New ionic liquids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions

Article abstract of DOI:10.1016/j.jfluchem.2005.04.017

The synthesis of new ionic liquids with tris(perfluoroalkyl) trifluorophosphate (FAP) anions is described. The physico-chemical properties (conductivity, viscosity, electrochemical and thermal stability) of this new generation of ionic liquids (molten salts) are discussed. FAP-ionic liquids show an excellent hydrolytic stability, low viscosity and high electrochemical and thermal stability that makes them attractive for use in electrochemical devices and as a new media for application in modern technologies and chemical synthesis.

Full text of DOI:10.1016/j.jfluchem.2005.04.017

Journal of Fluorine Chemistry 126 (2005) 1150–1159
www.elsevier.com/locate/fluor
New ionic liquids with tris(perfluoroalkyl)trifluorophosphate
(
FAP) anions
a,
N.V. Ignat’ev , U. Welz-Biermann ,
a
*
b
A. Kucheryna , G. Bissky , H. Willner
b
b
a
Merck KGaA, New Ventures - Materials, Frankfurter Str. 250, D-64293 Darmstadt, Germany
b
Inorganic Chemistry, Bergische University Wuppertal, Gaußstr.20, D-47097 Wuppertal, Germany
Received 10 February 2005; received in revised form 25 April 2005; accepted 30 April 2005
Available online 18 July 2005
Abstract
The synthesis of new ionic liquids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions is described. The physico-chemical properties
conductivity, viscosity, electrochemical and thermal stability) of this new generation of ionic liquids (molten salts) are discussed. FAP-ionic
(
liquids show an excellent hydrolytic stability, low viscosity and high electrochemical and thermal stability that makes them attractive for use
in electrochemical devices and as a new media for application in modern technologies and chemical synthesis.
#
2005 Elsevier B.V. All rights reserved.
Keywords: Ionic liquids; Tris(perfluoroalkyl)trifluorophosphate; Viscosity; Conductivity; Electrochemical stability
1
. Introduction
by Bannett et al. [8]. These compounds were obtained by
difficult, time consuming procedures, which requires high
pressure (autoclave) and results in a complex mixture of
trifluoromethyl containing phosphines (Scheme 2).
Commonly used ionic liquids with hexafluorophosphate,
ꢀ
[
PF6] (hydrophobic), are hydrolytically unstable, espe-
cially at elevated temperature [1]. The instability of the
hexafluorophosphate anion is due to the facial protonation of
the fluorine atom, followed by HF elimination and reaction
Later, Burg et al. have modified this procedure by
generation of CF I in situ from silver trifluoroacetate and
3
iodine [9] but still the isolation of individual compounds
remains a difficult task. G o¨ rg et al. have recently developed
an alternative method [10] (Scheme 3).
ꢀ
with water. This mechanism of the hydrolysis of [PF6]
salts, for example, LiPF , has been discussed in the literature
6
[
2,3]. To address this disadvantage of the hexafluoropho-
Trifluoromethyl-fluorophosphoranes
undergo
slow
sphate anion, the replacement of some fluorine atoms by
hydrophobic perfluoroalkyl-groups looks promising as a
way to increase the hydrolytic stability of fluorophosphates
decomposition even at room temperature, releasing difluor-
ocarbene [11]. In contrast, perfluoroalkylfluorophosphor-
anes with longer carbon chain are more stable [12].
Synthesis of these compounds can be carried out to the
method of Emeleus [13], followed by chlorination [13] and
(
see Scheme 1).
Salts with perfluoroalkylfluorophosphate anions are
known for more than 40 years [4–6]. The common method
of their synthesis is based on the addition of alkali metal
fluorides to perfluoroalkylfluorophosphoranes [7]. Trifluor-
omethyl phosphoranes can be prepared by chlorination/
fluorination of trifluoromethylphosphines, synthesized first
fluorination with SbF [14] (Scheme 4).
3
However, this method is not suitable for the preparation
of tris(perfluoroalkyl)difluoro-phosphoranes [13].
In 1995, Kampa et al. [15] reported the direct fluorination
of trialkylphosphines with F yielding the corresponding
2
tris(perfluoroalkyl)difluorophosphoranes. The reaction was
carried out with diluted F (by helium) in a mixture of CFC-
11 and CFC-113 as solvent, at low temperature, with
*
Corresponding author. Fax: +49 203 3792231.
2
E-mail address: nikolai.ignatiev@merck.de (N.V. Ignat’ev).
0022-1139/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2005.04.017

N.V. Ignat’ev et al. / Journal of Fluorine Chemistry 126 (2005) 1150–1159
1151
Scheme 5.
Scheme 1.
Scheme 2.
Scheme 6.
subsequent slow increase in the temperature up to RT. This
difficult technique allows small quantities of tris(perfluor-
oalkyl)difluorophosphoranes (yield is not given) to be
obtained and requires the use of expensive materials.
Another synthesis of tris(perfluoroalkyl)difluorophosphor-
anes, developed by Semenii et al., is based on the
electrochemical fluorination (Simons process) of trialk-
ylphosphine oxides [16] (Scheme 5).
2. Results and discussion
2.1. Synthesis of ionic liquids with the FAP-anion
Recently Merck KGaA (Darmstadt, Germany) has
developed a convenient method of the synthesis of ionic
liquids with the tris(perfluoroalkyl)trifluorophosphate-anion
Disadvantages of this method are moderate yields of the
desired perfluorinated products and formation of an
equimolar quantity of toxic OF , which can cause a severe
ꢀ
(FAP-anion), as replacement of [PF ] . Tris(perfluoroalk-
6
yl)difluorophosphoranes (1) [17,18] were applied as starting
material for the synthesis of FAP-anions.
2
explosion in the mixture with hydrogen released in the
electrochemical fluorination process.
Tris(perfluoroalkyl)difluorophosphoranes (1) are very
reactive compounds. They react readily with organic or
inorganic fluorides [5–8,19–22] with formation of the
corresponding salts of FAP-anions. The fluoride ion affinity
of tris(perfluoroalkyl)difluorophosphoranes (1) is so high
that in aqueous HF the hydrolysis of phosphoranes (1) is
suppressed and the corresponding tris(perfluoroalkyl)tri-
fluorophosphoric acid, HFAP (2) is formed in nearly
quantitative yield [23,24] (Scheme 7).
