Fluorous imidazolium room-temperature ionic liquids based on HFPO trimer

Article abstract of DOI:10.1016/j.jfluchem.2009.04.006

Imidazole substituted with a polyfluoropolyether chain based on HFPO trimer combined with various polyfluoroalkyl triflates produced novel highly fluorous ionic liquids. Their metathesis with four different anions generated a final set of 20 fluorous ionic liquids of waxy or viscous liquid character, which are all soluble in perfluorinated solvents. Two model reactions using selected ionic liquid, the opening of a THF ring with benzoyl chloride under Friedel-Crafts conditions and substitution of benzyl chloride with sodium azide, led to decomposition of the ionic liquid. However, Diels-Alder reaction of 2,3-dimethylbuta-1,3-diene with dimethyl acetylenedicarboxylate in a fluorous ionic liquid resulted in a reasonable enhancing of the reaction rate with smooth recycle of the fluorous solvent. The fluorophilicity of these fluorous ionic liquids ranges from more than 10 for water, toluene or dichloromethane to less than 0.2 for acetonitrile or methanol.

Full text of DOI:10.1016/j.jfluchem.2009.04.006

Journal of Fluorine Chemistry 130 (2009) 629–639
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Fluorous imidazolium room-temperature ionic liquids based on HFPO trimer
a
a
a
b
ˇ
´
´ ˇ
´
´
´ˇ
´
Ondrej Kysilka , Marketa Rybackova , Martin Skalicky , Magdalena Kvıcalova ,
c
a,
*
ˇ
´ˇ
Josef Cvacka , Jaroslav Kvıcala
a
´
Department of Organic Chemistry, Institute of Chemical Technology in Prague, Technicka 5, 166 28 Prague 6, Czech Republic
b
c
ˇ
ˇ
ˇ
ˇ
Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Husinec-Rez 1001, 250 68 Rez, Czech Republic
´
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, v.v.i., Flemingovo nam. 2, 166 10 Prague 6, Czech Republic
A R T I C L E I N F O
A B S T R A C T
Article history:
Imidazole substituted with a polyfluoropolyether chain based on HFPO trimer combined with various
polyfluoroalkyl triflates produced novel highly fluorous ionic liquids. Their metathesis with four
different anions generated a final set of 20 fluorous ionic liquids of waxy or viscous liquid character,
which are all soluble in perfluorinated solvents. Two model reactions using selected ionic liquid, the
opening of a THF ring with benzoyl chloride under Friedel–Crafts conditions and substitution of benzyl
chloride with sodium azide, led to decomposition of the ionic liquid. However, Diels–Alder reaction of
2,3-dimethylbuta-1,3-diene with dimethyl acetylenedicarboxylate in a fluorous ionic liquid resulted in a
reasonable enhancing of the reaction rate with smooth recycle of the fluorous solvent. The fluorophilicity
of these fluorous ionic liquids ranges from more than 10 for water, toluene or dichloromethane to less
than 0.2 for acetonitrile or methanol.
Received 16 March 2009
Received in revised form 15 April 2009
Accepted 16 April 2009
Available online 24 April 2009
Keywords:
Ionic liquid
RTIL
Fluorous
Fluorophilic
Imidazolium salt
Fluoropolyether
Diels–Alder reaction
ß 2009 Elsevier B.V. All rights reserved.
1. Introduction
[14,15]. Recently, a new type of highly fluorinated ionic liquids and
its electrochemical applications have been reported but no details
Ionic liquids are a class of organic compounds which displays
two characteristic features: first, they are composed only of ions,
and second, they are liquids below 100 8C. If the ionic liquids are
liquid at room temperature, they are called room-temperature
ionic liquids (RTILs). Due to their unique properties they found
applications in many areas of chemistry, e.g. as solvents for
synthesis and catalysis, biocatalysis, electrochemistry, as thermal
fluids, in liquid–liquid extractions, etc. Their synthesis, properties
and applications have been thoroughly reviewed [1–9]. Among
numerous types of ionic liquids, 1,3-disubstituted imidazolium
salts attract most attention mainly due to low price, easy synthesis
and low crystallinity [1–4].
Various ionic liquids containing long perfluorinated chain have
been reported based on various types of heterocyclic cationic core,
e.g. pyridinium, pyrimidinium, triazolium, pyrrolidium or other
ring type [10,11]. An alternative approach employs polyfluor-
oalkylated ammonium salts [10]. Also, several types of ionic liquids
bearing polyfluoroalkylated anions have been synthesized and
applied for recycling of polyfluoroalkylated homogeneous cata-
lysts [12,13] or as solvents for enzymatic or catalytic reactions
were given about its synthesis and fluorous properties [16].
Nevertheless, in analogy to non-fluorinated ionic liquids most
attention has been devoted to polyfluoroalkylated imidazolium
salts, which were studied as surfactants for ionic liquids [17],
solvents for metal ion extraction [18] or Diels–Alder reactions [19],
or ionic liquid/CO2 biphase systems for homogeneous catalysis
[20,21]. However, all of the published polyfluoroalkylated imida-
zolium-based ionic liquids do not have a sufficient fluorine content
to be soluble in perfluorinated solvents. The sole example of
(polyfluoroalkylated) imidazolium salt was synthesized but it is a
high temperature-melting solid [22].
In the course of the last few years we oriented our research was
oriented towards the study of cyclopentadiene-based fluorous
ligands [23–26] but found out that for multiple-polyfluoroalkylated
cyclopentadienes their complexation ability ceases [27]. Looking for
other fluorous ligands substituting commonly used phosphines we
started to investigate the area of fluorous imidazolylidene carbenes
(NHC ligands). We recently submitted a paper regarding the
synthesis and properties of a series of bis(polyfluoroalkylated)
imidazolium salts [28], and this together with our previous
experience in the synthesis of chloropolyfluoropolyethers [29]
initiated our interest in the preparation of imidazolium salts in
which the polyfluoroalkyl group would be substituted by a
perfluoropolyether chain. In this paper we report the synthesis of
* Corresponding author.
ˇ
E-mail address: kvicalaj@vscht.cz (J. Kvı´cala).
0022-1139/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2009.04.006

630
O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
a novel class of highly fluorinated ionic liquids (including several
metathetic reactions), which have either a waxy or a viscous oil
character, with a reasonable solubility in perfluorinated solvents.
2. Results and discussion
2.1. Synthesis
Scheme 1.
In contrast to the compounds bearing long perfluorinated chains
which tend to crystallize starting with C6F13 chains, perfluorinated
polyethers are liquids over a wide range of molecular weights. For
the incorporation of the perfluoropolyether segment in the
imidazole ring, the simple transformation to the amide was not
chosen due to the high sensitivity of the polyfluorinated acyl group
to hydrolysis [30]. We also avoided the simple addition of imidazole
on commercially available, and industrially extensively used
perfluorovinylether, because the CF2-CHF group formed by this
reaction is highly prone to HF elimination [31,32]. Following our
positive experience with the modification of imidazole ring by
triflates of polyfluorinated alcohols [28], we employed for the
synthesis triflate 2a of a commercially available alcohol based on
hexafluoropropene-1,2-oxide (HFPO) trimer. This novel fluorinated
building block displayed limited reactivity but afforded the key
intermediate, fluorinated imidazole 1 to be obtained, in an
acceptable yield [33] (Scheme 1).
was formed, which could be isolated as a white sublimate from the
crude reaction mixture by prolonged heating in vacuum. Its
structure corresponds to the triflate salt 5 of polyfluoroalkoxylated
imidazole 1. As its fluorophilicity is remarkably lower than that of
the disubstituted imidazolium salts 3, it is virtually insoluble in
perfluorinated solvents. Moreover, its solubility in common
dipolar aprotic solvents such as acetone or acetonitrile is also
significantly lower. It could hence be removed from the crude
reaction mixtures as an insoluble solid by trituration with dipolar
aprotic or perfluorinated solvents. The side-product 5 is probably
formed by the thiophilic attack of fluoroimidazole 1 at the sulfur
atom of the triflates 2, a side-reaction which is characteristic for
triflates of polyfluorinated alcohols with methylene spacer [34],
followed by the hydrolysis of the intermediary imidazolide of triflic
acid.
In a preliminary experiment, we found that polyfluoroalk-
oxylated imidazole 1 can be reacted with polyfluoroalkylated
triflate 2b to produce the corresponding fluorinated imidazolium
salt 3b, which have a waxy consistence [33] in contrast to the
crystalline bis(polyfluoroalkylated) imidazolium salts with high
melting points [28]. To understand better the behaviour of this
novel class of compounds, we proceeded to react fluoroimidazole 1
with other three fluoroalkylated triflates 2a, 2c and 2d and
obtained the corresponding imidazolium salts 3a, 3c and 3d in
good yields (Scheme 2). Attempts to substitute the triflate 3c with
analogous commercially available, but less reactive iodide 4,
resulted even on prolonged heating to reflux in only minimal
conversion to the target imidazolium iodide. While imidazolium
salts 3b, 3c bearing long perfluorinated chain have waxy
consistence, imidazolium salts 3a and 3d are highly viscous oils
and hence represent a first example of fluorous RTIL’s (room-
temperature ionic liquids).
2.2. Metathesis of polyfluoroalkylated imidazolium triflates 3
To improve the properties of imidazolium-based ionic liquids,
namely, decrease the melting point, metathetic reactions with
appropriate non-nucleophilic fluorinated counteranions such as
hexafluorophosphate, tetrafluoroborate or bis(trifluoromethane-
sulfonyl)amide anion are a frequently employed procedure. On the
other hand, for some experiments ionic liquids bearing a reactive
iodide anion are required. We therefore performed metatheses of
the four synthesized bis(polyfluoroalkylated) imidazolium triflates
3a–3d with the four above mentioned anions. For the three
fluorinated anions, the simple mixing with 5- to 20-fold excess of
the corresponding ammonium or lithium salt in aqueous acetone
was used, while for the iodide anion stirring with sodium iodide in
anhydrous acetone (Finkelstein conditions) was preferred (Scheme
3). The completeness of the metathesis was confirmed by the
absence of the triflate signal in 19F NMR spectra. The corresponding
imidazolium salts 6–9 were obtained in good to excellent yields
(Table 1).
Detailed inspection of the NMR spectra disclosed that in some
experiments (especially in the case of the preparation of
bis(polyfluoroalkoxylated) imidazolium salt 3a) a side product
Scheme 2.

