Greener fluorous chemistry: Convenient preparation of new types of 'CF 3-rich' secondary alkyl mesylates and their use for the synthesis of azides, amines, imidazoles and imidazolium salts

Article abstract of DOI:10.1016/j.jfluchem.2010.10.001

2,2,2-Trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, and nonafluoro-tert-butyl alcohol were used as precursors for the preparation of the appropriate bis(polyfluoroalkoxymethyl)carbinols [(R_FHOCH ₂)₂CHOH, 1a-c, R

Full text of DOI:10.1016/j.jfluchem.2010.10.001

Journal of Fluorine Chemistry 131 (2010) 1368–1376
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Greener fluorous chemistry: Convenient preparation of new types of ‘CF3-rich’
secondary alkyl mesylates and their use for the synthesis of azides, amines,
imidazoles and imidazolium salts
*
´
´
´
´
¨
´
´
´
Aniko Nemes, Laszlo Tolgyesi, Andrea Bodor, Jozsef Rabai, Denes Szabo
´
Institute of Chemistry, Eo¨tvo¨s Lorand University, P.O. Box 32, H-1518, Budapest 112, Hungary
A R T I C L E I N F O
A B S T R A C T
Article history:
2,2,2-Trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, and nonafluoro-tert-butyl alcohol were used
as precursors for the preparation of the appropriate bis(polyfluoroalkoxymethyl)carbinols [(RFHOCH2)2-
CHOH, 1a–c, RFH = (a) CF3CH2, (b) (CF3)2CH, and (c) (CF3)3C] and the corresponding mesylates
[(RFHOCH2)2CHOSO2CH3, 2a–c]. This novel design paradigm is introduced to eliminate the persistence
and bioaccumulation problems of fluorous chemistry, which are associated with the use of longer linear
perfluoroalkyl groups (e.g. Rfn ꢁ n-C8F17, n-C7F15). Secondary mesylates 2a,b and the primary tosylate
[(CF3)3COCH2CH2OTs, 2d] displayed acceptable reactivity towards azide and imidazole nucleophiles to
allow the syntheses of novel fluorous azides, which on hydrogenolysis with H2/Pd-C offered fluorous
amines [(RFHOCH2)2CHNH2, 8a,b], and 1-(polyfluoroalkyl)imidazoles (5a,b,d), respectively, while 2c
showed no reactivity due to steric hindrance. The reaction of 8a,b with formaline, glyoxal and
hydrochloric acid gave symmetrical 1,3-dialkylated imidazolium chlorides (9a,b), while 5a,b,d were
effectively alkylated using n-C8F17(CH2)3I, methyl iodide, 2-bromoethanol, and 2d to yield the
corresponding 1,3-dialkylimidazolium iodides, bromides, and tosylates (7aa–ec). Some physical
properties of new compounds including mp, bp and solubility patterns were also analyzed; and the
fluorophilicity values of 1a–c, and 2a–c were experimentally determined by GC and/or 19F NMR
spectroscopy.
Received 8 July 2010
Received in revised form 8 October 2010
Accepted 13 October 2010
Available online 20 October 2010
Keywords:
Alkylation
Fluorous secondary carbinols
Fluorous secondary mesylates
Fluorous imidazolium salts
ß 2010 Elsevier B.V. All rights reserved.
1. Introduction
tert-butoxy)alkyl azodicarboxylates (e.g. (CF3)3CO(CH2)3O2CN55
NCO2(CH2)3OC(CF3)3)
[10],
a,a-bis[(perfluoro-tert-butoxy)-
Sustainable fluorous chemistry [1] is an emerging paradigm,
which calls for the elimination of the problems associated with the
persistency of perfluoroalkanes and the bioaccumulation of
compounds with longer perfluoroalkyl chains, such as C7F15CO2H
or C8F17SO3H [2]. One obvious solution for these issues could be the
replacement of volatile perfluoroalkanes and fluids with the more
environmentally friendly polyfluoroalkyl-alkyl ethers (HFEs) [3] or
by the introduction of novel fluorous ponytails, which are
assembled from shorter perfluoroalkyl segments and expected
to display higher degradability under environmental conditions
[4].
One family of fluorous compounds traces back to nonafluoro-
tert-butyl alcohol as a final precursor [5]. Fluorophilic ethers (e.g.
(CF3)3CO(CH2)3Rfn) [6], amines (e.g. [(CF3)3CO(CH2)2]xN3ꢀx, x = 0–
2) [7], alcohols (e.g. [(CF3)3COCH2]3CCH2OH) [8], triflates (e.g.
[(CF3)3COCH2]3CCH2OSO2CF3) [9], second-generation (perfluoro-
methyl] substituted
b-amino acids (e.g. H2NCH2C[CH2OC(CF3)3]2
CO2H) [11], spherical acetic acids (e.g. [(CF3)3COCH2]3CCH2OCH2
CO2H) [12], fluorous amphiphilic dendrimers [13], and other bulky
structures [14] are based on this branched F-alcohol.
The above reagents are prototypes for a greener second
generation of fluorous reagents bearing tags that are not expected
to degrade in the environment to compounds that are highly
persistent or that bioaccumulate in higher organisms [10].
Moreover, many of them display only a single 19F NMR signal
caused by the symmetry of the fluorinated spherical cone and
consequently have high potential as 19F MRI agents [8,9,11,12].
Other type of greener fluorous phase labels (RFOCH2) that could
be a substitute for longer perfluoroalkyl ponytails are accessible by
the reduction of HFPO based trimeric acid fluorides (RFOCOF) and
consecutive activation of the formed RFOCH2OH with Tf2O, as
´ˇ
described by Kvıcala et al. [15]. In analogy to similar polyfluori-
nated triflates with methylene spacer, the reactivity of RFOCH2OTf
is limited to strong and soft nucleophiles (imidazole, azide, and
iodide). They have been used for the preparation of imidazolium
* Corresponding author. Tel.: +36 1 372 2500; fax: +36 1 372 2620.
E-mail address: szabod@elte.hu (D. Szabo´).
0022-1139/$ – see front matter ß 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2010.10.001

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A. Nemes et al. / Journal of Fluorine Chemistry 131 (2010) 1368–1376
1369
O
O
CH CF
O
O
CH CF
2 3
2
3
O
O
MsCl, 0 °C-rt., 6 h
93%
100 °C, 1.5 h
56%
CF CH OH
HO
MsO
+
2
3
2
Cl
Cl
CH CF
CH CF
2 3
2
3
1a
2a
O
O
CH(CF )
CF
3
O
O
CH(CF )
3 2
3 2
MsCl, 0 °C-rt., 6 h
97%
100 °C, 36 h
MsO
+ 2
OH
HO
40%
CH(CF )
CF
3
CH(CF )
3 2
3 2
2b
1b
CF
3
O C(CF )
3 3
CH Br
2
O
C(CF )
3 3
MsCl, 0 °C-rt., 6 h
91%
120 °C, 20 h
37%
F C
3
O- Na+
MsO
+ 2
HO
HO
O
C(CF )
3 3
CH Br
2
O
C(CF )
3 3
CF
3
2c
1c
Scheme 1. Synthesis of some ‘CF3-rich’ isopropyl alcohols (1a–c) and mesylates (2a–c).
salt based room temperature ionic liquids; however those
molecules display rather complex 19F NMR patterns [16].
The present study is related to the synthesis of novel ‘‘CF3-rich’’
and conformationally flexible fluorous reagents, and to reveal their
reactivity depending on the steric hindrance caused by the
increasing number of the CF3-groups. Additionally our aim is to
investigate the molecular structure–phase property correlations
including melting and boiling points, volatility and fluorophilicity.
We disclose here effective methods for the synthesis of fluorous
secondary mesylates having structures of [(CF3)3ꢀnCHn-O-
CH2]2CH-OMs (n = 0–2) and demonstrate their ability for the
alkylation of thioacetate, azide and imidazole nucleophiles.
In the literature there are many examples of alkylation of
various C-, N-, O-, and S-nucleophiles with primary alkyl mesylates
to afford the appropriate organic or fluorous products in excellent
yields [17].
reacting 1,3-dibromopropan-2-ol and sodium nonafluoro-tert-
butoxide in dimethyl formamide. The latter salt can be prepared
easily from the commercially available (CF3)3COH by titration with
aqueous NaOH. Then we prepared fluorous mesylates 2a–c, as new
potential fluorous alkylating agents, by the reaction of the precursor
alcohols 1a–c with methanesulfonyl chloride in dichloromethane
in the presence of triethylamine (Scheme 1).
For testing the reactivity of ‘CF3-rich’ mesylates 2a–c, we
selected strong and soft nucleophiles such as azide, thioacetate, and
imidazole. We were also interested in the comparison of the
substitution patterns with a similar alkylating agent, but having
the leaving group in a primary position. Thus, 2-(perfluoro-tert-
butoxy)ethyl tosylate (2d) was included here as a reference
compound (Scheme 2), which has been introduced by us as a novel
generation fluorous alkylating agent [7]. The results of these
alkylation tests are summarized in Scheme 2.
We chose here mesylates as leaving group of the fluorous
secondary alkyl sulfonates (Scheme 1, 2a–c) for atom economy,
since they are the lightest one among sulfonates and halosulfates
(MW: CH3SO3H (96.11) < FSO3H (100.07) < ClSO3H (116.52)
First of all, it is a remarkable fact that reaction conditions and
chemical yields are highly influenced by steric properties of these
substrates. Thus mesylate 2c did not react with any nucleophiles
tested, even with the smallest azide-anion, perhaps due to its six
bulky CF3-groups which may cause considerable steric hindrance.