Recently, we have improved this procedure by use of
trialkylphosphines as starting material in an electrochemical
fluorination process [17,18]. This allowed an increase in the
yield of tris(perfluoroalkyl)difluorophosphoranes and
avoided the formation of the dangerous side product, OF2
(
Scheme 6).
HFAP is preferably formed with the meridional
unsymmetrical) structure but the subsequent formation of
(
the facial (symmetrical) structure (up to 15 mol%) can be
1
9
observed by F NMR spectroscopy. Acid (2) is a convenient
starting material for the synthesis of various salts [23,24]
with ionic liquid properties (Scheme 8).
Scheme 3.
Scheme 7.
Scheme 4.
Scheme 8.

1152
N.V. Ignat’ev et al. / Journal of Fluorine Chemistry 126 (2005) 1150–1159
Table 1
The imidazolium salt (3) is not soluble in water and can
ꢀ
2 5 3 3
F ) PF ] (FAP) anion
Water uptake by ionic liquids containing the [(C
be separated easily from the reaction mixture as a liquid
phase at the bottom of the reactor. After washing and drying,
hexyl-methylimidazolium (HMIM) FAP (3) can be obtained
with a very low content of chloride and residual water (10–
Ionic liquid
Maximium water
uptake (ppm)
1
1
-Hexyl-3-methylimidazolium FAP
-Hexyl-3-methylimidazolium
2030
10670
1
5 ppm). HMIM FAP (3) is a hydrophobic room temperature
bis(trifluoromethylsulfonyl)imide
-Butyl-1-methylpyrrolidinium FAP
-Butyl-1-methylpyrrolidinium
ionic liquid, which possesses high hydrolytic stability; no
detectable HF formation after 5 h in boiling water
1
1
3500
14800
(
unpublished result from the QUILL Centre, Queen’s
bis(trifluoromethylsulfonyl)imide
ꢀ
1
-Butyl-3-methylimidazolium PF
6
22600
University, Belfast, UK) and a large electrochemical
window (more than 5.5 V). Viscosity of HMIM FAP (3)
is comparable with the viscosity of HMIM bis(trifluor-
omethylsulfonyl)imide.
(more than 220 8C) for practical application as ionic liquids
(see Table 2 and Fig. 1.)
A similar procedure was applied for the synthesis of
pyridinium, pyrrolidinium, alkylammonium, alkylphospho-
nium, guanidinium [25], uronium [26] and thiouronium [27]
salts with the FAP anion. Many of these salts are liquids at
room temperature and by definition they belong to the class
of room temperature ionic liquids. Alkali-metal salts with
the FAP anion can be used for the synthesis of ionic liquids
in the same manner as HFAP (2) [28].
2.2.3. Electrochemical stability
Electrochemical stability is commonly determined by
cyclic voltammetry. In the case of ionic liquids, small
additional peaks in the cathodic and/or anodic part of cyclic
ꢀ
voltammogram can be related to impurities (usually Cl ,
ꢀ
Br ). For this reason Merck KGaA has developed and
ꢀ
ꢀ
applied halogen free (Cl , Br -free) technology for the
preparation of some ionic liquids (for example, triflates
[25–27,29–30]).
2.2. Physico-chemical properties of ionic liquids with
the FAP-anion
FAP-ionic liquids possess a very broad electrochemical
window (Table 3). The electrochemical stability of ionic
liquids with the FAP-anion is comparable with that of
bis(trifluoromethylsulfonyl)imide-based ionic liquids, and
much better than for tetrafluoroborates.
2
.2.1. Water uptake by FAP-ionic liquids
The FAP-ionic liquids are hydrophobic. They are
immiscible with water but miscible with polar organic
solvents. The water uptake (saturation with water) for these
ionic liquids is much less then for the popular ionic liquids
with the bis(trifluoromethylsulfonyl)imide-anion and more
Tetrabutylammonium tris(pentafluoroethyl)trifluoropho-
sphate (mp 62 8C) shows an extremely broad electroche-
mical window, close to 7 V (Table 3 and Fig. 2).
This is a new non-hygroscopic conducting salt for non-
aqueous supporting electrolytes in electrochemical cells.
than 10 times less in comparison with the commonly used
ꢀ
ionic liquids with the [PF ] anion (see Table 1). This allows
6
access to FAP-ionic liquids with a very low content of
residual water, 10–15 ppm, or even less.
2.2.4. Viscosity
Ionic liquids appear to be more viscous then conventional
2
.2.2. Thermal stability
Ionic liquids listed in Table 2 show a low melting point
organic solvents. Table 4 presents data, which demonstrate
the dramatic influence of the nature of the anion on the
viscosity of ionic liquids. For example, replacement of three
(
glass transition point), typically below ꢀ50 8C. Ionic
liquids with the FAP anion also possess high thermal
stability (Table 2), for example, imidazolium based ionic
liquids with the FAP-anion start to decompose at
temperatures above 280 8C.
Uronium [26] and thiouronium [27] salts with FAP anion
are less stable, but still show sufficient thermal stability
ꢀ
fluorine atoms in the [PF6] anion by pentafluoroethyl-
groups decreases drastically the viscosity of imidazolium
ionic liquids (Table 4). Replacement of chloride anion in
trihexyl(tetradecy)phosphonium chloride with tris(penta-
fluoroethyl)trifluorophosphate anion reduced the viscosity
Table 2
ꢀ
Thermal stability of the ionic liquids containing the [(C
2
F
5
)
3
PF
3
]
(FAP) anion
Ionic liquid
mp (8C)
Decomposition (8C)
1
1
1
1
-Ethyl-3-methylimidazolium FAP
-Pentyl-3-methylimidazolium FAP
-Hexyl-3-methylimidazolium FAP
-Butyl-1-methylpyrrolidinium FAP
ꢀ37
300
300
290
250
240
220
250
<ꢀ50
ꢀ50
<ꢀ50
68–69
32–34
0–2
0
0
00
00
N,N,N ,N ,N -Pentamethyl-N -i-propylguanidinium FAP [25]
O-Ethyl-tetramethyluronium FAP [26]
S-Ethyl-tetramethylthiouronium FAP [27]

N.V. Ignat’ev et al. / Journal of Fluorine Chemistry 126 (2005) 1150–1159
1153
Fig. 1. TGA of S-ethyl-tetramethylthiouronium tris(pentafluoroethyl)trifluorophosphate (FAP).
