7424
H. Loghmani-Khouzani et al. / Tetrahedron 64 (2008) 7419–7425
(C]O); 19F NMR (235 MHz, CDCl3)
d
ꢁ102.7 (d, J 48.9 Hz, F, CFH); IR
6.3 Hz, 1H) and 7.90 (d, J 7.8 Hz, 2H); 13C NMR (101 MHz, CDCl3)
d 27.4, 114.4 (t, J 300.21 Hz, CF2), 129.6, 130.6, 135.9, 136.4 and 191.8
(KBr, cmꢁ1) 3097, 2879,1705 (C]O),1546,1455,1314,1237, 922 and
855; HRMS (EI) Found: Mþ, 292.0632. C15H13FO3S requires Mþ,
292.0645; LRMS m/z (EI): 292 (Mþ, 94%) and 293 (27%). Elemental
analysis: Found (%): C, 61.76; H, 4.54; S, 11.07. Calcd for C15H13FO3S:
C, 61.63; H, 4.48; S, 10.97, and the difluoro product 8c in 41% yield;
(C]O); 19F NMR (235 MHz, CDCl3)
d
ꢁ110.7 (s, 2F, CF2); IR (KBr,
cmꢁ1) 3037, 2973, 2906, 1714 (C]O), 1566, 1450, 1355, 1345, 1211,
1155 and 1087; HRMS (EI) Found: Mþ, 234.0234. C9H8F2O3S re-
quires Mþ, 234.0265. Elemental analysis: Found (%): C, 46.32; H,
3.34; S, 13.56. Calcd for C9H8F2O3S: C, 46.15; H, 3.44; S, 13.69.
mp 71 ꢀC (ethanol); 1H NMR (500 MHz, CDCl3)
d 2.93 (s, 3H), 7.61 (t,
J 7.5 Hz, 2H), 7.68 (ddd, J 8.5, 2.5 and 1.2 Hz, 1H), 7.82–7.84 (m, 2H),
7.87 (d, J 8.5 Hz, 2H) and 8.1 (dd, J 8.5 and 1.2 Hz, 2H); 13C NMR
Acknowledgements
(126 MHz, CDCl3)
d 78.9, 111.4 (t, J 301.3 Hz, CF2), 130.7, 131.2, 131.8,
132.2, 132.9, 133.2, 134.6, 139.8 and 182.3 (C]O); IR (KBr, cmꢁ1
)
We thank the Department of Chemistry, University of Isfahan,
Iran, for financial support and the Department of Chemistry, The
University of Sheffield, UK, for 1H, 13C and 19F, NMR, HRMS and GC–
mass spectra.
3092, 2912, 1713 (C]O), 1550, 1301, 1110, 1009, 830 and 760; HRMS
(EI) Found: Mþ, 310.0543. C15H12F2O3S requires Mþ, 310.0502;
LRMS m/z (EI): 310 (Mþ, 100%), 311 (23%) and 246 (MꢁSO2, 8%).
Elemental analysis: Found (%): C, 58.32; H, 3.98; S, 10.56. Calcd for
C
15H12F2O3S: C, 58.06; H, 3.90; S, 10.33.
Supplementary data
3.5.5. 2-Fluoro-2-(naphthalen-2-ylsulfonyl)-1-phenylethanone
(7d) and 2,2-difluoro-2-(naphthalen-2-ylsulfonyl)-1-
phenylethanone (8d)
Supplementary data associated with this article can be found in
Following the typical procedure for fluorination of
sulfones, the monofluoro product 7d was obtained in 10% yield; mp
136 ꢀC; 1H NMR (500 MHz, CDCl3)
6.40 (d, J 48.0 Hz, 1H, CFH),
b-keto-
References and notes
d
7.53–7.62 (m, 2H), 7.70–7.64 (m, 2H), 7.73 (ddd, J 8.3, 7.0 and 1.3 Hz,
1H), 7.83 (ddd, J 8.6, 2.0 and 1.0 Hz, 1H), 8.01–8.15 (m, 5H) and 8.47
1. Mogi, R.; Morisaki, K.; Hu, J. B.; Prakash, G. K. S.; Olah, G. A. J. Fluorine Chem.
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2. Brigaud, T.; Laurent, E. Tetrahedron Lett. 1990, 31, 2287–2290.
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McDonald, J. J.; Mischke, D. A.; Nagy, M. A.; Perrone, E.; Schmidt, M. A.;
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Bonin, W.; Stark, H.; Pasenok, S.; Cabrera, I. WO/2000/007998, 2000.
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1991, 39, 981–986.
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Nakagawa, E. WO/1998/13324, 1998.
18. Fluorine-Containing Molecules: Structure, Reactivity, Synthesis and Applications;
Liebman, J. F., Greenberg, A., Dolbier, W. R., Jr., Eds.; VCH: New York, NY, 1988.
