acidic impurity. They were then dried over magnesium sulfate,
suction filtered, and reduced in vacuo first on a rotovap and
then on a high vacuum line (4 Pa, 100 ◦C) for 16 hr to yield
the final product as a white solid (380 g, 76% yield). 19F NMR
(DMSO-d6) d -73.7 ( (s, 3F); -114.6, -120.9 (ABq, J = 258 Hz,
2F); -210.5 (m, JHF = 41.5 Hz, 1F). 1H NMR (DMSO-d6) d 0.8
(t, J = 7.0 Hz, 3H); 0.9 (t, J = 7.0 Hz, 9H); 1.3 (br s, 20H);
1.4 (m, 16H); 2.2 (m, 8H); 5.9 (m, JHF = 42 Hz, 1H).% Water
by Karl-Fisher titration: 895 ppm. Analytical calculation for
C29H57F6O3PS: C, 55.2: H, 9.1: N, 0.0. Experimental Results: C,
55.1: H, 8.8: N, 0.0. TGA (air): 10% wt. loss @ 373 ◦C, 50% wt.
loss @ 421 ◦C. TGA (N2): 10% wt. loss @ 383 ◦C, 50% wt. loss
@ 436 ◦C.
References
1 P. T. Anastas and T. C. Williamson, Green Chemistry: Frontiers in
Benign Chemical Syntheses and Processes, Oxford University Press,
1998.
2 M. A. Harmer, C. Junk, V. Rostovtsev, L. G. Carcani, J. Vickery and
Z. Schnepp, Green Chem., 2007, 9, 30–37.
3 V. V. Rostovtsev, L. M. Bryman, C. P. Junk, M. A. Harmer and L. G.
Carcani, J. Org. Chem., 2008, 73, 711–714.
4 J.-P. Simonato, Chem. Ind., 2005, 20–21.
5 E. Marx, Speciality Chemicals Magazine, 2004, 24, 24–25.
6 Y. Katsuhara, M. Aramaki, A. Ishii, T. Kume, C. Kawashima and S.
Mitsumoto, J. Fluor. Chem., 2006, 127, 8–17.
7 G. A. Olah, G. K. Surya Prakash and J. Sommer, Superacids, Wiley,
1985.
8 J. A. Horsley, Chemtech, 1997, 27, 45–49.
9 A. de Angelis, C. Flego, P. Ingallina, L. Montanari, M. G. Clerici, C.
Carati and C. Perego, Cat. Today, 2001, 65, 363–371.
10 J. A. Kocal, B. V. Vora and T. Imai, Appl. Cat. A: General, 2001, 221,
295–301.
Catalyst testing
11 S. J. Miller, Stud. Surf. Sci. Cat., 1994, 84, 2319–2326.
12 G. A. Olah, Friedel–Crafts Chemistry, Wiley, 1973.
13 G. Sartori and R. Maggi, Chem. Rev., 2006, 106, 1077–1104.
14 R. Bringue, J. Tejero, M. Iborra, J. F. Izquierdo, C. Fite and F. Cunill,
Ind. Eng. Chem. Res., 2007, 46, 6865–6872.
15 J. Tejero, F. Cunill, M. Iborra, J. F. Izquierdo and C. Fite, J. Mol.
Cat. A: Chem., 2002, 182–183, 541–554.
16 J. H. Clark, Catalysis of Organic Reactions by Supported in Inorganic
Reagents, John Wiley & Sons, 1994.
17 K. E. Johnson, R. M. Pagni and J. Bartmess, Monatsh. Chem., 2007,
138, 1077–1101.
All reagents were reagent grade.