Table 3
ꢀ
Redox stability of the ionic liquids containing the [(C
2
F
5
)
3
PF
3
]
(FAP) anion in comparison to the ionic liquids with bis(trifluoromethylsulfonyl)imide-anion
Ionic liquid
E
(ox) (V) vs. ferrocene
E(red) (V) vs. ferrocene
Window (V)
Tetrabutylammonium FAP
3.7
3.3
3.1
3.7
3.5
3.9
3.7
2.6
ꢀ3.3
ꢀ3.0
ꢀ3.4
ꢀ2.9
ꢀ3.3
ꢀ2.6
ꢀ2.6
ꢀ2.6
7.0
6.3
6.5
6.6
6.8
6.5
6.3
5.2
Trihexyl(tetradecyl)phosphonium FAP
Trihexyl(tetradecyl)phosphonium Bis(trifluoromethylsulfonyl)imide
1
1
1
1
1
-Butyl-1-methylpyrrolidinium FAP
-Butyl-1-methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide
-Pentyl-3-methylimidazolium FAP
-Hexyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide
ꢀ
-Ethyl-3-methylimidazolium BF
4
2
ꢀ1
2
ꢀ1
from 2757 to 393 mm s (at 20 8C), in spite of increasing
the molecular weight.
ophosphate has a of viscosity 594 mm s , which is much
higher then the viscosity of 1-hexyl-3-methylimidazolium
tris(heptafluoropropyl)trifluorophosphate and 1-hexyl-
3-methylimidazolium tris(pentafluoroethyl)trifluoropho-
sphate (Table 4).
Ionic liquids with long-chain perfluoroalkyl-groups in
the FAP anion have a higher viscosity. For instance, 1-
pentyl-3-methylimidazolium tris(nonafluorobuty)trifluor-
Fig. 2. CVA of tetrabutylammonium tris(pentafluoroethyl)trifluorophosphate.

1154
N.V. Ignat’ev et al. / Journal of Fluorine Chemistry 126 (2005) 1150–1159
Table 4
Kinematic viscosity and density of the 1-alkyl-3-methylimidazolium ionic liquids containing different anions
2
ꢀ1
ꢀ3
)
Ionic liquid
Viscosity (20 8C) (mm s
)
Density (20 8C) (g cm
1
1
1
1
1
1
1
-Hexyl-3-methylimidazolium chloride
7453
548
594
227
74
1.050
1.297
1.693
1.620
1.560
1.377
1.150
ꢀ
-Hexyl-3-methylimidazolium [PF
6
]
ꢀ
ꢀ
ꢀ
-Pentyl-3-methylimidazolium [(C
4
F
9
)3PF
)3PF3]
F5)3PF
3
]
-Hexyl-3-methylimidazolium [(C
3 7
F
-Hexyl-3-methylimidazolium [(C
2
3
]
ꢀ
-Hexyl-3-methylimidazolium [(CF
3
ꢀ
SO
2
)
2
N]
44
-Hexyl-3-methylimidazolium [BF
4
]
195
2
.2.5. Conductivity
The conductivity of a pure ionic liquid should depend on
liquids are negligible. It appears, that the interaction
between the weekly coordinating anions, like FAP and
bis(trifluoromethylsulfonyl)imide, with the cationic part is
indeed weak. The triflate anion, and especially the
trifluoroacetate anion coordinate more strongly to the cation
and that hinders their mobility and reduces the conductivity
of ionic liquids with these anions.
the mobility of the ions, which is greatly influenced by the
viscosity, ion size and the ion association. The data of
Table 5 show that the conductivity of the ionic liquids with
FAP-anions decrease with increasing size of cations.
Probably, this can be also correlated with the viscosity of
ionic liquids, which is increasing for more bulky cations.
The conductivity of 1-ethyl-3-methylimidazolium bis(-
trifluoromethylsulfonyl)imide is slightly higher then the
conductivity of 1-ethyl-3-methylimidazolium FAP, probably
because the imide-anion is less bulky than the FAP-anion.
The conductivity of FAP-ionic liquids is drastically
increased with increasing of temperature.
The electrochemical behavior of previously studied
phenyl(perfluoropropyl)iodonium [31] and bis(pentafluor-
ophenyl)iodonium salts [32] also indicates stronger inter-
action of the trifluoroacetate and the triflate anions with the
cationic centre. The reduction potentials of these salts are
more cathodic in comparison to the iodonium salts with
ꢀ
ꢀ
weakly coordinated anions, like [BF ] and [AsF ] .
4
6
Table 6 demonstrates the influence of the inter-ionic
interaction in ionic liquids on the conductivity. The ionic
liquids listed in Table 6 contain the same cation but different
anions. We would expect an increase in the conductivity by
replacement of the bulky bis(trifluoromethyl sulfonyl)i-
mide-anion with the less bulky trifluoromethylsulfonate
The conductivity of ionic liquids can be increased by
diluting with polar organic solvents, probably related to
decreasing viscosity and separation of ion-pairs. Fig. 3
presents the conductivity of tetrabutylammonium FAP in
different organic solvents. The diagram shows a typical
dependence of conductivity on the concentration of
conducting salt.
(triflate) anion and, in particular, with trifluoroacetate. But
the differences in conductivity between these three ionic
3
. Experimental
Table 5
ꢀ
Solvent free conductivity of the ionic liquids containing the [(C
FAP) anion
2 5 3 3
F ) PF ]
3.1. Chemicals
(
Ionic liquid
Conductivity
ꢀ
1
Tris(perfluoroalkyl)difluorophosphoranes were synthe-
(
20 8C) (mS cm )
sized via electrochemical fluorination of trialkylphosphines
in anhydrous HF (Simons process) as described in [17,18].
Tris(perfluoroalkyl)trifluorophosphoric acid pentahydrate
was prepared by slow addition at 0 8C of 1 mol of the
corresponding tris(perfluoroalkyl)difluorophosphorane to
1
1
1
1
-Hexyl-3-methylimidazolium FAP
-Pentyl-3-methylimidazolium FAP
-Ethyl-3-methylimidazolium FAP
-Ethyl-3-methylimidazolium
1.32
1.66
4.40
7.63
bis(trifluoromethylsulfonyl)imide
-Ethyl-3-methylimidazolium FAP (60 8C)
1
14.25
110.1 g of stirred aqueous HF (18.17 wt.% concentration)
[23]. Imidazolium, pyridinium, pyrrolidinium, phospho-
Table 6
nium, ammonium, guanidinium, uronium and thiouronium
salts with chloride, triflate and methylsulfate anions were
prepared by procedures, described in the literature [25–
Solvent free conductivity of the 1-ethyl-3-methylimidazolium ionic liquids
containing different anions
Ionic liquid
Conductivity
20 8C) (mS cm
27,33]. Tri(n-hexyl)tetradecylphosphonium chloride was
purchased from Cytec company.
