Full Papers

Mixture Synthesis of Fluorous Ketals: Mitsunobu Reaction of

Homologous 3-Perfluoroalkyl-propanols with Hexafluoroacetone
Sesquihydrate and Collective Determination of Fluorophilicity
Values
József Rábai*, Ana-Maria Bálint, Csongor Sz-jjártó and Dénes Szabó
Department of Organic Chemistry, Institute of Chemistry, Eçtvçs Loránd University, P.O. Box 32, H-1518, Budapest 112, Hungary,
E-mail: rabai@elte.hu

Keywords: Combinatorial chemistry, Elution order, Fluorophilicity, Gas chromatography, Synthesis

Received: April 17, 2006; Accepted: April 17, 2006

DOI: 10.1002/qsar.200640046

Abstract
The reaction of hexafluoroacetone sesquihydrate (1, 2 mmol) with a mixture of 3-perfluor-
oalkyl-propanols (CnF2n þ 1 (CH2)3OH; 2a – d: n ¼ 4, 6, 8, 10; 1 mmol each) in an ether solu-
tion using the classical Ph3P/diisopropyl azodicarboxylate reagent pair afforded a mixture
of ten ketals [(CF3)2C(O(CH2)3CnF2n þ 1)2, 3{a – d}  {a – d}]. The mixture of the ten fluoro-
philic ketals was easily separated from side products using fluorous extraction (FC-72/
CH3OH). The composition of this fluorous ketal mixture was quantitatively analyzed by
GC, and the results obtained were in agreement with predictable trends based on a
statistical model. A method for collective fluorophilicity determination of the individual
fluorous ketals was supplemented with the calculation of fluorous isotherms and the
analysis of gas chromatographic elution orders.

1 Introduction In discovery chemistry fluorous Mitsunobu reactions re-

The rapidly developing fluorous chemistry now encom-
passes diverse fields of chemistry, which are the subjects of
timely reviews [1]. The “classical” Fluorous Biphasic Cat-
alysis (FBC) [2], Fluorous Synthesis (FS) [3], and Fluorous
Mixture Synthesis (FMS) [4] techniques have recently
been supplemented with the introduction of Fluorous
Electrochemical Sensors (FECS) [5]. All of these activities
call for an easy access to fluorous molecules.
The synthesis of fluorous molecules in principle can be
accomplished by appending fluorous ponytails (e.g., n-per-
fluoroalkyl group, Rfn ¼ F(CF2)n  ) of appropriate number,
length, and shape to target molecules [2, 6]. It was shown
that the strong electron withdrawing effect of perfluor-
oalkyl groups on the reaction centers can be insulated by
the insertion of an (CH2)n(n  3) fragment inbetween
the fluorous-ponytail and the parent compound [7].
Several hundred fluorous compounds have been synthe-
sized and many supplied with experimentally determined
fluorous partition coefficient (PFBS) and fluorophilicity
(f ¼ ln PFBS) values. Recent communications demonstrated
that the shortest ponytail (Rf1 ¼ CF3) is the most effective
for increasing compoundGs specific fluorophilicity or fluo-
rousness values [8].
ceive increasing attention because a range of fluorous azo-
dicarboxylates and phosphines are commercially available
[9, 10].
We and others have applied the classical Ph3P/DIAD
couple for the synthesis of fluorophilic ethers, ketals, and
esters which is parallel to the recent introduction of fluo-
rous Mitsunobu reagents. The latter method sometimes is
referred as inverse fluorous Mitsunobu reaction [11].
2 Results and Discussion
Here, we report on the mixture synthesis of fluorous ketals
(3{a – d}  {a – d}) using hexafluoroacetone sesquihydrate
(1) and 3-perfluoroalkyl-propanol (2a – d, n ¼ 4, 6, 8, 10)
precursors under standard Mitsunobu conditions and the
development of a method for the collective determination
of fluorophilicity values of individual ketal components
(Scheme 1).
We thought that alcohols 2a – d should have equal reac-
tivity as their C1 – C6 fragments are the same, and the dif-
ferences appear only at the C7 position (Scheme 2) [7].
The seven bonds distance between the RfmCF2 and OH
groups along with the very similar electron withdrawing
effect of linear perfluoroalkyl groups (RfmCF2) justifies

QSAR Comb. Sci. 00, 0000, No. &, 1 – 5 L 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim &1&
These are not the final page numbers! ÞÞ
Full Papers József Rábai et al.

Scheme 1. Mitsunobu synthesis of the mixture of ten fluorous ketals (n ¼ 4, 6, 8, 10).

