Fluorination reaction of diphenylchlorophosphate. To a solu-
tion of 5 g (18.6 mmol) 1c in 5 ml tetraglyme was added 2.25 g
(20.5 mmol) of sodium tetraÑuoroborate and the mixture was
heated, under nitrogen, as described above for 15 min. The
distillate (b.p. 125È130 ¡C at 0.5 Torr) consisted of
diphenylÑuorophosphate (25% yield). [(C H O) ]P(:O)F: 1H
Experimental
General
Bis(dimethylamino)phosphoro chloridate, diethyl chloro-
phosphate, diphenyl chlorophosphate, 1,2-phenylene phos-
phorochloridite, bis(2,2,2-trichloroethyl)phosphoro chloridate,
the sodium salts of the perÑuorinated complex anions, tetra-
butylammonium Ñuoride, and tetraglyme were commercially
available as reagents from Aldrich. Tetraglyme was dried over
sodium according to literature procedure.18 Boiling and
melting points are uncorrected. 1H, 13C, 31P and 19F NMR
spectra were recorded on a Varian superconducting NMR
spectrometer at 400 MHz operating frequency for 1H, 100.58
MHz for 13C, 162 MHz for 31P and 376 MHz for 19F NMR
spectroscopy. In these experiments, TMS (internal) was used
for 1H and 13C, 85% phosphoric acid (external) for 31P and
6
5
2
NMR, d 7.17 (d, 8 Hz), 7.05 (q, 7 Hz), 6.97 (t, 8 Hz); 31P NMR,
d [ 24.52 (d, J 1001 Hz); 19F NMR, d [ 77.20 (d, J 1012
PvF
FvP
Hz) [Lit.20 [78.40].
Fluorination reaction of 1,2-phenylene phosphorochloridite.
To a solution of 4 g (22.9 mmol) 1d in 4 ml tetraglyme was
added 2.77 g (25.5 mmol) of sodium tetraÑuoroborate and the
mixture was heated for 15 min as described above. The reac-
tion mixture was analyzed for both 1,2-phenylene phos-
phoroÑuoridite and -Ñuoridate. Vacuum distillation gave 1,2-
phenylene phosphoroÑuoridite in 35% yield (b.p. 30 ¡C at 1
Torr) [Lit.21 b.p. 38 ¡C at Torr]. 1,2-C H (O) PF: 1H NMR,
CFCl (external) for 19F NMR spectroscopy as references,
3
respectively.
6
4
2
d 7.13 (t, 10 Hz), 7.02 (t, 10 Hz) [Lit.22 7.0 and 6.8]; 31P
1306
Syntheses and reactions
NMR, d 120.72 (d, J
1306 Hz) [Lit.22 123.1 (d, J
PvF
PvF
Hz)]; 19F NMR, d [ 37.72 (d, J 1306 Hz) [Lit.22 [ 37.0 (d,
FvP
Preparation of bis(dimethylamino)phosphoro Ñuoridate. To a
solution of 5.23
J
J
1207 Hz)]. 1,2-C H (O) P(:O)F: 31P NMR, d [ 24.37 (d,
FvP
PvF
6
4
2
g (20 mmol) (20 g of 1 M) tetra-
901 Hz).
butylammonium Ñuoride in THF was added 2.90 g (17 mmol)
of bis(dimethylamino)phosphoro chloridate under dry argon
and the mixture was heated to reÑux for 14 h. An aliquot of
the reaction mixture showed only a doublet in the 31P NMR
spectrum at 17.1 ppm. From the reaction mixture, THF was
removed in vacuum and the remaining was subjected to
vacuum distillation. Bis(dimethylamino)phosphoro Ñuoridate,
2a, was distilled at 60È65 ¡C (6 Torr) as a colorless liquid,
which was further characterized by its NMR spectra.
[(CH ) N] P(:O)F: 1H NMR d 1.95 (d, 10.3 Hz; td, 1.7 Hz);
Fluorination reaction of bis(2,2,2-trichloroethyl)phosphoro
chloridate. To a solution of 2 g (5.27 mmol) 1e in 2 ml tetra-
glyme was added 0.89 g (5.30 mmol) of sodium hexa-
Ñuorophosphate and the mixture was heated as described
above for 10 min. The reaction mixture was analyzed for both
bis(2,2,2-trichloroethyl)Ñuorophosphate and 2,2,2-trichloro-
ethyldiÑuorophosphate. Distillation in vacuo gave bis(2,2,2-tri-
chloroethyl)Ñuorophosphate in 30% yield (b.p. 98È104 ¡C at
0.5 Torr). (Cl CCH O) P(:O)F: 1H NMR, d 4.78 (d, 8.3 Hz);
3 2
2
13C NMR, d 34.39; 31P NMR, d 16.85 (d, J 947 Hz, quint,
3
2
2
PvF
31P NMR, d [ 12.15 (d, J
997 Hz). Cl CCH OP(:O)F :
J
11 Hz); 19F NMR, d [86.65 (d, J 946 Hz).
PvF
3
2
2
HvPvF
FvP
31P NMR, d [ 21.22 (t, J 1025 Hz).