ꢀ1
(
)
ꢀ
1
-Ethyl-3-methylimidazolium [(C
-Ethyl-3-methylimidazolium
2
F
5
)3PF
3
]
4.40
7.63
1
3.2. Analytical procedures
bis(trifluoromethylsulfonyl)imide
1
-Ethyl-3-methylimidazolium triflate
-Ethyl-3-methylimidazolium
trifluoroacetate
7.74
8.53
1
19 31
H, F and P NMR spectra were measured on a
1
1
Brucker Avance 300 (300.13 MHz for H and 282.40

N.V. Ignat’ev et al. / Journal of Fluorine Chemistry 126 (2005) 1150–1159
1155
Fig. 3. Concentration dependence of tetrabutylammonium tris(pentafluoroethyl)-trifluorophosphate conductivity in different solvents at 30 8C.
1
9
for
acetonitrile-D . CCl F and TMS were used as internal
F) and Brucker WP 80 SY spectrometers in
trifluorophosphate was quantitative. Melting point (after
crystallisation from the mixture of methanol–water) was 73–
74 8C.
3
3
1
references for F NMR and the proton spectra correspond-
1
ingly. The external reference for P NMR, 85% H PO in
9
3
Analyses, found: C 37.3%, H 5.1; calculated for
C H F P (mol. mass 704.45): C 37.5%, H 5.15%.
3
4
D O, was positioned at the frequency 230.11 Hz (measured
2
22 36 18
2
1
9
in separate experiment in acetonitrile-D3).
The purity (quality) of FAP-ionic liquids was proved
by measuring of residual water (Karl-Fischer titration;
F NMR spectrum, d, ppm: ꢀ43.6 d, m (PF); ꢀ79.7 m
(CF ); ꢀ81.4 m (2CF ); ꢀ87.0 d, m (PF ); ꢀ115.1 d, m
2 2 P,F P,F
3
3
2
1
1
(CF ); ꢀ115.7 d, m (2CF ); J = 890 Hz; J = 902 Hz;
2
2
8
31 KF-Coulobmetr, Metrohm) and of chloride or
J
= 86 Hz; J = 98 Hz.
P,F P,F
1
bromide (ion-chromotography, Metrohm Advanced IC
System; stationary phase: Metrosep A SUPP4–150).
Contents of residual water and halides were usually below
H NMR spectrum, d, ppm: 0.95 t (4CH ); 1.48 m
3
3
(8CH ); 2.05 m (4CH ); J = 7.2 Hz.
H,H
2
2
3
1
P NMR, d, ppm: 33.0 m (1P); ꢀ148.6 d, t, m (1P).
2
0 ppm.
Viscosity, density and thermal stability (TGA) of ionic
3.3.2. Tri(n-hexyl)tetradecylphosphonium
tris(pentafluoroethyl)trifluorophosphate,
liquids were measured with the use of Viscosimeter SVM
000 (Anton Paar) and TG-SDTA 851 (Mettler Toledo)
+
ꢀ
[(C H ) (C H )P] [(C F ) PF ]
6 13 3 14 29 2 5 3 3
3
correspondingly. Conductivity was measured on Conduct-
ometer 703 (Knick) and for cyclic voltammetry an Autolab
PGSTAT 30 (Eco Chemie) was used. Cyclic voltammo-
Tris(pentafluoroethyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (819.8 g, 1.53 mol), was added
2
5 3
3
2
at room temperature to the stirred solution of tri(n-
hexyl)tetradecylphosphonium chloride (793 g, 1.53 mol)
in 1 l of methanol. The mixture was left stirring for 0.5 h and
the solvent was distilled off on a rotary evaporator. The
liquid material was washed with water until pH 6–7 and the
test for chloride with silver nitrate was negative. The residue
was dried at 13.3 Pa and 80 8C within 8 h. A liquid material
(1395 g) was obtained. The yield of tri(n-hexyl)tetradecyl-
phosphonium tris(pentafluoroethyl)-trifluorophosphate was
98.2%.
gramms were recorded for 0.5 M solutions in CH CN at
3
glassy carbon (gc) working electrode; auxiliary electrode
was Pt and Ag/AgNO (CH CN) was used as reference
3
3
electrode. The potential’s values were normalized to E8 of
ferrocene.
3
3
.3. Synthesis of ionic liquids with FAP-anion
.3.1. Tetra(n-butyl)phosphonium
tris(pentafluoroethyl)trifluorophosphate,
Analyses, found: C 49.2%, H 7.1%; calculated for
C H F P (mol. mass 928.88): C 49.1%, H 7.4%.
+
ꢀ
(C H ) P] [(C F ) PF ]
4 9 4 2 5 3 3
[
38 68 18
2
1
9
A solution of tris(pentafluoroethyl)trifluorophosphoric
acid, H[(C F ) PF ] (16.68 g, 37.4 mmol) in diethylether
F NMR spectrum, d, ppm: ꢀ43.8 d, m (PF); ꢀ79.8 m
(CF ); ꢀ81.4 m (2CF ); ꢀ87.2 d, m (PF ); ꢀ115.2 d, m
2
5 3
3
3
3
2
1
1
(
14.52 g) was slowly added at room temperature to a stirred
0% solution of tetra(n-butyl)phosphonium chloride
10.25 g, 34.8 mmol) in toluene. The mixture was left
stirring for 0.5 h and the solvent mixture was distilled off at
3.3 Pa. A white solid material (24.46 g) was obtained. The
yield of tetra(n-butyl)phosphonium tris(pentafluoroethyl)-
(1CF ); ꢀ115.7 d, m (2CF ); J = 890 Hz; J = 902 Hz;
2
2
P,F
P,F
2
2
5
J
= 87 Hz; J = 97 Hz.
H NMR spectrum, d, ppm: 0.89–0.99 m (4CH ), 1.28–
3
P,F P,F
1
(
1.41 m (16CH ), 1.42–1.62 m (8CH ), 2.01–2.16 m
2
2
1
(4CH ).