Scheme 2. Structures and topologies of fluorous propanols.

this supposition [12, 13]. However, the molar volume dif-

ferences of alcohols (i.e., entropy effects) have not been
considered in this approach.
Here, we assume that under homogeneous reaction con- Figure 1. GC trace of the mixture of ten ketals, solvent ether,
ditions all alcohols will react at the same rate, and the and internal standard BTF (GC parameters: 120 8C, 5 min;
composition of the “mixture of ten” ketals will be control- 10 8C/min; 250 8C, 15 min; PONA 50 m).
led by statistical probabilities. Pro-nucleophile 1 and two
equivalents of ROH can be transformed in a Mitsunobu
reaction to the appropriate ketal 3 via a hemiketal inter- the ten individual ketals in nearly statistical molar ratios
mediate I (Scheme 3). (Figure 1 and Table 2, Section 4).
As the off-diagonal combinations of R1@R2 have twice The quantitative analysis of the mixture of ten ketals
as much probability than the symmetrical ones (Table 1), a was performed by GC. First, a calibration curve for diago-
ketal mixture with statistical composition should display nal components was determined by taking the ratio of the
their symmetrical and unsymmetrical components in a 1 : 2 integrals of reference solutions of 3aa, 3bb, 3cc, and 3dd in
molar ratio if the stoichiometry of the reactants is the ether with internal standard BTF [11c], then the concen-
same as shown in Scheme 1. tration data for the off-diagonal components were calcu-
Indeed, experiments run with (CF3)2C(OH)2 (1, lated by interpolation using the appropriate ketal/BTF in-
2.00 mmol), and the four fluorous alcohols (2a – d, tegral ratios.
1.00 mmol each) resulted in the formation of a mixture of The assignment of retention times for each components
of the mixture of ten was done indirectly, as no specimens
of the single off-diagonal components were available, and
furthermore no molecular ions were seen in the mass spec-
tra of the symmetrical ketals [11c].
Consequently, retention times for the 4-4, 6-6; 8-8, and
10-10 combinations were first measured on pure samples.
Scheme 3. Sequential steps of the ketal formation reaction Then a “mixture of six” ketals was prepared from 1 and
(R1@R2). 2b – d (Section 4) and analyzed by GC to afford retention
times for the 6-6, 6-8, 6-10, 8-8, 8-10, and 10-10 combina-
tions. Retention times for the 6-8 < 6-10 and < 8-10 compo-
Table 1. Theoretical combinations of R1@R2 for (CF3)2 nents were identified here. Finally, with the knowledge of
C(OR1)(OR2) ketals.
R1@R2 A B c D Table 2. Molar ratios of the individual ketals in the mixture of
a 4-4 6-4 8-4 10-4 ten as determined by GC.
b 4-6 6-6 8-6 10-6 Entry {4, 4} {4, 6} {6, 6} {4, 8} {6, 8} {4, 10} {8, 8} {6, 10} {8, 10} {10, 10}
c 4-8 6-8 8-8 10-8
d 4-10 6-10 8-10 10-10 Ratio 1.00 1.99 1.00 1.88 1.84 1.85 0.91 1.85 2.01 1.16

&2& L 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.qcs.wiley-vch.de QSAR Comb. Sci. 00, 0000, No. &, 1 – 5
ÝÝ These are not the final page numbers!
Mixture Synthesis of Fluorous Ketals&

