two steps from the nucleophilic substitution of 4-bromophenate to 1,2-dibromotetrafluor-
oethane. The [(a,b,b-trifluorovinyl)oxy]benzene dialkyl phosphonate was prepared according to various methods of phosphonation like a
Michaelis–Arbuzov or a Michaelis–Becker or a palladium catalysed arylation in the presence of various reactants. The influence of the nature
of the method and of the reactants onto the yields is discussed. It was shown that reaction involving a palladium triphenyl phosphine catalyst
led to the best yield. All different aromatic intermediates and fluoromonomers were characterised by 1H, 31P and 19F NMR, mass spectrometry
(EI), and by FTIR.
# 2004 Elsevier B.V. All rights reserved.
Keywords: [(a,b,b-Trifluorovinyl)oxy]benzene phosphonic acid; Michaelis–Arbuzov reaction; Michaelis–Becker reaction; Palladium catalyst; Nuclear
magnetic resonance; Fluoromonomers
1. Introduction
Although prepared for the first time by Beckerbauer [2a],
aromatic trifluorovinyl have received much attention by
various research groups from 1990s [2,6]. Babb et al.
[2b,2c,7] developed methods for the preparation and the
characterisation of trifluorovinyl ethers synthesised from the
readily bis- and tris-phenols, such as tris(hydroxypheny-
l)ethane (Scheme 1). A high Tg thermoset polymers
endowed with a good thermal stability (they are stable up
to 434 8C), thermal/oxidative stability and mechanical prop-
erties, was prepared with such monomer [2d,8].
In 1996, Smith and Babb [2f] synthesised perfluorocy-
clobutane aromatic polyethers incorporating siloxane
groups such as bis[1,3-[4-[(trifluorovinyl)oxy]phenyl]]-
1,1,3,3-tetramethyldisiloxane (employed commercially as
high-temperature lubricants, elastomers, and adhesives with
excellent chemical, thermal, and oxidative resistance).
In 2000, a series of different perfluorocyclobutane
(PFCB) polyarylethers was synthesised by the same group
[8]. Authors reported the synthesis of poly(aryl vinyl ether)
based on a two steps synthetic route (Scheme 1) [9]: the first
one concerned a fluoroalkylation with BrCF2CF2Br while
the second one dealt with a zinc mediated elimination.
In the past few decades, the synthesis and (co)polymer-
isation of functionalised [(a,b,b-trifluorovinyl)oxy]benzene
have drawn a growing interest [1] especially for polymers
incorporating such a monomer because of the combination
of processability and performance (chemical and thermal
stability) provided by trifluorovinyl ethers.
The most important properties of aromatic trifluorovinyl
ethers arise from the fact that they could undergo thermal
cyclopolymerisation [2p þ 2p] giving a thermoplastic and
thermoset polymers containing perfluorocyclobutane rings
(PFCB) (Scheme 1) [2]. This thermodynamically favoured
[2p þ 2p] thermocyclodimerisation arises from an increase
of the double bond strain [3], a lower C¼C p-bond energy
[4], and the strength of the resulting fluorinated C–C single
bond. Such thermocyclodimerisation is usually observed at
temperatures ranging from 140 to 210 8C [5].
* Corresponding author. Tel.: þ33-4671-44368; fax: þ33-4671-47220.
E-mail address: ameduri@cit.enscm.fr (B. Ameduri).
0022-1139/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2004.03.010

1318
R. Souzy et al. / Journal of Fluorine Chemistry 125 (2004) 1317–1324
F
F
F
F
F
F
F
F
1) KOH / BrCF2CF2Br
2) Zn / CH3CN
F
F
F
F
HO Ar OH
O
Ar
O
O
O Ar
n
CH3
Ar :
OCF=CF2
H3C
F3C CF3
Scheme 1. Formation of aromatic perfluorocyclobutane polymers (PFCB) [2,7,9].
Materials prepared from aromatic trifluorovinyl ethers
mer using different methodologies and the characterisation
of all intermediates (by 19F, 1H, 31P NMR and FTIR spectro-
scopies, and Mass spectrometry (EI)).
can find relevant applications in ion exchange resins [6e],
fuel cell membranes [6e,10a,10b], microphonics [11], optics
[12], liquid crystals [13], interlayer dielectrics [14], and
coating applications [8,15].
In the course of the last decades, fluoropolymers incor-
porating aromatic or aliphatic monomers and bearing sul-
phonic [6e,16] and phosphonic [17] acid functionalities have
led to a growing interest due to their potential applications in
proton exchange membranes for fuel cells (PEMFC) and
ionomer membranes [6e,16].
The current intensified interests in the preparation of
PEMFC based on electrolyte polymers has prompted us
to develop the syntheses of aromatic monomers such as
trifluorovinyl ethers functionalised by acid groups. In parti-
cular, we report the preparation of 4-[(a,b,b-trifluoroviny-
l)oxy]benzene phosphonic acid which, to the best of our
knowledge, has never been described in the literature. This
present paper focuses on the synthesis of fluorinated mono-
2. Results and discussion
4-[(a,b,b-trifluorovinyl)oxy]bromo benzene, Monomer 1,
was prepared by published method [2f]. The synthesis of
Monomer 1 is based on a nucleophilic substitution of 4-
bromophenate to 1,2-dibromotetrafluoroethane followed by
a dehalogenation reaction.