O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
631
Scheme 3.
2.3. Model reactions in fluorous ionic liquids
product, 4-iodobutyl benzoate, were detected in the crude reaction
mixture by NMR. However, the ionic liquid 9a was completely
decomposed into the complex mixture of products.
Many reactions proceed with better yields or with better
separation of products in ionic liquids. Among them, we chose
three characteristic reactions and tested whether they can be
performed in our fluorous ionic liquids. The respective reactions
were the nucleophilic substitution of benzyl chloride with sodium
azide [35], opening of the tetrahydrofuran ring with benzoyl
chloride under Friedel–Crafts conditions [36], and the Diels–Alder
reaction of 2,3-dimethylbuta-1,3-diene (DMB) with dimethyl
acetylenedicarboxylate (DMAD) [37].
Substitution of benzyl chloride with sodium azide was
performed in three parallel experiments for 100 h at 40 8C, in
the fluorous ionic liquid 3a, in DMF, and without solvent. Whereas
no reaction was detected without solvent, more than 99%
conversion was achieved in DMF. On the other hand, we observed
limited conversion (about 22%) in the ionic liquid 3a, thus this
solvent being inferior to DMF. Moreover, significant decomposition
(about 40% according to NMR) of the ionic liquid into a complex
mixture of products occurred, probably due to attack of the
imidazolium ring by the azide anion.
The Diels–Alder reaction was again performed in three parallel
experiments for 2 h at 80 8C, in the fluorous ionic liquid 3a, in THF
and without solvent. The conversion of the starting compounds
into the final product was estimated from the 1H NMR spectrum of
the crude product. Thus, the reaction without solvent provided a
61% conversion to the final product while the reaction in THF
reached a 65% conversion. However, the reaction was nearly
completed (> 99% conversion) in the fluorous ionic liquid,
although even at 80 8C the reaction mixture was not looking
homogeneous. After cooling, the product was separated from the
fluorous ionic liquid as an upper layer containing less then 1% of
the fluorous ionic liquid. The bottom layer, consisting exclusively
of the ionic liquid 3a, was reused in a replicate experiment, under
identical conditions, and the same result, i.e. complete conversion
into the final product, that was easily separated with no
decomposition of the ionic liquid 3a.
2.4. Solubility and fluorous partition coefficients of
For the second reaction, an ionic liquid bearing the iodide anion
is required and we hence employed the fluorous ionic liquid 9a.
According to the standard procedure [36], imidazolium iodide 9a
was stirred first with aluminum trichloride at room temperature
for 5 h, followed by the addition of THF and benzoyl chloride. After
12 h of continuous stirring at room temperature, only traces of the
bis(polyfluoroalkylated) imidazolium salts 3
Fluorous imidazolium salts 3 and 6–9 display unique solubility
patterns. They are highly soluble in polar protic or aprotic solvents
such as methanol, acetone, acetonitrile and diethyl ether, and
moderately soluble in non-polar fluorinated compounds such as
1,2-dibromotetrafluoroethane (FC114B2) or perfluoro(methylcy-
clohexane). On the other hand, they are virtually insoluble both in
non-fluorinated solvents of lower polarity (toluene, dichloro-
methane) and in water. Interestingly, their solubility in perfluori-
nated solvents is at least an order of magnitude higher than that of
bis(polyfluoroalkylated) imidazolium salts with two perfluori-
nated chains and reaches more than 50 mg/ml. We measured the
fluorous partition coefficients Pi(FBS) [38] of fluorous ionic liquid
Table 1
Results of metatheses of imidazolium salts 3a–3d.
Label
R1
R2
Anion
Yield (%)
6a
6b
6c
6d
7a
7b
7c
7d
8a
8b
8c
8d
9a
9b
9c
9d
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C2F5[CF2OCF(CF3)]2CH2
C6F13CH2
[PF6]À
[PF6]À
[PF6]À
[PF6]À
[BF4]À
[BF4]À
[BF4]À
[BF4]À
[NTf2]À
[NTf2]À
[NTf2]À
[NTf2]À
IÀ
91
96
98
93
90
87
97
87
77
94
93
85
87
97
79
87
C6F13CH2CH2
CF3CH2
C2F5[CF2OCF(CF3)]2CH2
C6F13CH2
Table 2
Fluorous partition coefficients of imidazolium salt 3c between
perfluoro(methylcyclohexane) and various solvents at 25 8C.
C6F13CH2CH2
CF3CH2
C2F5[CF2OCF(CF3)]2CH2
C6F13CH2
Entry
Solvent
Pi (FBS)
C6F13CH2CH2
CF3CH2
1
2
3
4
5
6
Toluene
49.1
10.7
2.05
0.047
0.11
36.5
Dichloromethane
Tetrahydrofuran
Acetonitrile
Methanol
C2F5[CF2OCF(CF3)]2CH2
C6F13CH2
IÀ
C6F13CH2CH2
CF3CH2
IÀ
IÀ
Water

632
O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
Table 3
(ESI, APCI) were measured with a LCQ Fleet (Finnigan) instrument,
HRMS spectra (ESI, APCI, FAB) with a LTQ Orbitrap XL (Thermo
Fisher Scientific) or ZAB-EQ (VG Analytical) instruments.
Fluorous partition coefficients of imidazolium salts 3a–3d in perfluoro(methylcy-
clohexane)/toluene mixture at 25 8C and their fluorophilicities.
Entry
Compound
Pi (FBS)
fi
All reactions were performed in dry inert atmosphere (Ar) in
an oven-dried flasks. 1-[2,4,4,5,7,7,8,8,9,9,9-Undecafluoro-2,5-
1
2
3
4
3a
3b
3c
3d
88.2
94.1
49.1
11.5
4.48
4.54
3.89
2.45
bis(trifluoromethyl)-3,6-dioxanonyl]imidazole (1,
RFOCH2Im),
2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl trifluoromethanesulfonate (2a, RFOCH2OTf) and 1-
( 2 , 2 , 3 , 3 , 4 , 4 , 5 , 5 , 6 , 6 , 7 , 7 , 7 - t r i d e c a fl u o r o h e p t y l ) - 3 -
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium trifluoromethanesulfonate (3b, RFO-
CH2Im+CH2C6F13-n ÀOTf) were prepared according to [33] from
perfluoro(2,5-dimethyl-3,6-dioxanonanoyl) fluoride (HFPO trimer,
CF3(CF2)2O-CF(CF3)CF2O-CF(CF3)COF)). 3,3,4,4,5,5,6,6,7,7,8,8,8-Tri-
decafluorooctyl trifluormethanesulfonate (2c, n-C6F13(CH2)2OTf)
was synthesized according to [39] and 2,2,2-trifluoroethyl
trifluoromethanesulfonate (2d, CF3CH2OTf) according to [40] from
the respective fluoroalcohols and trifluoromethanesulfonic anhy-
dride. 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluoroctan-1-ol
(1H,1H,2H,2H-perfluorooctan-1-ol, n-C6F13(CH2)2OH) and
3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-iodooctane (4,
1H,1H,2H,2H-perfluorooctyl iodide, n-C6F13(CH2)2I) were kindly
donated by Atochem. Perfluoro(2,5-dimethyl-3,6-dioxanonanoyl)
fluoride (HFPO trimer, CF3(CF2)2O-CF(CF3)CF2O-CF(CF3)COF, RFO-
COF), 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptan-1-ol (1H,1H-
perfluoroheptan-1-ol, n–C6F13CH2OH) and trifluoromethanesulfo-
nic anhydride (triflic anhydride) were purchased from Apollo
Scientific, imidazole from Fluka, 2,2,2-trifluoroethanol, ammo-
nium hexafluorophosphate, ammonium tetrafluoroborate and
lithium-bis(trifluoromethylsulfonyl)imide from Sigma-Aldrich.
Acetone and acetonitrile were distilled over P2O5, dichloro-
methane and DMF over CaH2, pyridine over KOH, THF over
sodium benzophenone ketyl and toluene over Na. 1,2-Dibromo-
1,1,2,2-tetrafluoroethane (FC114B2, BrCF2CF2Br) was distilled and
dried over molecular sieves.
3c between perfluoro(methylcyclohexane) and various solvents at
25 8C, which correspond to the above mentioned solubility pattern
(Table 2). Thus, fluorous partition coefficients are larger than 10 for
water, toluene and dichloromethane (Entries 6, 1 and 2) and on the
other hand lower than 0.2 for methanol and acetonitrile (Entries 4
and 5). Fluorous ionic liquids 3 and 6–9 can thus be characterized
as lipophobic and hydrophobic amphiphiles. We could not
measure the fluorous partition coefficients for pentane, hexane
and diethylether as they mix with perfluoro(methylcyclohexane).
To clarify the role of various fluorinated side-chains, we also
compared fluorophilicities (natural logarithms of fluorous parti-
tion coefficients for perfluoro(methylcyclohexane)/toluene mix-
tures [38]) of the imidazolium salts 3a–3d (Table 3). From these
results it can be seen that enlarging the non-fluorinated spacer
lowers a little the fluorophilicity (Entries 2 and 3), substitution of
the perfluorohexyl chain for the polyether chain with eight
fluorinated carbons has negligible effect (Entries 1 and 2) and
substitution of perfluorohexyl group by trifluoromethyl signifi-
cantly diminishes the fluorophilicity (as well as the solubility in the
perfluorinated solvent to about 20 mg/ml) (Entries 2 and 4).
3. Conclusions
Using a novel polyfluorinated building block based on HFPO
trimer, we synthesized a series of 20 fluorous ionic liquids
containing an imidazolium core, which have either a waxy or
viscous liquid character. These liquids exhibit unique solubility
and fluorophilicity patterns with high solubility in perfluorinated
and dipolar aprotic solvents but negligible in toluene and water.
4.1. 1,3-Bis[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-
bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium
trifluoromethanesulfonate (3a)
These ionic liquids are decomposed by reactive nucleophiles
limiting thus their synthetic value as solvents, however, they
accelerate Diels–Alder-type reactions and are easy to separate and
recycle.