Table 3. Retention times of the individual components of the Table 4. Fluorous partition coefficent and fluorophilicity data of
mixture of ten ketalsa. ketals 3{a – d}  {a – d}.
Entry 3aa 3ab 3bb 3ac 3bc 3ad 3cc 3bd 3cd 3dd Entry R1, R2 Pexpa f ¼ lnPexp Pmixb f ¼ lnPmix n1 þ n2
R1@R2 4-4 4-6 6-6 4-8 6-8 4-10 8-8 6-10 8-10 10-10 3aa {4, 4} 11.3 2.42 12.5 2.53 8
tRet (min) 8.60 10.41 12.02 12.10 13.51 13.64 14.80 14.87 16.01 17.07 3ab {4, 6}, {6, 4} – – 23.2 3.14 10
a
3ac {4, 8}, {8, 4} – – 44.7 3.80 12
Ether 2.99 min; BTF 3.52 min.
3bb {6, 6} 44.6 3.80 45.2 3.81 12
3ad {4, 10}, {10, 4} – – 82.6 4.41 14
3bc {6, 8}, {8, 6} – – 81.9 4.41 14
the values for 4-4, 6-6, 6-8, 6-10, 8-8, 8-10, and 10-10, the 3bd {6, 10}, {10, 6} – – 141 4.95 16
GC analysis of a sample of the mixture of ten ketals af- 3cc {8, 8} 142 4.96 144 4.97 16
forded the missing last three figures for the 4-6, 4-8, and 4- 3cd {8, 10}, {10, 8} – – 240 5.48 18
3dd {10, 10} 186 5.23 330 5.80 20
10 components (Figure 1, Table 3).
a
These fluorous ketals leave the highly apolar stationary Individual determination, cf. [11c] (experimental, 10 mg of the single ke-
tal per 1:1 mL toluene/CF3C6F11).
phase GC column in the order of their increasing fluorous b
Collective determination (experimental, 100 mg mixture of ten ketals
contents. It should be noted that among isomeric ketal per 1 : 1 mL toluene/CF3C6F11).
pairs (6-6, 4-8; 6-8, 4-10; and 8-8, 6-10) the one with a lon-
ger tail displays somewhat larger retention time. The base-
line separation of these isomers also deserves attention isotherms with a group contribution method as described
(Figure 1), although the mechanism of the latter separa- earlier [11c].
tion selectivity phenomenon is not yet well understood. The results obtained for molar volumes (Vm, Barton,
The above evaluation of the reactivity of the homolo- Vm, de Wolf) using either Barton or de Wolf parameters are
gous alcohols in ether solution revealed that the mixture very similar. However, the calculated cohesions (dBarton, dde
of alcohols 2a – d in this media behaves as an ideal solu- Wolf) have significant differences in the two sources (cf.
tion. Under nonideal conditions, such statistical result is [11c], Table 5).
hardly expected to occur. Although we found here that specific fluorophilicity val-
We thought that collective determination of fluorous ues have good linear correlation with both the Hildebrand
partition coefficients for each individual ketal component [14] and the de Wolf et al. [8f] cohesion parameters (Ta-
in the mixture of ten sample could be a probe of their ble 5), the former fluorous isotherm (Figure 2) has a seri-
phase behavior. Moreover, such collective method for the ous error of displaying increasing specific fluorophilicity
determination of PFBS values could result in the saving of with increasing calculated Hildebrand parameter (Eq. 1).
significant amount of GC instrument occupation time.
Our preliminary results showed that this novel method fspec, Barton ¼  58.559 þ 4.478 dBarton (1)
affords agreeable figures to those determined earlier using
single samples of the symmetrical ketal components (Ta- Only the latter de Wolf isotherm (Figure 3) displays real
ble 4). physical meanings: the lower the soluteGs cohesion param-
Fluorous partition coefficients of the symmetrical ketals eter, the larger the specific fluorophilicity of the solute
(3aa, 3bb, 3cc, and 3dd) obtained using either single or col- (Eq. 2).
lective determinations have rather good matching.
To show the linear correlation between specific fluoro- fspec, de Wolf ¼ 14.2901.032 dde Wolf (2)
philicity and cohesion parameter, we calculated fluorous

Table 5. Specific fluorophilicity values and calculated cohesion parameters of ketals 3a,b.
Entry 3-R1, R2 P f ¼ ln P dBarton ( MPa1/2) Vm, Barton (cm3/mol) fspec, Barton dde Wolf ( MPa1/2) Vm, de Wolf (cm3/mol) fspec, de Wolf
{4, 4} 12.5 2.53 13.33 453 1.09 12.72 443 1.12
{4, 6} 23.2 3.14 13.36 499 1.23 12.61 489 1.26
{4, 8} 44.7 3.80 13.38 545 1.366 12.51 535 1.391
{6, 6} 45.2 3.81 13.38 545 1.371 12.51 535 1.395
{4, 10} 82.6 4.41 13.40 591 1.464 12.43 581 1.488
{6, 8} 81.9 4.41 13.40 591 1.46 12.43 581 1.485
{6, 10} 141 4.95 13.42 637 1.52 12.37 628 1.545
{8, 8} 143.5 4.97 13.42 637 1.53 12.37 628 1.551
{8, 10} 240 5.48 13.43 683 1.57 12.30 674 1.59
{10, 10} 330 5.79 13.44 729 1.56 12.24 720 1.58
a
fspec, Barton ¼ A þ B*dBarton (for definitions, cf. [11c, 14]).
b
fspec, de Wolf ¼ A þ B*dde Wolf (for definitions, cf. [8f, 11c]).

