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M.M. Kremlev et al. / Journal of Fluorine Chemistry 126 (2005) 1327–1331
3.1.4. 4-Chlorophenyl(20,30,40,50,60-
pentafluorophenyl)ketone (2d)
3.1.9. trans-Styryl(20,30,40,50,60-
pentafluorophenyl)ketone (2j)
Colourless crystals. Yield 0.77 g (84%), m.p. 62–64 8C
(n-hexane), lit. m.p. 63–63.5 8C [15]. 19F NMR, d (ppm):
ꢁ140.0 (m, 2F, F-20,60), ꢁ150.0 (tt, 1F, F-40), ꢁ159.8 (m, 2F,
F-30,50), 1H NMR, d (ppm): 7.78 (d, 3JH,H = 8.8 Hz, 2H, H-
2,6), 7.49 (d, 3JH,H = 8.8 Hz, 2H, H-3,5); 13C {1H} NMR, d
(ppm): 184.0 (s, C O), 141.7 (s, C-1), 130.9 (s, C-2,6),
129.4 (s, C-3,5), 134.7 (s, C-4); 113.4 (t, C-10), 137.6 (dm, C-
20,60), 143.8 (dm, C-30,50), 142.6 (dm, C-40). MS: m/z (rel.
int.): 306 [M]+ (100), 195 [C6F5CO]+ (12), 123 [FC6H4CO]+
(10). Anal. Calcd. for C13H4ClF5O: C, 50.9; H, 1.3. Found:
C, 50.8; H, 1.2.
Colourless to pale yellow crystals. Yield 0.51 g (85%),
m.p. 102–103 8C (benzene:hexane = 1:1), lit. m.p. 102–
19
103 8C [8]. F NMR, d (ppm): ꢁ140.9 (m, 2F, F-20,60),
1
ꢁ150.6 (tt, 1F, F-40), ꢁ160.3 (m, 2F, F-30,50); H NMR, d
3
(ppm): 7.56 (m, 3H, phenyl), 7.52 (d, JH,H = 16.6 Hz, 1H,
3
CH); 7.44 (m, 2H, phenyl), 7.02 (d, JH,H = 16.6 Hz, 1H,
CH); 13C{1H} NMR, d (ppm): 183.8 (s, C=O), 148.1 (s,
PhC ), 126.0 (s, CCO); 133.5 (s, C-1), 129.1 (s, C-2,6),
128.9 (s, C-3,5), 131.7 (s, C-4); 114.5 (t, C-10), 137.6 (dm, C-
20,60), 144.1 (dm, C-30,50), 142.6 (dm, C-40). MS: m/z (rel.
int.): 298 [M]+ (78), 297 [M–H]+ (100), 195 [C6F5CO]+ (4),
131 [C9H7O]+ (15), 103 [C8H7]+ (12).
3.1.5. 4-Bromophenyl(20,30,40,50,60-
pentafluorophenyl)ketone (2e)
3.1.10. 2,6-Bis(20,30,40,50,60-
pentafluorobenzoyl)pyridine (2k)
Pale yellow solid. Yield 1.00 g (71%), m.p. 87–88 8C (n-
hexane). 19F NMR, d (ppm): ꢁ139.9 (m, 2F, F-20,60), ꢁ149.9
(tt, 1F, F-40), ꢁ159.7 (m., 2F, F-30,50); 1H NMR, d (ppm): 7.7
(‘‘s’’, 2H, H-2,6), 7.6 (‘‘s’’, 2H, H-3,5); 13C{1H} NMR, d
(ppm): 184.2 (s, C O), 134.7 (s, C-1), 132.4 (s, C-2,6),
130.9 (s, C-3,5), 130.6 (s, C-4); 113.4 (t, C-10), 137.7 (dm, C-
20,60), 143.8 (dm, C-30,50), 142.6 (dm, C-40). MS: m/z (rel.
int.): 350 [M]+ (100), 195 [C6F5CO]+ (10), 183 [C6F5O]+
(80), 155 [C6H4Br]+ (10). Anal. Calcd. for C13H4BrF5O: C,
44.4; H, 1.1. Found: C, 44.7; H, 1.2.