A flask was loaded with fluoroalkylimidazole 1 (5.19 g,
9.8 mmol), fluoroalkyl triflate 2a (5.99 g, 9.8 mmol) and toluene
(10 ml). The mixture was heated to 120 8C for 4 days under
continous stirring. After cooling to r.t., toluene was removed using
a rotary vacuum evaporator (50 8C/2 h/2 kPa) and the residue was
heated in vacuo (70 8C/48 h/10 Pa) to obtain the product 3a (8.45 g,
75.6%) as a light yellow highly viscous oil. 1H NMR (299.97 MHz,
4. Experimental
Temperature data were uncorrected. NMR spectra were
recorded with a Varian MercuryPlus spectrometer, 1H NMR
spectra at 299.97 MHz and 13C NMR spectra at 75.43 MHz using
residual deuterated solvent signals as the internal standards, 19F
NMR spectra at 282.22 MHz using CCl3F as the internal standard.
Chemical shifts are given in ppm, coupling constants in Hz.
Anisochronic signals (strongly coupled AB systems) of non-
equivalent fluorine atoms in CF2- groups are marked with lower
case letters (a,b), diastereomer signals with upper case letter (A,B).
In some cases, 19F gCOSY experiments were performed in some
cases to allow full assignment of signals. In the case of the 19F NMR
spectra, signals are given separately for the erythro/threo config-
uration of the polyether chain wherever possible. Mass spectra
acetone-d6)
d 5.66 m, 4H (CH2); 8.19 m, 2H (CH CH); 9.87 m; 1H
(N–CH N). 19F NMR (282.23 MHz, acetone-d6)
d
À77.3 dm, 2F, 2JF-
F = 155 Hz (F3a); À78.4 s, 6F (F9); À79.5 m, 6F (F5); À80.4 dm, 2F,
2JF-F = 140 Hz (F6a); À80.6 dm, 2F, 2JF-F = 140 Hz (F6b); À81.2 m, 6F
(F8); À81.3 m, 6F (F2); À81.6 dm, 6F, JF–F = 155 Hz (F3b); À129.3
2
m, 4F (F7); À134.8 m, 2F (F1); À144.2 m, 2F (F4). 13C NMR
2
(75.44 MHz, acetone-d6)
d
49. 6 d, 2C, JC-F = 20.1 Hz (CH2); 100–
1
126 m, 16C (CF, CF2 and CF3 groups); 120.3 q, 1C, JC-F = 316.8 Hz
(CF3SO2O); 125.9s, 2C (CH CH); 141.2s, (N–CH N). MS (ESI), m/z
(%): 997 [MÀTfOÀ]+, 100; 149 [TfO]À, 100.
During heating under vacuum, 1,26 g (18.9%) of white crystal-
linic sublimate (s.p. 154–156 8C) was obtained, which was
identified as 1-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluor-

O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
633
omethyl)-3,6-dioxanonyl]imidazolium trifluoromethanesulfonate
(5).
(10 ml). The mixture was heated to 110 8C for 7 days under
continuous stirring. Analysis of the crude reaction mixture by 1H
NMR spectroscopy indicated that less then 5% conversion to the
target imidazolium iodide was achieved.
4.4. 1-(2,2,2-Trifluoroethyl)-3-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-
2,5-bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium
trifluoromethanesulfonate (3d)
1H NMR (299.97 MHz, acetone-d6)
d 5.60 m, 2H (CH2); 7.96 m,
1H (CH CH); 8.03 m, 1H (CH CH); 9.45 s, 1H (N–CH N). 19F NMR
(282.23 MHz, acetone-d6)
d
À77.4 m, 1F (F3a); À78.8s, 3F (F9);
À79.5 m, 3F (F5); À80.5 m, 1F (F6a); À80.2 m, 1F (F6b); À81.3 m, 3F
(F8); À81.3 m, 3F (F2); À81.7 m, 3F (F3b); À129.4 m, 2F (F7); À134.8
m (F1); À144.2 m, 1F (F4). MS (ESI), m/z (%): 533 [MÀTfOÀ]+, 100.
13C NMR spectrum could not be recorded due to a low solubility of
salt 5 in common NMR solvents.
A glass ampoule equipped with a magnetic stirrer was loaded
with toluene (20 ml), fluoroalkylimidazole 1 (3.22 g, 6.3 mmol)
and fluoroalkyl triflate 2d (1.53 g, 6.6 mmol), sealed and heated to
100 8C for 6 days while stirring. After cooling, toluene was
removed from the reaction mixture using a rotary vacuum
evaporator (70 8C/12 h/2 kPa). The crude product was triturated
4.2. 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)-3-
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium trifluoromethanesulfonate (3c)
A
flask was loaded with fluoroalkylimidazole
1
(0.45 g,
three times with acetone (5 ml) to remove small amount of the
side product 5 as insoluble solid. By heating in vacuo (80 8C/70 h/
10 Pa), the residual solvent was removed and 3d (3.28 g, 70.8%)
0.90 mmol), fluoroalkyl triflate 2c (0.42 g, 0.90 mmol) and toluene
(10 ml). The mixture was heated to 100 8C for 6 days under
continuous stirring. After cooling to r.t., toluene was removed
using a rotary vacuum evaporator (50 8C/2 h/2 kPa). The residue
was dissolved in FC114B2 (10 ml), washed with deionized water
(3 Â 10 ml) and the organic layer was separated. Removal of the
was obtained as a highly viscous light yellow oil. 1H NMR
3
(299.97 MHz, acetone-d6)
d
5.62 q, 2H, JH-F = 8.7 Hz (CF3-CH2);
5.77 m, 2H (CF–CH2); 8.20 m, 1H (CH CH); 8.22 m, 1H (CH CH);
9.80 s, 1H (N–CH N). 19F NMR (282.23 MHz, acetone-d6)
d
À71.5
solvent using
a
rotary vacuum evaporator (50 8C/2 h/2 kPa)
t, 6F, 3JH-F = 8 Hz (F9); À77.9 dm, 1F, 2JF-F = 150 Hz (F3aB); À78.0 s,
6F (CF3SO2O); À78.2 dm, 1F, 2JF-F = 150 Hz (F3aA); À79.4 q, 3F, 4JF-
F = 5JF-F = 8 Hz (F5A or F5B); À79.5 q, 3F, 4JF-F = 5JF-F = 9 Hz (F5A or
F5B); À80.4 dm, 1F, 2JF-F = 150 Hz (F6); À80.9 dm, 1F, 2JF-F = 140 Hz
(F3bB); À81.0 dm, 1F, 2JF-F = 140 Hz (F3bA); À81.0 t, 3F, 4JF-F = 6 Hz
(F8A or F8B); À81.1 t, 3F, 4JF-F = 6 Hz (F8A or F8B); À81.3 d, 3F, 5JF-
F = 13 Hz (F2A or F2B); À81.3 dm, 3F, 2JF-F = 150 Hz (F6bB); À81.5
followed by heating of the residue in vacuo (70 8C/12 h/10 Pa)
yielded product 3c (0.822 g, 94.5%) as a light brown wax. 1H NMR
(299.97 MHz, acetone-d6)
H = 6.7 Hz (CF2-CH2); 5.04 t, 2H, JH-H = 6.7 Hz (CF2-CH2-CH2);
5.70 d, 2H, 3JH-F = 19.0 Hz (CF–CH2); 8.05 m, 1H, (CH CH); 8.21 m,
1H (CH CH); 9.69s, 1H (N–CH N). 19F NMR (282.23 MHz,
3
3
d 3.19 tt, 2H, JH-F = 19.0 Hz, JH-
3
2
2
5
acetone-d6)
d
À77.8 dm, 1F, JF-F = 145 Hz (F3a); À78.0 s, 6F
dm, 1F, JF-F = 150 Hz (F6bA); À81.5 d, 3F, JF-F = 13 Hz (F2A or
(CF3SO2O); À79.4 q, 6F, JF-F = 5JF-F = 10 Hz (F5); À79.5 q, 3F, JF-
F2B); À129.1 s, 2F (F7A or F7B); À129.3 s, 2F (F7A or F7B); À134.5
4
4
F = 5JF-F = 10 Hz (F5A or F5B); À80.4 dm, 1F, JF-F = 145 Hz (F6a);
dq, 1F, JF-F = 3JH-F = 22 Hz (q), JF-F = 15 Hz (d) (F1B); À135.0 dq,
2
4
4
À80.6 t, 3F, JF-F = 10 Hz (F14A or F14B); À80.7 t, 3F, JF-F = 10 Hz
(F14A or F14B); À80.8 dm, 1F, 2JF–F = 145 Hz (F3b); À81.0 t, 3F, 4JF-
F = 6 Hz (F8A or F8B); À81.1 t, 3F, 4JF-F = 6 Hz (F8A or F8B); À81.3 d,
1F,4JF-F = 3JH-F = 22 Hz (q), JF-F = 15 Hz (d) (F1A); À144.0 tm, 1F,
4
4
4
4JF-F = 22 Hz (F4A or F4B); À144.1 m, 1F (F4A or F4B). 13C NMR
2
(75.44 MHz, acetone-d6)
d
49.8 q, 1C, JC-F = 37.1 Hz (CF3CH2);
5
2
3F, JF-F = 13 Hz (F2A or F2B); À81.3 dm, 1F, JF-F = 145 Hz (F6b);
À81.4 d, 3F, 5JF-F = 13 Hz (F2A or F2B); À113.4 m, 4F (F9); À121.4 m,
4F (F11); À122.4 m, 4F (F10); À123.1 m, 4F (F12); À125.7 m, 4F
(F13); (129.1 s, 2F (F7A or F7B); À129.2 s, 2F (F7A or F7B); À134.5
dq, 1F, 4JF-F = 3JH-F = 22 Hz (q), 4JF-F = 15 Hz (d) (F1A); À134.9 dq, 1F,
49.4 d, 1C, 2JC-F = 20.6 Hz (CFCH2); 100–126 m, 8C (CF, CF2 and CF3
groups); 120.3 q, 1C, 1JC-F = 316.8 (CF3SO2O); 125.1 s, 1C (CH CH);
125.8 s, 1C (CH CH); 140.9 s, (N–CH N). MS (ESI), m/z (%): 615
[MÀTfOÀ]+, 100; 149 [TfO]À, 100.