19. Lal, G. S.; Pez, G. P.; Syvret, R. G. Chem. Rev. 1996, 96, 1737–1755.
20. Stahly, G. P. J. Fluorine Chem. 1989, 43, 53–66.
(d, J 1.8 Hz, 1H); 13C NMR (126 MHz, CDCl3)
d 100.5 (d, J 232.3 Hz, F,
CFH), 123.6, 127.9, 128.1, 128.8, 129.6, 129.7, 129.8, 130.1, 131.6, 132.0,
132.5, 134.0, 135.0, 136.0 and 186.6 (C]O); 19F NMR (235 MHz,
CDCl3)
d
ꢁ179.0 (d, J 48.0 Hz, 1F, CFH); IR (KBr, cmꢁ1) 3104, 3066,
2924, 2839, 1731 (C]O), 1545, 1437, 1363, 1236, 934, 853 and 811;
HRMS (EI) Found: Mþ, 328.1042. C18H13FO3S requires Mþ, 328.1060;
LRMS m/z (EI): 328 (Mþ, 5%), 264 (MꢁSO2, 2%), 127 (100%) and 105
(85%). Elemental analysis: Found (%): C, 65.66; H, 4.01; S, 9.87. Calcd
for C18H13FO3S: C, 65.84; H, 3.99; S, 9.76, and the difluoro product
8d in 52% yield; mp 142 ꢀC (ether); 1H NMR (500 MHz, CDCl3)
d 7.54
(dd, J 8.3 and 7.5 Hz, 2H), 7.69–7.72 (m, 2H), 7.75 (ddd, J 8.3, 6.9 and
1.3 Hz, 1H), 7.96–8.00 (m, 2H), 8.05 (dd, J 11.7 and 8.2 Hz, 2H), 8.20
(td, J 2.3 and 1.1 Hz, 2H) and 8.62 (d, J 1.5 Hz, 1H); 13C NMR
(126 MHz, CDCl3)
128.9, 129.4, 129.7, 129.9, 130.5, 130.8, 132.0, 134.0, 135.4, 136.4 and
183.8 (C]O); 19F NMR (235 MHz, CDCl3)
d 116.7 (t, J 301.4 Hz, 2F, CF2), 124.3, 128.1, 128.1,
d
ꢁ102.6 (s, 2F); IR (KBr,
cmꢁ1) 3100, 3055, 1746 (C]O), 1545, 1492, 1436, 1361, 1245, 954,
843 and 817; HRMS (EI) Found: Mþ, 346.1132. C18H12F2O3S requires
Mþ, 346.1211; LRMS m/z (EI): 346 (Mþ, 3%), 264 (MꢁSO2, 2%), 127
(65%) and 105 (100%). Elemental analysis: Found (%): C, 62.32; H,
3.59; S, 9.57. Calcd for C18H12F2O3S: C, 62.42; H, 3.49; S, 9.26.
3.5.6. 2,2-Difluoro-2-(4-methoxybenzylsulfonyl)-1-
phenylethanone (8f)
21. Prakash, G. K. S.; Hu, J. B.; Mathew, T.; Olah, G. A. Angew. Chem., Int. Ed. 2003, 42,
5216–5219.
22. Prakash, G. K. S.; Hu, J. B.; Ying, W.; Olah, G. A. Angew. Chem., Int. Ed. 2004, 43,
5203–5206.
Following the typical procedure for fluorination of
sulfones, the difluoro product 8f was obtained in 73% yield, recrys-
tallized from ethanol; mp 92 ꢀC; 1H NMR (500 MHz, CDCl3)
3.88 (s,
b-keto-
d
23. Middleton, W. J. J. Org. Chem. 1975, 40, 574–578.
3H), 4.21 (s, 2H), 6.96 (d, J 8.3 Hz, 2H), 7.35 (d, J 8.3 Hz, 2H), 7.52 (t, J
24. Olah, G. A.; Nojima, M.; Kerekes, I. J. Am. Chem. Soc. 1974, 96, 925–927.
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Wiley: New York, NY, 1992.
7.5 Hz, 2H), 7.68 (t, J 7.5 Hz, 1H) and 7.98 (d, J 7.5 Hz, 2H); 13C NMR
(101 MHz, CDCl3)
d 56.3, 57.8, 108.7 (t, J 301.3 Hz, CF2), 115.2, 121.5,
128.9, 129.3, 131.9, 135.3, 136.8, 160.1 and 190.2 (C]O); 19F NMR
´
´
27. Garcıa Martınez, A.; Barcina, J. O.; Rys, A. Z.; Subramanian, L. R. Tetrahedron Lett.
ꢁ134.3 (s, 2F, CF2); IR (KBr, cmꢁ1) 3877, 2982,
1992, 33, 7787–7788.
(235 MHz, CDCl3)
d
28. Gonzalez, J.; Foti, C. J.; Elsheimer, S. J. Org. Chem. 1991, 56, 4322–4325.
29. Hine, J.; Porter, J. J. J. Am. Chem. Soc. 1960, 82, 6178–6181.
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Ogawa, M. Chem. Pharm. Bull. 2000, 48, 1097–1100.
2923, 1706 (C]O), 1566, 1455, 1365, 1350, 1201, 1145 and 1097;
HRMS (EI) Found: Mþ, 340.0645. C16H14F2O4S requires Mþ,
340.0683. Elemental analysis: Found (%): C, 56.71; H, 4.34; S, 9.56.
Calcd for C16H14 F2O4S: C, 56.46; H, 4.14; S, 9.42.
34. Pedersen, O. S.; Pedersen, E. B. Synthesis 2000, 479–495.
35. Suryakiran, N.; Prabhakar, P.; Reddy, T. S.; Mahesh, K. C.; Rajesh, K.;
Venkateswarlu, Y. Tetrahedron Lett. 2007, 48, 877–881.
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3.5.7. 1,1-Difluoro-1-(phenylsulfonyl)propan-2-one (8j)
Following the typical procedure for fluorination of
sulfones, the difluoro product 8j (30%) was isolated as an oil; 1H
NMR (500 MHz, CDCl3) 2.49 (s, 3H), 7.58 (t, J 7.8 Hz, 2H), 7.73 (t, J
b-keto-
d