T. Takagi et al. / Journal of Fluorine Chemistry 101 (2000) 15±17
17
reagents were dried by heating under vacuum, followed by
3.5. Reaction of octafluoro-2-butene (8)
the treatment of CsF and KF with ¯uorine at room tem-
perature for 1 h. And then, hydrogen ¯uoride was removed
from CsF and KF by heating under vacuum. Compounds 2
and 1 were introduced into the reactor at ±1968C using a
vacuum line. The reactor was heated under the reaction
conditions as indicated in Table 1. The crude products were
transferred from the reactor using a vacuum line and puri®ed
by trap-to-trap distillation. The traps were cooled at ±1968C,
Compounds 8 (0.6 mmol) and 1 (1.2 mmol) were intro-
duced into the reactor in the presence of CsF (1.52 g,
10 mmol). The reactor was heated at 4008C for 270 min.
The crude product was transferred from the reactor using a
vacuum line and puri®ed by trap-to-trap distillation. The
traps were cooled at � 1968C, � 1458C, � 1258C, � 1008C.
Compound 9 was collected in the cooled trap at � 1008C.
Compound 10 was collected in the cooled trap at � 1258C.
The by-products, CF CF(NF )CF , CF CF CF NF , penta-
±
1458C, ±1238C, ±908C. Compounds 3 and 4 were collected
in the cooled trap at � 1238C. Compound 5 was collected in
3
2
3
3
2
2
2
the cooled trap at � 1458C.
¯uoro-1-azabutene (CF CF CF=NF, [14]), CF CF NF ,
3
2
3
2
2
1
9
19
CF CF=NF, and CF NF , were detected with F-NMR.
3 3 2
3
:
F-NMR (CDCl , CFCl ) ppm: � 23.04 (2F, bs), 73.88
3
3
1
9
(
1
6F, td, J 12.82, 4.27 Hz), 170.42 (1F, m). IR: 1320, 1297,
9: F-NMR (CDCl , CFCl ) ppm: � 23.29 (1F, bs),
3
3
�
1
262, 1181, 1017, 957, 929 cm [6].
� 23.04 (1F, bs), 71.29 (3F, m), 81.04 (3F, m), 120.89
1
9
4
:
F-NMR (CDCl , CFCl ) ppm: � 17.04 (2F, bs), 81.81
(1F, m), 121.46 (1F, m), 165.44 (2F, bs). IR: 1351, 1285,
3
3
�
1
1250, 1195, 1112, 1068, 974, 947, 922, 899 cm .
(
7
1
3F, ttt, J 7.94, 2.44, 1.22 Hz), 116.57 (2F, q, J
1
9
.94 Hz), 127.35 (2F, tq, J 9.77, 1.22 Hz). IR: 1320,
10: F-NMR (CDCl , CFCl ) ppm: 81.59 (6F, m), 127.68
3 3
�
1
297, 1262, 1181, 1017, 957, 929 cm [9].
(4F, m) [13].
1
9
5: F-NMR (CDCl , CFCl ) ppm: 82.45 (6F, bs), 131.01
3 3
2F, bs). IR: 1349, 1261, 1207, 1153, 1006 cm [10].
�
1
(
References
3
.4. Reaction of tetrafluoroethylene (6)
[1] C.J. Hoffman, R.G. Neville, Chem. Rev. 62 (1961) 1.
[
[
[
[
[
2] J.K. Ruff, Chem. Rev. 67 (1967) 665.
3] C.B. Colburn, A. Kennedy, J. Am. Chem. Soc. 80 (1958) 5004.
4] R.C. Petry, J.P. Freeman, J. Org. Chem. 32 (1967) 4034.
5] K.J. Martin, J. Am. Chem. Soc. 87 (1965) 394.
6] R.D.D. Dresdner, F.N. Tlumac, J.A. Young, J. Am. Chem. Soc. 82
(1960) 5831.
Compounds 6 (0.6 mmol) and 1 (1.2 mmol) were intro-
duced into the reactor in the presence of CsF (1.52 g,
1
0 mmol). The reactor was heated at 4008C for 90 min.
The crude product was transferred from the reactor using a
vacuum line and puri®ed by trap-to-trap distillation. The
traps were cooled at � 1968C, � 1458C, � 1268C, � 1008C.
Compound 7 was collected in the cooled trap at � 1458C.
[
[
7] R.K. Pearson, R.D. Dresdner, J. Am. Chem. Soc. 84 (1962) 4743.
8] B.C. Bishop, J.B. Hynes, L.A. Bigelow, J. Am. Chem. Soc. 86 (1964)
1827.
[
9] J.K. Ruff, J. Org. Chem. 32 (1967) 1675.
The by-products, per¯uorobutylamine (CF CF CF CF NF ,
3
2
2
2
2
[10] H.F. White, Anal. Chem. 38 (1966) 625.
[
N,N,N ,N -tetra¯uoro-1,2-diamino-1,1,2,2-tetra¯uoroethane
11]), CF CF CF NF , CF CF NF , CF CF=NF, CF NF ,
0
[11] B.C. Bishop, J.B. Hynes, L.A. Bigelow, J. Am. Chem. Soc. 85 (1962)
3
0
2
2
2
3
2
2
3
3
2
1
606.
12] P. Sartori, D. Velayuthan, N. Ignat'ev, M. Noel, J. Fluorine Chem. 83
1997) 1.
[
[
(
[
(CF NF ) , [12]), and per¯uorobutane (CF (CF ) CF ,
2 2 2 3 2 2 3
(
19
13]), were detected with F-NMR.
1
13] N. Muller, P.C. Lauterbur, G.F. Suatos, J. Am. Chem. Soc. 79 (1957)
1807.
[14] A. Sekiya, D.D. DesMarteau, J. Org. Chem. 46 (1981) 277.
9
7
.60 Hz), 119.24 (2F,bs) [7].
:
F-NMR (CDCl , CFCl ) ppm: 81.12 (3F, t, J
3
3
8