4JF-F = 3JH-F = 22 Hz (q), JF-F = 15 Hz (d) (F1B); À144.0 tm, 1F, JF-
4.5. Preparation of bis(polyfluoroalkyl)imidazolium
4
4
F = 21 Hz (F4A); À144.1 m, 1F (F4B). 13C NMR (75.44 MHz, acetone-
hexafluorophosphates 6: general procedure
3
4
d6)
d 30.9 t, 1C, JC-F = 20.7 Hz (CF2CH2); 42.9 t, 1C, JC-F = 4.8 Hz
2
(CF2CH2CH2,); 49.2 d, 1C, JC-F = 21.0 Hz (CFCH2); 100–140 m 14C
(CF, CF2 and CF3 groups); 120.5 q, 1C, 1JC-F = 316.8 (CF3SO2O); 123.9
s, 1C (CH CH); 124.9 s, 1C (CH CH); 139.6 s, 1C, (N–CH N). MS
(ESI), m/z (%): 997 [MÀTfOÀ]+, 100; 149 [TfO]À, 100. HRMS (EI), m/z
(%): calcd. for C20H9F30N2O2 [M]+, 879,01794; found 879,01742.
Bis(polyfluoroalkylated) imidazolium trifluoromethanesulfo-
nate 3 (about 0.1 mmol) was dissolved in a 3:1 acetone/deionized
water mixture (15 ml). NH4PF6 (about 10 to 20-fold excess) was
added and the mixture was stirred for 5 h at r.t. Acetone was
removed using a rotary vacuum evaporator (40 8C/1 h/2 kPa) and
the residue was dissolved in the 1:1 1,2-dibromotetrafluoroethane
(CFC 114B2)/deionized water mixture (100 ml). The separated
organic phase was washed with deionized water (5 Â 50 ml) and
dried over anhydrous MgSO4. Removal of the solvent using a rotary
vacuum evaporator (40 8C/1 h/2 kPa) followed by heating the
residue in vacuo (75 8C/12 h/10 Pa) yielded the target hexafluor-
ophosphate salt 6.
4.3. Attempted preparation of 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-
tridecafluorooctyl)-3-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-
bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium iodide
A
flask was loaded with fluoroalkylimidazole
1 (0.45 g,
0.90 mmol), fluoroalkyl iodide 4 (0.42 g, 0.90 mmol) and toluene

634
O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
4.6. 1,3-Bis[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-
bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium
hexafluorophosphate (6a)
From the metathesis of 82 mg (0.08 mmol) of fluoroimidazo-
lium triflate 3c and 195 mg (1.75 mmol) of NH4PF6, 80 mg (98%) of
product 6c was obtained according to the general procedure. 1H
3
3
From the metathesis of 111 mg (0.11 mmol) of fluoroimidazo-
lium triflate 3a and 247 mg (1.65 mmol) of NH4PF6, 114 mg (91%)
of product 6a was obtained according to the general procedure. 1H
NMR (299.97 MHz, acetone-d6) d 3.21 tt, JH-F = 18.7 Hz, JH-
3
H = 6.70 Hz (CF2-CH2-CH2); 5.07 t, 2H, JH-H = 6.70 Hz (CF2-CH2-
3
CH2); 5.72 d, 2H, JH-F = 19.5 Hz (CF–CH2); 8.11 m, 1H, (CH CH);
NMR (299.97 MHz, acetone-d6)
d
5.82 m, 4H (CH2); 8.22 m, 2H
8.27 m, 1H (CH CH); 9.78 m, 1H (N–CH N). 19F NMR
1
(CH CH); 9.88 m, 1H, (N–CH N). 19F NMR (282.23 MHz, acetone-
(282.23 MHz, acetone-d6)
d
À71.4 d, 12F, JP-F = 707 Hz (PF6);
2
4
d6)
d
À71.5 d, 12F, 1JP-F = 707 Hz (PF6); À77.3 dm, 2F, 2JF-F = 155 Hz
À77.8 dm, 2F, JF-F = 145 Hz (F3a); À79.4 q, 3F, JF-F = 5JF-F = 10 Hz
(F3a); À79.5 m, 6F (F5); À80.4 dm, 2F, JF-F = 140 Hz (F6a); À80.6
(F5A or F5B); À79.5 q, 3F, JF-F = 5JF-F = 10 Hz (F5A or F5B); À80.4
2
4
dm, 2F, JF-F = 140 Hz (F6b); À81.2 m, 6F (F8); À81.3 m, 6F (F2);
dm, 2F, 2JF-F = 145 Hz (F6); À80.6 t, 3F, 4JF-F = 10 Hz (F14A or F14B);
À80.7 t, 3F, 4JF-F = 10 Hz (F14A or F14B); À80.8 dm, 2F, 2JF-F = 145 Hz
(F3b); À81.0 t, 3F, 4JF-F = 6 Hz (F8A or F8B); À81.1 t, 3F, 4JF-F = 6 Hz
(F8A or F8B); À81.3 d, 3F, 5JF-F = 13 Hz (F2A or F2B); À81.3 dm, 2F,
2JF-F = 145 Hz (F6b); À81.4 d, 3F, 5JF-F = 13 Hz (F2A or F2B); À113.5
m, 4F (F9); À121.4 m, 4F (F11); À122.4 m, 4F (F10); À123.1 m, 4F
(F12); À125.7 m, 4F (F13); À129.1 s, 2F (F7A or F7B); À129.2 s, 2F
(F7A or F7B); À134.5 dq, 1F, 4JF-F = 3JH-F = 22 Hz (q), 4JF-F = 15 Hz (d)
(F1B); À134.9 dq, 1F, 4JF-F = 3JH-F = 22 Hz (q), 4JF-F = 15 Hz (d) (F1B);
2
À81.6 dm, 2F, 2JF-F = 155 Hz (F3b); À129.3 m, 4F (F7); À134.8 m, 2F
(F1); À144.2 m, 2F (F4). 13C NMR (75.44 MHz, acetone-d6)
d 49.6 d,
2C 2JC-F = 20.1 Hz (CH2); 100–126 m, 16C (CF, CF2 and CF3 groups);
125.9 s, 2C (CH CH); 141.2 s, 1C (N–CH N). MS (ESI), m/z (%): 997
[MÀPF6À]+, 100; 145 [PF6]À, 100.
4.7. 1-(2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoroheptyl)-3-
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium hexafluorophosphate (6b)
À144.0 tm, 1F, JF-F = 21 Hz (F4A); À144.1 m, 1F (F4B). 13C NMR
4
From the metathesis of 127 mg (0.12 mmol) of fluoroimidazo-
lium triflate 3b and 226 mg (2.16 mmol) of NH4PF6, 116 mg (96%) of
product 6b was obtained according to the general procedure. 1H
(75.44 MHz, acetone-d6)
d
30.9 t, 1C, 3JC-F = 20.7 Hz (CF2-CH2-CH2);
4
2
42.9 t, 1C, JC-F = 4.8 Hz (CF2-CH2-CH2); 49.2 d, 1C, JC-F = 21.0 Hz
(CF–CH2); 100 - 140 m, 14C (CF, CF2 and CF3 groups); 123.9 s, 1C,
(CH CH); 124.9 s, 1C, (CH CH); 139.6 s, (N–CH N). MS (ESI), m/z
(%): 879 [MÀPF6À]+, 100; 145 [PF6]À, 100.
NMR (299.97 MHz, acetone-d6) d 5.68–5.88 m, 4H (CH2); 8.20 m, 1H
(CH CH); 8.25 m, 1H (CH CH); 9.80 s, 1H (N–CH N). 19F NMR
(282.23 MHz, acetone-d6)
d
À71.4 d, 12F, 1JP-F = 707 Hz (PF6); À77.8
dm, 1F, JF-F = 150 Hz (F3aA); À78.0 dm, 1F, JF-F = 150 Hz (F3aB);
À78.2 s, 6F (F15); À79.5 q, 3F, 4JF-F = 5JF-F = 9 Hz (F5A or F5B); À79.6 q,
3F, 4JF-F = 5JF-F = 9 Hz (F5A or F5B); À80.4 dm, 2F, 2JF-F = 140 Hz (F6a);
À80.6m, 6F, (F14); À81.0 t, 3F, 4JF-F = 7 Hz (F8A orF8B); À81.1 dm, 1F,
2JF-F = 150 Hz (F3bB); À81.0 t, 3F, 4JF-F = 7 Hz (F8A or F8B); À81.3 d,
4.9. 1-(2,2,2-Trifluoroethyl)-3-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-
2,5-bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium
hexafluorophosphate (6d)
2
2
5
2
1F, JF-F = 11 Hz (F2A or F2B); À81.3 dm, 1F, JF-F = 150 Hz (F3bA);
À81.4 dm, 2F, 2JF-F = 140 Hz (F6b); À81.5 d, 3F, 5JF-F = 11 Hz (F2A or
F2B); À116.7 m, 4F (F9); À121.4 m, 4F (F11); À122.1 m, 4F (F10);
122.2m, 4F(F12);125.7m, 2F(F13);À129.1 s, 2F(F7A orF7B);À129.3
s, 2F (F7A or F7B); À134.5 dq, 1F, 4JF-F = 3JH-F = 22 Hz (q), 4JF-F = 15 Hz
From the metathesis of 163 mg (0.21 mmol) of fluoroimidazo-
lium triflate 3d and 784 mg (2.73 mmol) of NH4PF6, 148 mg (93%)
of product 6d was obtained according to the general procedure. 1H
NMR (299.97 MHz, acetone-d6)
CH2); 5.76 m, 2H, (CF–CH2); 8.16 m, 1H (CH CH); 8.20 m, 1H
(CH CH); 9.70 m, 1H (N–CH N). 19F NMR (282.23 MHz, acetone-
(d) (F1B); À135.2 dq, 1F,4JF-F = 3JH-F = 22 Hz (q), JF-F = 15 Hz (d)
4
4
(F1B); À143.9 tm, 2F, JF-F = 21 Hz (F4). 13C NMR (75.44 MHz,
3
d
5.57 q, 2H, JH-F = 8.6 Hz (CF3-
2
2
acetone-d6)
d 48.8 t, 1C, JC-F = 23 Hz (CF2-CH2); 49.6 d, 1C, JC-
F = 20 Hz (CF–CH2); 100–126 m, 14C (CF, CF2 and CF3 groups); 125.7
s, 1C (CH CH); 125.8 s, 1C (CH CH); 141.0 s, 1C (N–CH N). MS
(ESI), m/z (%): 865 [MÀPF6À]+, 100; 145 [PF6]À, 100.