Therefore we tried to synthesize the corresponding
[(CF3)3COCH2]2CHOSO2CF3, having a much better leaving group,
from 1c and Tf2O, but its isolation in pure form failed due to quick
decomposition even at 0 8C. However, the reactions of the other
alkylating agents 2a, 2b, and 2d with sodium azide afforded
fluorous azides 3a, 3b, and 3d in good to excellent isolated yields
under same conditions (DMSO, 100 8C, and 3 h) (Scheme 2).
The reaction of thioacetate anion was successful with the
primary (18) tosylate 2d and the least hindered secondary (28)
mesylate 2a during one week reaction time with moderate yields,
but the conversion of the more bulky mesylate 2b into the
corresponding thioacetate failed (Scheme 2).
CF3SO3H
(150.08) < C6H5SO3H
(158.18) < p-CH3C6H4SO3H
(172.20) < n-C4F9SO2OH (300.10)). Their reactivity often matches
that of tosylates [18].
We synthesized some novel fluorous azides, thioacetates, and
1-alkylimidazoles with branched tails as well (Scheme 2), then
converted the latter compounds into unsymmetrical 1,3-disubsti-
tuted imidazolium salts (Scheme 3) or prepared the symmetrical
ones with ring syntheses (Scheme 4), since imidazolium salts
belong to a class of compounds receiving increasing interest both
in basic and applied research [19].
2. Results and discussion
2.1. Synthesis
For the N-alkylation of imidazole we applied this substrate in
threefold excess to avoid the formation of 1,3-dialkylated
imidazolium salts. While the reaction of the reference 18 tosylate
2d gave the appropriate fluorous imidazole 5d in relatively good
yield (62%) within 1 h heating at 100 8C in DMF, those with the 28
mesylates 2a or 2b were rather sluggish and offered 5a and 5b,
respectively, in 43 and 25% yields (Scheme 2).
We prepared a series of N,N0-dialkylimidazolium salts (7a, a–d;
7b, a–d; 7d, a–d; 7e, b–c) by the reaction of 1-alkylimidazoles (5a–
b,d–e) with one equivalent of a different alkylating agent (6a–d)
(Scheme 3).
Reactants and reagents were loaded in a glass ampoule with
acetonitrile, sealed and heated to 80 8C for 48 h. These reactions
afforded the expected products only when the second alkyl groups
(R2) were primary. Thus we could apply this type of reaction with
tosylate 2d successfully, but with mesylates 2a–c as alkylating
Bis(polyfluoroalkoxy)isopropyl alcohol intermediates are
formed when polyfluorinated alcohols are treated with epichloro-
hydrin in the presence of KOH or pyridine [20]. Although
compound 1a has been used for some physico-chemical measure-
ments [20a] or for the synthesis of new swallow-tailed liquid
crystals [20b], and compound 1b as an intermediate for the
synthesis of fluorinated acrylate polymers [20c], they remained
poorly characterized. We disclose here improved procedures for
the synthesis of symmetrical 28 alcohols 1a–b and our original
method for 1c (Scheme 1). The reaction of two equivalents of 2,2,2-
trifluoroethanol or 1,1,1,3,3,3-hexafluoropropan-2-ol with one
equivalent of epichlorohydrin in the presence of aqueous NaOH
resulted in the formation of 1a and 1b, while with (CF3)3COH failed
to afford 1c. Compound 1c was prepared in moderate yield by

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A. Nemes et al. / Journal of Fluorine Chemistry 131 (2010) 1368–1376
O
O
CH CF
2
3
3
NaN , DMSO, 100 °C, 3 h, 95%
3
N
3
CH CF
2
3a
O
O
CH CF
2
O
O
CH CF
2
CH COSK, DMF, 80 °C, 170 h, 41%
3
3
3
3
3
CH CO
S
MsO
3
CH CF
2
CH CF
2
4a
5a
2a
N
NH
O
O
CH CF
2
DMF, 100 °C, 20 h, 43%
3
N
N
CH CF
2
3
O
CH(CF )
3 2
NaN , DMSO, 100 °C, 3 h, 94%
3
N
3
O
3b
CH(CF )
3 2
O
O
CH(CF )
3 2
MsO
CH(CF )
3 2
N
NH
O
O
CH(CF )
3 2
DMF, 100 °C, 170 h, 25%
2b
N
N
CH(CF )
3 2
5b
O
C(CF )
3 3
MsO
no reaction with NaN , CH COSK and imidazole
3 3
O
C(CF )
3 3
2c
NaN , DMSO, 100 °C, 3 h, 58%
3
O
(CF ) C
N
3
3 3
3d
O
CH COSK, DMF, 80 °C, 170 h, 34%
3
O
(CF ) C
OTs
3 3
(CF ) C
SCOCH
3
3 3
2d
4d
N
NH
DMF, 100 °C, 1 h, 62%
N
N
C(CF )
3 3
O
5d
Scheme 2. Alkylation potential of ‘CF3-rich’ mesylates/tosylate for strong and soft nucleophiles.
reagents failed completely. This is in contrary to the successful
double alkylation of imidazole with 2-bromopropane [21].
3-(Perfluorooctyl)propyl iodide (6a), methyl iodide (6b), and 2-
bromoethanol (6c) were used as further alkylating agents, while 1-
[3-(perfluorooctyl)propyl]imidazole (5e) as another fluorous
substrate (Scheme 3).
Since imidazolium salts with two 28 N-alkyl groups could not be
prepared by direct alkylation with 2a and 2b, we introduced an
alternative method for the synthesis of the symmetrical 1,3-
dialkylimidazolium salts by a three components ring construction
reaction in analogy to literature examples [22]. Starting azides 3a
and 3b were converted into amines 8a and 8b by catalytic
hydrogenation, which then reacted with CH2O, glyoxal and
hydrochloric acid in benzene solution to afford imidazolium
chlorides 9a and 9b in good yields (Scheme 4).
clohexane) phase by GC or 19F NMR methods due their low fluorous
solubility, the fluorophilicity values obtained for the other samples
were in agreement with the expected trends [23]. Only the
perfluoro-tert-butoxy-substituted analytes 1c and 2c are fluor-
ophilic (f = ln P > 0), while the fluorous partition coefficients are
increasing by the number of the CF3-groups for compounds in both
series (Table 1).
It should also be commented that the volatility of these alcohols
and mesylates steeply increases with the number of CF3-groups
and compensates for their higher molecular weights so that the
boiling points are decreasing in the order of 1a > 1b > 1c and
2a > 2b > 2c (Table 1). The shielding effect of CF3-groups on
intermolecular attractive interactions could be responsible for this
volatility phenomenon, which increases as the CF3CH2O–
< (CF3)2CHO– < (CF3)3CO– structural fragments are in use. The
chemical reactivity of 1a–c and 2a–c is also affected by the steric
and electronic effects of these CF3-rich fluorous building blocks (cf.
Scheme 2).
2.2. Phase properties of selected compounds
We thought that the determination of fluorophilicity values
The solubility patterns and the state of matter (i.e. liquid or
solid) of the compounds shown above can be analyzed qualita-
tively (cf. Schemes 3 and 4). Compounds with lower melting points
display higher absolute solubilities in the solvents tested (cf.
( f ¼ ln PCF
5 ) for 1a–c and 2a–c could be a probe of
=CH C H
11 3 6
C
F
3
6
their phase behaviour. Although we could not determine the
equilibrium concentrations of 1a or 2a in the perfluoro(methylcy-

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A. Nemes et al. / Journal of Fluorine Chemistry 131 (2010) 1368–1376
1371
-
X
2
CH CN, 80 °C, 48 h
+
3
N
2
N
1
X
+
R
N
N
R
R
1
R
6a-c, 2d
7aa-7ec
5a,b,d,e
o
1
2
Mp C
N-alkyl-imidazole
R
R -X
Yield (%)
Product
5a
5a
5a
5a
5b
5b
5b
5b
5d
5d
5d
5d
5e
5e
CH(CH OCH CF )
2 2 3 2
6a C F (CH ) I
7aa
7ab
7ac
7ad
7ba
7bb
7bc
7bd
7da
7db
7dc
7dd
7eb
7ec
72
80
77
83
93
81
67
77
72
97
77
66
63
56
8
17
2 3
88-93
oil
oil
CH(CH OCH CF )
3 2
6b CH I
2
2
3
CH(CH OCH CF )
3 2
6c HOCH CH Br
2
2
2
2
CH(CH OCH CF )
3 2
2d (CF ) COCH CH OTs
2
2
3 3
2
2
98-105
waxy solid
waxy solid
waxy solid
96-99
148.5-161
123-132
oil
CH[CH OCH(CF ) ]
6a C F (CH ) I
2
3 2 2
8
17
2 3
CH[CH OCH(CF ) ]
6b CH I
2
3 2 2
3
CH[CH OCH(CF ) ]
6c HOCH CH Br
2
3 2 2
2
2
CH[CH OCH(CF ) ]
2d (CF ) COCH CH OTs
2
3 2 2
3 3
2
2
CH CH OC(CF )
3 3
6a C F (CH ) I
2
2
8
17
2 3
CH CH OC(CF )
3 3
6b CH I
2
2
3
CH CH OC(CF )
3 3
6c HOCH CH Br
2
2
2
2
CH CH OC(CF )
3 3
2d (CF ) COCH CH OTs
2
2
3 3
2
2
162-164
101-106
waxy solid
(CH ) C F
6b CH I
2 3
8
17
17
3
(CH ) C F
6c HOCH CH Br
2 3
8
2
2
Scheme 3. Synthesis of fluorous imidazolium salts by alkylation of N-alkylimidazoles.
