N. Ignat'ev, P. Sartori / Journal of Fluorine Chemistry 103 (2000) 57±61
61
(
in total 690 g) was added into the cell to keep the volume
tdec. These spectra coincide with those described in the
literature [11].
of the liquid in the cell constant. After completion of
the electrolysis the liquid phase was removed from the
cell into a separating funnel and the product was separated
from the HF layer. Altogether 440 g of a transparent liquid,
which according to the F and P NMR spectra was the
mixture of tris(nona¯uoro-iso-butyl)di¯uorophosphorane
Some amount of tris(tri¯uoromethyl)di¯uorophosphor-
ane (X) (approximately 10 g) was found to be dissolved
3
in the HF (70 cm ) collected above the bottom layer in the
19
31
FEP trap. Besides the compound (X) the HF layer also
contains partially ¯uorinated compounds: CH (CF ) PF
2
3
3 2
(
(
ꢁ35 mol%), tris(nona¯uoro-n-butyl)di¯uorophosphorane
(XI) and CH CF PF (XII).
3 3 3
31
ꢁ15 mol%),
[bis(nona¯uoro-n-butyl)](nona¯uoro-iso-
CH (CF ) PF (XI): P NMR in HF solution at � 408C,
3
3 2
2
2
butyl)di¯uorophosphorane (ꢁ5 mol%), [bis(nona¯uoro-
iso-butyl)](nona¯uoro-n-butyl)di¯uorophosphorane (ꢁ25
mol%), and partially ¯uorinated compounds with 1±3
hydrogen atoms in the molecule (ꢁ20 mol%), was obtained
from the cell (yield: 57.2% calculated on per¯uorinated
product). By fractional distillation in a Te¯on-apparatus
tris(nona¯uoro-iso-butyl)di¯uorophosphorane can be iso-
lated as the main product.
d: � 36.0 tsepq; JP,H 18.3 Hz; (Ref. [12]: d: � 35.9;
2
19
19.3 Hz). F NMR in HF solution at � 408C, d:
J
P,H
1
� 48.5 dsepq (2F, PF); � 68.0 dt (6F, 2CF ); J 832 Hz;
3
P,F
2
3
3
J
[12]:
156 Hz;
J
17.1 Hz;
J
F,H
12.1 Hz; (Ref.
F,F
P,F
F,F
1
2
3
J
840 Hz;
J
154 Hz;
J
16.5 Hz;
P,F
P,F
3
JF,H 12.3 Hz).
CH CF PF (XII): P NMR in HF solution at � 408C, d:
19
3
1
3
3
3
2
� 19.6 qqq; JP,H 18.3 Hz; (Ref. [13]: d: � 11.2;
1
9
2
F NMR, d: � 45.98 dm (2F, PF ); � 74.07 m (18F,
J
17.5 Hz). F NMR in HF solution at � 408C, d:
2
P,H
1
6
CF ); � 99.20 dm (6F, 3CF ); � 180.49 m (3F, 3CF);
� 80.3 br,d (2F, PF); � 70.7 dq (3F, CF ); J 946 Hz;
3
2
3
P,F
1
2
31
2
3
1
J
tsep.
1087 Hz; J 124.9 Hz. P NMR, d: � 41.35
P,F
J
161.7 Hz;
J
13.1 Hz; (Ref. [12]:
J
P,F
P,F
P,F
F,F
2
3
955 Hz; J 156 Hz; J 12.0 Hz). The ratio of the
P,F
F,F
compounds (X), (XI) and (XII) in the HF solution trapped at
788C is 75, 10 and 15 mol%, respectively.
�
3
.5. Electrochemical fluorination of trimethylphosphine
ECF of trimethylphosphine was done in the same way as
described above. A stainless-steel cylindrical cell (total
Acknowledgements
3
volume 310 cm ) with an array of nickel anodes (effective
The authors thank Merck KGaA (Germany) for the
®nancial support of this work.
2
anodic area: S 3.75 dm ) and cathodes with the same
effective area was used for this experiment. The temperature
of the cell body was maintained at 08C and the temperature
of the condenser was kept at � 258C.
References
The solution containing 121.0 g of trimethylphosphine in
HF, with the concentration of 41.3%, was added in ®ve
equal portions (every 36 h) to 220 g of liquid HF previously
electrolysed in the cell for 45 h. The gaseous products from
the cell were passed through condenser and two FEP traps at
[1] Y.W. Alsmeyer, W.V. Childs, R.M. Flynn, G.G.I. Moor, J.C.
Smeltzer, in: R.E. Banks, B.E. Smart, J.C. Tatlow (Eds.), Organo-
fluorine Chemistry, ch. 5, Plenum Press, New York, 1994, p. 121.
[
2] V.Ya. Semenii, V.A. Stepanov, N.V. Ignat'ev, G.G. Furin, L.M.
Yagupolskii, Zh. Obshch. Khim. 55 (1985) 2716.
�
788C. The electrolysis, which proceeded at a cell voltage
[
3] P. Sartori, N. Ignat'ev, DE 19 846 636, 1998.
2
of 4.2±4.8 V and a current density of 0.53 A/dm , was
completed after consumption of 437.5 A h (124.2% of the
theoretical amount of electricity calculated on 20 electron
process).
[4] V.S. Plashkin, L.N. Pushkina, S.V. Sokolov, Zh. Org. Khim. 10
1974) 1215 (in Russian).
(
[
5] G.P. Gambaretto, M. Napoli, L. Gonte, A. Sciponi, R. Armelli, J.
Fluorine Chem. 27 (1985) 149.
[
6] T. Abe, H. Fukaya, E. Hayashi, Y. Hayakawa, M. Nishida, H. Baba,
J. Fluorine Chem. 66 (1994) 193.
After completion of the ECF process the content of the
1
9
31
FEP traps was investigated by F and P NMR spectro-
scopies. The ®rst in the line of FEP trap contained two
layers: bottom layer and HF solution above. The bottom
layer (7 g of clear liquid) which was separated from the HF
solution consisted of practically pure tris(tri¯uoromethyl)-
di¯uorophosphorane (X) (yield: 3.9%).
[7] P. Sartori, N. Ignat'ev, J. Fluorine Chem. 87 (1998) 157.
[
8] M. Hudlicky, Chemistry of Organic Fluorine Compounds, ch. 5, 2nd
ed., Ellis Horwood, New York, 1976, p. 491.
[
9] N. Bartlett, R.D. Chambers, A.J. Roche, R.C.H. Spink, L. Chacon,
J.M. Whalen, J. Chem. Soc., Chem. Commun. (1996) 1049.
[
10] J.J. Kampa, J.W. Nail, R.J. Lagow, Angew. Chem. 107 (1995) 1334.
[11] M. G oÈ rg, G.-V. R oÈ schenthaler, A.A. Kolomeitsev, J. Fluorine Chem.
9 (1996) 103.
[12] K.I. The, R.G. Cavell, Inorg. Chem. 16 (1977) 1463.
13] N.T. Yap, R.G. Cavell, Inorg. Chem. 18 (1979) 1301.
1
9
7
F NMR (neat liquid, � 408C), d: � 60.8 ddec (2F, PF);
31
1
2
�
65.0 dt (9F, 3CF );
3
J
989 Hz;
J
P,F
167 Hz;
P,F
[
3
JF,F 17.2 Hz. P NMR (neat liquid, � 408C), d: � 62.2