d6)
d
À71.4 d, 12F, 1JP-F = 707 Hz (PF6); À71.5 t, 6F 3JF-H = 8 Hz (F9);
2
2
À77.9 dm, 1F, JF-F = 150 Hz (F3aB); À78.2 dm, 1F, JF-F = 150 Hz
(F3aA); À79.4 q, 3F, 4JF-F = 5JF-F = 8 Hz (F5A or F5B); À79.5 q, 3F, 4JF-
F = 5JF-F = 9 Hz (F5A or F5B); À80.4 dm, 2F, JF-F = 150 Hz (F6a);
2
4.8. 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)-3-
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium hexafluorophosphate (6c)
À80.9 dm, 1F, JF-F = 140 Hz (F3bB); À81.0 dm, 1F, JF-F = 140 Hz
(F3bA); À81.0 t, 3F, 4JF-F = 6 Hz (F8A or F8B); À81.1 t, 3F, 4JF-F = 6 Hz
(F8A or F8B); À81.3 d, 3F, 5JF-F = 13 Hz (F2A or F2B); À81.3 dm, 3F,
2
2

O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
635
2JF-F = 150 Hz (F6bB); À81.5 dm, 1F, 2JF-F = 150 Hz (F6bA); À81.5 d,
3F, 5JF-F = 13 Hz (F2A or F2B); À129.2 s, 2F (F7A or F7B); À129.3 s, 2F
(F7A or F7B); À134.6 dq, 1F, 4JF-F = 3JH-F = 22 Hz (q), 4JF-F = 15 Hz (d)
(F1B); À135.0 dq, 1F,4JF-F = 3JH-F = 22 Hz (q), 4JF-F = 15 Hz (d) (F1A);
product 7b was obtained according to the general procedure. 1H
NMR (299.97 MHz, acetone-d6) 5.88 m, 2H (CF2-CH2); 5,95 m, 2H
d
(CF–CH2); 8.20 m, 1H (CH CH); 8.25 m, 1H (CH CH); 10.17 s, 1H
(N–CH N). 19F NMR (282.23 MHz, acetone-d6)
d
À77.8 dm, 1F, 2JF-
À144.0 tm, 1F, 4JF-F = 22 Hz (F4A or F4B); À144.1 m, 1F (F4A or F4B).
F = 150 Hz (F3aA); À78.0 dm, 1F, 2JF-F = 150 Hz (F3aB); À79.5 q, 3F,
4JF-F = 5JF-F = 9 Hz (F5A or F5B); À79.6 q, 3F, 4JF-F = 5JF-F = 9 Hz (F5A or
F5B); À80.4 dm, 2F, 2JF-F = 140 Hz (F6a); À80.6 m, 6F, (F14); À81.0 t,
2
13C NMR (75.44 MHz, acetone-d6)
d
49.8 q, JC-F = 37.1 Hz (CF3-
CH2); 49.4 d, 2JC-F = 20.6 Hz (CF–CH2); 100–126 m, 8C (CF, CF2 and
CF3 groups); 125.1 s (CH CH); 125.8 s, (CH CH); 140.9 s, (N–
CH N). MS (ESI), m/z (%): 615 [MÀPF6À]+, 100; 145 [PF6À]À, 100.
4
2
3F, JF-F = 7 Hz (F8A or F8B); À81.1 dm, 1F, JF-F = 150 Hz (F3bB);
À81.0 t, 3F, 4JF-F = 7 Hz (F8A or F8B); À81.3 d, 3F, 5JF-F = 11 Hz (F2A or
F2B); À81.3 dm, 1F, JF-F = 150 Hz (F3bA); À81.4 dm, 2F, JF-
2
2
5
4.10. Preparation of bis(polyfluoroalkylimidazolium)
F = 140 Hz (F6b); À81.5 d, 3F, JF-F = 11 Hz (F2A or F2B); À116.4 t,
tetrafluoroborates 7: general procedure
2F, 3JF-H = 15 Hz (F9A or F9B); À116.8 m, 2F (F9A or F9B); À121.5 m,
4F (F11); À122.1 m, 4F (F10); 122.3 m, 4F (F12); 125.7 m, 4F (F13);
À129.2s,2F(F7AorF7B);À129.3s,2F(F7AorF7B);À134.5dq, 1F, 4JF-
F = 3JH-F = 22 Hz (q), 4JF-F = 15 Hz (d) (F1B); À135.2 dq, 1F,4JF-F = 3JH-
F = 22 Hz (q), 4JF-F = 15 Hz (d) (F1A); À144.0 tm, 2F, 4JF-F = 21 Hz (F4);
À150.0 s, 8F (10BF4); À150.1 s, 4F (11BF4). 13C NMR (75.44 MHz,
Bis(polyfluoroalkylated) imidazolium trifluoromethanesulfo-
nate 3 (about 0.1 mmol) was dissolved in a 3:1 acetone/deionized
water mixture (15 ml). NH4BF4 (about 10 to 20-fold excess) was
added and the mixture was stirred for 5 h at r.t. Acetone was then
removed using a rotary vacuum evaporator (40 8C/1 h/2 kPa) and
the residue was dissolved in the 1:1 1,2-dibromotetrafluoroethane
(CFC 114B2)/deionized water mixture (100 ml). The separated
organic phase was washed with deionized water (5 Â 50 ml) and
dried over anhydrous MgSO4. Removal of the solvent using a rotary
vacuum evaporator (40 8C/1 h/2 kPa) followed by heating the
residue in vacuo (75 8C/12 h/10 Pa) yielded the target tetrafluor-
oborate salt 7.
2
2
acetone-d6)
d 48.8 t, 1C, JC-F = 23 Hz (CF2-CH2); 49.6 d, 1C, JC-
F = 20 Hz (CF–CH2); 100–126 m, 14C (CF, CF2 and CF3 groups); 125.7
s, 1C (CH CH); 125.8 s, 1C (CH CH); 141.0 s, 1C (N–CH N). MS
(ESI), m/z (%): 865 [MÀBF4À]+, 100; 87 [BF4]À, 100.
4.13. 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)-3-
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium tetrafluoroborate (7c)
4.11. 1,3-Bis[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis
(trifluoromethyl)-3,6-dioxanonyl]imidazolium tetrafluoroborate (7a)
From the metathesis of 180 mg (0.16 mmol) of fluoroimidazo-
lium triflate 3a and 197 mg (1.89 mmol) of NH4BF4, 190 mg (90%)
of product 7a was obtained according to the general procedure. 1H
From the metathesis of 150 mg (0.15 mmol) of fluoroimida-
zolium triflate 3c and 183 mg (1.74 mmol) of NH4BF4, 137 mg
(97%) of product 7c was obtained according to the general
3
NMR (299.97 MHz, acetone-d6)
d
6.02 m, 4H (CH2); 8.21 m, 2H
procedure. 1H NMR (299.97 MHz, acetone-d6)
d
3.19 tt, JH-
(CH CH); 10.41 m, 1H, (N–CH N). 19F NMR (282.23 MHz,
F = 19.1 Hz, 3JH-H = 6.8 Hz (CF2-CH2-CH2); 5.02 t, 2H, 3JH-H = 5.6 Hz
2
3
acetone-d6)
d
À77.3 dm, 2F, JF-F = 155 Hz (F3a); À79.5 m, 6F
(CF2-CH2-CH2); 5.70 d, 2H, JH-F = 19.5 Hz (CF–CH2); 8.05 m, 1H,
(F5); À80.4 dm, 2F, 2JF-F = 140 Hz (F6a); À80.6 dm, 2F, 2JF-F = 140 Hz
(CH CH); 8.21 m, 1H (CH CH); 9.69 m, 1H (N–CH N). 19F NMR
(F6b); À81.2 m, 6F (F8); À81.3 m, 6F (F2); À81.6 dm, 2F, JF-
(282.23 MHz, acetone-d6)
d
À77.8 dm, 2F, JF-F = 145 Hz (F3a);
2
2
F = 155 Hz (F3b); À129.3 m, 4F (F7); À134.8 m, 2F (F1); À144.2 m,
À79.4 q, 3F, 4JF-F = 5JF-F = 10 Hz (F5A or F5B); À79.5 q, 3F, 4JF-F = 5JF-
2F (F4); À150.2 s, 8F (10BF4); À150,3 s, 8F (11BF4). 13C NMR
F = 10 Hz (F5A or F5B); À80.4 dm, 2F, JF-F = 145 Hz (F6); À80.6 t,
2
4
4
(75.44 MHz, acetone-d6)
d
49.6 d, 2C 2JC-F = 20.1 Hz (CH2); 100–126
3F, JF-F = 10 Hz (F14A or F14B); À80.7 t, 3F, JF-F = 10 Hz (F14A or
2
4
m, 16C (CF, CF2 and CF3 groups); 125.9 s, 2C (CH CH); 141.2 s, 1C
(N–CH N). MS (ESI), m/z (%): 997 [MÀBF4À]+, 100; 87 [BF4]À, 100.
F14B); À80.8 dm, 2F, JF-F = 145 Hz (F3b); À81.0 t, 3F, JF-F = 6 Hz
(F8A or F8B); À81.1 t, 3F, 4JF-F = 6 Hz (F8A or F8B); À81.3 d, 3F, 5JF-
F = 13 Hz (F2A or F2B); À81.3 dm, 2F, 2JF-F = 145 Hz (F6b); À81.4 d,
5
4.12. 1-(2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoroheptyl)-3-
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium tetrafluoroborate (7b)
3F, JF-F = 13 Hz (F2A or F2B); À113.5 m, 4F (F9); À121.4 m, 4F
(F11); À122.4 m, 4F (F10); À123.1 m, 4F (F12); À125.7 m, 4F (F13);
À129.1 s, 2F (F7A or F7B); À129.2 s, 2F (F7A or F7B); À134.5 dq, 1F,
4
4
4JF-F = 3JH-F = 22 Hz (q), JF-F = 15 Hz (d) (F1B); À134.9 dq, 1F, JF-
From the metathesis of 115 mg (0.11 mmol) of fluoroimidazo-
lium triflate 3b and 164 mg (1.57 mmol) of NH4BF4, 92 mg (87%) of
F = 3JH-F = 22 Hz (q), JF-F = 15 Hz (d) (F1B); À144.0 tm, 1F, JF-
4
4

636
O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
F = 21 Hz (F4A); À144.1 m, 1F (F4B); À150.3 s, 8F (10BF4); À150.4 s,
deionized water (5 Â 50 ml) and dried over anhydrous MgSO4.