[()TD$FIG]
Cl
O
CH2CF3
CH2CF3
O
O
CH2CF3
CH2CF3
F3CCH2
F3CCH2
O
O
O
O
CH2CF3
CH2CF3
ii
i
N3
H2N
H2N
N
N
85%
70%
O
9a
3a
8a
Cl
(F3C)2CH
(F3C)2CH
O
O
O
O
CH(CF3)2
CH(CF3)2
O
CH(CF3)2
CH(CF3)2
O
O
CH(CF3)2
CH(CF3)2
i
ii
N
N
N3
60%
52%
O
9b
8b
3b
i: H2, Pd/C, EtOH, 280 kPa, 10 h; ii: H-CHO, benzene, 0 °C, 1 h then OHC-CHO, HCl, 100 °C, 24 h
Scheme 4. Synthesis of symmetrical 1,3-dialkylimidazolium salts by ring construction from 28 amines.
[23b]). Typical solubility patterns at room temperature are
disclosed below.
The crystalline imidazolium salts (7aa, 7ad, 7bd, 7da, 7db, 7dd
and 7eb, Scheme 3) are easily soluble in CH2Cl2, CHCl3, DMSO,
methanol and ethyl acetate, while slightly soluble in ether and
practically insoluble in water, hexane and c-CF3C6F11. The lower
melting ones show higher solubilities in CH2Cl2, CHCl3, DMSO, and
ethyl acetate, and moreover, they are soluble in ether and
Compounds 1a–c and 2a–c are practically insoluble in H2O, but
miscible with ether and CH2Cl2, and soluble in DMSO, CDCl3, and
toluene. Azides 3a, 3b and 3d are miscible with ether and CH2Cl2,
highly soluble in EtOH. Amines 8a and 8b are soluble in CH3OH,
CH2Cl2, CHCl3, ether and toluene, but insoluble in water.
methanol, while insoluble in n-hexane and c-CF3C6F11
.
Table 1
Boiling points and fluorophilicity values of secondary fluorous alcohols and alkyl mesylates.
Compounds
MW
Bp (8C/kPa)
%F
f = ln P
1a (CF3CH2OCH2)2CH-OH
256.15
392.14
528.14
334.24
470.23
606.23
93–96/2.67
86–88/2.67
74–79/2.67
138–140/0.07
112–114/0.07
79–80/0.07
44.50
58.14
64.75
34.10
48.48
56.41
n.d.
1b ((CF3)2CHOCH2)2CH-OH
1c ((CF3)3COCH2)2CH-OH
ꢀ0.45 ꢂ 0.15
2.3 ꢂ 0.05
n.d.
2a (CF3CH2OCH2)2CH-OSO2CH3
2b ((CF3)2CHOCH2)2CH-OSO2CH3
2c ((CF3)3COCH2)2CH-OSO2CH3
ꢀ2.3 ꢂ 0.3
0.9 ꢂ 0.1
n.d., not determined.

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A. Nemes et al. / Journal of Fluorine Chemistry 131 (2010) 1368–1376
3. Conclusions
86 8C/2.13 kPa, and 42–45 8C/1.20 kPa). 1H NMR (CDCl3):
d 2.64
(1H, s, OH), 3.65–3.76 (4H, m, CH2-O), 3.90 (4H, q, JHF = 8.75 Hz,
3
A series of ‘CF3-rich’ secondary mesylates 2a–c was synthesized
and their reactivity compared with that of a primary fluorous
tosylate [2d, (CF3)3COCH2CH2OTs]. All but 2c of them could
supplement the inventory of fluorous alkylating agents as proved
by the synthesis of selected fluorous azides, thioacetates and N-
alkyl-imidazoles. When such ‘CF3-rich’ 18 and 28 fluorous
alkoxyalkyl groups are incorporated in the molecules of 1,3-
dialkylated imidazolium salts, their physical properties display
larger diversity due to the conformational flexibility of these novel
generation ponytails and symmetry factors opposed to the use of
the classical ones [24]. The continuous move to the use of ‘CF3-rich’
fluorous building blocks could facilitate the elimination of the
environmental problems associated with the use of longer
perfluoroalkyl groups.
CF3-CH2), 4.00 (1H, p, 3JHH = 5.50 Hz, CH). 13C NMR (CDCl3):
d
69.2
2
(q, JCF = 34 Hz, CH2CF3), 69.7 (CH), 73.4 (CH2-O), 124.2 (q,
1JCF = 280 Hz, CF3). 19F NMR (CDCl3):
HRMS: m/z = 255.0461; calcd. for [C7H9F6O3] 255.0466.
d
ꢀ74.9 (6F, s, CF3). ESI-
4.3. 1,3-Bis[2,2,2-trifluoro-1-(trifluoromethyl)ethoxy]propan-2-ol
(1b)
To a stirred solution of sodium hydroxide (10.61 g, 0.265 mol)
in water (126 ml) was added slowly 1,1,1,3,3,3-hexafluoropropan-
2-ol (33.5 ml, 53.50 g, 0.318 mol) at 0 8C. After stirring for 5 min
epichlorohydrin (12.5 ml, 14.73 g, 0.16 mol) was added and the
mixture was stirred at 100 8C for 36 h. After cooling to room
temperature the organic layer was separated. The aqueous layer
was extracted with CH2Cl2 (2ꢃ 100 ml), the organic phases were
combined, then washed with water (25 ml) and dried (Na2SO4).
The solvent was removed under vacuum and the crude product
was distilled to afford the title alcohol 1b. Yield: 25.33 g (41%),
colourless liquid, bp 86–88 8C/2.67 kPa (Lit. [20c] bp 56.5–57 8C/
4. Experimental
4.1. General description of materials and methods
CF3CH2OH, (CF3)2CHOH, (CF3)3COH and c-CF3C6F11 were
purchased from Fluorochem, while (CF3)3CONa [7a], 2d [7a], 6a
[25], and (BrCH2)2CHOH [26] were prepared as reported. The other
reagents and solvents were Alfa-Aesar and Molar Chemicals, Ltd
(Budapest) products. 1H NMR, 13C NMR and 19F NMR spectra were
recorded on a Bruker Avance 250 (250 MHz for 1H) spectrometer
using a 5 mm inverse 1H/13C/31P/19F probe head at 25 8C. Chemical
0.67 kPa). 1H NMR (CDCl3):
(4H, m, CH2O), 4.08 (1H, p, 3JHH = 5.5 Hz, CHOH), 4.20 (2H, septet,
3JHF = 5.9 Hz, CH(CF3)2). 13C NMR (CDCl3):
69.6 (CHOH), 74.9
d
2.47 (1H, d, 3JHH = 5.5 Hz, OH), 3.995
d
(CH2O), 77.2 (septet, 2JCF = 32 Hz, CH(CF3)2), 121.7 (q, 1JCF = 282 Hz,
CF3). 19F NMR (CDCl3):
z = 392.0265; calcd. for [C9H8F12O3] 392.0282.
d
ꢀ74.5 (d, 1JCF = 5.9 Hz, CF3). ESI-HRMS: m/
shift values are in ppm relative to TMS (1H,
d
= 0), CDCl3
(
13C,
4.4. 1,3-Bis[2,2,2-trifluoro-1,1-bis(trifluoromethyl)ethoxy]propan-2-
d
= 77.0) or CCl3F (19F,
d
= 0) on the scale. Coupling constants J
d
ol (1c)
were given in Hz. Oily and waxy samples in several cases caused
line broadening in NMR spectra, therefore no exact coupling
constants can be given. Agilent Technologies 6210A Time-of-Flight
A
stirred mixture of 1,3-dibromopropan-2-ol (0.84 g,
3.85 mmol) and sodium nonafluoro-tert-butoxide (2.40 g,
9.30 mmol) in dry DMF (10 ml) was heated at 120 8C under N2
for 20 h. Water (20 ml) and ether (10 ml) was added, then the
aqueous phase was separated and extracted with ether (2ꢃ 10 ml).
The organic layers were combined, washed with water (3ꢃ 100 ml)
and dried over Na2SO4. The solvent was removed under vacuum
the crude product was distilled to afford the title alcohol 1c. Yield:
0.75 g (37%), colourless liquid, bp 74–79 8C/2.67 kPa. 1H NMR
MS instrument equipped with
a dual-nebulizer ESI source,
operated in positive ion mode, was employed to acquire high
resolution mass spectra. Melting points were determined on a
Boetius micromelting point apparatus and are uncorrected. All
reactions were monitored by GC (Hewlett-Packard 5890 Series II,
PONA [cross-linked methylsilicone gum] 50 m ꢃ 0.2 mm ꢃ 0.5
mm
column, H2 carrier gas, FID detection) and/or using TLC Aluminium
sheets (Silica gel 60 F254, Merck KGaA, Darmstadt) with a
CH2Cl2:methanol (9:1, v/v) eluent system. Fluorous partition
coefficients (P) were determined by GC [7a] or by 19F NMR as
follows. In a 2 ml volumetric flask the given compound (30 mg)
was extracted in a 1.00 ml to 1.00 ml mixture of pre-equilibrated c-
CF3C6F11 and toluene. The closed vessel was first immersed in a
water bath (50 8C) for 30 min with frequent shaking, and then
allowed to cool to 25 8C. After standing overnight at this
temperature 50 ꢂ 0.5 ml aliquots of the separated upper and lower
phases were withdrawn and added to 20 ꢂ 0.2 mg C6H5CF3 in 100 ml
(CDCl3):
CH2CHCH2). 13C NMR (CDCl3):
(q, 1JCF = 292 Hz, CF3). 19F NMR (CDCl3):
d
2.40 (1H, s, OH), 4.00–4.20 (5H, overlapping signals,
d
68.8 (CH-OH), 69.0 (CH2-O), 120.5
d
ꢀ71.0 (s, CF3). ESI-HRMS:
m/z = 528.0009; calcd. for [C11H6F18O3] 528.0030.