Pale yellow crystals. Yield 0.51 g (54%), m.p. 164–
166 8C (n-hexane:benzene = 1:1). 19F NMR, d (ppm):
ꢁ139.1 (m, 2F, F-20,60), ꢁ149.3 (tt, 1F, F-40), ꢁ160.5 (m,
2F, F-30,50); 1H NMR, d (ppm): 8.41 (‘‘m’’, 2H, H-3,5), 8.14
(‘‘t’’, 1H, H-4); 13C{1H} NMR, d (ppm): 185.0 (s, C O),
151.4 (s, C-2,6), 127.3 (s, C-3,5), 139.3 (s, C-4); 113.0 (t, C-
10), 137.1 (dm, C-20,60), 144.1 (dm, C-30,50), 142.6 (dm, C-
40). MS: m/z (rel. int.): 467 [M]+ (28), 439 [M–CO]+ (86),
411 [M–2CO]+ (100), 195 [C6F5CO]+ (36). Anal. Calcd. for
C19H3F10NO2: C, 48.8; H, 0.6; N 3.0. Found: C, 49.4; H, 0.7;
N, 3.7. The analytical data and low intensity signals in the
NMR spectra indicated the monosubstituted product 2-
(C6F5CO)-6-COOH-C5H3N as an impurity.
3.1.6. Decafluorobenzophenone (2f)
Colourless solid. Yield 0.49 g (68%), m.p. 91–92 8C (n-
hexane), lit. m.p. 94 8C [24]. 19F NMR, d (ppm): ꢁ141.3 (m,
4F, F-2,6); ꢁ145.7 (tt, 2F, F-4); ꢁ160.1 (m, 4F, F-3,5);13C
NMR, d (ppm): 175.8 (s, C O), 114.1 (t, C-10), 145.1 (dm,
C-20,60), 137.7 (dm, C-30,50), 144.1 (dm, C-40).
Acknowledgement
3.1.7. 2-Furyl(20,30,40,50,60-pentafluorophenyl)ketone
(2g)
Financial support of this work by the Deutsche
Forschungsgemeinschaft (436 UKR 136/26) is gratefully
acknowledged.
19
Orange oil. F NMR, d (ppm): ꢁ140.6 (m, 2F, F-20,60),
ꢁ150.5 (tt, 1F, F-40), ꢁ160.6 (m, 2F, F-30,50), 13C {1H}
NMR, d (ppm): 171.6 (s, C O), 151.9 (s, C-2), 121.7 (s, C-
3), 113.3 (s, C-4), 148.9 (s, C-5); 112.7 (broad, C-10), 137.5
(dm, C-20,60), 143.9 (dm, C-30,50), 142.6 (dm, C-40). The
sample was contaminated by up to 10% of furan-2carboxylic
acid.
References
[1] K.K. Sun, W.T. Miller, J. Am. Chem. Soc. 92 (1970) 6985–6987.
[2] W. Tyrra, M.S. Wickleder, Z. Anorg. Allg. Chem. 628 (2002) 1841–
1847.
[3] For example
3.1.8. 2-Thienyl(20,30,40,50,60-pentafluorophenyl)ketone
(2h)
(a) W. Tyrra, Heteroatom. Chem. 13 (2002) 561–566;
(b) W.E. Tyrra, J. Fluorine Chem. 112 (2001) 149–152;
(c) B.E. Carpenter, W.E. Piers, M. Parvez, G.P.A. Yap, S.J. Rettig,
Can. J. Chem. 79 (2001) 857–867;
Yellow waxy solid. Yield 0.47 g (84.5%), m.p. 20–22 8C
19
(n-hexane). F NMR, d (ppm): ꢁ140.3 (m, 2F, F-20,60),
(d) W.J. Schlientz, J.K. Ruff, J. Organomet. Chem. 33(1971)C64–C66;
For review
1
ꢁ150.6 (tt, 1F, F-40), ꢁ160.1 (m, 2F, F-30,50), H NMR, d
(ppm): 7.84 (m, 1H), 7.51 (m, 1H), 7.17 (m, 1H); 13C{1H}
NMR, d (ppm): 176.5 (s, C O), 142.9 (s, C-2), 136.1 (s, C-
3), 137.3 (s, C-4) 128.7 (s, C-5); 113.9 (t, C-10), 137.5 (dm,
C-20,60), 143.6 (dm, C-30,50), 142.4 (dm, C-40). MS: m/z (rel.
int.): 278 [M]+ (100), 195 [C6F5CO]+ (22), 111 [C4H3SCO]+
(40), 83 [C4H3S]+ (16). Anal. Calcd. for C11H3F5OS: C,
47.5; H, 1.1; S, 11.5. Found: C, 47.1; H, 0.9; S, 11.7.
(e) W. Tyrra, D. Naumann, J. Fluorine Chem. 125 (2004) 823–830.
[4] D. Naumann, W. Tyrra, R. Herrmann, I. Pantenburg, M.S. Wickleder,
Z. Anorg. Allg. Chem. 628 (2002) 833–842.
[5] For example
W.J. Doucette, J. Kim, J.A. Kautz, S.L. Gipson, Inorg. Chim. Acta 304
(2000) 237–240;
M.P. Garcia, M.V. Jimenez, F.J. Lahoz, L.A. Oro, Inorg. Chem. 34
(1995) 2153–2159;