Removal of the solvent uisng rotary vacuum evaporator
(40 8C/1 h/2 kPa) followed by heating the residue in vacuo
(75 8C/12 h/10 Pa) yielded the target bis(trifluoromethanesulfo-
nyl)amide salt 8.
3
8F (11BF4). 13C NMR (75.44 MHz, acetone-d6)
d
30.9 t, 1C, JC-
a
4
F = 20.7 Hz (CF2-CH2-CH2); 42.9 t, 1C, JC-F = 4.8 Hz (CF2-CH2-
CH2); 49.2 d, 1C, 2JC-F = 21.0 Hz (CF–CH2); 100 - 140 m, 14C (CF, CF2
and CF3 groups); 123.9 s, 1C, (CH CH); 124.9 s, 1C, (CH CH);
139.6 s, (N–CH N). MS (ESI), m/z (%): 879 [MÀBF4À]+, 100; 87
[BF4]À, 100.
4.16. 1,3-Bis[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-
bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium
bis(trifluoromethanesulfonyl)amide (8a)
4.14. 1-(2,2,2-Trifluoroethyl)-3-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-
2,5-bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium
tetrafluoroborate (7d)
From the metathesis of 110 mg (0.09 mmol) of fluoroimidazo-
lium triflate 3a and 386 mg (1.34 mmol) of LiNTf2, 88 mg (77%) of
product 8a was obtained according to the general procedure. 1H
NMR (299.97 MHz, acetone-d6)
d 5.82 m, 4H (CH2); 8.22 m, 2H
(CH CH); 9.88 m, 1H, (N–CH N). 19F NMR (282.23 MHz, acetone-
d6)
d
À77.3 dm, 2F, 2JF-F = 155 Hz (F3a); À79,1 s, 12F (CF3SO2); (79.5
2
2
From the metathesis of 122 mg (0.16 mmol) of fluoroimidazo-
m, 6F (F5); À80.4 dm, 2F, JF-F = 140 Hz (F6a); À80.6 dm, 2F, JF-
lium triflate 3d and 284 mg (2.71 mmol) of NH4BF4, 95 mg (87%) of
F = 140 Hz (F6b); À81.2 m, 6F (F8); À81.3 m, 6F (F2); À81.6 dm, 2F,
product 7c was obtained according to the general procedure. 1H
2JF-F = 155 Hz (F3b); À129.3 m, 4F (F7); À134.8 m, 2F (F1); À144.2
3
2
NMR (299.97 MHz, acetone-d6)
d
5.60 q, 2H, JH-F = 8.5 Hz (CF3-
m, 2F (F4). 13C NMR (75.44 MHz, acetone-d6)
d
49.6 d, 2C JC-
CH2); 5.79 m, 2H, (CF–CH2); 8.18 m, 1H (CH CH); 8.20 m, 1H
(CH CH); 9.79 m, 1H (N–CH N). 19F NMR (282.23 MHz, acetone-
d6) À71.5 t, 6F, 3JF-H = 8 Hz (F9); À77.9 dm, 1F, 2JF-F = 150 Hz (F3aB);
F = 20.1 Hz (CH2); 100–126 m, 16C (CF, CF2 and CF3 groups); 120.4
1
q, JC-F = 316.8 (CF3SO2); 125.9 s, 2C (CH CH); 141.2 s, 1C (N–
CH N). MS (ESI), m/z (%): 997 [MÀNTf2À]+, 100; 280 [NTf2]À, 100.
2
4
À78.2 dm, 1F, JF-F = 150 Hz (F3aA); À79.4 q, 3F, JF-F = 5JF-F = 8 Hz
(F5A or F5B); À79.5 q, 3F, 4JF-F = 5JF-F = 9 Hz (F5A or F5B); À80.4 dm,
2F, 2JF-F = 150 Hz (F6a); À80.9 dm, 1F, 2JF-F = 140 Hz (F3bB); À81.0
dm, 1F, 2JF-F = 140 Hz (F3bA); À81.0 t, 3F, 4JF-F = 6 Hz (F8A or F8B);
4.17. 1-(2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoroheptyl)-3-
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium bis(trifluoromethanesulfonyl)amide (8b)
À81.1 t, 3F, 4JF-F = 6 Hz (F8A or F8B); À81.3 d, 3F, 5JF-F = 13 Hz (F2A
From the metathesis of 199 mg (0.20 mmol) of fluoroimida-
zolium triflate 3b and 845 mg (2.94 mmol) of LiNTf2, 215 mg
(94%) of product 8b was obtained according to the general
d 5.72–5.90 m, 4H
(CH2); 8.23 m, 1H (CH CH); 8.28 m, 1H (CH CH); 9.84 s, 1H (N–
2
2
or F2B); À81.3 dm, 3F, JF-F = 150 Hz (F6bB); À81.5 dm, 1F, JF-
F = 150 Hz (F6bA); À81.5 d, 3F, 5JF-F = 13 Hz (F2A or F2B); À129.2 s,
2F (F7A or F7B); À129.3 s, 2F (F7A or F7B); À134.6 dq, 1F, 4JF-F = 3JH-
procedure. 1H NMR (299.97 MHz, acetone-d6)
4
F = 22 Hz (q), JF-F = 15 Hz (d) (F1B); À135.0 dq, 1F,4JF-F = 3JH-
4
4
2
F = 22 Hz (q), JF-F = 15 Hz (d) (F1A); À144.0 tm, 1F, JF-F = 22 Hz
CH N). 19F NMR (282.23 MHz, acetone-d6)
d
À77.8 dm, 1F, JF-
(F4A or F4B); À144.1 m, 1F (F4A or F4B); À150.3 s, 8F (10BF4);
F = 150 Hz (F3aA); À78.0 dm, 1F, JF-F = 150 Hz (F3aB); À79.0 s,
2
À150.4 s, 8F (11BF4). 13C NMR (75.44 MHz, acetone-d6)
d
49.8 q, 2JC-
12F (CF3SO2); (79.5 q, 3F, 4JF-F = 5JF-F = 9 Hz (F5A or F5B); À79.6 q,
F = 37.1 Hz (CF3-CH2); 49.4 d, 2JC-F = 20.6 Hz (CF–CH2); 100–126 m,
8C (CF, CF2 and CF3 groups); 125.1 s (CH CH); 125.8 s, (CH CH);
140.9 s, (N–CH N). MS (ESI), m/z (%): 615 [MÀBF4À]+, 100; 87
[BF4À]À, 100.
3F, JF-F = 5JF-F = 9 Hz (F5A or F5B); À80.4 dm, 2F, JF-F = 140 Hz
4
2
(F6a); À80.6 m, 6F, (F14); À81.0 t, 3F, JF-F = 7 Hz (F8A or F8B);
4
À81.1 dm, 1F, JF-F = 150 Hz (F3bB); À81.1 t, 3F, JF-F = 7 Hz (F8A
or F8B); À81.3 d, 3F, 5JF-F = 11 Hz (F2A or F2B); À81.3 dm, 1F, 2JF-
F = 150 Hz (F3bA); À81.4 dm, 2F, 2JF-F = 140 Hz (F6b); À81.5 d, 3F,
5JF-F = 11 Hz (F2A or F2B); À116.7 t, 4F, 3JF-H = 15 Hz (F9); À121.4
m, 4F (F11); À122.1 m, 4F (F10); 122.2 m, 4F (F12); 125.7 m, 4F
(F13); À129.1 s, 2F (F7A or F7B); À129.3 s, 2F (F7A or F7B); À134.5
2
4
4.15. Preparation of bis(polyfluoroalkyl)imidazolium
bis(trifluoromethanesulfonyl)amides 8: general procedure
4
4
Bis(polyfluoroalkylated) imidazolium trifluoromethanesulfo-
nate 3 (about 0.1 mmol) was dissolved in a 3:1 acetone/deionized
water mixture (15 ml). Lithium bis(trifluoromethanesulfonyl)a-
mide (about 10 to 20 fold excess) was added and the mixture was
stirred for 5 h at r.t. Acetone was removed using a rotary vacuum
evaporator (40 8C/1 h/2 kPa) and the residue was dissolved in the
1:1 1,2-dibromotetrafluoroethane (CFC 114B2)/deionized water
mixture (100 ml). The separated organic phase was washed with
dq, 1F, JF-F = 3JH-F = 22 Hz (q), JF-F = 15 Hz (d) (F1B); À135.2 dq,
1F, JF-F = 3JH-F = 22 Hz (q), JF-F = 15 Hz (d) (F1A); À143.9 tm, 2F,
4
4
4JF-F = 21 Hz (F4). 13C NMR (75.44 MHz, acetone-d6)
d 48.8 t, 1C,
2JC-F = 23 Hz (CF2-CH2); 49.6 d, 1C, JC-F = 20 Hz (CF–CH2); 100–
2
1
126 m, 14C (CF, CF2 and CF3 groups); 120.5 q, JC-F = 317 Hz
(CF3SO2); 125.7 s, 1C (CH CH); 125.8 s, 1C (CH CH); 141.0 s, 1C
(N–CH N). MS (ESI), m/z (%): 865 [MÀNTf2À]+, 100; 280 [NTf2]À,
100.