4.5. General procedure for the synthesis of mesylates 2a–c
To a solution of 1a or 1b (10.25 g or 15.68 g; 40 mmol) and
triethylamine (6.41 ml, 4.65 g, 46 mmol) in anhydrous CH2Cl2
(150 ml) was added with stirring a solution of CH3SO2Cl (3.56 ml,
5.27 g, 46 mmol) in anhydrous CH2Cl2 (50 ml) at 0 8C. The
suspension was warmed to room temperature and stirred for
4 h. Then ice-water (50 ml) was added and stirred for 1 h. Alcohol
1c was reacted analogously on a 2.11 g (4.0 mmol) scale. The
organic phase was separated, washed with water and dried
(Na2SO4). The solvent was evaporated and the product was purified
by distillation.
CDCl3, which served as an internal standard for NMR analysis (1c/19
F
NMR, Table 1).
4.2. 1,3-Bis(2,2,2-trifluoroethoxy)propan-2-ol (1a)
To a stirred solution of sodium hydroxide (10.00 g, 0.25 mol) in
water (120 ml) was added slowly 2,2,2-trifluoroethanol (21.8 ml,
30.0 g, 0.30 mol) at 0 8C. After stirring for 5 min epichlorohydrin
(11.7 ml, 13.87 g, 0.15 mol) was added and the mixture was stirred
at 100 8C for 1.5 h. The resulting solution was cooled to room
temperature and the organic layer was separated. The aqueous
phase was extracted with ether (2ꢃ 25 ml), the organic layers were
combined, then washed with water (25 ml) and dried (Na2SO4).
The solvent was removed under vacuum and the crude product
was distilled to afford the title alcohol 1a. Yield: 21.50 g
(56%) colourless liquid, bp 93–96 8C/2.67 kPa (Lit. [20a,b] bp
4.5.1. 1,3-Bis(2,2,2-trifluoroethoxy)propan-2-yl methanesulfonate
(2a)
Yield: 12.42 g (93%) colourless liquid, bp 138–140 8C/66.7 Pa.
1H NMR (CDCl3):
d
3.08 (3H, s, SO2CH3), 3.9–4.0 (8H, m, CH2OCH2),
4.86 (1H, p, JHH = 4.8 Hz, CH). 13C NMR (CDCl3):
d 38.6 (SO2CH3),
3
2
69.2 (q, JCF = 34 Hz, CF3CH2), 71.6 (CH2O), 79.2 (CH), 124.0 (q,
1JCF = 280 Hz, CF3). 19F NMR (CDCl3):
d
ꢀ74.8 (t, 3JHF = 8.5 Hz, CF3).
ESI-HRMS: m/z = 334.0310; calcd. for [C8H12F6O5S]+ 334.0316.

A. Nemes et al. / Journal of Fluorine Chemistry 131 (2010) 1368–1376
1373
4.5.2. 1,3-Bis[2,2,2-trifluoro-1-(trifluoromethyl)ethoxy]propan-2-yl
methanesulfonate (2b)
NMR (CDCl3):
d
31.0 (CH3), 43.0 (CH), 68.9 (q, 2JCF = 34 Hz, CH2CF3),
1
71.0 (CH2O), 124.2 (q, JCF = 280 Hz, CF3), 194.9 (CO). 19F NMR
3
Yield: 17.48 g (97%) colourless liquid, bp 112–114 8C/66.7 Pa.
(CDCl3):
d
ꢀ74.8 (t, JHF = 8.6 Hz, CF3).
1H NMR (CDCl3):
CH2CH), 4.19 (2H, septet, JHF = 5.8 Hz, CH(CF3)2), 4.90 (1H, p,
3JHF = 4.8 Hz, CHCH2). 13C NMR (CDCl3):
d
3.07 (3H, s, SO2CH3), 4.14 (4H, d, 3JHH = 4.8 Hz,
3
4.7.2. 5,5,5-Trifluoro-4,4-bis(trifluoromethyl)-3-oxapentan-1-yl
d
38.5 (SO2CH3), 73.1 (CH-
thioacetate (4d)
2
OSO2), 77.3 (CH2O), 77.1 (septet, JCF = 32 Hz, CH(CF3)2), 121.5 (q,
Yield: 6.90 g (34%) yellow liquid, bp 160–163 8C. 1H NMR
1JCF = 284 Hz, CF3). 19F NMR (CDCl3):
d
ꢀ74.4 (d, 3JHF = 5.8 Hz, CF3).
(CDCl3):
d
2.36 (3H, s, CH3), 3.16 (2H, t, JHH = 6.4 Hz, CH2S), 4.10
3
ESI-HRMS: m/z = 470.0057; calcd. for [C10H10F12O5S]+ 470.0061.
(2H, t, 3JHH = 6.4 Hz, CH2O). 13C NMR (CDCl3):
d
28.9 (S-CH2), 30.8
(CH3), 68.5 (CH2-O), 120.6 (q, JCF = 295 Hz, CF3), 195.4 (CO). 19F
1
4.5.3. 1,3-Bis[2,2,2-trifluoro-1,1-bis(trifluoromethyl)ethoxy]propan-
NMR (CDCl3):
d
ꢀ71.0 (s, CF3).
2-yl methanesulfonate (2c)
Yield: 2.20 g (91%) colourless liquid, bp 79–80 8C/66.7 Pa. 1H
4.8. General procedure for the synthesis of N-alkylimidazoles 5a, 5b
and 5d
3
NMR (CDCl3):
d
3.07 (3H, s, SO2CH3), 4.30 (4H, d, JHH = 5.0 Hz,
CH2), 4.94 (1H, p, JHH = 5.0 Hz, CH). 13C NMR (CDCl3):
(SO2CH3), 67.4 (CH2O), 75.7 (CH), 120.4 (q, JCF = 292 Hz, CF3). 19F
d 38.4
3
1
A stirred solution of the alkylating agent (halide, toluenesulfo-
nate, or methanesulfonate; 1 equiv.) and imidazole (3 equiv.) in
CH2Cl2 was heated at 100 8C for 1–170 h. The reaction mixture was
poured into 1 M NaOH (3.3 equiv.), extracted with CH2Cl2 (3ꢃ). The
organic layers were combined, washed with water (3ꢃ), dried
(Na2SO4) and evaporated. The residue was purified by vacuum
distillation to afford the N-alkylimidazole.
NMR (CDCl3):
d
ꢀ71.0 (s, CF3).
4.6. General procedure for the synthesis of azides 3a, 3b and 3d
To a solution of mesylate 2a, 2b or tosylate 2d (30 mmol) in
anhydrous DMSO (75 ml) was added sodium azide (4.10 g,
63 mmol) with stirring, and the mixture was heated to 100 8C
and stirred for 3 h. Then it was poured into water (300 ml) and
extracted with ether (3ꢃ 100 ml). The organic layers were
combined, washed with water (3ꢃ 30 ml) and dried (Na2SO4).
The solvent was evaporated at room temperature (CAUTION:
overheating of azides could lead to violent decompositions) and the
product obtained was used without further purification.
4.8.1. 1-(1,1,1,9,9,9-Hexafluoro-3,7-dioxanonan-5-yl)imidazole (5a)
The reaction of mesylate 2a (5.00 g, 15 mmol) and imidazole
(3.08 g, 45 mmol) in DMF (8 ml) took place at 120 8C for 20 h to
yield 1.97 g (43%) of 5a as a colourless liquid, bp 115–117 8C/
66.7 Pa. 1H NMR (CDCl3):
d
3.84 (4H, q, 3JHF = 8.6 Hz, CH2-CF3), 3.97
3
3
(4H, t, JHH = 4.5 Hz, CH-CH2), 4.41 (1H, p, JHH = 5.0 Hz, CH), 7.06
(2H, s, Im4,5), 7.59 (1H, s, Im2). 13C NMR (CDCl3):
d 57.2 (N-CH),
2
4.6.1. 5-Azido-1,1,1,9,9,9-hexafluoro-3,7-dioxanonane (3a)
69.1 (q, JCF = 35 Hz, CH2CF3), 71.7 (CH2CH), 118.6 (Im5), 124.0
Yield: 8.01 g (95%) pale yellow oil. 1H NMR (CDCl3):
d
3.77–3.82
(CF3, q, 1JCF = 280 Hz), 129.9 (Im4), 137.2 (Im2). 19F NMR (CDCl3):
d
3
3
(5H, m, CH2CHCH2), 3.89 (4H, q, JHF = 8.6 Hz, CF3CH2). 13C NMR
ꢀ74.7 (t, JHF = 8.6 Hz, CF3). ESI-HRMS: m/z = 306.0803; calcd. for
2
(CDCl3):
d
60.5 (CH), 69.2 (q, JCF = 34 Hz, CF3CH2), 71.9 (CH2O),
[C10H12F6N2O2]+ 306.0806.
124.1 (q, JCF = 280 Hz, CF3). 19F NMR (CDCl3):
d
ꢀ74.7 (t,
1
3JHF = 8.6 Hz, CF3).