2.1. Synthesis and characterisation of 4-[(a,b,b-
trifluorovinyl)oxy]benzene phosphonic acid (Monomer 3)
The various chemical pathways to prepare 4-[(a,b,b-tri-
fluorovinyl)oxy]benzene (diethyl or dimethyl)phosphonate
(Monomer 2, Scheme 2) consecutively dealkylated into
P(OR)3
NiCl2
(I)
HP(O)(OEt)2
(II)
NaH
Ö
F2C=CFO
Br
F2C=CFO
P
OR
OR
HP(O)(OEt)2
Pd(PPh3)4
Monomer 1
tBuLi
Monomer 2
(III)
(R : Et or Me)
(IV)
Et2O
-80˚C
ClP(O)(OR)2
F2C=CFO
Li
Scheme 2. Synthesis of 4-[(a,b,b-trifluorovinyl)oxy]benzene (diethyl or dimethyl)phosphonate (Monomer 2).

R. Souzy et al. / Journal of Fluorine Chemistry 125 (2004) 1317–1324
1319
4-[(a,b,b-trifluorovinyl)oxy]benzene phosphonic acid
(Monomer 3, Scheme 4) made this study attractive. The
synthesis of 4-[(a,b,b-trifluorovinyl)oxy]benzene (dialkyl)
phosphonate was carried out according to methods of
Michaelis–Arbuzov reaction (synthetic route I, Scheme 2)
or Michaelis–Becker (synthetic route II, Scheme 2) or a
palladium catalysed arylation of diethyl phosphite (synthetic
route III, Scheme 2) or by a reaction between a chloropho-
sphate and aryl lithium of Monomer 1 (synthetic route IV,
Scheme 2). These methods are detailed below.
protons were observed between 7.2 and 7.8 ppm. In the
31P NMR (Spectrum B in Fig. 1), a singlet was noted at
17.9 ppm assigned to the phosphorus atom in the aromatic
phosphonate group [17c]. 19F NMR (Spectrum C in Fig. 1)
spectrum exhibits three doublet of doublets centred at
À119.1, À126.2 and À135.4 ppm characteristic of Fa, Fb
and Fc atoms, respectively (Table 2).
2.1.2. Synthesis of Monomer 2 via a Michaelis–Becker
reaction
In addition, a further interest was focused on a Michaelis–
Becker reaction (synthetic route II, Scheme 2) [18d,19] to
obtain the Monomer 2 with better yields. The Michaelis–
Becker reaction was carried out at low temperature (0 8C) in
two steps. The first one dealt with the preparation of the
phosphonic salt from diethylphosphite and sodium hydride.
The second step involves in the addition of the phosphonic
salt onto the Monomer 1. After purification by distillation,
Monomer 2 was obtained in 12%, which was slightly better
than those obtained via the Michaelis–Arbuzov reaction.
2.1.1. Synthesis of Monomer 2 via a Michaelis–Arbuzov
reaction
Michaelis–Arbuzov reactions (synthetic route I,
Scheme 2) [18] were carried out by dropwise addition of
Monomer 1 [2f] to trimethyl (R: Me, Scheme 2) or triethyl
(R: Et, Scheme 2) phosphite at 110 8C. These experiments
led to several statements. (i) A first series of experiments (#1
and #2, Table 1) has shown that the Michaelis–Arbuzov
reaction required to be performed in the presence of Lewis
acid such as NiCl2 (12 mol%) under nitrogen conditions
which catalysed the nucleophilic substitution of bromine by
the trialkyl phosphite. (ii) In a second series of experiment
(#2 and #3, Table 1), was noted that the use of triethylpho-
sphite instead of trimethylphosphite slightly increases the
yields of the synthesis. Using an excess of triethylphosphite
(2 equivalent) about Monomer 1 (1 equivalent) led to better
yields of phosphonated monomer. (iii) Last experiments (#4
and #5, Table 1) showed that the uses of sonication condi-
tions instead of heating conditions at 110 8C did not improve
the overall yield of the synthesis of Monomer 2. (iv) Finally,
Experiment 6 evidenced that the Mickaelis–Arbuzov carried
out sonic conditions at room temperature (instead of 110 8C)
did not improve the yields of phosphonation. This first study,
using a Michaelis–Arbuzov reaction, allowed us to synthe-
sise Monomer 2 in 10% yield.
2.1.3. Synthesis of Monomer 2 via a palladium catalysed
reaction
To improve the yields of the phosphonylation of Monomer
1, a palladium catalysed arylation (synthetic route III,
Scheme 2) was investigated [20] using diethyl hydrogen
phosphonate and tetrakis[triphenylphosphine]palladium in
the presence of triethylamine. This arylation, realised in
toluene and under nitrogen conditions, afforded us better
yields (32%) than those obtained in the previous reactions.