O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
637
4
4.18. 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)-3-
(F8A or F8B); À81.1 t, 3F, JF-F = 6 Hz (F8A or F8B); À81.3 d, 3F, 5JF-
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium bis(trifluoromethanesulfonyl)amide (8c)
F = 13 Hz(F2AorF2B);À81.3dm, 3F, 2JF-F = 150 Hz(F6bB);À81.5dm,
1F, JF-F = 150 Hz (F6bA); À81.5 d, 3F, JF-F = 13 Hz (F2A or F2B);
2
5
À129.2s,2F(F7AorF7B);À129.3s,2F(F7AorF7B);À134.6dq, 1F, 4JF-
F = 3JH-F = 22 Hz (q), 4JF-F = 15 Hz (d) (F1B); À135.0 dq, 1F,4JF-F = 3JH-
F = 22 Hz (q), 4JF-F = 15 Hz (d) (F1A); À144.0 tm, 1F, 4JF-F = 22 Hz (F4A
or F4B); À144.1 m, 1F (F4A or F4B). 13C NMR (75.44 MHz, acetone-d6)
From the metathesis of 67 mg (0.07 mmol) of fluoroimidazo-
lium triflate 3c and 187 mg (0.70 mmol) of LiNTf2, 75 mg (93%) of
product 8c was obtained according to the general procedure. 1H
3
3
NMR (299.97 MHz, acetone-d6)
d 3.07 tt, JH-F = 18.7 Hz, JH-
d
49.8 q, 2JC-F = 37.1 Hz (CF3-CH2); 49.4 d, 2JC-F = 20.6 Hz (CF–CH2);
3
H = 6.7 Hz (CF2-CH2-CH2); 4.93 t, 2H, JH-H = 6.7 Hz (CF2-CH2-
CH2); 5.63 m, 2H (CF–CH2); 7.97 m, 1H, (CH CH); 8.13 m, 1H
(CH CH); 9.57 m, 1H (N–CH N). 19F NMR (282.23 MHz, acetone-
1
100–126 m, 8C (CF, CF2 and CF3 groups); 120.3 q, JC-F = 316.8
(CF3SO2); 125.1 s (CH CH); 125.8 s, (CH CH); 140.9 s, (N–CH N).
MS (ESI), m/z (%): 615 [MÀNTf2À]+, 100; 280 [NTf2À]À, 100.
2
d6)
d
À77.8 dm, 2F, JF-F = 145 Hz (F3a); (À78.9 s, 12F (CF3SO2);
À79.4 q, 3F, 4JF-F = 5JF-F = 10 Hz (F5A or F5B); (À79.5 q, 3F, 4JF-F = 5JF-
F = 10 Hz (F5A or F5B); À80.4 dm, 2F, 2JF-F = 145 Hz (F6); À80.6 t, 3F,
4JF-F = 10 Hz (F14A or F14B); À80.7 t, 3F, 4JF-F = 10 Hz (F14A or F14B);
4.20. Preparation of bis(polyfluoroalkyl)imidazolium iodides 9:
general procedure
À80.8 dm, 2F, JF-F = 145 Hz (F3b); À81.0 t, 3F, JF-F = 6 Hz (F8A or
2
4
F8B); À81.1 t, 3F, 4JF-F = 6 Hz (F8A or F8B); À81.3 d, 3F, 5JF-F = 13 Hz
Bis(polyfluoroalkylated) imidazolium trifluoromethanesulfo-
nate 3 (about 0.1 mmol) was dissolved in acetone (10 ml). Sodium
iodide (5 to 10 fold excess) was added and the mixture was stirred
for 5 h at r.t. Precipitated sodium triflate was filtered off, while
acetone was removed using a rotary vacuum evaporator (40 8C/
1 h/2 kPa) and the residue was dissolved in the 2:1 diethyl ether/
deionized water mixture (150 ml). The separated organic phase
was washed with deionized water (4 Â 100 ml) and dried over
anhydrous MgSO4. Removal of the solvent using a rotary vacuum
evaporator (40 8C/1 h/2 kPa) followed by heating the residue in
vacuo (75 8C/12 h/10 Pa) yielded the target iodide 9.
(F2A or F2B); À81.3 dm, 2F, JF-F = 145 Hz (F6b); À81.4 d, 3F, JF-
F = 13 Hz (F2A or F2B); À113.5 m, 4F (F9); À121.4 m, 4F (F11);
À122.4 m, 4F (F10); À123.1 m, 4F (F12); À125.7 m, 4F (F13); À129.1
2
5
s, 2F (F7A or F7B); À129.2 s, 2F (F7A or F7B); À134.5 dq, 1F, JF-
4
F = 3JH-F = 22 Hz (q), 4JF-F = 15 Hz (d) (F1B); À134.9 dq, 1F, 4JF-F = 3JH-
F = 22 Hz (q), JF-F = 15 Hz (d) (F1A); À144.0 tm, 1F, JF-F = 21 Hz
4
4
(F4A); À144.1 m, 1F (F4B). 13C NMR (75.44 MHz, acetone-d6)
d 30.9
3
4
t, 1C, JC-F = 20.7 Hz (CF2-CH2-CH2); 42.9 t, 1C, JC-F = 4.8 Hz (CF2-
2
CH2-CH2); 49.2 d, 1C, JC-F = 21.0 Hz (CF–CH2); 100 - 140 m, 14C
(CF, CF2 and CF3 groups); 123.9 s, 1C, (CH CH); 124.9 s, 1C,
(CH CH); 139.6 s, (N–CH N). MS (ESI), m/z (%): 879 [MÀNTf2À]+,
100; 87 [NTf2]À, 100.
4.21. 1,3-Bis[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-
bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium iodide (9a)
4.19. 1-(2,2,2-Trifluoroethyl)-3-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-
2,5-bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium
From the metathesis of 159 mg (0.14 mmol) of fluoroimida-
zolium triflate 3a and 104 mg (0.70 mmol) of NaI, 139 mg
(87%) of product 9a was obtained according to the general
tetrafluoroborate bis(trifluoromethanesulfonyl)amide (8d)
procedure. 1H NMR (299.97 MHz, acetone-d6)
d 6.02 m, 4H
(CH2); 8.25 m, 2H (CH CH); 10.45 m, 1H, (N–CH N). 19F NMR
2
(282.23 MHz, acetone-d6)
d
À77.3 dm, 2F, JF-F = 155 Hz
(F3a); À79.5 m, 6F (F5); À80.4 dm, 2F, JF-F = 140 Hz (F6a);
2
À80.6 dm, 2F, 2JF-F = 140 Hz (F6b); À81.2 m, 6F (F8); À81.3 m, 6F
(F2); À81.6 dm, 2F, JF-F = 155 Hz (F3b); À129.3 m, 4F (F7);
2
À134.8 m, 2F (F1); À144.2 m, 2F (F4). 13C NMR (75.44 MHz,
From the metathesis of 230 mg (0.30 mmol) of fluoroimidazo-
lium triflate 3d and 1.04 g (3.61 mmol) of LiNTf2, 228 mg (85%) of
product 8d was obtained according to the general procedure. 1H
NMR(299.97 MHz, acetone-d6)d
5.61q, 2H,3JH-F = 8.5 Hz(CF3-CH2);
2
acetone-d6)
d
49.6 d, 2C JC-F = 20.1 Hz (CH2); 100–126 m,
16C (CF, CF2 and CF3 groups); 120.4 q, 125.9 s, 2C (CH CH);
141.2 s, 1C (N–CH N). MS (ESI), m/z (%): 997 [MÀIÀ]+, 100; 127
[I]À, 100.
5.76 m, 2H, (CH2); 8.21 m, 1H (CH CH); 8.22 m, 1H (CH CH); 9.78 s,
1H (N–CH N). 19F NMR (282.23 MHz, acetone-d6) À71.5 t, 6F, 3JF-
H = 8 Hz (F9); À77.9 dm, 1F, 2JF-F = 150 Hz (F3aB); À78.2 dm, 1F, 2JF-
4.22. 1-(2,2,3,3,4,4,5,5,6,6,7,7,7-Tridecafluoroheptyl)-3-
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium iodide (9b)
4
F = 150 Hz (F3aA); À79.0 s, 12F (CF3SO2); À79.4 q, 3F, JF-F = 5JF-
4
F = 8 Hz (F5A or F5B); À79.5 q, 3F, JF-F = 5JF-F = 9 Hz (F5A or F5B);
2
2
À80.4 dm, 2F, JF-F = 150 Hz (F6a); À80.9 dm, 1F, JF-F = 140 Hz
(F3bB); À81.0 dm, 1F, 2JF-F = 140 Hz (F3bA); À81.0 t, 3F, 4JF-F = 6 Hz

638
O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
From the metathesis of 190 mg (0.18 mmol) of fluoroimidazo-
lium triflate 3b and 169 mg (1.12 mmol) of NaI, 175 mg (97%) of
product9b was obtained according to the general procedure. 1H
From the metathesis of 174 mg (0.23 mmol) of fluoroimidazo-
lium triflate 3d and 159 mg (1.4 mmol) of NaI, 150 mg (87%) of
product 9d was obtained according to the general procedure. 1H
NMR(299.97 MHz, acetone-d6)d
5.96q, 2H, 3JH-F = 8.5 Hz(CF3-CH2);
NMR (299.97 MHz, acetone-d6)
d
6.00 m, 2H (CF2-CH2); 6.07 m, 2H
(CF–CH2); 8.22 m, 1H (CH CH); 8.29 m, 1H (CH CH); 10,60 s, 1H
6.03 m, 2H, (CF2-CH2); 8.20 m, 1H (CH CH); 8.21 m, 1H (CH CH);
10.78 m, 1H (N–CH N). 19F NMR (282.23 MHz, acetone-d6) À71.5 t,
6F, 3JF-H = 8 Hz (F9); À77.9 dm, 1F, 2JF-F = 150 Hz (F3aB); À78.2 dm,
1F, 2JF-F = 150 Hz (F3aA); À79.4 q, 3F, 4JF-F = 5JF-F = 8 Hz (F5A or F5B);
(N–CH N). 19F NMR (282.23 MHz, acetone-d6)
d
À77.8 dm, 1F, 2JF-
F = 150 Hz (F3aA); À78.0 dm, 1F, 2JF-F = 150 Hz (F3aB); À79.5 q, 3F,
4
4JF-F = 5JF-F = 9 Hz (F5A or F5B); À79.6 q, 3F, JF-F = 5JF-F = 9 Hz (F5A
2
4
2
or F5B); À80.4 dm, 2F, JF-F = 140 Hz (F6a); À80.6 m, 6F, (F14);
À79.5 q, 3F, JF-F = 5JF-F = 9 Hz (F5A or F5B); À80.4 dm, 2F, JF-
F = 150 Hz (F6a); À80.9 dm, 1F, 2JF-F = 140 Hz (F3bB); À81.0 dm, 1F,
2JF-F = 140 Hz(F3bA);À81.0t,3F,4JF-F = 6 Hz(F8AorF8B);À81.1t,3F,
4JF-F = 6 Hz (F8A or F8B); À81.3 d, 3F, 5JF-F = 13 Hz (F2A or F2B); À81.3
4
2
À81.0 t, 3F, JF-F = 7 Hz (F8A or F8B); À81.1 dm, 1F, JF-F = 150 Hz
(F3bB); À81.1 t, 3F, JF-F = 7 Hz (F8A or F8B); À81.3 d, 3F, JF-
4
5
F = 11 Hz (F2A or F2B); À81.3 dm, 1F, JF-F = 150 Hz (F3bA); À81.4
2
dm, 2F, 2JF-F = 140 Hz (F6b); À81.5 d, 3F, 5JF-F = 11 Hz (F2A or F2B);
dm, 3F, JF-F = 150 Hz (F6bB); À81.5 dm, 1F, JF-F = 150 Hz (F6bA);
2
2
À116.7 t, 4F, JF-H = 15 Hz (F9); À121.4 m, 4F (F11); À122.1 m, 4F
À81.5 d, 3F, JF-F = 13 Hz (F2A or F2B); À129.2 s, 2F (F7A or F7B);
3
5
(F10); 122.2 m, 4F (F12); 125.7 m, 4F (F13); À129.1 s, 2F (F7A or F7B);
À129.3 s, 2F (F7A or F7B); À134.5 dq, 1F, 4JF-F = 3JH-F = 22 Hz (q), 4JF-
À129.3 s, 2F (F7A or F7B); À134.6 dq, 1F, 4JF-F = 3JH-F = 22 Hz (q), 4JF-
F = 15 Hz(d)(F1B);À135.0dq,1F,4JF-F = 3JH-F = 22 Hz(q),4JF-F = 15 Hz
F = 15 Hz (d) (F1B); À135.2 dq, 1F, JF-F = 3JH-F = 22 Hz (q), JF-
(d)(F1A); À144.0 tm, 1F, 4JF-F = 22 Hz(F4A orF4B); À144.1 m, 1F (F4A
4
4
F = 15 Hz (d) (F1A); À143.9 tm, 2F, JF-F = 21 Hz (F4). 13C NMR
or F4B). 13C NMR (75.44 MHz, acetone-d6)
d
49.8 q, JC-F = 37.1 Hz
4
2
(75.44 MHz, acetone-d6)
d
48.8 t, 1C, 2JC-F = 23 Hz (CF2-CH2); 49.6 d,
(CF3-CH2); 49.4 d, 2JC-F = 20.6 Hz (CF–CH2); 100–126 m, 8C (CF, CF2
and CF3 groups); 125.1 s (CH CH); 125.8 s, (CH CH); 140.9 s, (N–
CH N). MS (ESI), m/z (%): 615 [MÀ8IÀ]+, 100; 147 [I]À, 100.