2
3
1
P NMR, d, ppm: 32.8 m (1P); ꢀ148.5 d, t, m (1P).

1156
N.V. Ignat’ev et al. / Journal of Fluorine Chemistry 126 (2005) 1150–1159
3
3
.3.3. 1-Hexyl-3-methylimidazolium
methylpyridinium chloride (185 g, 0.996 mol) in 300 cm of
water. The mixture was left stirring for 15 min. The bottom
phase was separated and washed with water until pH 6–7 and
the test for chloride with silver nitrate was negative. The
residue was dried at 13.3 Pa and 100 8C within 12 h. A liquid
material (581 g) was obtained. The yield of 1-butyl-4-
methylpyridinium tris(pentafluoroethyl)trifluorophosphate
was 98.0%.
tris(pentafluoroethyl)trifluorophosphate,
+
ꢀ
C H N ] [(C F ) PF ]
10 19 2 2 5 3 3
[
Tris(pentafluoroethyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (2700 g, 5.04 mol) was added at
2
5 3
3
2
room temperature to the stirred solution of 1-hexyl-3-
methylimidazolium chloride (1018 g, 5.02 mol) in 1.5 l of
water. The mixture was left stirring for 0.5 h. The bottom
phase was separated and washed with water until pH 6–7 and
the test for chloride with silver nitrate was negative. The
residue was dried at 13.3 Pa and 90 8C within 22 h. A liquid
material (2998 g) was obtained. The yield of 1-hexyl-3-
methylimidazolium tris(pentafluoroethyl)trifluorophosphate
was 97.5%.
Analyses, found: C 32.4%, H 2.2, N 2.6; calculated for
C H F N P (mol. mass 595.25): C 32.3%, H 2.7%, N 2.4.
1
6 19 18 2
1
9
F NMR spectrum, d, ppm: ꢀ43.6 d, m (PF); ꢀ79.7 m
(CF ); ꢀ81.4 m (2CF ); ꢀ87.0 d, m (PF ); ꢀ115.0 d, m
3
3
2
1
1
(1CF ); ꢀ115.6 d, m (2CF ); J = 888 Hz; J = 903 Hz;
2
2
P,F
P,F
2
2
J
= 85 Hz; J = 98 Hz.
P,F
P,F
1
Analyses, found: C 31.0%, H 2.4, N 4.6; calculated for
C H F N P (mol. mass 612.29): C 31.4%, H 3.1%, N 4.7.
H NMR, d, ppm: 0.95 t (CH ); 1.35 m (CH ); 1.91 m
3 2
(CH ); 2.61 s (CH ); 4.42 t (CH ); 7.79 m (2CH); 8.46 m
2
1
6
1
19 18
2
3
2
9
3
(2CH); J
3
F NMR spectrum, d, ppm: ꢀ43.6 d, m (PF); ꢀ79.7 m
CF ); ꢀ81.4 m (2CF ); ꢀ87.0 d, m (PF ); ꢀ115.1 d, m
= 7.4 Hz; JH,H(A, B) = 6.6 Hz.
H,H
3
1
(
P NMR, d, ppm: ꢀ148.0 d, t, m.
3
3
2
1
1
(
1CF ); ꢀ115.7 d, m (2CF ); J = 891 Hz; J = 909 Hz;
2
2
P,F
P,F
2
J
2
= 83 Hz; J = 98 Hz.
3.3.6. Tetraethylammonium
P,F
1
P,F
H NMR, d, ppm: 0.89 m (CH ); 1.30 m (3CH ); 1.81 m
3
tris(pentafluoroethyl)trifluorophosphate,
ꢀ
[(C H ) N] [(C F ) PF ]
2 5 4 2 5 3 3
2
+
(
CH ); 3.80 s (CH ); 4.10 t (CH ); 7.30 d, d (CH); 7.34 d, d
2
3
2
3
CH); 8.35 br.s (CH); J
3
= 7.2 Hz; J
(
= 1.5 Hz.
H,H
A 20% aqueous solution (11.37 g, 15.44 mmol) of
tetraethylammonium hydroxide was slowly, within 2 min,
added to tris(pentafluoroethyl)trifluoro-phosphoric acid
pentahydrate, H[(C F ) PF ]ꢁ5H O (8.28 g, 15.44 mmol)
H,H
31
P NMR, d, ppm: ꢀ148.0 d, t, m.
3.3.4. 1-Butyl-1-methylpyrrolidinium
tris(pentafluoroethyl)trifluorophosphate,
2
5 3
3
2
by stirring and cooling of the reaction mixture with
+
C H N] [(C F ) PF ]
ꢀ
[
ice–water bath. The reaction mixture was diluted with
9
20
2
5 3
3
3
100 cm of water and stirred additionally 10 min at room
temperature. White precipitate was filtered off and washed
Tris(pentafluoroethyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (214 g, 0.399 mol) was added at
2
5 3
3
2
3
two times with 30 cm of water. After drying on air
room temperature to the stirred solution of 1-butyl-1-
methylpyrrolidinium methylsulfate (100 g, 0.395 mol) in
over the night, a white solid material (8.55 g) was
obtained. The yield of tetraethylammonium tris(penta-
fluoroethyl)trifluorophosphate was 96.3%. Melting point
was 95 8C. After crystallization of this product from the
mixture of methanol–water, the melting point was not
changed.
3
00 cm of water. The mixture was left stirring for 10 min.
3
The bottom phase was separated and washed with water
until pH 6–7. The residue was dried at 13.3 Pa and 80 8C
within 8 h. A liquid material (215.1 g) was obtained. The
yield of 1-butyl-1-methylpyrrolidinium tris(pentafluor-
oethyl)trifluorophosphate was 92.7%.
Analyses, found: C 29.1%, H 3.4%, N 2.5%; calculated
for C H F NP (mol. mass 575.26): C 29.2%, H 3.5%, N
2.4%.
Analyses, found: C 30.6%, H 3.1%, N 2.6%; calculated
for C H F NP (mol. mass 587.28): C 30.7%, H 3.4%, N
1
4 20 18
1
5 20 18
1
9
2
.4%.