4.8.2. 1-[1,1,1,9,9,9-Hexafluoro-3,7-dioxa-2,8-
bis(trifluoromethyl)nonan-5-yl]imidazole (5b)
4.6.2. 5-Azido-1,1,1,9,9,9-hexafluoro-3,7-dioxa-2,8-
The reaction of mesylate 2b (2.00 g, 4.26 mmol) and imidazole
(0.87 g, 12.77 mmol) in DMF (3 ml) took place at 120 8C during 1
week to yield 0.47 g (25%) of 5b as a colourless liquid, bp 115–
bis(trifluoromethyl)nonane (3b)
Yield: 11.8 g (94%) pale yellow oil. 1H NMR (CDCl3):
d
3.83 (1H, p,
3
3JHH = 5.4 Hz, CHN3), 4.00 (4H, m, JHH = 5.4 Hz, CH2O), 4.14 (2H,
132 8C/66.7 Pa. 1H NMR (CDCl3):
d
4.13–4.30 (6H, m, CH2-O-CH),
septet, 3JHF = 5.8 Hz, CH(CF3)2). 13C NMR (CDCl3):
d
59.9 (CHN3), 73.4
4.56 (1H, p, JHH = 5.0 Hz, CH), 7.04 (1H, s, Im4), 7.07 (1H, s, Im5),
3
(CH2O), 77.1 (septet, 2JCF = 33 Hz, CH(CF3)2), 121.5 (q, 1JCF = 284 Hz,
7.57 (1H, s, Im2). 13C NMR (CDCl3):
(p, 2JCF = 33 Hz, CH(CF3)2), 118.5 (Im5), 121.5 (q, 1JCF = 284 Hz, CF3),
d 56.6 (N-CH), 73.1 (CH2), 76.8
CF3). 19F NMR (CDCl3):
d
ꢀ74.5 (12F, d, 3JHF = 5.8 Hz, CF3).
129.9 (Im4), 136.9 (Im2). 19F NMR (CDCl3):
d
ꢀ74.3 (6F, m,
4.6.3. 5-Azido-1,1,1-trifluoro-2,2-bis(trifluoromethyl)-3-oxapentane
3JHF = 6.5 Hz, CH(CF3)2), ꢀ74.4 (6F, m, 3JHF = 6.5 Hz, CH(CF3)2). ESI-
HRMS: m/z = 442.0551; calcd. for [C12H10F12N2O2]+ 442.0554.
(3d)
Yield: 5.31 g (58%) pale yellow viscous oil. 1H NMR (CDCl3):
d
3.48 (2H, t, 3JHH = 4.8 Hz, CH2N3), 4.20 (2H, t, 3JHH = 4.8 Hz, CH2O).
4.8.3. 1-[5,5,5-Trifluoro-3-oxa-4,4-
13C NMR (CDCl3):
d
50.7 (CH2N3), 69.2 (CH2O), 120.6 (q,
bis(trifluoromethyl)pentyl]imidazole (5d)
1JCF = 292 Hz, CF3). 19F NMR (CDCl3):
d
ꢀ71.0 (s, CF3).
The reaction of tosylate 2d (13.03 g, 30 mmol) and imidazole
(6.12 g, 90 mmol) in DMF (12.5 ml) took place at 100 8C during 1 h
to yield 6.18 g (62%) of 5d as a colourless liquid, which slowly
4.7. General procedure for the synthesis of thioacetates 4a and 4d
crystallized upon standing, mp ꢄ28 8C, bp 110 8C/66.7 Pa. 1H NMR
3
A stirred solution of mesylate 2a or tosylate 2d (20.10 g or
26.06 g; 60 mmol) and potassium thioacetate (7.50 g, 66 mmol) in
anhydrous DMF (120 ml) was heated at 100 8C under N2 for a week.
The resulting brown gel was treated with water (120 ml), and then
the organic phase was separated. The aqueous layer was extracted
with ether (3ꢃ 100 ml) and the organic phase was washed with
water (2ꢃ 30 ml), dried over Na2SO4 and evaporated. The residue
was purified by distillation under reduced pressure.
(CDCl3):
d
4.18 (4H, s, CH2), 6.874 (1H, t, JHH = 1.3 Hz, Im4), 7.00
(1H, t, 3JHH = 1.0 Hz, Im5), 7.42 (1H, s, Im2). 13C NMR (CDCl3):
(CH2N), 69.3 (CH2O), 119.6 (Im5), 120.4 (q, JCF = 293 Hz, CF3),
130.1 (Im4), 137.7 (Im2). 19F NMR (CDCl3) ꢀ71.0 (s, CF3). ESI-
HRMS: m/z = 330.0415; calcd. for [C9H7F9N2O]+ 330.0423.
d
46.9
1
4.8.4. 1-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
Heptadecafluoroundecyl)imidazole (5e)
The reaction of C8F17(CH2)3I (5.88 g, 10 mmol) and imidazole
(2.04 g, 30 mmol) in DMF (10 ml) took place at 100 8C during 5 h to
yield 3.0 g (57%) of 5e as white crystals, mp 47.5–53 8C/toluene (lit.
[27] mp 48–50 8C).
4.7.1. 1,3-Bis(2,2,2-trifluoroethoxy)propan-2-yl thioacetate (4a)
Yield: 7.73 g (41%) yellow liquid, bp 88 8C/66.7 Pa. 1H NMR
(CDCl3):
d C
2.36 (3H, s, CH3), 3.75–3.96 (9H, m, (CH2OCH2)2CH). 13

1374
A. Nemes et al. / Journal of Fluorine Chemistry 131 (2010) 1368–1376
3
3
1H NMR (CDCl3):
d
2.04 (4H, broad m, CH2CH2), 4.03 (2H, t,
(4H, m, JHF = 9 Hz, CH2CF3), 4.02 (4H, m, JHH = 4.5 Hz, CH2CH),
3
3
3JHH = 6.5 Hz, CH2), 6.88 (1H, s, Im4), 7.11 (1H, s, Im5), 7.60 (1H, s,
4.28 (2H, t, JHH = 4.5 Hz, CH2N), 4.66 (2H, t, JHH = 4.5 Hz, CH2O),
4.98 (1H, p, 3JHH = 4.5 Hz, CH), 7.13 (2H, d, 3JHH = 8.1 Hz, m-Ar), 7.37
Im2). 19F NMR (CDCl3):
d
ꢀ82.9 (3F, t, 3JFF = 10 Hz, CF3), ꢀ114.9 (2F,
3
broad m, JFF = 15 Hz, CF2-4), ꢀ123.3 (6F, broad m, CF2-6, 7, 8),
ꢀ124.4 (4F, broad m, CF2-5, 9), 127.9 (2F, broad m, CF2-10).
(1H, d, 3JHH = 1.3 Hz, Im5), 7.52 (1H, d, 3JHH = 1.5 Hz, Im4), 7.67 (2H,
d, JHH = 8.1 Hz, o-Ar), 9.73 (1H, s, Im2). 13C NMR (CDCl3):
d 21.5
3
(ArCH3), 49.8 (CH2N), 60.3 (CHN), 68.4 (CH2OC(CF3)3), 69.7 (q,
4.9. General procedure for the synthesis of asymmetric imidazolium
salts (cf. Scheme 3)
2JCF = 34 Hz, CH2CF3), 126.0 (m-Ar), 129.1 (o-Ar), 138.4 (Im2), 140.1
(g-Ar), 143.9 (p-Ar). 19F NMR (CDCl3):
d
ꢀ74.9 (6F, t, 3JHF = 9.0 Hz,
CH2CF3), ꢀ71.1 (9F, s, C(CF3)3). ESI-HRMS: m/z = 569.0940; calcd.
A solution of N-alkylimidazole (5a, b, d, e; 1 equiv.) and the
alkylating agent (6a–c, 2d; 1 equiv.) in anhydrous acetonitrile
were heated at 80 8C for 48 h. When the product was crystallized
from the solvent at room temperature it was filtered, and the
crystals were washed with ether and dried. When the product is
soluble in acetonitrile, the solvent was removed in vacuum, and
then the crude product was washed with ether and dried.
for [C16H16F15N2O3]+ 569.0921.
4.9.5. 1-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
Heptadecafluoroundecyl)-3-[1,1,1,9,9,9-hexafluoro-3,7-dioxa-2,8-
bis(trifluoromethyl)nonan-5-yl]imidazolium iodide (7ba)
The reaction of 5b (0.77 g, 1.74 mmol) and 6a (0.30 g,
2.26 mmol) in acetonitrile (3 ml) afforded imidazolium salt 7ba.
Yield: 1.67 g (93%) brown wax. 1H NMR (DMSO-d6):
d 2.00–2.15
3
4.9.1. 1-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
(4H, broad s, CH2CH2N), 4.34 (4H, d, JHH = 5.8 Hz, CH2CH), 4.38
(2H, broad s, CF2CH2), 5.10 (2H, p, 3JHH = 5.8 Hz, CH-N), 5.60 (2H, p,
Heptadecafluoroundecyl)-3-(1,1,1,9,9,9-hexafluoro-3,7-dioxanonan-
5-yl)imidazolium iodide (7aa)
The reaction of 5a (1.00 g, 3.27 mmol) and 6a (1.92 g,
3.27 mmol) in acetonitrile (15 ml) afforded imidazolium salt
7aa. Yield: 2.24 g (72%), mp 88–93 8C 1H NMR (DMSO-d6):
2.03–2.24 (4H, broad m, CH2CH2N), 3.98–4.18 (8H, m, CH2OCH2),
4.34 (2H, t, 3JHH = 6.3 Hz, NCH2), 4.96 (1H, p, 3JHH = 5.3 Hz, CH), 7.88
(1H, s, Im4), 7.92 (1H, s, Im5), 9.31 (1H, s, Im2). 13C NMR (DMSO-
3JHF = 6.5 Hz, CH(CF3)2), 7.94 (1H, s, Im5), 7.99 (1H, s, Im4), 9.43
(1H, s, Im2). 19F NMR (DMSO-d6):
d
ꢀ74.2 (6F, m, JHF = 7.1 Hz,
3
3
CH(CF3)2), ꢀ74.6 (6F, m, JHF = 7.1 Hz, CH(CF3)2), ꢀ81.4 (3F, t,
3JFF = 11 Hz, CF3CF2), ꢀ114.4 (2F, t, 3JFF = 15 Hz, CF2-4), ꢀ122.7 (6F,
broad s, CF2-6, 7, 8), ꢀ123.5 (2F, s, CF2-9), ꢀ124.1 (2F, s, CF2-5),
ꢀ126.8 (2F, s, CF2-10). ESI-HRMS: m/z = 903.0773; calcd. for
[C23H16F29N2O2]+ 703.0749.