Akylation2
The ionic liquid 1-dodecyl-3-methylimidazolium 1,1,2,2-
tetrafluoroethanesulfonate (0.19 g) was placed in a round
bottomed flask and dried at 150 ◦C for 48 hours. 1,1,2,3,3,3-
Hexafluoropropanesulfonic acid (0.5 g) was added, followed by
the addition of 5 ml of 1-dodecene and 15 ml of p-xylene. The
mixture was heated to 100 ◦C under a nitrogen atmosphere. After
2 hours reaction time, gas chromatographic analysis showed
near complete reaction (>95%) of the 1-dodecene to give the
alkylated product. The ionic liquid and acid formed a distinct
second phase that separated out at the bottom of the flask. GC
analysis was performed as follows. Samples were diluted 1 to
20 in ether for GC analysis. All of the samples were analyzed
by a Hewlett Packard 5890 Series II GC equipped with FID
detectors. Product identification was carried out with a GC-
18 V. I. Parvulescu and C. Hardacre, Chem. Rev., 2007, 107, 2615–2665.
19 Crystal data for EMIM-TFES (04307): C8H12F4N2O3S, FW =
˚
292.26, monoclinic, space group P21/n, a◦= 8.770(8) A, b =
3
˚
˚
˚
9.766(9) A, c = 14.282(12) A, b = 95.363(12) , U = 1217.9(18) A ,
T = -100.◦C, Z = 4, Dcalcd = 1.59g/cm3. Data were collected using a
Bruker Apex-II CCD system equipped with MoKa radiation yielding
9216 total reflections, 2998 unique, Rint = 0.041. Structure solved
and refined on F2 using SHELXTL94.38 All non-hydrogen atoms
were refined with anisotropic thermal parameters. Hydrogen atoms
were idealized using a riding model. The final R values were wR2 =
0.123 and R1 = 0.049 using all data. Crystallographic data have
been deposited at the Cambridge Crystallographic Data Centre with
deposition number CCDC 715667.
1
MS analysis and H NMR. The products were identified by
comparison of their spectra and retention time in GC with those
of authentic samples. In the case of the alkylation reactions
(carried out at 100 ◦C with conversion close to 99%), the
products contain >95% linear alkylate and the remainder (<5%)
are the 4% branched alkylates from the ~ 4% branched olefins
(impurity in the feed), and dimers of 1-dodecene. Full details for
these reactions has been reported previously.2
20 Crystal data for EMIM-nonaflate (05219): C10H11F9N2O3S, FW =
˚
410.27, monoclinic, space group P21/c, a = 9.178(4) A, b =
◦
3
˚
˚
˚
34.444(13) A, c = 10.022(4) A, b = 91.711(7) , U = 3167(2) A ,
T = -100.◦C, Z = 8, Dcalcd = 1.72g/cm3. Data were collected using
a Bruker Apex-II CCD system equipped with MoKa radiation
on a non-merohedrally twinned crystal. Cell_now, Saintplus and
Twinabs used to integrate data on two domains yielding 11349 total
reflections. Structure solved and refined on F2 using SHELXTL94.38
All non-hydrogen atoms were refined with anisotropic thermal
parameters. Hydrogen atoms were idealized using a riding model.
The final R values were wR2 = 0.258 and R1 = 0.171 using all
data. The high-r factors are attributed to some un-modeled overlap
twinned crystal. Crystallographic data have been deposited at the
Cambridge Crystallographic Data Centre with deposition number
CCDC 715668.
Polyol Formation (etherification)
1,3-Propanediol (20 g) was placed in a three-neck round-bottom
flask. To this was added TFESA (0.16 g, 0.8 wt% in the final
solution). BMIM-TFES (4 g) was also added and the solution
and contents were purged with nitrogen for two hours. The
21 P. Bonhote, A.-P. Dias, N. Papageorgiou, K. Kalyanasundaram and
M. Graetzel, Inorg. Chem., 1996, 35, 1168–1178.
22 A. R. Choudhury, N. Winterton, A. Steiner, A. I. Cooper and K. A.
Johnson, CrystEngComm, 2006, 8, 742–745.
23 C. Perego and P. Ingallina, Cat. Today, 2002, 73, 3–22.
24 K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry,
WILEY-VCH, Weinheim, 2003.
◦
homogeneous solution was heated using an oil bath at 160 C
under a nitrogen atmosphere. Water slowly evolved and was
collected in a condenser. After approximately 9–10 hours the
solution went from a single phase to a two-phase system. Upon
cooling to 75 ◦C, two phases were clearly visible. The top
25 N. V. Plechkova and K. R. Seddon, Chem. Soc. Rev., 2008, 37, 123–
150.
1
phase was shown via H NMR spectroscopy to be essentially
26 M. J. Earle, J. M. S. S. Esperanca, M. A. Gilea, J. N. Canongia Lopes,
L. P. N. Rebelo, J. W. Magee, K. R. Seddon and J. A. Widegren,
Nature, 2006, 439, 831–834.
polymerized propanediol (polyol). The molecular weight (Mn)
was 2907, after a reaction time of 10.5 hours. The acid and ionic
liquid were found to be essentially in the lower phase with polyol
in the upper phase. The lower phase can easily be separated and
recycled.
27 C. E. Song, E. J. Roh, W. H. Shim and J. H. Choi, Chem. Comm.,
2000, 1695–1696.
28 C. Thomazeau, H. Olivier-Bourbigou, L. Magna, S. Luts and B.
Gilbert, J. Am. Chem. Soc., 2003, 125, 5264–5265.
524 | Green Chem., 2009, 11, 517–525
This journal is
The Royal Society of Chemistry 2009
©