QSAR Comb. Sci. 00, 0000, No. &, 1 – 5 www.qcs.wiley-vch.de L 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim &3&
These are not the final page numbers! ÞÞ
Full Papers József Rábai et al.

Table 6. Regression and statistical parameters of fluorous iso- Baseline separations were achieved even for isomeric
therms for ketals 3{a – d}  {a – d}. fluorous ketals using GC with a 50 m capillary column
Method A B R2 S.D. N holding a very apolar crosslinked methylsilicon gum sta-
tionary phase.
Barton  58.559 4.478 0.9569 0.0343 10
de Wolf 14.29031  1.032 0.9476 0.0370 10
4 Experimental Section

Hexafluoroacetone sesquihydrate, FC-72 (mix of perfluor-

Figure 2. Fluorous isotherm of ketals calculated from Barton
group contribution increments. (Note the erroneous figures for
dHildebrand, e.g., 10-10 has higher dHildebrand than 4-4!)
Figure 3. Fluorous isotherm of ketals calculated from de Wolf
group contribution increments.
ohexanes), and perfluoro(methyl-cyclohexane) were pur-
chased from Fluorochem, whereas the alcohols CnF2n þ 1
(CH2)3OH, n ¼ 4, 6, 8, 10 were prepared as reported [15].
The other reagents and solvents were Aldrich or Fluka
products. Fourier transformed infrared spectra were re-
corded neat, as a film on a Bruker Equinox FTIR spectro-
photometer, nmax in cm1. The intensity of the bands are
characterized as broad (br), strong (s), medium (m) or
weak (w). 1H NMR, 13C NMR, and 19F NMR spectra were
recorded on Bruker Avance 250 and DRX500 spectrome-
ters using 5 mm inverse 1H/13C/31P/19F and 1H/13C/15N probe
heads at Room Temperature (r.t.), respectively. Data were
expressed as chemical shifts in parts per million (ppm) rel-
ative to residual chloroform (1H d 7.27), CDCl3 (13C d
77.0) or an external standard for 19F (CFCl3, d ¼ 0) on the
d scale.
All reaction steps were monitored by gas chromatogra-
phy [Hewlett-Packard 5890 Series II, PONA (crosslinked
methylsilicone gum) 50 m  0.2 mm  0.5 mm column, H2
carrier gas, FID).
Partition coefficients were determined by GC as follows:
In a 2 mL volumetric flask the given compounds (10 mg
for individual, 100 mg for collective determination) were
extracted in a 1 : 1 mL mixture of pre-equilibrated per-
fluoro(methylcyclohexane) 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 or longer at this temperature 300 
3 mL aliquots of the separated upper and lower phases
were withdrawn and diluted with 300  3 mL benzotrifluor-
ide, which served as an internal standard for GC analysis.

3 Conclusions
Fluorous isotherms are only the first approximations for
the treatment of the fluorous partition phenomenon. This
“paper-and-pencil” method gives better performance with
the use of de Wolf cohesion increments [8f] in particular
for fluorine rich molecules [11c].
The homologous series of perfluoroalkyl propanols dis-
play very similar reactivities in a homogeneous solution
phase reaction and have predictable fluorophilicities as
proved by mixture synthesis of ketals and collective parti-
tion coefficient determinations, respectively.
Mixture of Ten Ketals (3aa, 3ab, 3ac, 3ad, 3bb, 3bc, 3bd,
3cc, 3cd, 3dd)
To a stirred solution of 1*0.5H2O (0.386 g, 2.00 mmol), 2a
(0.280 g, 1.00 mmol), 2b (0.380 g, 1.00 mmol), 2c (0.480 g,
1.00 mmol), 2d (0.580 g, 1.00 mmol), and Ph3P (1.572 g,
6.00 mmol) in absolute ether (20 mL) is added at 0 – 5 8C a
solution of Diisopropyl Azodicarboxylate (DIAD, 1.212 g,
6.0 mmol) in absolute ether (5 mL) during 30 min. Then it
is stirred at r.t. overnight and the solvent evaporated. The
residue was partitioned between CH3OH (5 mL) and FC-
72 (3  5 mL). The separated FC-72 phase consecutively is
washed with CH3OH (3  2 mL), then the fluorous solvent
is distilled off at 1 atm (bath temperature 75 8C).

