816
W. Tyrra et al. / Journal of Fluorine Chemistry 128 (2007) 813–817
corresponding alkenes and R H; alkyl chlorides appear to be
f
32.1, 29.6, 29.4, 29.0, 22.9, 22.2 (q, J ꢀ 2 Hz), 14.1. EIMS (EI,
+
20 eV, m/z): 182 (M ).
non-reactive under those conditions.
4
. Experimental
4.2.2. 1,1,1-Trifluoro-n-tridecane (2d) [22]
1
Oil. NMR: H NMR (200.1 MHz, neat): 1.97 (m, 2H), 1.49
1
(m, 2H), 1.25 (broad s, 18 H), 0.85 (t, 3H); F NMR
9
4
.1. Materials and methods
1
3
(
188.3 MHz, neat): À66.9 (t, J = 10.8 Hz);
C NMR
(50.3 MHz, neat): 125.9 (q, J = 276 Hz), 32.4 (q, J = 29 Hz),
All reactions were carried out in a dry argon (nitrogen)
atmosphere using Schlenk techniques.
30.8, 28.5 (2C), 28.4, 28.2 (2C), 28.1, 27.6, 21.5, 20.6 (q,
+
J ꢀ 2 Hz), 12.4. EIMS (EI, 20 eV,): m/z = 238 (M ).
Me SiCF was purchased from ABCR, Me SiC F was
3
3
3
2 5
prepared from C F I, Me SiCl and tetrakis(dimethylami-
2
5
3
no)ethen following the Petrov procedure [24]. CsF (Acros)
was carefully dried prior to use. 15-Crown-5 was purchased
from Fluka, alkyl halides from ACROS and used as received.
All solvents were purified according to literature procedures
4
.2.3. 1,1,1,2,2-Pentafluoro-n-decane (3c)
1
Oil. NMR: H NMR (200.1 MHz, neat): 1.94 (m, 2H), 1.53
1
m, 2H), 1.27 (broad s, 10 H), 0.85 (t, 3H); F NMR
9
(
(
188.3 MHz, neat): À86.2 (s, 3F), À118.8 (t, J = 18 Hz, 2F);
1
3
[
25].
Approximately 90 experiments for optimization of the
conditions (Me SiCF ) were carried out varying the fluoride
C NMR (50.3 MHz, neat): 119.3 (qt, J = 284/37 Hz), 115.7
tq, J = 251/37 Hz), 31.7, 30.4 (t, J = 22 Hz), 29.1, 29.0 (2C),
(
+
3
3
22.4, 20.1 (t, J ꢀ 3 Hz), 13.3. EIMS (EI, 20 eV, m/z): 232 (M ).
source ([NMe ]F, TASF, [K(18-crown-6)]F, CsF, [Cs(15-
4
crown-5) ]F), the solvent (THF, diglyme, DME, diethylether,
2
4.2.4. 1,1,1,2,2-Pentafluoro-n-tetradecane (3d)
1
Oil. NMR: H NMR (200.1 MHz, neat): 1.85 (m, 2H), 1.50
propionitrile), the relative ratio Me SiCF to fluoride (5:1 up to
3
3
1
:2), the temperature range (À60 8C to ambient) and the ratio of
19
m, 2H), 1.22 (broad s, 18 H), 0.81 (t, 3H); F NMR
(
1
to Me SiCF (5:1 to 1:2).
3
3
(188.3 MHz, neat): À86.2 (s, 3F), À118.5 (t, J = 18 Hz, 2F);
NMR spectra were recorded on a Bruker AC-200 spectro-
13
C NMR (50.3 MHz, neat): 118.7 (qt, J = 285/37 Hz), 115.0
tq, J = 251/37 Hz), 31.4, 30.0 (t, J = 22 Hz), 29.12, 29.11,
1
19
13
1
meter: H (200.1 MHz) and F (188.3 MHz) and C{ H}
50.3 MHz) NMR spectra. Chemical shifts are given in ppm
relative to Me Si and CCl F as external standards. Acetone-d
(
(
2
9.04, 28.87, 28.85, 28.67, 28.55, 22.0, 19.6 (t, J ꢀ 3 Hz), 12.9.
+
EIMS (EI, 20 eV, m/z): 288 (M ).