2.1.4. Synthesis of Monomer 2 via an organometallic
reaction
Furthermore, a last synthetic route was performed via
an organometallic reaction (synthetic route IV, Scheme 2).
As a matter of fact, 4-[(trifluorovinyl)oxy)]bromobenzene
(Monomer 1, Scheme 2) can be converted to a reactive
Grignard (M: Mg, Scheme 3) [21] or lithium (M: Li,
Scheme 3) compound [22]. Followed by a condensation
reaction with different reactants, a wide range of organic–
inorganic fluorinated compounds can be prepared
[2f,22a,23] such as 3-(4-trifluorovinyloxy phenyl)thiophene
[21], novel triaryl phosphine oxide trifluorovinyl ether
monomers [24], 1,3,5-tris[(4-trifluorovinyloxy)phenyl]ben-
The structure of 4-[(a,b,b-trifluorovinyl)oxy]benzene
diethyl phosphonate was confirmed by 31P, 1H, and 19F
1
NMR spectroscopy. The H NMR spectrum of Monomer
2 (R: Et, Spectrum A in Fig. 1) shows a triplet
(3JHH ¼ 7:1 Hz) and a multiplet (2JHP ¼ 3:5 Hz) centred
at 1.09 and 3.91 ppm, characteristics of the six protons of
the methyl groups and four methylene protons of the phos-
phonate group, respectively. As expected, the aromatic
Table 1
Attempted for phosphonylation of Monomer 1 via a Michaelis–Arbuzov reaction
Exp. #
Monomer 1
(mol in feed)
P(OR)3
(mol in feed)
NiCl2
Temperature
Sonic conditions
Yields (%)
(mol in feed)
(8C)/time (h)
R
1
2
3
4
5
6
0.08
0.08
0.09
0.07
0.07
0.07
Et
Et
Me
Et
Et
Et
0.16
0.16
0.17
0.15
0.15
0.15
0
110/72
110/72
110/72
110/72
110/72
RT/72
No
No
No
No
Yes
Yes
0
10
6
0.03
0.03
0.03
0.03
0.03
10
10
10

1320
R. Souzy et al. / Journal of Fluorine Chemistry 125 (2004) 1317–1324
Fig. 1. (a) 1H, (b) 31P and (c) 19F NMR spectra recorded in deuterated acetone of Monomer 2.
zene [9b], 1,2-bis[4-(dimethylhydroxysilyl)phenoxy]-1,2,3,
3,4,4-hexafluorocyclobutane and 1,2-bis[3-(dimethylhy-
droxysilyl)phenoxy]1,2,3,3,4,4-hexafluorocyclobutane [23],
aromatic trifluorovinyl ether containing the sulphonamide
and the sulphonic acid functionality [22c]. Furthermore,
aromatic perfluorovinyl ether monomers containing
chromophores [12d], heterocycles [25] and macrocyclic
ligands [26] have been also synthesised. According to
Neilson et al. [27], Grignard reagent from 4-[(a,b,b-trifluor-
ovinyl)oxy]bromobenzene monomer was not reactive
enough (compared to the lithium agent) toward many elec-
trophiles.
In our study, the synthetic route is similar to that of the
former example, using a lithium reagent from the 4-[(tri-
fluorovinyl)oxy]bromobenzene (Monomer 1) which was
reacted at À80 8C with dimethyl-chlorophosphate. Mono-
mer 2 (R: Me, Scheme 2) was obtained in 25% overall yield.
2.1.5. Dealkylation of Monomer 2
As previously mentioned, Monomer 2 possesses phos-
phonic ethyl groups which could be dealkylated with either
concentrated acidic solution (HCl or HBr) [20,28], or alka-
line solution [20,29], or using silylating reagents [28b,30], or
inorganic halides [18d,31] (this deprotection method led

R. Souzy et al. / Journal of Fluorine Chemistry 125 (2004) 1317–1324
1321
Table 2
Chemical shifts and IR frequencies of [(a,b,b-trifluorovinyl)oxy]bromobenzene functionalised by dialkylphosphonate or phosphonic or halogensulfonyl or
sulphonic acid groups
X
Fa d (ppm) Fb d (ppm) Fc d (ppm) Ha d (ppm) Hb d (ppm) 31P d (ppm) n (X) (cmÀ1
)
Br
À119.8
À126.7
À126.4
À126.2
À125.4
À124.7
À124.1
À122.2
À134.9
À135.2
À135.4
À134.4
À136.1
À136.2
À137.1
7.1
7.1
7.2
7.2
7.2
7.4
7.5
7.5
7.6
7.8
7.8
8.1
8.2
8.1
–
P(O)(OMe)2 À119.5
P(O)(OEt)2 À119.1
P(O)(OH)2 À118.5
20.1
17.9
18.1
–
1260 (P¼O stretch) 1190 (P–O–C stretch)
1253 (P¼O stretch) 1026 (P–O–C stretch)
2955 (P(O)(OH)2 stretch) 2285 (P(O)(OH)2 stretch)
1381 (O¼S¼O stretch)
SO2Cl
SO2F
SO3H
À117.8
À117.1
À115.1
–
1421 (O¼S¼O stretch)
–
3373 (S(O)(OH)2 stretch) 1029 (S(O)(OH)2 stretch)
F
F
F
was necessary to use palladium catalyst (synthetic route III,
Scheme 2) to afford the best overall yields.