&4& L 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.qcs.wiley-vch.de QSAR Comb. Sci. 00, 0000, No. &, 1 – 5
ÝÝ These are not the final page numbers!
Mixture Synthesis of Fluorous Ketals&
Yield: 1.89 g (94%) colorless oil. 1H NMR: d 2.0 (m,
CH2CH2O), 2.21 (m, CF2CH2), 3.84 (t, CH2O); 13C NMR
(partial): d 20.9, 27.7, 63.7; 19F NMR: d  76.3 (s, C(CF3)2),
 82.2,  82.4,  115.5,  122.7,  123.7,  124.5,  125.5,
 127.2; IR (BaF2, film): 2978w, 1231s, 1147s.
Mixture of Six Ketals (3bb, 3cc, 3dd, 3bc, 3bd, 3cd)
To a stirred solution of 1*0.5H2O (0.29 g, 1.50 mmol), 2b
(0.38 g, 1.00 mmol), 2c (0.48 g, 1.00 mmol), 2d (0.58 g,
1.00 mmol), and Ph3P (1.18 g, 4.50 mmol) in absolute ether
(15 mL) is added at 0 – 5 8C a solution of DIAD (1.01 g,
5.0 mmol) in absolute ether (5 mL) during 30 min. Then it
is stirred at r.t. overnight and the solvent evaporated at at-
mospheric pressure. The residue was partitioned between
CH3OH (5 mL) and FC-72 (3  5 mL). The separated FC-
72 phase consecutively is washed with CH3OH (3  2 mL),
then the fluorous solvent is distilled off at ambient pres-
sure (bath temp. 75 8C).
Yield: 1.47 g (89%) colorless oil. 1H NMR: d 2.0 (m,
CH2CH2O), 2.23 (m, CF2CH2), 3.84 (t, CH2O); 13C NMR
(partial): d 21.0, 27.7, 63.7; 19F NMR: d  76.2 (s, C(CF3)2),
 82.1,  115.3,  122.6,  123.6,  124.4,  127.1; IR
(BaF2, film): 2878w, 1225s, 1147s.
Acknowledgements
We thank the Hungarian Scientific Research Foundation
(OTKA T 043738) for financial support. A.-M. B. thanks
the Gedeon Richter Centenary Foundation for a half-year
fellowship.
References
[1] a) I. T. Horváth, Acc. Chem. Res. 1998, 31, 641 – 650; b) D. P.
Curran, Angew. Chem. Int. Ed. 1998, 37, 1175 – 1196; c) J.
Rábai, Z. Szlávik, I. T. Horváth, Chemistry in Fluorous Bi-
phasic Systems, in: J. Clark, D. MacQuarrie (Eds.), Hand-
book of Green Chemistry and Technology, Blackwell Sci-
ence, Oxford, 2002, pp. 502 – 523; d) J. A. Gladysz, D. P. Cur-
ran, Tetrahedron 2002, 58, 3823 – 4131; e) A. P. Dobbs, M. R.
Kimberley, J. Fluorine Chem. 2002, 118, 3 – 17; f) J. A. Gla-
dysz, D. P. Curran, I. T. Horváth (Eds.), Handbook of Fluo-
rous Chemistry, Wiley-VCH, Weinheim, 2004; g) J. A. Gla-
dysz, Angew. Chem. Int. Ed. 2005, 44, 5766 – 5768.
[2] a) I. T. Horváth, J. Rábai, Science 1994, 266, 72 – 75; b) I. T.
Horváth, J. Rábai, US Patent 5,463,082 (Exxon Research
and Engineering Co.) October 31, 1995 (application: July 8,
1993); Chem. Abstr. 1995, 123 87349.
[3] a) A. Studer, S. Hadida, R. Ferritto, S.-Y. Kim, P. Jeger, P.
Wipf, D. P. Curran, Science 1997, 275, 823 – 826; b) J. Yoshi-
da, K. Itami, Chem. Rev. 2002, 102, 3693 – 3716.
QSAR Comb. Sci. 00, 0000, No. &, 1 – 5 www.qcs.wiley-vch.de
[4] Y. Oderaotoshi, Q. Zhang, Z. Luo, D. P. Curran, Science
2001, 291, 1766 – 1769.
[5] a) P. G. Boswell, P. BWhlmann, J. Am. Chem. Soc. 2005, 127,
8958 – 8959; b) P. G. Boswell, E. C. Lugert, J. Rábai, E. A.