F NMR spectrum, d, ppm: ꢀ43.5 d, m (PF); ꢀ79.6 m
1
9
F NMR spectrum, d, ppm: ꢀ43.6 d, m (PF); ꢀ79.7 m
(CF ); ꢀ81.3 m (2CF ); ꢀ86.9 d, m (PF ); ꢀ115.0 d, m
3
3
2
1
1
(
CF ); ꢀ81.4 m (2CF ); ꢀ87.0 d, m (PF ); ꢀ115.0 d, m
(CF ); ꢀ115.7 d, m (CF ); J = 888 Hz; J = 902 Hz;
3
3
2
2
2
P,F
P,F
1
1
2
2
(
2
1CF ); ꢀ115.7 d, m (2CF ); J = 888 Hz; J = 903 Hz;
J
= 86 Hz; J = 98 Hz.
H NMR spectrum, d, ppm: 1.39 t, m (4CH ), 3.48 q
3
2
2
P,F
P,F
P,F P,F
2
= 82 Hz; J = 98 Hz.
1
J
P,F
1
P,F
3
(4CH ); J
H NMR, d, ppm: 0.96 t (CH ); 1.37 m (CH ); 1.71 m
3
= 7.3 Hz.
H,H
2
2
3
1
(
CH ); 2.14 m (2CH ); 2.92 s (CH ); 3.20 m (CH ); 3.38 m
3
P NMR, d, ppm: ꢀ148.6 d, t, m.
2
2
2
3
2CH ); J
(
= 7.4 Hz.
H,H
2
31
P NMR, d, ppm: ꢀ148.1 d, t, m.
3.3.7. Tetrabutylammonium
tris(pentafluoroethyl)trifluorophosphate,
ꢀ
[(C H ) N] [(C F ) PF ]
4 9 4 2 5 3 3
+
3
.3.5. 1-Butyl-4-methylpyridinium
tris(pentafluoroethyl)trifluorophosphate,
Tris(pentafluoroethyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (407.5 g, 0.76 mol) was slowly,
+
ꢀ
C H N] [(C F ) PF ]
10 16 2 5 3 3
[
2
5 3
3
2
Tris(pentafluoroethyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (537 g, 1.002 mol) was added at
within 1 h, added by stirring and cooling of the reaction
mixture with ice–water bath to of 40% aqueous (493.2 g,
0.76 mol) solution of tetrabutylammonium hydroxide,
2
5 3
3
2
room temperature to the stirred solution of 1-butyl-4-

N.V. Ignat’ev et al. / Journal of Fluorine Chemistry 126 (2005) 1150–1159
1157
diluted with 2 l of water. White precipitate was filtered off
3
and washed two times with 300 cm of water. After drying at
Analyses, found: C 25.6%, H 2.9%, N 4.6%; calculated
for C H F N PS (mol. mass 606.30): C 25.8%, H 2.8%,
N 4.6%.
1
3 17 18 2
1
3.3 Pa and 50 8C within 8 h a solid material (504.6 g) was
1
9
obtained. The yield of tetrabutylammonium tris(pentafluor-
oethyl)-trifluorophosphate was 96.6%. Melting point was
F NMR spectrum, d, ppm: ꢀ43.6 d, m (PF); ꢀ79.6 m
(CF ); ꢀ81.3 m (2CF ); ꢀ86.9 d, m (PF ); ꢀ114.9 d, m
3
3
2
1
1
6
2 8C.
Analyses, found: C 38.3%, H 5.1%, N 1.8%; calculated
for C H F NP (mol. mass 687.48): C 38.4%, H 5.3%, N
(1CF ); ꢀ115.5 d, m (2CF ); J = 890 Hz; J = 904 Hz;
2
2
P,F
P,F
2
2
J
= 86 Hz; J = 97 Hz.
H NMR spectrum, d, ppm: 1.34 t (CH ); 3.03 q (CH );
P,F P,F
1
2
2
36 18
3
2
3
3.25 s (4CH ); J
2
.0%.
1
= 7.4 Hz.
H,H
3
9
31
1
F NMR spectrum, d, ppm: ꢀ43.6 d, m (PF); ꢀ79.6 m
P NMR, d, ppm: ꢀ148.6 d, t, m; JP,F = 890 Hz;
JP,F = 902 Hz.
1
(
CF ); ꢀ81.3 m (2CF ); ꢀ87.0 d, m (PF ); ꢀ115.0 d, m
3
3
2
1
1
(
2
1CF ); ꢀ115.6 d, m (2CF ); J = 889 Hz; J = 902 Hz;
2
2
P,F
P,F
2
= 83 Hz; J = 97 Hz.
J
3.3.10. N-i-Propyl-N-pentamethylguanidinium
tris(pentafluoroethyl)trifluorophosphate,
P,F
1
P,F
H NMR spectrum, d, ppm: 1.00 t (4CH ), 1.38 q, t
3
3
4CH ); 1.63 m (4CH ); 3.11 m (4CH ); J
+
[(CH ) N] C[N(CH )(i-C H )] [(C F ) PF ]
ꢀ
3
(
3
= 7.3 Hz;
2
2
2
H,H
3 2
2
3
3
7
2
5 3
J
= 7.4 Hz.
H,H
1
P NMR, d, ppm: ꢀ148.6 d, t, m.
Tris(pentafluoroethyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (11.4 g, 0.021 mol) was added
3
2
5 3
3
2
0
0
00
at room temperature to the stirred solution of N,N,N ,N ,N -
0
0
3.3.8. O-ethyl-tetramethyluronium
tris(pentafluoroethyl)trifluorophosphate,
pentamethyl-N -i-propyl-guanidinium triflate [25] (6.8 g,
3
0.021 mol) in 100 cm of water. White precipitate was
+
(CH ) N] C(OC H )] [(C F ) PF ]
ꢀ
3
filtered off and washed three times with 30 cm of water.
[
3
2
2
2
5
2
5 3
3
Tris(pentafluoroethyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (36.0 g, 0.067 mol) was added
After drying at 7.0 Pa and 60 8C within 3 h a solid material
(12.3 g) was obtained. The yield of N,N,N ,N ,N -penta-
0 0 00
2
5 3
3
2
0
0
at room temperature to the stirred solution of O-ethyl-
tetramethyluronium triflate [26] (18.8 g, 0.064 mol) in
methyl-N -i-propyl-guanidinium tris(pentafluoroethyl)tri-
fluorophosphate was 94.0%. Melting point was 68–69 8C.
Analyses, found: C 29.3%, H 3.5%, N 6.8%; calculated
for C H F N P (mol. mass 617.30): C 29.2%, H 3.6%, N
3
0 cm of water. White precipitate was filtered off and
7
washed four times with 30 cm of water. After drying at
3
1
5 22 18 3
7
.0 Pa and 60 8C within 3 h a solid material (36.7 g) was
6.8%.