PvF
Fluorination reaction of bis(dimethylamino)phosphoro chlori-
date. To a solution of 5 g (29.3 mmol) 1a in 5 ml tetraglyme
was added 3.5 g (32.2 mmol) sodium tetraÑuoroborate and the
reaction mixture was heated to about 200 ¡C for 15 min. The
reaction mixture, when analyzed by 31P NMR spectroscopy,
was found to consist of di†erent Ñuorophosphorus com-
ponents. Bis(dimethylamino)phosphoro Ñuoridate, 2a, was dis-
tilled at 45È52 ¡C (0.5 Torr) in 66% yield and characterized by
comparing its NMR spectra with those of an authentic sample
prepared as described above. The reaction of 1a with sodium
hexaÑuorophosphate was carried out in a similar fashion and
bis(dimethylamino)phosphoro Ñuoridate was obtained in 77%
yield. [(CH ) N] P(:O)F: 1H NMR, d 2.46 (d, 10.5 Hz, td, 1.6
References
1
M. R. C. Gerstenberger and A. Haas, Angew. Chem., Int. Ed.
Engl., 1981, 20, 647.
2
(a) R. Schmutzler, Chem. Ber., 1965, 98, 552; (b) C. Brown, M.
Murray and R. Schmutzler, J. Chem. Soc. (C), 1970, 878; (c) H.
W. Roesky, Inorg. Nucl. Chem. L ett., 1969, 5, 891.
(a) L. Heuer, M. Sell, R. Schmutzler and D. Schomburg, Poly-
hedron, 1987, 6, 1295; (b) L. Heuer, P. G. Jones and R. Schmutz-
ler, New J. Chem., 1990, 14, 891.
3
4
(a) R. Schmutzler, Inorg. Chem., 1964, 3, 410; (b) W. Albers, W.
Kruger, W. Storzer and R.Schmutzler, Synth. React. Inorg. Met.-
Org. Chem., 1985, 15, 187; (c) K. Sasse, Organische Phos-
phorverbindungen, Methoden der Organischen Chemie, Georg
Thieme Verlag, Stuttgart, 1963, vol. XII, pt 1.
3 2
2
Hz); 13C NMR, d 33.70; 31P NMR, d 15.65 (d, J
958 Hz,
PvF
quint, J
10 Hz); 19F NMR, d [ 85.34 (d, J
952 Hz).
HvPvF
FvP
5
6
(a) R. Schmutzler, Inorg. Chem., 1964, 3, 415; (b) L. M.
YagupolÏskii and Z. M. Ivanova, Zh. Obsch. Khim., 1959, 29, 3766
(Gen. Chem. USSR, 1959, 29, 3726).
(a) E. L. Lines and L. F. Centofanti, Inorg. Chem., 1973, 12, 598;
(b) E. L. Lines and L. F. Centofanti, ibid., 1974, 13, 1517; (c) E. L.
Lines and L. F. Centofanti, ibid., 1974, 13, 2796.
K. M. Doxsee, E. M. Hanawalt and T. J. R. Weakley, Inorg.
Chem., 1992, 31, 4420.
J. A. Gibson, R. K. Marat and A. F. Janzen, Can. J. Chem., 1975,
53, 3044.
S. A. Lermontov, A. V. Popov, S. I. Zavorin, I. I. Sukhojenko, N.
V. Kuryleva, I. V. Martynov, N. S. ZeÐrov and P. Stang, J. Fluo-
rine Chem., 1994, 66, 233.
[(CH ) N]P(:O)F : 1H NMR, d 2.84 (d, 11.0 Hz); 31P NMR,
3 2
2
d [ 6.65 (t, J 999 Hz).
PvF
Fluorination reaction of diethylchlorophosphate. To a solu-
tion of 2 g (11.6 mmol) 1b in 1 m of tetraglyme was added 2.1
g (12.7 mmol) sodium hexaÑuorophosphate and the reaction
mixture was heated as described above for 10 min. Distillation
in vacuo gave a mixture of products within the range 70È80 ¡C
(0.5 Torr). DiethylÑuorophosphate, 2b, was obtained in about
12% yield. The products were identiÐed by their NMR
7
8
9
spectra. (EtO) P(:O)F: 1H NMR, d 1.41 (t, 7 Hz), 4.3 (q, 8
2
Hz); 31P NMR, d [ 13.17 (d, J
977 Hz, td, J
995 Hz) [Lit.19 [77.5].
10 Hz);
10 P. P. OnysÏko, E. A. Suvalova, T. I. Chudakova and A. D.
Sinitsa, Zh. Obshch. Khim., 1992, 62, 577 (J. Gen. Chem., 1992, 62,
473).
11 O. Farooq and G. V. D. Tiers, J. Org. Chem., 1994, 59, 2122.
12 O. Farooq, J. Fluorine Chem., 1997, 86, 189.
13 O. Farooq, J. Chem. Soc., Perkin T rans. 1, 1998, 661., .
14 O. Farooq, J. Fluorine Chem., submitted.
PvF
HvPvF
19F NMR, d [ 78.60 (d,
J
FvP
EtOP(:O)F : 1H NMR, d 1.21 (t, 7 Hz), 4.34 (q, 8 Hz) [Lit.16
2
1.11 (t, 5.3 Hz), 4.38 (q, 7.2 Hz)]; 31P NMR, d [ 22.92 (t, J
PvF
993 Hz, tt, J
10 Hz) [Lit.16 [ 21.35 (t, J
1014 Hz),
HvPvF
PvF
Lit.19 [ 20.20 (J 1014 Hz)]; 19F NMR, d [ 85.31 (d, J
PvF
FvP
1017 Hz) [Lit.16 [84.60 (d, J
1034 Hz), Lit.19 [85.0 (d,
15 O. Farooq, J. Fluorine Chem., 1995, 70, 225.
16 O. Farooq, J. Chem. Soc., Perkin T rans. 1, 1998, 839.
FvP
J
1008 Hz)].
FvP
New J. Chem., 2000, 24, 81È84
83