d
d6):
(q, 2JCF = 34 Hz, CH2CF3), 69.8 (CH2CH), 120.8 (q, 1JCF = 227 Hz, CF3),
122.2 (Im5), 122.9 (Im4), 136.8 (Im2). 19F NMR (DMSO-d6):
(6F, t, JHF = 9.8 Hz, CH(CF3)2), ꢀ81.6 (3F, t, JFF = 10.5 Hz, CF2CF3),
ꢀ114.3 (2F, t, 3JFF = 18.5 Hz, CF2-4), ꢀ122.7 (6F, broad s, CF2-6, 7, 8),
ꢀ123.9 (4F, broad s, CF2-5, 9), 126.9 (2F, s, CF2-10). ESI-HRMS:
m/z = 767.1001; calcd. for [C21H18F23N2O2]+ 767.0978.
d 21.2 (CH2CH2CF3), 27.2 (CH2CF2), 48.2 (CH2N), 59.6 (CH), 67.5
4.9.6. 1-Methyl-3-[1,1,1,9,9,9-hexafluoro-3,7-dioxa-2,8-
d
ꢀ74.1
bis(trifluoromethyl)nonan-5-yl]imidazolium iodide (7bb)
The reaction of 5b (1.00 g, 2.26 mmol) and 6b (0.30 g,
2.26 mmol) in acetonitrile (3 ml) afforded imidazolium salt 7bb.
3
3
Yield: 1.07 g (81%) brown wax. 1H NMR (DMSO-d6):
d 3.90 (3H, s,
CH3), 4.34 (4H, d, 3JHH = 5.8 Hz, CH2), 5.09 (1H, p, 3JHH = 5.8 Hz, CH-
N), 5.63 (2H, p, 3JHF = 6.5 Hz, CH(CF3)2), 7.84 (2H, s, Im4, Im5), 9.31
4.9.2. 1-Methyl-3-(1,1,1,9,9,9-hexafluoro-3,7-dioxanonan-5-
yl)imidazolium iodide (7ab)
The reaction of 5a (0.32 g, 1.05 mmol) and 6b (0.12 g,
1.05 mmol) in acetonitrile (1 ml) afforded the title imidazolium
(1H, s, Im2). 13C NMR (DMSO-d6):
d
36.3 (CH3), 59.2 (CH-N), 71.7
2
(CH2), 74.3 (t, JCF = 32 Hz, CH(CF3)2), 121.4 (Im5), 124.4 (Im4),
137.4 (Im2). 19F NMR (DMSO-d6):
d
ꢀ73.8 (6F, m, JHF = 7.3 Hz,
3
3
CH(CF3)2), ꢀ74.2 (6F, m, JHF = 7.7 Hz, CH(CF3)2). ESI-HRMS: m/
salt 7ab. Yield: 1.06 g (80%) pale yellow oil. 1H NMR (CDCl3):
d
3.94
z = 457.0798; calcd. for [C13H13F12N2O2]+ 457.0785.
3
(4H, m, JHF = 8.6 Hz CH2CF3), 4.03 (3H, s, CH3-N), 4.15 (4H, d,
3
3JHH = 4.8 Hz, CH2-CH), 5.17 (1H, p, JHH = 4.8 Hz, CH), 7.48 (1H, s,
4.9.7. 1-(2-Hydroxyethyl)-3-[1,1,1,9,9,9-hexafluoro-3,7-dioxa-2,8-
bis(trifluoromethyl)nonan-5-yl]imidazolium bromide (7bc)
Im5), 7.61 (1H, s, Im4), 9.69 (1H, s, Im2). 13C NMR (CDCl3):
d 37.5
2
(CH3), 57.2 (CH), 69.0 (q, JCF = 34 Hz, CH2CF3), 70.5 (CH2), 122.6
The reaction of N-alkylimidazole 5b (1.00 g, 2.26 mmol) and 6c
(0.29 g, 2.26 mmol) in acetonitrile (3 ml) afforded imidazolium salt
1
(Im5), 123.6 (Im4), 124.0 (q, JCF = 280 Hz, CF3), 137.3 (Im2). 19F
3
NMR (CDCl3):
d
ꢀ74.6 (t, JHF = 8.6 Hz, CF3). ESI-HRMS:
7bc. Yield: 0.87 g (67%) brown wax. 1H NMR (DMSO-d6):
d 3.71
m/z = 321.1038; calcd. for [C11H15F6N2O2]+ 321.1039.
(2H, t, JHH = not readable, CH2-O), 4,28 (2H, t, JHH = 5.0 Hz, CH2-
N), 4.36 (4H, d, 3JHH = 5.8 Hz, CH2CH), 5.14 (1H, p, 3JHH = 5.8 Hz, CH-
N), 5.43 (1H, s, OH), 5.70 (2H, p, 3JHF = 6.4 Hz, CH(CF3)2), 7.88 (1H, s,
3
3
4.9.3. 1-(2-Hydroxyethyl)-3-(1,1,1,9,9,9-hexafluoro-3,7-
dioxanonan-5-yl)imidazolium bromide (7ac)
Im5), 7.88 (1H, s, Im4), 9.37 (1H, s, Im2). 13C NMR (DMSO-d6):
d
The reaction of 5a (1.00 g, 3.27 mmol) and 6c (0.41 g,
3.27 mmol) in acetonitrile (4 ml) afforded imidazolium salt 7ac
52.1 (CH2-N), 59.2 (CH2-O), 59.6 (CH), 71.7 (CH2CH), 74.3 (t,
2JCF = 32 Hz, CH(CF3)2), 121.3 (Im5), 123.6 (Im4), 137.2 (Im2). 19F
3
as brownish liquid. Yield: 1.1 g (77%). 1H NMR (DMSO-d6):
d
4.00–
NMR (DMSO-d6):
d
ꢀ73.8 (6F, m, JHF = 8.2 Hz, CH(CF3)2), ꢀ74.1
3
3
4.20 (10H, overlapping signals, CH2), 4.27 (2H, t, JHH = 5.0 Hz,
(6F, m, JHF = 8.0 Hz, CH(CF3)2). ESI-HRMS: m/z = 705.0669; calcd.
CH2OH), 5.03 (1H, m, CH), 5.18 (1H, s, OH), 7.85 (1H, Im5), 7.88 (1H,
for [C18H14F21N2O3]+ 705.0684.
Im4), 9.34 (1H, Im2). 13C NMR (DMSO-d6):
d 52.1 (CH2N), 59.3
2
(CH2OH), 59.5 (CH), 67.5 (q, JCF = 33 Hz, CH2CF3), 70.0 (CH2O),
4.9.8. 1-[5,5,5-Trifluoro-3-oxa-4,4-bis(trifluoromethyl)pentyl]-3-
[1,1,1,9,9,9-hexafluoro-3,7-dioxa-2,8-bis(trifluoromethyl)nonan-5-
yl]imidazolium 4-toluenesulfonate (7bd)
121.5 (Im5), 123.3 (Im4), 124.6 (q, 1JCF = 280 Hz, CF3), 136.9 (Im2).
3
19F NMR (DMSO-d6):
d
ꢀ73.5 (t, JHF = 9.3 Hz, CF3). ESI-HRMS:
m/z = 351.1143; calcd. for [C12H17F6N2O]+ 351.1155.
The reaction of 5b (1.00 g, 2.26 mmol) and 2d (0.98 g,
2.26 mmol) in acetonitrile (3.5 ml) afforded imidazolium salt
4.9.4. 1-[5,5,5-Trifluoro-3-oxa-4,4-bis(trifluoromethyl)pentyl]-3-
(1,1,1,9,9,9-hexafluoro-3,7-dioxanonan-5-yl)imidazolium 4-
toluenesulfonate (7ad)
7bd. Yield: 1.52 g (77%) mp 96–99 8C. 1H NMR (DMSO-d6):
d 2.27
(3H, s, CH3), 4.32 (4H, t, 3JHH = 4.3 Hz, CHCH2O), 4.45 (2H, s, CH2N),
4.62 (2H, t, 3JHH = 4.0 Hz, CH2CH2O), 5.15 (1H, p, 3JHH = 4.0 Hz, CH-
3
3
The reaction of 5a (0.5 g, 1.63 mmol) and 2d (0.71 g, 1.63 mmol)
in acetonitrile (5 ml) afforded imidazolium salt 7ad. Yield: 1.00 g
N), 5.61 (2H, p, JHF = 6.0 Hz, CH(CF3)2), 7.10 (2H, d, JHH = 8.0 Hz,
m-Ar), 7.48 (2H, d, 3JHH = 8.0 Hz, o-Ar), 7.90 (1H, s, Im5), 7.94 (1H, s,
(83%), mp 98–104.5 8C. 1H NMR (CDCl3):
d
2.32 (3H, s, ArCH3), 3.80
Im4), 9.44 (1H, s, Im2). 13C NMR (DMSO-d6):
d (missing signal), 21.1

A. Nemes et al. / Journal of Fluorine Chemistry 131 (2010) 1368–1376
1375
(CH3), 49.2 (CH2N), 59.6 (CH-N), 68.9 (CH2OC(CF3)3), 71.7
(CH(CF3)2), 74.8 (CH2CH), 121.6 (Im5), 123.7 (Im4), 125.8 (m-
Yield: 1.19 g (63%) pale yellow solid, mp 101–106 8C. 1H NMR
(DMSO-d6):
2.08 (2H, m, CH2), 2.49 (2H, t, 3JHH = 1.5 Hz, CH2), 3.85
(3H, s, CH3), 4.28 (2H, t, 3JHH = 7.0 Hz, CH2), 7.70 (1H, s, Im4), 7.78
(1H, s, Im5), 9.13 (1H, s, Im2). 13C NMR (DMSO-d6):
(missing signal
for CF2CH2), 21.4 (CH2CH2CH2), 36.2 (CH3), 48.0 (CH2N), 122.6
(Im4), 124.1 (Im5), 137.2 (Im2). 19F NMR (DMSO-d6):
d
Ar), 128.4 (o-Ar), 137.6 (Im2) 138.0 (g-Ar), 146.0 (p-Ar). 19F NMR
3
(DMSO-d6):
d
ꢀ70.9 (9F, s, C(CF3)3), ꢀ74.0 (6F, m, JHF = 7.6 Hz,
d
3
CH(CF3)2), ꢀ74.3 (6F, m, JHF = 7.4 Hz, CH(CF3)2). ESI-HRMS:
m/z = 705.0684; calcd. for [C18H14F21N2O3]+ 705.0699.