2
1C, JC-F = 20 Hz (CF–CH2); 100–126 m, 14C (CF, CF2 and CF3
groups); 125.7 s, 1C (CH CH); 125.8 s, 1C (CH CH); 141.0 s, 1C (N–
CH N). MS (ESI), m/z (%): 865 [MÀIÀ]+, 100; 127 [I]À, 100.
4.25. Model reaction 1: attempted nucleophilic substitution of benzyl
chloride with sodium azide in fluorous ionic liquid
4.23. 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)-3-
[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis(trifluoromethyl)-3,6-
dioxanonyl]imidazolium iodide (9c)
Aflaskwasloadedwithfluoroalkoxylatedimidazoliumtriflate3a
(0.70 g, 0.61 mmol), NaN3 (1.04 g, 16.0 mmol) and benzyl chloride
From the metathesis of 41 mg (0.04 mmol) of fluoroimidazo-
lium triflate 3c and 30 mg (0.20 mmol) of NaI, 32 mg (79%) of
product9c was obtained according to the general procedure. 1H
(1.33 g, 10.5 mmol). The heterogeneous mixture was stirred for 4
days at 40 8C. After cooling with ice-water mixture, the upper
organic layer was separated and analyzed by 1H NMR, showing 22%
conversion of benzyl chloride to benzyl azide without any other
products formed. The bottom fluorous layer was dissolved in diethyl
ether (25 ml) and washed with water (3 Â 20 ml). From the organic
layer, the solvent was removed using a rotary vacuum evaporator
(40 8C/1 h/2 kPa) followed by heating the residue in vacuo (75 8C/
12 h/10 Pa). Analysis of the residue by 1H and 19F NMR spectroscopy
indicated a partial degradation (about 40%) of the ionic liquid 3a into
3
3
NMR (299.97 MHz, acetone-d6)
d 3.25 tt, JH-F = 19.4 Hz, JH-
3
H = 6.7 Hz (CF2-CH2-CH2); 5.07 t, 2H, JH-H = 7.3 Hz (CF2-CH2-
CH2); 5.85 m, 2H (CF–CH2); 8.09 m, 1H, (CH CH); 8.30 m, 1H
(CH CH); 10.10 m, 1H (N–CH N). 19F NMR (282.23 MHz, acetone-
2
4
d6)
d
À77.8 dm, 2F, JF-F = 145 Hz (F3a); À79.4 q, 3F, JF-F = 5JF-
F = 10 Hz (F5A or F5B); À79.5 q, 3F, 4JF-F = 5JF-F = 10 Hz (F5A or F5B);
À80.4 dm, 2F, 2JF-F = 145 Hz (F6); À80.6 t, 3F, 4JF-F = 10 Hz (F14A or
F14B); À80.7 t, 3F, JF-F = 10 Hz (F14A or F14B); À80.8 dm, 2F, JF-
a complex mixture containing fluoroalkoxylated imidazole 1
together with other non-identified side products.
4
2
F = 145 Hz (F3b); À81.0 t, 3F, JF-F = 6 Hz (F8A or F8B); À81.1 t, 3F,
4
4JF-F = 6 Hz (F8A or F8B); À81.3 d, 3F, JF-F = 13 Hz (F2A or F2B);
5
À81.3 dm, 2F, 2JF-F = 145 Hz (F6b); À81.4 d, 3F, 5JF-F = 13 Hz (F2A or
F2B); À113.5 m, 4F (F9); À121.4 m, 4F (F11); À122.4 m, 4F (F10);
À123.1 m, 4F (F12); À125.7 m, 4F (F13); À129.1 s, 2F (F7A or F7B);
À129.2 s, 2F (F7A or F7B); À134.5 dq, 1F, 4JF-F = 3JH-F = 22 Hz (q), 4JF-
4.26. Model reaction 2: attempted reaction of tetrahydrofuran with
benzoyl chloride in fluorous ionic liquid
A flask was loaded with fluoroalkoxylated imidazolium triflate
3a (0.56 g, 0.5 mmol) and anhydrous AlCl3 (0.13 g, 1.0 mmol) and
the mixture was stirred for 5 h at r.t. THF (60 mg, 0.9 mmol) was
added followed after 15 min by dropwise addition of benzoyl
chloride (0.12 g, 0.9 mmol). The reaction mixture was stirred
overnight at r.t., then water (20 ml) was added and the mixture
was extracted with chloroform (3 Â 20 ml). The organic layer was
dried over anhydrous MgSO4 and chloroform was removed using a
rotary vacuum evaporator (40 8C/1 h/2 kPa). Analysis of the
residue by 1H NMR showed only traces of the targeted product
in a complex mixture of side-products.
F = 15 Hz (d) (F1B); À134.9 dq, 1F, JF-F = 3JH-F = 22 Hz (q), JF-
4
4
F = 15 Hz (d) (F1A); À144.0 tm, 1F, 4JF-F = 21 Hz (F4A); À144.1 m, 1F
(F4B). 13C NMR (75.44 MHz, acetone-d6)
d
31.1 t, JC-F = 20.7 Hz
3
4
2
(CF2-CH2-CH2); 42.9 t, JC-F = 4.8 Hz (CF2-CH2-CH2); 49.4 d, JC-
F = 21.0 Hz (CF–CH2); 100(140 m, 14C (CF, CF2 and CF3 groups);
123.9 s, (CH CH); 125.0 s (CH CH); 139.7 s, (N–CH N). MS (ESI),
m/z (%): 879 [MÀIÀ]+, 100; 127 [I]À, 100.
4.24. 1-(2,2,2-Trifluoroethyl)-3-[2,4,4,5,7,7,8,8,9,9,9-undecafluoro-
2,5-bis(trifluoromethyl)-3,6-dioxanonyl]imidazolium iodide (9d)
4.27. Model reaction 3: Diels–Alder reaction of 2,3-dimethylbuta-1,3-
diene (DMB) with dimethyl acetylenedicarboxylate (DMAD) in a
fluorous ionic liquid
A flask was loaded with ionic liquid 3a (0.61 g, 0.6 mmol), DMB
(0.13 g, 1.6 mmol) and DMAD (0.22 g, 1.5 mmol). The flask was

O. Kysilka et al. / Journal of Fluorine Chemistry 130 (2009) 629–639
639
sealed and the heterogeneous mixture was stirred for 2 h at 80 8C.
After cooling the mixture with a ice/water mixture, the upper
organic layer was separated and checked by 1H NMR showing no
presence of DMAD. The bottom fluorous layer was washed with
hexane (1 ml), and then the organic layers were combined. The
solvents were removed using a rotary vacuum evaporator (40 8C/
1 h/2 kPa) obtaining 0.32 g (94%) of dimethyl 4,5-dimethylcyclo-
hexa-1,4-diene-1,2-dicarboxylate (10). The bottom fluorous layer
was washed again with hexane (5 Â 1 ml) and traces of solvent
were removed by vacuum (150 8C/10 h/10 Pa). Control by 1H and
19F NMR spectroscopy indicated no decomposition of the ionic
liquid 3a. In the recycling experiment, to the imidazolium salt 3a
were added again DMB (0.13 g, 1.6 mmol) and DMAD (0.22 g,
1.5 mmol). After sealing, heating for 2 h at 80 8C and analogous
work-up 0.33 g (98%) of diester 10 was obtained. Analogous
repurification of the fluorous layer produced 0.56 g (95%) of
imidazolium salt 3a with unchanged 1H and 19F NMR spectra.
after equilibration from the 0.25 ml portions of the respective
PFMC and toluene layers, which corresponds to Pi(FBS) = 49.1 and
fi = 3.89.
Acknowledgments
We are greatful both to the Grant Agency of the Czech Republic
(grant No. 203/06/1511) and the Ministry of Education, Youth and
Sports (Research Centre LC 06070, Research Project No.
6046137301) for their financial support.
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´ ˇ
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ˇ
ˇ´
´ˇ
´
´
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