4
3
6
was used as an external lock (5 mm tube) in reaction control
measurements and for neat compounds while an original
sample of the reaction mixture or the neat compound,
respectively, was measured in a 4 mm insert. NMR data not
reported so far for known compounds are added after the
corresponding reference (cf. Table 1). EI mass spectra were run
on a Finnigan MAT 95 spectrometer (20 eV).
4
.2.5. 1,1,1,2,2-Pentafluoro-5-chloro-n-pentane (3e)
1
NMR: H NMR (200.1 MHz, DME): 3.44 (t, J = 6 Hz, 2H),
19
.15 (m, 2H), 1.99 (m, 2H); F NMR (188.3 MHz, DME)
2
À86.2 (s, 3F), À118.7 (t, J = 17 Hz, 2F).
Acknowledgement
4
.2. General procedure (preparative scale)
Generous financial support of this work by the DFG (grant
36 UKR 113) is gratefully acknowledged.
4
A solution of 15 mmol of the corresponding alkyl halide 1
and 25.5 mmol Me SiR (R = CF , C F ) in 50 mL of glyme
3
f
f
3
2 5
References
was cooled on an ice-bath to À18 8C (ice/sodium chloride).
Solid, carefully dried CsF (25.5 mmol) was added in one
portion. Finally, 51 mmol 15-crown-5 were added. The
temperature was allowed to reach room temperature over a
period of approximately 1 h (R = CF ) or 16 h (R = C F ).
[
[
1] (a) G.K.S. Prakash, A.K. Yudin, Chem. Rev. 97 (1997) 757–786;
(b) R.P. Singh, J.M. Shreeve, Tetrahedron 56 (2000) 7613–7632;
(
(
c) G.G. Furin, Russ. J. Org. Chem. 33 (1997) 1209–1242;
d) E. Abele, E. Lukevics, Main Group Met. Chem. 24 (2001) 315–
f
3
f
2 5
3
50.
[
Cs(15-crown-5) ]I was filtered off and all easily volatile
2
2] (a) N.V. Kirij, Yu.L. Yagupolskii, N.V. Petukh, W. Tyrra, D. Naumann,
Tetrahedron Lett. 42 (2001) 8181–8183;
compounds were removed in vacuo. From the pale brown
residues, oily compounds 2, 3 were extracted with n-pentane or
obtained as volatile derivatives after trap-to-trap condensation.
Compounds were mainly analyzed by NMR spectroscopic
means (in comparison with literature data) and in part by mass
spectrometry.
(b) Yu.L. Yagupolskii, N.V. Kirij, A.V. Shevchenko, W. Tyrra, D. Nau-
mann, Tetrahedron Lett. 43 (2002) 3029–3031;
(
c) L.A. Babadzhanova, N.V. Kirij, Yu.L. Yagupolskii, W. Tyrra, D.
Naumann, Tetrahedron 61 (2005) 1813–1819;
d) L.A. Babadzhanova, N.V. Kirij, Yu.L. Yagupolskii, J. Fluorine Chem.
25 (2004) 1095–1098;
e) R.P. Singh, J.M. Shreeve, Chem. Commun. (2002) 1818–1819.
(
1
(
[
3] (a) W. Tyrra, D. Naumann, B. Hoge, Yu.L. Yagupolskii, J. Fluorine Chem.
119 (2003) 101–107;
4
.2.1. 1,1,1-Trifluoro-n-nonane (2c) [22]
1
Oil. NMR: H NMR (200.1 MHz, neat): 2.07 (m, 2H), 1.48
(
(
(
b) W. Tyrra, D. Naumann, Yu.L. Yagupolskii, J. Fluorine Chem. 123
2003) 183–187;
1
9
m, 2H), 1.26 (broad s, 10 H), 0.84 (t, 3H); F NMR
(
(
(
1
3
188.3 MHz, neat): À66.3 (t, J = 11.4 Hz);
C NMR
50.3 MHz, neat): 127.8 (q, J = 276 Hz), 33.6 (q, J = 28 Hz),
c) W. Tyrra, N.V. Kirij, D. Naumann, Y.L. Yagupolskii, J. Fluorine
Chem. 125 (2004) 1435–1438.