F
F
F
O
O
2.2. Characterisation of the aromatic perfluorovinyl ethers
Metal
As mentioned above, phosphonic compounds (Monomers
2 and 3) were characterised by 31P, 1H, and 19F NMR. The
31P NMR showed a singlet corresponding to the phosphorus
atom in the aromatic phosphonate group. 19F NMR spectrum
exhibits three doublet of doublets characteristic of Fa, Fb and
Br
M
M : Li or MgBr
Scheme 3. Grignard [21] and lithium agent [22] of 4-[(trifluorovinyl)
oxy)]bromobenzene.
1
Fc. H NMR exhibits signals characteristics of the dialkyl
phosphonate and of the aromatic protons. FTIR was utilised
as a means of determining the presence of the phosphonate
or phosphonic acid functions in the aromatic perfluorovinyl
ether (Table 2). Furthermore, it was worth examining the
influence of the functional groups (P(O)(OR)2, R: H, Me or
Et, SO2R0, R0: Cl, OH)) on the chemical shifts in the 19F, 1H
and 31P NMR spectra. However, the results listed in Table 2,
showed that the presence of P(O)(OR)2 (R: Et, H) or SO2X
(X: Cl, F, OH) functions, which are electron-withdrawing
groups, induced a low field shift (from À119.8 to
À115.1 ppm when X stands for Br or SO3H, respectively).
Hence, the results listed in Table 2 clearly showed that
sulphonic (X: SO3H, Table 2) or phosphonic (X: P(O)(OH)2,
Table 2) acid functions have stronger electron-withdrawing
behaviours than those of their halogenosulfonyl (X: SO2Cl,
SO2F) or phosphonate (X: P(O)(OR)2, R: Et) or brominated
(X: Br) homologues, respectively.
only to monoacid structures). In our work, Monomer 2 was
dealkylated using silylating reagents such as BrSiMe3 in
dichloromethane at room temperature (Scheme 4). The
hydrolysis reaction was monitored by 1H NMR (by checking
the absence of signals centred at 1.1 and 3.8 ppm, charac-
teristic of methyl and methylene groups of the diethylpho-
sphonate, respectively). Monomer 3 was obtained in 85%
yield.
From these results, the different synthetic ways afforded
fair to good overall yields. As a matter of fact, Michaelis–
Arbuzov and Michaelis–Becker reactions are based on a
substitution of bromine by a nucleophile such as P(OEt)3 or
NaP(O)(OEt)2. Furthermore, this reaction was carried out
with difficulties without any catalyst or a strong electron-
withdrawing group linked onto the aromatic ring. Also, it
Ö
Ö
1) BrSiMe3 / CH2Cl2
2) MeOH
F2C=CFO
P
F2C=CFO
P
OH
OH
OR
OR
(R : Et or Me)
Monomer 3
Monomer 2
Scheme 4. Dealkylation of Monomer 2.

1322
R. Souzy et al. / Journal of Fluorine Chemistry 125 (2004) 1317–1324
3. Conclusion
4.3. Synthesis
This study describes the synthesis of [(a,b,b-trifluorovi-
nyl)oxy]benzene phosphonic acid (Monomers 3). The pre-
paration of ester form of Monomer 3 was carried out
according to various methods of phosphonation such as
Michaelis–Arbuzov, Michaelis–Becker, organometallic
techniques or palladium catalysed arylation described in
the literature. These different synthetic routes afforded
moderate to fair yields. The best overall yields were
obtained when the reaction was catalysed by a complex
of palladium [Pd(PPh3)4]. These new aromatic perfluorovi-
nyl ether derivatives are potential monomers for proton
exchange membranes for fuel cells (PEMFC), and their
(co)polymerisations are under investigation.
4-[(a,b,b-Trifluorovinyl)oxy]bromobenzene (Monomer 1)
was prepared by known method [2f].
4.3.1. Synthesis of Monomer 2 according to Michaelis–
Arbuzov reaction
Into a two-necked round bottom flask equipped with a
reflux condenser and a magnetic stirrer were introduced,
under nitrogen atmosphere, 28.203 g of triethylphosphite
(0.170 mol) and 4.011 g of nickel dichloride (0.031 mol).
The mixture was heated at 110 8C. To this solution, 22.701 g
of Monomer 1 (0.090 mol) were slowly added. After com-
plete addition, the mixture was stirred at 110 8C for 72 h
(bromoethane was eliminated in the course of the reaction).
