Polyfluoroaryldimethylphosphanes
4612±4622
components were distilled off in vacuo ꢀꢁ0.1 mbar) and the residue was
sublimed in vacuo ꢀ0.05 mbar) at bath temperatures up to 758C. Traces of
typically smelling tin compounds were sublimed off in vacuo ꢀ0.05 mbar) at
a bath temperature of 408C to afford compound 9 ꢀ0.33 g, 63%).
precipitated white crystals were filtered off, washed with pentane and dried
in vacuo to afford an additional quantity of the crude product ꢀ0.035 g,
21%); this brought the total yield of 14 to close to 100%.
Reaction of C6H5F with Me3SiPMe2: Me3SiPMe2 ꢀ0.059 g, 0.438 mmol),
fluorobenzene ꢀ0.421 g, 4.38 mmol) and C6D6 ꢀca. 0.05 mL) were con-
densed in an evacuated NMR tube cooled with liquid nitrogen. The
ampoule was sealed under vacuum, allowed to warm up to ambient
temperature ꢀ17 ± 208C) and then kept at 1808C while periodically
recording NMR spectra. The yield of dimethylꢀphenyl)phosphane reached
19, 37 and 60% after 6.5, 29 and 90 h, respectively. 1H NMR: d 7.5 ꢀm,
Dimethyl<4-chloro-2,3,5,6-tetrafluorophenyl)phosphane sulfide <10):
A
mixture of dimethylꢀ4-chloro-2,3,5,6-tetrafluorophenyl)phosphane
ꢀ0.73 g, 3.9 mmol) and S8 ꢀ0.12 g, 3.6 mmol) was kept at 95 ± 1008C for
1 h. After cooling to room temperature, traces of substrate were distilled
off in vacuo ꢀ0.1 mbar), and the residue was dissolved in pentane ꢀca.
25 mL) and filtered. The resultant solution was concentrated by evapo-
ration of the solvent ꢀ15 mL) and cooled to À208C. The precipitated white
crystals were filtered off, washed with pentane and dried in vacuo to give
2
5H), 1.20 ꢀd, JꢀP,H) 3.2 Hz, 6H);[15] 31P NMR: d À47.11 ꢀs).
Reactions of C6F5H and C6F5Cl with Me3SnPMe2: Me3SnPMe2 ꢀ0.3 g,
1.3 mmol) and pentafluorobenzene ꢀ0.27 g, 1.6 mmol) or pentafluorochloro-
benzene ꢀ0.32 g, 1.6 mmol) were condensed in an evacuated 5 mL ampoule
cooled with liquid nitrogen. The ampoule was sealed, allowed to warm up
to ambient temperature ꢀ208C) and kept at this temperature for 16 h. It was
then heated up to 608C and held at this temperature for 2 h. The reaction
mixture was cooled, Me3SnFwas filtered off as a white solid, and the
solution was immediately transferred to a NMR tube. The solid was washed
twice with C6D6 ꢀca. 0.3 mL) and the resulting solutions were added to the
same tube. After sealing under vacuum, the NMR spectra were recorded.
In the case of C6F5Cl the reaction mixture was also analysed by mass
spectrometry, which showed the presence of all three isomeric derivatives
Me2PC6F4Cl in accord with the NMR spectroscopy results.
compound 10 ꢀ0.52 g, 62%). MS ꢀ70 eV, EI): m/z ꢀ%): 276 ꢀ100) [M] , 261
ꢀ52) [M À Me] , 246 ꢀ8) [M À 2Me] , 244 ꢀ8) [M À S] , 243 ꢀ17) [M À S À
H] ; elemental analysis calcd ꢀ%) for C8H6ClF4PS ꢀ276.62): C 34.74, H
2.19; found C 34.21, H 2.31. After evaporation of the solvent from the
filtrate, an additional amount of crude product ꢀ0.25 g, 30%) was obtained.
This brought the total yield of compound 10 to almost 90%.