Amin, P. BWhlmann, J. Am. Chem. Soc. 2005, 127, 16976 –
16984.
[6] a) E. de Wolf, G. van Koten, B.-J. Deelman, Chem. Soc.
Rev. 1999, 28, 37 – 41; b) R. D. Fish, Chem. Eur. J. 1999, 5,
1677 – 1680; c) M. Cavazzini, F. Montanari, G. Pozzi, S. Qui-
ci, J. Fluorine Chem. 1999, 94, 183 – 193.
[7] a) I. T. Horváth, G. Kiss, R. A. Cook, J. E. Bond, P. A. Ste-
vens, J. Rábai, E. J. Mozeleski, J. Am. Chem. Soc. 1998, 120,
3133 – 3143; b) L. P. Barthel-Rosa, J. A. Gladysz, Coord.
Chem. Rev. 1999, 192, 587 – 605; c) Z. Szlávik, G. Tárkányi,
Á. Gçmçry, G. Tarczay, J. Rábai, J. Fluorine Chem. 2001,
108, 7 – 14.
[8] a) L. E. Kiss, J. Rábai, L. Varga, I. Kçvesdi, I. Synlett 1998,
1243 – 1245; b) V. Herrera, P. J. F. de Rege, I. T. Horváth,
T. L. Husebo, R. P. Hughes, Inorg. Chem. Commun. 1998, 1,
197 – 199; c) Z. Szlávik, G. Tárkányi, Gy. Tarczay, Á. Gçmç-
ry, J. Rábai, J. Fluorine Chem. 1999, 98, 83 – 87; d) L. E.
Kiss, I. Kçvesdi, J. Rábai, J. Fluorine Chem. 2001, 108, 95 –
109; e) J. A. Gladysz, C. Emnet, J. Rábai, Partition Coeffi-
cents Involving Fluorous Solvents, in: J. A. Gladysz, D. P.
Curran, I. T. Horváth (Eds.), Handbook of Fluorous
Chemistry, Wiley-VCH, Weinheim, 2004, pp. 56 – 100; f) E.
de Wolf, P. Ruelle, J. van den Broeke, B.-J. Deelman, G.
van Koten, J. Phys. Chem. B 2004, 108, 1458 – 1466.
[9] a) E. G. Hope, A. M. Stuart, J. Fluorine Chem. 1999, 100,
75 – 83; b) A. P. Dobbs, C. McGregor-Johnson, Tetrahedron
Lett. 2002, 43, 2807 – 2810; c) R. Dembinski, Approaches to
the Fluorous Mitsunobu Reaction, in: J. A. Gladysz, D. P.
Curran, I. T. Horváth (Eds.), Handbook of Fluorous
Chemistry, Wiley-VCH, Weinheim, 2004, pp. 190 – 202; d) S.
Dandapani, D. P. Curran, J. Org. Chem. 2004, 69, 8751 –
8757; e) D. P. Curran, X. Wang, Q. Zhang, J. Org. Chem.
2005, 70, 3716 – 3719.
[10] http://www.fluorous.com.
[11] a) J. Rábai, D. Szabó, E. K. Borbás, I. Kçvesi, I. Kçvesdi,
A. Csámpai, Á. Gçmçry, V. E. Pashinnik, Yu. G. Shermolo-
vich, J. Fluorine Chem. 2002, 114, 199 – 207; b) M. W. Mar-
kowicz, R. Dembinski, Org. Lett. 2002, 4, 3785 – 3787; c) D.
Szabó, A.-M. Bonto, I. Kçvesdi, Á. Gçmçry, J. Rábai, J.
Fluorine Chem. 2005, 126, 641 – 652; d) D. Szabó, J. Mohl,
A.-M. Bálint, A. Bodor, J. Rábai, J. Fluorine Chem. 2006
(submitted).
[12] J. A. Gladysz, Ponytails: Structural and Electronic Consider-
ations, in: J. A. Gladysz, D. P. Curran, I. T. Horváth (Eds.),
Handbook of Fluorous Chemistry, Wiley-VCH, Weinheim,
2004, pp. 41 – 55.
[13] B. E. Smart, J. Fluorine Chem. 2001, 109, 3 – 11.
[14] A. F. M. Barton, CRC Handbook of Solubility Parameters
and Other Cohesion Parameters, CRC Press, Inc., Boca Ra-
ton, FL, 1983, pp. 64 – 66.
[15] a) N. O. Brace, J. Fluorine Chem. 1982, 20, 313 – 328; b) Z.
Szlávik, G. Tárkányi, Gy. Tarczay, Á. Gçmçry, J. Rábai, J.
Fluorine Chem. 1999, 98, 83 – 87.
L 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim &5&
These are not the final page numbers! ÞÞ