d
ꢀ126.4 (2F),
3
ꢀ123.5 (2F), ꢀ123.1 (2F), ꢀ122.3 (8F), ꢀ113.9 (2F, t, JFF = 15 Hz,
3
4.9.9. 1-[5,5,5-Trifluoro-3-oxa-4,4-bis(trifluoromethyl)pentyl]-3-
(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
CF2), ꢀ80.9 (3F, t, JFF = 10 Hz, CF3). ESI-HRMS: m/z = 543.0761;
calcd. for [C15H12F17N2]+ 543.0729.
heptadecafluoroundecyl)imidazolium iodide (7da)
The reaction of N-alkylimidazole 5d (1.00 g, 3.03 mmol) and 6a
(1.78 g, 3.03 mmol) in acetonitrile (15 ml) afforded imidazolium
salt 7da. Yield: 2.00 g (72%) white crystals, mp 148.5–161 8C. 1H
4.9.14. 1-(2-Hydroxyethyl)-3-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
heptadecafluoroundecyl)imidazolium iodide (7ec)
The reaction of N-alkylimidazole 5e (0.24 g, 1.89 mmol) and 6c
(0.24 g, 1.89 mmol) in acetonitrile (6 ml) afforded imidazolium salt
NMR (DMSO-d6):
d 2.0–2.3 (4H, m, NCH2CH2CH2), 4.35 (2H, t,
3
3JHH = 6.0 Hz, NCH2CH2O), 4.48 (2H, t, JHF = 4.0 Hz, CH2CF2), 4.57
7ec. Yield: 0.70 g (56%) white waxy solid. 1H NMR (DMSO-d6):
2.0–2.3 (4H, m, N-CH2), 3.72 (2H, p, JHH = 4.5 Hz, CH2OH), 4.21
d
3
3
(2H, t, JHH = 4.8 Hz, CH2OC(CF3)3), 7.83 (1H, s, Im4), 7.89 (1H, s,
Im5), 9.26 (1H, s, Im2). 19F NMR (DMSO-d6):
d
ꢀ71.5 (9F, s, C(CF3)3),
(2H, t, JHH = 5.0 Hz, CH2CH2OH), 4.29 (2H, t, JHH = 7.0 Hz,
3
3
ꢀ82.4 (3F, t, 3JFF = 11 Hz, CF3CF2), ꢀ114.9 (2F, CF2-4), ꢀ122.9 (2F, s,
CF2-6), ꢀ123.2 (4F, s, CF2-7, 8), ꢀ124.0 (2F, CF2-9), ꢀ124.4 (2F, CF2-
5), ꢀ127.6 (2F, s, CF2-10). ESI-HRMS: m/z = 791.0613; calcd. for
[C20H13F26N2O]+ 791.0598.
CH2CH2OC(CF3)3), 5.14 (1H, t, JHH = 5.0 Hz, CH2OC(CF3)3), 7.76
(1H, s, Im4), 7.82 (1H, s, Im5), 9.17 (1H, s, Im2). 13C NMR (DMSO-
3
d6):
d 21.3 (CH2CH2CH2), 27.3 (CH2OH), 47.9 (CH2N), 52.1 (CH2N),
59.6 (CH2CF2), 122.5 (Im4), 123.3 (Im5), 136.9 (Im2). 19F NMR
(DMSO-d6):
d
ꢀ126.8 (2F), ꢀ123.7 (4F), ꢀ122.6 (6F), ꢀ114.0 (2F),
4.9.10. 1-Methyl-3-[5,5,5-trifluoro-3-oxa-4,4-
ꢀ81.5 (3F). ESI-HRMS: m/z = 573.0852; calcd. for [C16H14F17N2O]+
bis(trifluoromethyl)pentyl]imidazolium iodide (7db)
573.0835.
The reaction of 5d (1.50 g, 4.55 mmol) and 6b (0.65 g,
4.55 mmol) in acetonitrile (3 ml) afforded imidazolium salt 7db.
4.10. General procedure for the synthesis of secondary amines
(Scheme 4)
Yield: 2.08 g (97%) pale yellow solid, mp 123–132 8C. 1H NMR
3
(CDCl3):
d
4.07 (3H, s, CH3), 4.46 (2H, t, JHH = 4.3 Hz, CH2O), 4.89
(2H, t, 3JHH = 4.8 Hz, CH2N), 7.55 (1H, s, Im4), 7.56 (1H, s, Im5), 9.87
d 37.7 (CH3), 50.0 (CH2N), 68.8
(CH2O), 120.3 (q, JCF = 293 Hz, CF3), 123.5 (Im4), 123.9 (Im5),
To a solution of the secondary azides 3a and 3b (7.03 g or
10.45 g; 25 mmol) in a mixture of ethanol-chloroform (110 ml;
10:1, v/v) was added 10% Pd/C (130 mg, 0.5 mol%) and shaken in a
Parr reaction bottle at 280 kPa hydrogen pressure for 10 h. The
mixture was filtered and then evaporated. To the residue 1 M
NaOH (40 ml) and ether (40 ml) was added and the aqueous layer
separated and washed with ether (2ꢃ 25 ml). The organic phases
were combined and dried over Na2SO4. The solvent was removed
under vacuum, and then the crude product was distilled to afford
the title 28 amines.
(1H, s, Im2). 13C NMR (CDCl3):
1
137.7 (Im2). 19F NMR (CDCl3):
d
ꢀ70.9 (s, CF3). ESI-HRMS: m/
z = 345.0663; calcd. for [C10H10F9N2O]+ 345.0649.
4.9.11. 1-(2-Hydroxyethyl)-3-[5,5,5-trifluoro-3-oxa-4,4-
bis(trifluoromethyl)pentyl]imidazolium bromide (7dc)
The reaction of 5d (2.00 g, 6.06 mmol) and 6c (0.76 g,
6.06 mmol) in acetonitrile (8 ml) afforded imidazolium salt 7dc.
Yield: 2.12 g (77%), pale yellow liquid. 1H NMR (CDCl3):
t, JHH = 4.5 Hz, CH2OH), 4.48 (4H, m, CH2N), 4.86 (2H, t,
3JHH = 4.5 Hz, CH2OC(CF3)3), 5.08 (1H, s, OH), 7.45 (1H, s, Im5),
7.61 (1H, s, Im4), 9.81 (1H, s, Im2). 13C NMR (CDCl3):
d
3.98 (2H,
3
4.10.1. 1,1,1,9,9,9-Hexafluoro-3,7-dioxanonan-5-amine (8a)
Yield: 4.46 g (70%) colourless liquid, bp 85–86 8C/2.67 kPa. 1H
3
d
50.0
NMR (CDCl3):
d
1.61 (2H, s, NH2), 3.18 (1H, p, JHH = 5.3 Hz, CH),
3
3
((CF3)3COCH2CH2N), 53.1 (HOCH2CH2N), 60.1 (CH2OH), 68.9
3.60 (4H, m, JHH = 5.0 Hz, O-CH2), 3.85 (4H, q, JHF = 8.6 Hz, CF3-
2
(CH2OC(CF3)3), 123.0 (Im4), 123.3 (Im5), 137.7 (Im2) (missing
CH2). 13C NMR (CDCl3):
d 51.1 (N-CH), 69.0 (q, JCF = 34 Hz, CF3-
signal for CF3). 19F NMR (CDCl3):
d
ꢀ71.9 (s, CF3). ESI-HRMS:
CH2), 74.7 (O-CH2), 124.3 (q, 1JCF = 280 Hz, CF3). 19F NMR (CDCl3):
d
m/z = 375.0755; calcd. for [C11H12F9N2O2]+ 375.0754.
ꢀ74.7 (t, JHF = 8.6 Hz, CF3). ESI-HRMS: m/z = 255.0694; calcd. for
3
[C7H11F6NO2]+ 255.0701.
4.9.12. 1,3-Bis[5,5,5-trifluoro-3-oxa-4,4-
bis(trifluoromethyl)pentyl]imidazolium 4-toluenesulfonate (7dd)
The reaction of 5d (1.486 g, 4.5 mmol) and 2d (1.954 g,
4.5 mmol) in acetonitrile (10 ml) afforded imidazolium salt 7dd.
Yield: 2.26 g (66%) white crystals, mp 162–164 8C.