Dimethyl<4-trifluoromethyl-2,3,5,6-tetrafluorophenyl)phosphane sulfide
<11): A mixture of dimethylꢀ4-trifluoromethyl-2,3,5,6-tetrafluorophenyl)-
phosphane ꢀ1.11 g, 4.0 mmol) and S8 ꢀ0.15 g, 4.8 mmol) was kept at 80 ±
908C for 1 h. After cooling the mixture to room temperature, traces of
substrate were distilled off in vacuo ꢀ0.1 mbar) and the residue was
dissolved in benzene ꢀ5 mL) and filtered. The resultant solution was diluted
with pentane ꢀca. 15 mL) and the precipitated white crystals were filtered
off, washed with pentane and dried in vacuo to give compound 11 ꢀ0.81 g,
Typical procedure for kinetic experiments: Me3SiPMe2 ꢀ0.13 ± 0.42 g, 1 ±
3 mmol), polyfluoroarene C6F5X ꢀX H, Cl, For CF 3, 1.2 ± 5.0 mmol) and,
in some cases ꢀsee Figures 6 ± 8), C6D6 ꢀ0.1 ± 0.3 mL) and C6H6 ꢀ0.3 ±
0.5 mL) were successively condensed in an evacuated NMR tube cooled
with liquid nitrogen. The ampoule was sealed under vacuum, allowed to
warm-up to ambient temperature ꢀ17 ± 208C) and then kept at the
temperature of the kinetic measurement ꢀsee Figures 6 ± 8) while periodi-
cally recording NMR spectra.
65%). MS ꢀ70 eV, EI): m/z ꢀ%): 310 ꢀ100) [M] , 295 ꢀ40) [M À Me] , 278
ꢀ11) [M À S] , 277 ꢀ16) [M À S À H] ; elemental analysis calcd ꢀ%) for
C9H6F7PS ꢀ310.18): 34.85, H 1.95; found C 34.18, H 1.95. After
C
evaporation of the solvents from the filtrate, additional 0.44 g ꢀ35%) of
crude 11 were obtained; this raised the yield to almost 100%.
4-Dimethylthiophosphanotetrafluoropyridine <12): A mixture of 4-dime-
thylphosphanotetrafluoropyridine ꢀ0.88 g, 4.2 mmol) and S8 ꢀ0.16 g,
5 mmol) was kept at 90 ± 1008C for 1 h. After cooling to room temperature,
traces of substrate were distilled off in vacuo ꢀ0.1 mbar) and the residue was
dissolved in benzene ꢀ2 mL) and filtered. The resultant solution was diluted
with pentane ꢀca. 5 mL) and the precipitated white crystals were filtered
off, washed with pentane and dried in vacuo to give 12 ꢀ0.74 g, 73%). MS
Acknowledgement
We thank the Stiftung Volkswagenwerk for financial support of the
Cooperation Project between the Institutes of Inorganic and Organic
Chemistry of the Universtät Münster ꢀGermany) and the Novosibirsk
Institute of Organic Chemistry, Siberian Division of RAS ꢀRussia). We also
gratefully acknowledge a stipend from the Deutsche Forschungsgemein-
schaft ꢀDFG) to L.I.G. for carrying out experimental work in Münster and
a postdoctoral grant of the Graduiertenkolleg ªHochreaktive Mehrfach-
bindungssystemeº to C.M.-L.
ꢀ70 eV, EI): m/z ꢀ%): 243 ꢀ100) [M] , 228 ꢀ27) [M À Me] , 211 ꢀ6) [M À S] ,
210 ꢀ15) [M À S À H] ; elemental analysis calcd ꢀ%) for C7H6F4NPS
ꢀ243,16): C 34.58, H 2.49; found C 34.62, H 2.41. After evaporation of the
solvents from the filtrate, additional 0.26 g ꢀ26%) of crude 12 were isolated,
so that the total yield was close to 100%.
1,4-Bis<dimethylthiophosphano)tetrafluorobenzene <13):
A mixture of
hexafluorobenzene ꢀ0.37 g, 2 mmol) and Me3SiPMe2 ꢀ0.54 g, 4 mmol) was
kept at 50 ± 558C for 15 h. The volatile components ꢀMe3SiF, C F6, traces of
6
reagent and 1) were distilled off in vacuo ꢀ0.1 mbar) over
a bath
[1] D. J. H. Smith in Comprehensive Organic Chemistry, Vol. 2 ꢀEd.: I. O.
Sutherland), Pergamon, Oxford, 1979, pp. 1129 ± 1131.
[2] K. Issleib, A. Tzschach, H.-U. Block, Chem. Ber. 1968, 101, 2931 ±
2937.