Afterwards, the mixture was allowed to cool at room tem-
perature. The unreacted triethylphosphite was evaporated
under vacuum. Monomer 2 was purified (yield 10%; colour-
less liquid) from the crude oil by distillation (bp, 110–
115 8C/5 mm Hg). 1H NMR (250 MHz, Fig. 1a, CDCl3)
4. Experimental
4.1. Materials
3
d: 1.1 (t, P(O)(OCH2CH3)2, JHH ¼ 7:0 Hz, 6H), 3.8 (m,
3
Trimethyl- or triethyl-phosphite, HP(O)(OMe)2, HP(O)-
(OEt)2, ClP(O)(OMe)2, NaH, BrSiMe3 were purchased from
Aldrich and distilled prior to use. Anhydrous THF and
diethyl ether were distilled over calcium hydride. All
reagents and all solvents were used as received.
P(O)(OCH2CH3)2, JHH ¼ 6:9 Hz, 4H), 7.2–7.3 (m, ArH,
2H), 7.7–7.8 (m, ArH, 2H); 31P{1H} NMR (250 MHz,
Fig. 1b, CDCl3); d: 17.9 (s); 19F NMR (250 MHz, Fig. 1c,
2
CDCl3); d: À119.1 (dd, cis-CF¼CF2, Fa, JF F ¼ 92 Hz,
a
b
3JF F ¼ 63 Hz, 1F, À126.2 (dd, trans-CF¼CF2, Fb,
a
c
2JF F ¼ 92 Hz, 3JF F ¼ 109 Hz, 1F), À135.4 (dd,
b
a
b
c
3
3
4.2. Analyses
CF¼CF2, Fc, JF F ¼ 63 Hz, JF F ¼ 109 Hz, 1F). FTIR:
c
a
c a
1253 (s, P¼O stretch), 1026 (s, P–O–C stretþch). Pos EI MS:
m/z ¼þ 310 (81%, [Mꢁ]þ), 282 (90%, [Mꢁ] ), 237 (100%,
[Mꢁ] –[O(C2H5)2]); 201 (55%); 167 (14%); 139 (90%); 103
(92%); 76 (45%); 50 (12%, CF2).
4.2.1. Characterisation by NMR spectroscopy
The produced fluorinated monomers were characterised
by 1H, 31P and 19F nuclear magnetic resonance (NMR)
spectroscopies. The spectra were recorded on a Bruker
AC 200 or Bruker A-250 MHz at room temperature in
deuterated acetone or DMF, using tetramethylsilane
4.3.2. Synthesis of Monomer 2 according to Michaelis–
Becker reaction
1
(TMS) or CFCl3 as internal references for H and 31P, or
The 1.203 g (0.050 mol) of sodium hydride in 40 ml of
anhydrous tetrahydrofuran were introduced into a two-
necked round bottom flask equipped with a reflux condenser
and a magnetic stirrer, under an nitrogen atmosphere. The
solution was cooled to 0 8C under magnetic stirring. The
7.402 g (0.061 mol) of diethyl phosphite were slowly added
to this solution. Hydrogen emission was observed. A solu-
tion of 12.604 g of 1 (0.051 mol) of Monomer 1 in anhy-
drous THF and 0.701 g of NaI (0.005 mol) was dropwise
added to the mixture at 0 8C. After addition, the mixture was
allowed to warm to room temperature and was stirred for
16 h. The salt formed was removed by precipitation from
ethyl acetate and then by filtration. The filtrate was con-
centrated and Monomer 2 was distilled (12% yield, colour-
less liquid) (bp, 110–115 8C/5 mm Hg).
19F NMR spectroscopies, respectively. The experimental
conditions for recording 1H (19F) NMR spectra were as
follows: flip angle 908 (308); acquisition time 4.5 s (0.7 s);
pulse delay 2 s (5 s); 64 (128) scans and pulse width of 5 ms
for 19F NMR. The chemical shifts, d, were given in ppm
relative to tetramethylsilane (TMS) used as s: singlet, d:
doublet, t: triplet, q: quartet and m: multiplet.
4.2.2. Characterisation by FTIR spectroscopy
Infrared spectra were recorded on a Nicolet 510P Fourier
Transformed spectrometer from KBr pellets and the inten-
sities of the absorption bands were noted as s: strong, m:
medium and w: weak, given in cmÀ1
.
4.2.3. Characterisation by mass spectrometry
Mass spectra (GC–MS) were recorded on an Agilent
Technologies 6890 N instrument with an Agilent 5973 N
mass detector (EI) and a HP5-MS 30 mꢀ0:25 mm capillary
apolar column (stationary phase: 5% diphenyldimethylpo-
lysiloxane film, 0.25 mm).
4.3.3. Synthesis of Monomer 2 according to palladium
catalysed reaction
The 10.801 g (0.040 mol) of Monomer 1 and 6.602 g
(0.050 mol) of diethyl phosphite (0.050 mol) in 70 ml of
dry toluene were placed into a two-necked round bottom

R. Souzy et al. / Journal of Fluorine Chemistry 125 (2004) 1317–1324
1323
flask equipped with a reflux condenser and a magnetic
Acknowledgements
stirrer, under nitrogen. The 5.007 g (0.004 mol) of tetrakis[-
triphenylphosphine]palladium and 15 ml of triethyl amine
were added. Then, the reaction mixture was heated at 110 8C
for 72 h. Afterwards, the mixture was cooled to room
temperature. Ethyl acetate was added and the solid was
filtered off. Monomer 2 was distilled (yield 32%, colourless
liquid, purity 96%) from the crude oil by distillation under
vacuum (bp, 110–115 8C/5 mm Hg).