9
1
obtained. The yield of O-ethyl-tetramethyluronium tris(-
pentafluoroethyl)trifluorophosphate was 97.3%. Melting
point was 32–34 8C.
Analyses, found: C 26.5%, H 3.0%, N 4.8%; calculated
for C H F N OP (mol. mass 590.24): C 26.5%, H 2.9%,
F NMR spectrum, d, ppm: ꢀ43.5 d, m (PF); ꢀ79.6 m
(CF ); ꢀ81.2 m (2CF ); ꢀ86.8 d, m (PF ); ꢀ114.9 d, m
3
3
2
1
1
(1CF ); ꢀ115.5 d, m (2CF ); J = 889 Hz; J = 901 Hz;
2
2
P,F
P,F
2
2
J
= 87 Hz; J = 97 Hz.
P,F P,F
1
H NMR spectrum, d, ppm: 1.22 br.s (CH ); 1.33 br.s
3
13
17 18
2
N 4.8%.
1
(CH ); 2.77 s (CH ); 2.91 s (4CH ); 3.74 hep (CH);
3
3
3
9
3
F NMR spectrum, d, ppm: ꢀ43.5 d, m (PF); ꢀ79.5 m
J
= 6.6 Hz.
H,H
3
1
1
(
CF ); ꢀ81.2 m (2CF ); ꢀ86.9 d, m (PF ); ꢀ114.9 d, m
P NMR, d, ppm: ꢀ148.6 d, t, m; JP,F = 890 Hz;
3
3
2
1
1
1
(
2
1CF ); ꢀ115.5 d, m (2CF ); J = 889 Hz; J = 900 Hz;
JP,F = 902 Hz.
2
2
P,F
P,F
2
J
= 84 Hz; J = 98 Hz.
P,F
P,F
1
H NMR spectrum, d, ppm: 1.42 t (CH ); 3.05 s (4CH ),
3
3.3.11. 1,3-Dimethyl-2-diethylaminoimidazolidinium
3
3
.37 q (CH ); J
4
= 7.0 Hz.
tris(pentafluoroethyl)trifluorophosphate,
2
H,H
3
1
1
+
ꢀ
[C H N ] [(C F ) PF ]
3
P NMR, d, ppm: ꢀ148.6 d, t, m; JP,F = 888 Hz;
JP,F = 902 Hz.
9
20
3
2
5 3
1
Tris(pentafluoroethyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (41.0 g, 0.077 mol) was added
2
5 3
3
2
3.3.9. S-ethyl-tetramethylthiouronium
tris(pentafluoroethyl)trifluorophosphate,
at room temperature to the stirred solution of 1,3-dimethyl-
2-diethylaminoimidazolidinium chloride [25] (15.0 g,
+
(CH ) N] C(SC H )] [(C F ) PF ]
ꢀ
3
0.073 mol) in 200 cm of water. White precipitate was
[
3
2
2
2
5
2
5 3
3
3
filtered off and washed three times with 50 cm of water.
Tris(pentafluoroethyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (31.0 g, 0.058 mol) was added
After drying at 7.0 Pa and 60 8C within 3 h a solid material
(43.9 g) was obtained. The yield of 1,3-dimethyl-2-
diethylaminoimidazolidinium tris(pentafluoroethyl)trifluor-
ophosphate was 97.8%. Melting point was 36–37 8C.
Analyses, found: C 29.2%, H 2.9%, N 7.0%; calculated
for C H F N P (mol. mass 615.29): C 29.3%, H 3.3%, N
2
5 3
3
2
at room temperature to the stirred solution of S-ethyl-
tetramethylthiouronium triflate [27] (17.1 g, 0.055 mol) in
3
0 cm of water. The bottom phase was separated
7
and washed four times with 30 cm of water. After
3
drying at 7.0 Pa and 60 8C within 3 h a liquid material
1
5 20 18 3
(
30.0 g) was obtained. The yield of S-ethyl-tetramethyl-
thiouronium tris(pentafluoroethyl)trifluorophosphate was
9.8%.
6.8%.
1
9
F NMR spectrum, d, ppm: ꢀ43.5 d, m (PF); ꢀ79.6 m
8
(CF ); ꢀ81.3 m (2CF ); ꢀ86.9 d, m (PF ); ꢀ114.9 d, m
3
3
2

1158
N.V. Ignat’ev et al. / Journal of Fluorine Chemistry 126 (2005) 1150–1159
1
1
1
4
1
2
2
(
1CF ); ꢀ115.5 d, m (2CF ); J = 888 Hz; J = 900 Hz;
JP,F = 905 Hz; J = 935 Hz; J = 83 Hz; J = 97 Hz;
P,F P,F P,F
2
2
P,F
P,F
2
2
= 85 Hz; J = 98 Hz.
5
J
J
= 10 Hz; J = 4 Hz.
F,F F,F
P,F
P,F
1
1
H NMR spectrum, d, ppm: 1.20 t (2CH ); 2.94 s (2CH );
3
H NMR, d, ppm: 0.92 t (CH ); 1.34 m (2CH ); 1.86 t, t
3 2
3
3
.34 q (2CH ); 3.68 s (2CH ); J
3
= 7.1 Hz.
1
(CH ); 3.84 s (CH ); 4.13 t (CH ); 7.32 d, d (CH); 7.36 d, d
2 3 2
2
2
H,H
31
3
(CH); 8.41 br.s (CH); JH,H = 7.1 Hz; JH,H = 7.4 Hz;
3
P NMR, d, ppm: ꢀ148.6 d, t, m; JP,F = 890 Hz;
1
3
JP,F = 902 Hz.
J
= 1.8 Hz.
P NMR, d, ppm: ꢀ141.9 d, t, m.