[3] J. E. Swartz, J. F. Bunnett, J. Org. Chem. 1979, 44, 340 ± 346.
[4] O. Herd, A. Hessler, K. P. Langhans, O. Stelzer, W. S. Sheldrick, N.
Weferling, J. Organomet. Chem. 1994, 475, 99 ± 111.
[5] A. M. Aguiar, H. J. Greenberg, K. E. Rubenstein, J. Org. Chem. 1963,
28, 2091 ± 2093; H. C. E. McFarlane, W. McFarlane, Polyhedron 1983,
2, 303 ± 304.
[6] Yu. A. Veits, E. B. Neganova, I. P. Beletskaya, Russ. J. Org. Chem.
1997, 33, 1351 ± 1352.
[7] a) M. F. Ernst, D. M. Roddick,Inorg. Chem. 1989, 28, 1624 ± 1627; b) J.
Grobe, M. Köhne-Wächter, D. Le Van, J. Organomet. Chem. 1985,
280, 331 ± 341.
[8] a) M. G. Hogben, W. A. G. Graham, J. Am. Chem. Soc. 1969, 91, 283 ±
291; b) M. G. Barlow, M. Green, R. N. Haszeldine, H. G. Higson, J.
Chem. Soc. B 1966, 1025 ± 1030.
[9] a) L. S. Kobrina, Fluorine Chem. Rev. 1974, 7, 1 ± 114; b) P. P.
Rodionov, G. G. Furin, J. Fluorine Chem. 1990, 47, 361 ± 434;
c) G. M. Brook, J. Fluorine Chem. 1997, 86, 1 ± 76; d) S. Sasaki, Y.
Tanabe, M. Yoshifuji, Bull. Chem. Soc. Jpn. 1999, 72, 563 ± 572.
[10] E. T. Denisov, Kinetics of Homogeneous Chemical Reactions, Vys-
shaya Shkola, Moscow, 1988, p. 53.
temperature range of 20 ± 508C. S8 ꢀ0.16 g, 5 mmol) and C6H6 ꢀca. 5 mL)
were added to the residue and the mixture was kept at 808C for 1 h. After
cooling the solution to 608C, the yellow residue was dissolved in hot CHCl3
ꢀ18 mL) and filtered through a thin layer of silica gel. The resultant solution
was diluted with pentane ꢀca. 10 mL) and cooled to À208C. The
precipitated white crystals were filtered off, washed with pentane and
dried in vacuo to give compound 13 ꢀ0.37 g, 68%). MS ꢀ70 eV, EI): m/z
ꢀ%): 334 ꢀ100) [M] , 319 ꢀ25) [M À Me] , 302 ꢀ20) [M À S] , 287 ꢀ12) [M À
Me À S À H] , 270 ꢀ12) [M À 2S] ; elemental analysis calcd ꢀ%) for
C10H12F4P2S2 ꢀ334.28): C 35.93, H 3.62; found C 36.21, H 3.58. After
evaporation of the solvents from the filtrate, additional 0.12 g ꢀ22%) of
crude 13 were isolated; this raised the total yield to close to 90%.
4,4'-Bis<dimethylthiophosphano)octafluorobiphenyl <14): A mixture of 7
ꢀ0.141 g, 0.337 mmol), S8 ꢀ0.024 g, 0.749 mmol) and benzene ꢀ2 mL) was
kept at 1008C for 1 h. After cooling the solution to about 758C, hot
benzene ꢀ12 mL) was added to the mixture and the resultant solution was
filtered and cooled to 08C. The precipitated white crystals were filtered off,
washed with pentane and dried in vacuo to afford compound 14 ꢀ0.125 g,
77%). MS ꢀ70 eV, EI): m/z ꢀ%): 482 ꢀ100) [M] , 467 ꢀ27) [M À Me] , 450
ꢀ15) [M À S] ; elemental analysis calcd ꢀ%) for C16H12F8P2S2 ꢀ482.34): C
39.84, H 2.51; found C 39.72, H 2.53. After evaporation of the solvents from
the filtrate, the resultant solid was dissolved in hot benzene ꢀ2 mL). The
solution was cooled to 208C, diluted with pentane ꢀca. 1.5 mL) and the
Chem. Eur. J. 2000, 6, No. 24
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
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4621