The authors acknowledge the Centre National de la
Recherche Scientifique, the GDR PACEM 2479, and the
`
Commissariat a l’Energie Atomique (CEA Grenoble, espe-
cially Dr. D. Marsacq and P. Capron) for the financial
support.
References
4.3.4. Synthesis of Monomer 2 according to
organometallic reaction
[1] R. Souzy, B. Ameduri, B. Boutevin, Prog. Polym. Sci. 29 (2) (2004)
75–106.
In a two-necked round bottom flask containing a septum
and a nitrogen purge, 20.205 g (0.080 mol) of Monomer 1
and 50 ml of diethyl ether were introduced under nitrogen
atmosphere, then cooled at À80 8C. The 50 ml of 1.7 M t-
butyl lithium (in hexane) (0.087 mol) was added dropwise to
this mixture over 45 min and additionally stirred for 2 h
while maintaining the temperature at À80 8C. This lithium
reagent was added dropwise, using a canular, into a separate
two-necked round bottom flask containing 25 ml of ether
and 26.801 g (25 ml) (0.180 mol) of ClP(O)(OMe)2 also
maintaining at À80 8C. The reaction mixture was stirred for
30 min at À80 8C. Then, 100 ml of deionised water was
added to the reaction forming an organic and an aqueous
layer. The two layers were separated. Monomer 2 was
purified by vacuum distillation (bp, 105–112 8C/5 mm
Hg) and was obtained in 25% yield (colourless liquid).
1H NMR (250 MHz, CDCl3) d: 3.5 (d, P(O)(OCH3)2,
JHP ¼ 10:9 Hz, 3H), 7.0–7.2 (m, ArH, 2H), 7.4–7.6 (m,
ArH, 2H); 31P{1H} NMR (250 MHz, CDCl3); d: 17.9 (s);
19F NMR (250 MHz, CDCl3); d: À119.5 (dd, cis-CF¼CF2,
[2] (a) R. Beckerbauer, US 3397191 Assigned to DuPont de Nemours,
1968;
(b) D.A. Babb, K.S. Clement, W.F. Richey, B.R. Ezzel, US 5037917,
US 5037919, US 5021602 Assigned to Dow Chemical, 1991;
(c) D.A. Babb, B.R. Ezzel, K.S. Clement, W.F. Richey, A.P.
Kennedy, J. Polym. Sci. Part A: Polym. Chem. 31 (13) (1993)
3465–3477;
(d) A.P. Kennedy, D.A. Babb, J.N. Bremmer, A.J. Pasztor Jr., J.
Polym. Sci. Part A: Polym. Chem. 33 (11) (1995) 1859–1865;
(e) D.A. Babb, N.G. Rondan, D.W. Smith Jr., Polym. Prepr. (Am.
Chem. Soc., Div. Polym. Chem.) 36 (1) (1995) 721–722;
(f) D.W. Smith Jr., D.A. Babb, Macromolecules 29 (3) (1996)
852–860;
(g) S.C. Ligon Jr., M. Krawieck, A. Kitaygorodskiy, D.W. Smith Jr.,
J. Fluorine Chem. 123 (1) (2003) 139–146.
[3] W.A. Bernett, J. Org. Chem. 34 (6) (1969) 1772–1776.
[4] S.Y. Wang, W.T. Borden, J. Am. Chem. Soc. 111 (18) (1989)
7282–7283.
[5] C.M. Cheatman, S.E. Lee, J. Laane, D.A. Babb, D.W. Smith Jr.,
Polym. Int. 46 (4) (1998) 320–324.
[6] (a) M. Watanabe, H. Ishiuchi, JP 5013070 Assigned to Hitachi
Maxell LTD., 1993;
(b) Z.Y. Yang, A.E. Feiring, B.E. Smart, J. Am. Chem. Soc. 116 (9)
(1994) 4135–4136;
2
3
Fa, JF F ¼ 98 Hz, JF F ¼59 Hz, 1F), À126.2 (dd, trans-
a
b
a c
2
3
CF¼CF2, Fb, JF F ¼ 98 Hz, JF F ¼ 105 Hz, 1F), À135.4
b
a
b
c
(c) A.E. Feiring, B.E. Smart, Z.Y. Yang, PCT Int. Appl. WO
9414741 Assigned to DuPont de Nemours, 1994;
(d) E. Bartmann, H. Plach, R. Eidenschink, V. Reiffenrath, D.
Pauluth, E. Poetsch, S. Schoen, V. Meyer, M. Junge, R. Hittich, US
5403512 Assigned to Merck, 1995;
3
3
(dd, CF¼CF2, Fc, JF F ¼ 59 Hz, JF F ¼ 105 Hz, 1F).
c
a
c
b
FTIR: 1260 (s, P¼O stretch), 1190 (s, P–O–C stretch).