H,H
3
1
3.3.12. 1-Hexyl-3-methylimidazolium
tris(heptafluoropropyl)trifluorophosphate,
3.3.14. Tetraethylammonium
+
C H N ] [(C F ) PF ]
ꢀ
[
bis(nonafluorobutyl)tetrafluorophosphate,
1
0
19
2
3
7 3
3
+
ꢀ
[(C H ) N] [(C F ) PF ]
2 5 4 4 9 2 4
Tris(heptafluoropropyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (27.0 g, 39.4 mmol) was added
A 85.9%-ige (wt.%) aqueous bis(nonafluoro-n-butyl)te-
trafluorophosphoric acid (3.95 g) was slowly, within 3 min,
added to aqueous tetraethylammonium hydroxide (54.58 g;
3
7 3
3
2
at room temperature to the stirred solution of 1-hexyl-3-
3
methylimidazolium chloride (7.97 g, 39.3 mmol) in 20 cm
of water. The mixture was left stirring for 10 min. The
+
ꢀ
prepared from 4.58 g of 20%-ige aqueous (C H ) N OH
2 5 4
3
bottom phase was separated and washed five times with
5
and 50 cm of water), by stirring and cooling of the reaction
mixture with ice–water bath. The reaction mixture was
stirred additionally 10 min at room temperature. White
precipitate was filtered off and washed two times with
3
0 cm of water until the test for chloride with silver nitrate
was negative. The residue was dried at 13.3 Pa and 50 8C
within 6 h. A liquid material (26.4 g) was obtained. The
yield of 1-hexyl-3-methylimidazolium tris(heptafluoropro-
pyl)trifluorophosphate was 88.1%.
3
10 cm of water. After drying on air over the night, a white
solid material (3.05 g) was obtained. The yield of
Analyses, found: C 30.2%, H 2.1%, N 4.1%; calculated
for C H F N P (mol. mass 762.31): C 29.9%, H 2.5%, N
tetraethylammonium
bis(nonafluoro-n-butyl)tetrafluoro-
phosphate is 72.6%. Melting point was 148–149 8C.
Analyses, found: C 38.5%, N 2.0%; calculated for
C H F NP (mol. mass 687.48): C 38.4%, N 2.0%.
1
9 19 24 2
3
.7%.
1
9
F NMR spectrum, d, ppm: ꢀ43.8 d, m (PF); ꢀ79.6 t
2
2
1
36 18
9
(
(
(
2CF ); ꢀ80.0 t (CF ); ꢀ84.7 d, m (PF ); ꢀ111.8 d, m
F NMR spectrum, d, ppm: ꢀ70.3 d, m (PF ); ꢀ80.7 m
3
3
2
4
1CF ); ꢀ112.9 d, m (2CF ); ꢀ122.8 m (1CF ); ꢀ124.6 m
(2CF ); ꢀ116.0 d, m (2CF ); 122.4 m (2CF ); 124.4 t
2 P,F P,F F,F
2
2
2
3
2
2
1
1
2
1
(2CF ); J = 931 Hz; J = 100 Hz; J = 15.3 Hz.
2
4
2CF );
J
= 101 Hz; J = 12 Hz.
= 897 Hz;
J
= 930 Hz;
J
= 82 Hz;
2
P,F
P,F
P,F
2
J
4
1
H NMR spectrum, d, ppm: 1.20 t, m (4CH ), 3.15 q
3
P,F
1
F,F
3
(4CH ); J
H NMR, d, ppm: 0.88 m (CH ); 1.30 m (3CH ); 1.81 m
3
= 7.1 Hz.
H,H
2
2
3
1
1
(
CH ); 3.80 s (CH ); 4.09 t (CH ); 7.30 m (CH); 7.34 m
2
P NMR, d, ppm: ꢀ148.2 quin, quin; J = 932 Hz;
P,F
2
3
3
CH); 8.35 br.s (CH); J
2
(
= 7.3 Hz.
JP,F = 100 Hz.
H,H
31
P NMR, d, ppm: ꢀ142.4 d, t, m.
Acknowledgements
3
.3.13. 1-Pentyl-3-methylimidazolium
tris(nonafluorobutyl)trifluorophosphate,
Authors thank Dr. O. Korbut and Mrs. A. Amann for the
measurements of physico-chemical properties of ionic
liquids.
+
ꢀ
C H N ] [(C F ) PF ]
9 17 2 4 9 3 3
[
Tris(nonafluorobutyl)trifluorophosphoric acid pentahy-
drate, H[(C F ) PF ]ꢁ5H O (133.2 g, 159.3 mmol) was
4
9 3
3
2
added within 5 min at room temperature to the stirred
solution of 1-pentyl-3-methylimidazolium chloride (30.0 g,
References
3
59.0 mmol) in 100 cm of water. The mixture was left
1
stirring for 10 min. The bottom phase was separated and
[
1] R.P. Swatloski, J.D. Holbrey, R.D. Rogers, Green Chem. 5 (4) (2003)
61–363.
[2] A.V. Plakhotnyk, L. Ernst, R. Schmutzler, J. Fluorine Chem. 126
2005) 27–32.
3] M. Ponikvar, B. Zemva, J.F. Liebman, J. Fluorine Chem. 123 (2003)
17–220.
3
washed 5 times with 50 cm of water until the test for
3
chloride with silver nitrate was negative. The residue was
dried 13.3 Pa and50 8C within5 h. A liquid material (128.4) g
was obtained. The yield of 1-pentyl-3-methylimidazolium
tris(nonafluorobutyl)trifluoro-phosphate was 89.9%.
(
[
2
[
4] S.S. Chan, C.J. Willis, Can. J. Chem. 46 (1968) 1237–1248.
5] J. Jander, D. B o¨ rner, U. Engelhardt, Liebigs Ann. Chem. 726 (1969)
19–24.
Analyses, found: C 28.4%, H 2.1%, N 3.7%; calculated
for C H F N P (mol. mass 898.31): C 28.1%, H 1.9%, N
[
1
9 19 24 2
[
6] E.O. Bishop, P.R. Carey, J.F. Nixon, J.R. Swain, J. Chem. Soc. A
(1970) 1074–1076.
3
.1%.
19
F NMR spectrum, d, ppm: ꢀ44.0 d, m (PF); ꢀ80.7 t, t
[
7] N.V. Pavlenko, L.M. Yagupolskii, Zh. Obshch. Khim. 59 (1989) 528–
(
(
(
1CF ); ꢀ80.8 t, t (2CF ); ꢀ84.5 d, m (PF ); ꢀ111.4 d, m
3
3
2
5
34.
1CF ); ꢀ112.5 d, m (2CF ); ꢀ119.2 m (1CF ); ꢀ121.2 m
2
2
2
[8] F.W. Bennet, H.J. Emeleus, R.N. Haszeldine, J. Chem. Soc. (1953)
2CF ); ꢀ124.7 t,
m
(2CF ); ꢀ125.2
m
(CF );
2
1565–1571.
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