4.10.2. 1,1,1,9,9,9-Hexafluoro-3,7-dioxa-2,8-
bis(trifluoromethyl)nonan-5-amine (8b)
Yield: 5.84 g (60%) colourless liquid, bp 128 8C/2.67 kPa. 1H
3
NMR (CDCl3):
d
1.44 (2H, s, NH2), 3.25 (1H, p, JHH = 5.3 Hz,
3
1H NMR (CDCl3–CD3OD (10:1)):
d
2.36 (3H, s, Ar-CH3), 4.37 (4H,
CHNH2), 3.87–3.89 (4H, m, CH2O), 4.11 (2H, septet, JHF = 5.9 Hz,
broad s, N-CH2), 4.65(4H, broad s, O-CH2), 7.20(2H, d, 3JHH = 10.0 Hz,
m-Ar), 7.37 (1H, s, Im4), 7.38 (1H, s, Im5), 7.69 (2H, d, 3JHH = 10.0 Hz,
CH(CF3)2). 13C NMR (CDCl3):
d
51.0 (CHNH2), 76.5 (CH2O), 77.0
2
1
(septet), JCF = 33 Hz, CH(CF3)2), 121.7 (q, JCF = 285 Hz, CF3). 19F
o-Ar), 9.54 (1H, s, Im2). 13C NMR (CDCl3–CD3OD (10:1)):
d
21.3 (Ar-
NMR (CDCl3):
d
ꢀ74.5 (12F, d, JHF = 5.9 Hz, CF3). ESI-HRMS:
3
CH3), 49.6 (N-CH2), 68.6 (O-CH2), 120.1 (CF3, q, 1JCF = 292 Hz), 123.1
m/z = 391.0442; calcd. for [C9H9F12NO2]+ 391.0448.
(Im4,5), 125.7 (m-Ar), 129.0 (o-Ar), 138.2 (Im2), 140.4 (g-Ar), 142.4
(p-Ar). 19F NMR (CDCl3–CD3OD (10:1)):
d
ꢀ71.2 (s, CF3). ESI-HRMS:
4.11. General procedure for the synthesis of symmetrical imidazolium
salts
m/z = 593.0533 [M*]+; calcd. for [C15H11F18N2O2]+ 593.0535; ESI-
MS: m/z = 171.0116; calcd. for [C7H7O3S]ꢀ 171.0116.
To a stirred solution of 8a or 8b (10.2 g and 15.6 g, respectively,
40 mmol) in benzene (35 ml) was added 35% aqueous formalde-
hyde (0.56 ml, 20 mmol) at 0 8C. The mixture was stirred for 1 h at
20 8C, cooled with ice-bath until mixed with 37% hydrochloric acid
(2.0 ml) and 40% aqueous glyoxal solution (0.34 ml, 20 mmol),
4.9.13. 1-Methyl-3-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-
heptadecafluoroundecyl)imidazolium iodide (7eb)
The reaction of 5e (1.00 g, 2.84 mmol) and 6b (0.18 ml, 0.41 g,
2.84 mmol) in acetonitrile (3 ml) afforded imidazolium salt 7eb.

1376
A. Nemes et al. / Journal of Fluorine Chemistry 131 (2010) 1368–1376
[3] (a) 3M Novec Fluids: Product Description, 2005.
(b) J.A. Gladysz, in: P. Anastas (Ed.), Handbook of green chemistry. Volume 1:
Homogeneous Catalysis; R. H. Crabtree, Volume Ed, Wiley/VCH, Weinheim, 2009,
pp. 17–38;
then heated at 100 8C for 24 h and evaporated to afford the title
products.
(c) G. Malinverno, I. Colombo, M. Visca, Regul. Toxicol. Pharmacol. 41 (2005) 228–
239.
[4] S. Dimitrov, V. Kamenska, J.D. Walker, W. Windlec, R. Purdy, M. Lewis, O.
Mekenyan, SAR QSAR Environ. Res. 15 (2004) 69–82.
[5] (a) I.L. Knunyants, B.L. Dyatkin, Izv. Akad. Nauk SSSR Ser. Khim. 5 (1964) 923–925;
(b) F.J. Pavlik, US Patent 3,385,904 (1968).
4.11.1. 1,3-Bis(1,1,1,9,9,9-hexafluoro-3,7-dioxanonan-5-
yl)imidazolium chloride (9a)
Yield: 8.89 g (77%) brownish liquid. 1H NMR (CDCl3):
d 3.92 (8H,
3
3
m, JHF = 8.5 Hz, CH2CF3), 4.13 (8H, d, JHH = 4.7 Hz, CH2O), 5.22
(2H, p, 3JHH = 5.0 Hz, CH), 7.579 (1H, s, Im5), 7.582 (1H, s, Im4), 9.99
(1H, s, Im2). 13C NMR (CDCl3):
´
[6] (a) J. Ra´bai, D. Szabo´, E.K. Borba´s, I. Ko¨vesi, I. Ko¨vesdi, A. Csa´mpai, A. Go¨mo¨ry, V.E.
2
d
60.2 (CHN), 68.8 (q, JCF = 35 Hz,
Pashinnik, Y.G. Shermolovich, J. Fluorine Chem. 114 (2002) 199–207;
1
´
(b) D. Szabo´, A.-M. Bonto, I. Ko¨vesdi, A. Go¨mo¨ry, J. Ra´bai, J. Fluorine Chem. 126
CH2CF3), 70.6 (CH2O), 121.9 (Im4,5), 124.0 (q, JCF = 280 Hz, CF3),
137.9 (Im2). 19F NMR (CDCl3):
d
ꢀ74.8 (t, JHF = 8.5 Hz, CF3). ESI-
3
(2005) 641–652.
[7] (a) D. Szabo´, J. Mohl, A.-M. Ba´lint, A. Bodor, J. Ra´bai, J. Fluorine Chem. 127 (2006)
1496–1504;
HRMS: m/z = 545.1310; calcd. for [C17H21F12N2O4]+ 545.1309.
(b) D. Szabo´, A. Nemes, I. Ko¨vesdi, V. Farkas, M. Hollo´si, J. Ra´bai, J. Fluorine Chem.
127 (2006) 1405–1414.
4.11.2. 1,3-Bis[1,1,1,9,9,9-hexafluoro-3,7-dioxa-2,8-
[8] Z.-X. Jiang, Y.B. Yu, Tetrahedron 63 (2007) 3982–3988.
[9] Z.-X. Jiang, Y.B. Yu, Synthesis (2008) 215–220.
[10] Q. Chu, C. Henry, D.P. Curran, Org. Lett. 10 (2008) 2453–2456.
[11] Z.-X. Jiang, Y.B. Yu, J. Org. Chem. 72 (2007) 1464–1467.
[12] Z.-X. Jiang, X. Liu, E.-K. Jeong, Y.B. Yu, Angew. Chem. Int. Ed. 48 (2009) 4755–4758.
[13] Z.-X. Jiang, Y.B. Yu, J. Org. Chem. 75 (2010) 2044–2049.
[14] Y. Yu, Z.-X. Yiang, WO Patent 2007/112100 (2007).
bis(trifluoromethyl)nonan-5-yl]imidazolium chloride (9b)
Yield: 8.88 g (52%) brownish liquid. 1H NMR (DMSO-d6):
d
4.32–
3
4.49 (8H, m, CH2), 5.24 (2H, p, JHH = 3.5 Hz, CH-N), 5.80 (4H,
septet, 3JHF = 6.3 Hz, CH(CF3)2), 8.12 (1H, s, Im5), 8.13 (1H, s, Im4),
9.82 (1H, s, Im2). 13C NMR (DMSO-d6):
d 59.8 (CHN), 71.6 (CH2),
74.2 (m, 2JCF = 32 Hz, CH(CF3)2), 121.7 (q, 1JCF = 283 Hz, CF3),121.9
´ ˇ
´
´
´ˇ
´
ˇ
´ˇ
[15] O. Kysilka, M. Rybackova, M. Skalicky, M. Kvıcalova, J. Cvacka, J. Kvıcala, Collect.
Czech. Chem. Commun. 73 (2008) 1799–1813.
(Im4,5), 137.6 (Im2). 19F NMR (DMSO-d6):
CF3).
d
ꢀ73.9 (d, 3JHF = 6.3 Hz,
ˇ
´
´
´ˇ
´
[16] (a) O. Kysilka, M. Ryba´ckova, M. Skalicky, M. Kvıcalova, J. Fluorine Chem. 130
(2009) 629–639;
ˇ
´ ˇ
´
´
(b) J. Kvı´cala, M. Rybackova, M. Skalicky, O. Kysilka, CZ Patent 301543 (2010).
[17] (a) R.K. Crossland, K.L. Servis, J. Org. Chem. 35 (1970) 3195–3196;
Acknowledgments
ˇ´
´
´
´
(b) T. Brıza, V. Kral, P. Martasek, R. Kaplanek, J. Fluorine Chem. 129 (2008) 235–247.
[18] P.J. Stang, M. Hanack, L.R. Subramanian, Synthesis (1982) 85–126.
ˇ
ˇ
´
´ˇ
´
ˇ
´ˇ
[19] M. Skalicky´, M. Ryba´ckova, O. Kysilka, M. Kvıcalova, J. Cvacka, J. Cejka, J. Kvıcala, J.
Fluorine Chem. 130 (2009) 966–973, and references cited therein.
[20] (a) M.L. Brey, P.J. Tarrant, J. Am. Chem. Soc. 79 (1957) 6533–6536;
(b) K.-T. Kang, S.K. Lee, C.W. Park, S.H. Cho, J.G. Lee, S.-K. Choi, Y.B. Kim, Bull.
Korean Chem. Soc. 27 (2006) 1364–1370;
These investigations were supported by the Hungarian
Scientific Research Foundation (OTKAK 062191 ‘‘Sustainable
fluorous chemistry’’). The European Union and the European
Social Fund have provided financial support to the project under
(c) L.G. Anello, R.F. Sweeney, (Allied Chemical Corp.) US Patent 3,409,602 (1968).
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(b) E. de Wolf, P. Ruelle, J. van den Broeke, B.-J. Deelman, G. van Koten, J. Phys.
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´
the grant agreement no. TAMOP 4.2.1./B-09/KMR-2010-0003. A.
´
Bodor acknowledges the Janos Bolyai Research Scholarship of the
Hungarian Academy of Sciences.
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