4.3.5. Dealkylation of Monomer 2
(e) D.D. DesMarteau, C.W. Martin, L.A. Ford, Y. Xie, US 6268532
Assigned to 3M Innovative Properties Company, 2001;
(f) K.P.U. Pereta, M. Krawiek, D.W. Smith Jr., Tetrahedron 58
(2002) 10197–10203;
A two-necked round bottom flask equipped with a reflux
condenser and a magnetic stirrer was charged, under a
nitrogen atmosphere, with 2.904 g (0.009 mol) of Monomer
2 and solubilised in 20 ml of dichloromethane. 6.101 g
(5 ml) of BrSiMe3 were added dropwise for 30 min. The
reaction mixture was stirred at room temperature for 6 h.
After the reaction, the solvent was evaporated and 50 ml of
methanol were added. The mixture was stirred for 2 h.
Monomer 3 was obtained after drying under vacuum line
(a yellow liquid was obtained in 80% yield). 1H NMR
(250 MHz, CDCl3) d: 5.5 (s, P(O)(OH)2, 2H), 7.1–7.3 (m,
ArH, 2H), 7.7À7.9 (m, ArH, 2H); 31P{1H} NMR (250 MHz,
CDCl3); d: 18.1 (s); 19F NMR (250 MHz, CDCl3); d: À118.5
(g) R. Souzy, B. Ameduri, B. Boutevin, J. Polym. Sci. Part A:
Polym. Chem., in press.
[7] D.A. Babb, K.S. Clement, B.R. Ezzel, US 5159038 Assigned to Dow
Chemical, 1992.
[8] D.W. Smith Jr., D.A. Babb, H. Shah, A. Hoeglund, R. Traiphol, D.
Perahia, H. Boone, J. Fluorine Chem. 104 (1) (2000) 109–117.
[9] (a) D.A. Babb, R.V. Snelgrove, D.W. Smith Jr., S.F. Mudrich, Step-
Growth Polymers for High-Performance Materials, ACS Symposium
Series 624, 1996 431–441;
(b) H.W. Boone, D.W. Smith Jr., D.A. Babb, Polym. Prepr. (Am.
Chem. Soc., Div. Polym. Chem.) 39 (2) (1998) 812–813.
[10] (a) S.E. Creager, J.J. Summer, R.D. Baily, J.J. Ma, W.T. Pennington,
D.D. DesMarteau, Electrochem. Solid State Lett. 2 (9) (1999)
434–436;
2
2
(dd, cis-CF¼CF2, Fa, JF F ¼ 96 Hz, JF F ¼ 63 Hz, 1F),
a
b
a c
2
2
À125.4 (dd, trans-CF¼CF2, Fb, JF F ¼ 96 Hz, JF F
¼
b
a
b
c
(b) R. Souzy, B. Ameduri, M. Pineri, D. Marsacq, FR 2843398
Asssigned to CEA, 2002.
2
114 Hz, 1F), À134.4 (dd, CF¼CF2, Fc, JF F ¼ 63 Hz,
c
a
2JF F ¼ 114 Hz, 1F). FTIR: 2955–2285 (s, P(O)(OH)2
[11] D.W. Smith Jr., S. Chen, S. Kumar, J. Ballato, H. Shah, C. Topping,
S. Foulger, Adv. Mater. 14 (21) (2002) 1585–1589.
c
b
stretch).

1324
R. Souzy et al. / Journal of Fluorine Chemistry 125 (2004) 1317–1324
[12] (a) S.H. Foulger, P. Jiang, A. Lattam, D.W. Smith Jr., J. Ballato,
Langmuir 17 (2001) 6023–6026;
[19] C. Carbonneau, R. Frantz, J.O. Durand, G.F. Lanneau, R.J.P. Corriu,
Tetrahedron Lett. 40 (1999) 5855.
(b) S.H. Foulger, A. Lattam, J. Ballato, P. Jiang, Y. Ying, D.W.
Smith Jr., Adv. Mater. 13 (24) (2001) 1898–1901;
(c) H. Zengin, W. Zhou, J. Jin, R. Czerw, D.W. Smith Jr., L.
Echegoyen, D. Caroll, S. Foulger, J. Ballato, Adv. Mater. 14 (20)
(2002) 1480–1483;
[20] H.J. Cristau, A. Herve, F. Loiseau, D. Virieux, Synthesis 14 (2003)
2216–2220.
[21] Y. Xu, D.C. Loveday, J.P. Ferraris, D.W. Smith Jr., Polym. Prepr.
(Am. Chem. Soc., Div. Polym. Chem.) 39 (1) (1998) 143–144.
[22] (a) J. Ji, S. Narayan-Sarathy, R.H. Neilson, J.D. Oxley, D.A. Babb,
N.G. Rondan, D.W. Smith Jr., Organometallics 17 (5) (1998)
783–785;
(d) J. Luo, S. Liu, M. Haller, L. Liu, H. Ma, A.K.Y. Jen, Adv. Mater.
14 (23) (2002) 1763–1768.
[13] (a) D.W. Smith Jr., H.W. Boone, R. Traiphol, H. Shah, D. Perahia,
Macromolecules 33 (4) (2000) 1126–1128;
(b) S. Narayan-Sarathy, R.H. Neilson, D.W. Smith Jr., Polym. Prepr.
(Am. Chem. Soc., Div. Polym. Chem.) 39 (1) (1998) 609–610;
(c) L.A. Ford, D.W. Smith Jr., D.D. DesMarteau, Polym. Mater. Sci.
Eng. (Am. Chem. Soc., Div. PMSE) 83 (2000) 10–11.
[23] J. Rizzo, F.W. Harris, Polymer 41 (13) (2000) 5125–5136.
[24] D.A. Babb, H.W. Boone, D.W. Smith Jr., P.W. Rudolph, J. Appl.
Polym. Sci. 69 (10) (1998) 2005–2012.
(b) R. Traiphol, H.V. Shah, D.W. Smith Jr., D. Perahia, Macro-
molecules 34 (12) (2001) 3954–3961;
(c) R. Traiphol, D.W. Smith Jr., D. Perahia, J. Polym. Sci. Part A:
Polym. Chem. 40 (24) (2002) 2817–2824.
[14] (a) P.H. Townsend, E.O. Shaffer, M.E. Mills, J. Blackson, M.J.
Radler, in: Materials Research Society Symposium Proceedings
on Low-Dielectric Constant Materials II, vol. 443, 1997,
pp. 33–40;
[25] F.L. Qing, R. Wang, B. Li, X. Zheng, W.D. Meng, J. Fluorine Chem.
120 (1) (2003) 21–24.
[26] C.M. Topping, J. Jin, S.C. Ligon Jr., A.V. Patil, S. Fallis, J.A. Irvin,
D.D. DesMarteau, D.W. Smith Jr., Polym. Prepr. (Am. Chem. Soc.,
Div. Polym. Chem.) 43 (1) (2002) 486–487.
(b) G. Fishbeck, R. Moosburger, C. Kostrzewa, A. Achen, K.
Petermann, Electron. Lett. 33 (6) (1997) 518–519.
[15] T.A. Tumolillo Jr., A. Thomas, P.R. Ashley, Appl. Phys. Lett. 62 (24)
(1993) 3068–3070.
[27] R.H. Neilson, H. Robert, J. Ji, S. Narayan-Sarathy, J. Oxley, D.W.
Smith Jr., Book of Abstracts, 213th ACS National Meeting, San
Francisco, April 13–17, 1997.
[16] (a) P.L. Heinze, D.J. Burton, J. Org. Chem. 53 (12) (1988)
2714–2720;
¨
[28] (a) R. Classen, G. Hagele, J. Fluorine Chem. 77 (1996) 71;
(b) M. Gaboyard, Y. Hervaud, B. Boutevin, J. Fluorine Chem. 107
(2001) 5–12.
(b) C. Stone, A.E. Steck, R.D. Lousenberg, US 5602185 Assigned to
Ballard Power Systems Inc., 1997.
[17] (a) I. Cabasso, J. Jagur-Grodzinski, D. Vofsi, US4073754, 1978;
(b) S.V. Kotov, S.D. Pedersen, W. Qiu, Z.M. Qiu, D.J. Burton, J.
Fluorine Chem. 82 (1996) 13;
[29] S. Ba-Saif, A. Williams, J. Am. Chem. Soc. 112 (1990) 8115.
[30] (a) Y. Machida, S. Nomoto, I. Saito, Synth. Commun. 9 (2) (1979)
97;
(c) S.T.S. Daynard, L.Q. Hu, C. Mah, A.E. Steck, J. New Mater.
Electrochem. Syst. 3 (1) (2000) 43–50.
(b) B. Boutevin, B. Hamoui, J.P. Parisi, J. Appl. Polym. Sci. 52
(1994) 449;
[18] (a) P. Tavs, Chem. Ber. 103 (1970) 2428–2436;
(b) M. Tatemoto, C. Yanagawa, S. Takatsuki, F. Osaka, EP
0398250B1 Assigned to Daikin Industries, 1990;
(c) S.R. Sandler, W. Karo, Polymer Synthesis, vol. 1, Academic
Press, Orlando, FL, 1992;
(c) C. Brondino, B. Boutevin, Y. Hervaud, N. Pelaprat, A. Manseri,
J. Fluorine Chem. 76 (1996) 193.
[31] (a) M. Hoffmann, J. Prakt. Chem. 330 (5) (1988) 820;
(b) C. Weis, P. Sutter, A.-G. Giba-Geigy, European Patent 0310559
(1989);
(d) B. Boutevin, Y. Hervaud, A. Boulahna, E.M. El Hadrami, Polym.
Int. 51 (2002) 450–457.
(c) B. Boutevin, Y. Hervaud, T. Jeanmaire, A. Boulahna, M. El Asri,
Phosphorus Sulfur Silicon 174 (2001) 1–14.