(dd, J = 7.7, 1.6 Hz, 1H), 7.41 (td, J = 7.7, 1.6 Hz, 1H), 7.35 (td,
J = 7.7, 1.6 Hz, 1H), 4.49 (s, 2H); 13C NMR (100 MHz, CDCl3) d
194.84, 138.63, 133.72, 132.51, 129.75, 127.58, 119.11, 33.88; MS
m/z 278 (M+), 183, 169, 155.
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in 7% yield, see: E. Ganin and I. Amer, Synth. Commun., 1995, 25,
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14 Recently, we reported the oxidation of acetophenones to benzoic acids
using 400 W Hg lamp, see: S. Hirashima, T. Nobuta, N. Tada and A.
Itoh, Synlett, 2009, 2017.
15 Decomposition of hydroperoxide, see: Y. V. Mitnik, M. L. Khar’kovskii,
I. Y. Litvintsev and V. N. Sapunov, Osn. Organ. Sintez I Neftekhimiya.
Yaroslavl., 1989, 25, 138.
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17 Separate experiments indicate that visible light irradiation and bromine
source are necessary for the formation of a-bromoketone from 1-(4-
bromophenyl)ethyl hydroperoxide.
18 Photochemicala-bromination of ketones, see: S. S. Arbuj, S. B.
Waghmode and A. V. Ramaswamy, Tetrahedron Lett., 2007, 48, 1411.
19 AIST: Integrated Spectral Database System of Organic Compounds.
(Data were obtained from the National Institute of Advanced Indus-
trial Science and Technology (Japan)).
20 M. Suzuki and M. Nagawa, Yakugaku Zasshi, 1952, 72, 305.
21 M. S. Azevedo, G. B. C. Alves, J. N. Cardoso, R. S. C. Lopes and C. C.
Lopes, Synthesis, 2004, 1262.
2-Bromo-2¢-acetonaphthone (Table 2, entry 9)19. Colorless
1
solid; H NMR (400 MHz, CDCl3) d 8.51 (s, 1H), 8.03 (dd, J =
8.8, 2.0 Hz, 1H), 7.98 (dd, J = 8.4, 0.6 Hz, 1H), 7.92 (d, J = 8.8 Hz,
1H), 7.89 (d, J = 7.6 Hz, 1H), 7.67–7.61 (m, 1H), 7.61–7.54 (m,
1H), 4.58 (s, 2H); 13C NMR (100 MHz, CDCl3) d 192.0, 136.6,
133.1, 132.0, 131.6, 130.4, 129.7, 129.5, 128.5, 127.8, 124.8, 31.7;
MS m/z 248 (M+), 158, 141, 127, 115, 101, 77.
2-Bromo-1-(5-bromo-2-thienyl)ethanone (Table 2, entry 10)22.
Colorless leaflets (recrystallized from dichloromethane–hexane);
mp 91–92 ◦C; 1H NMR (400 MHz, CDCl3) d 7.55 (d, J = 4.0 Hz,
1H), 7.15 (d, J = 4.0 Hz, 1H), 4.29 (s, 2H); 13C NMR (100 MHz,
CDCl3) d 183.6, 142.4, 134.0, 131.8, 124.7, 29.9; MS m/z 284
(M+), 189, 175, 111. Anal. Calcd for C6H4Br2OS: C, 25.38; H,
1.42. Found: C, 25.78; H, 1.60.
m-Bis(bromoacetyl)benzene (Table 2, entry 11)23. Colorless oil;
1H NMR (400 MHz, CDCl3) d 8.58 (t, J = 1.7 Hz, 1H), 8.23 (dd,
J = 7.7, 1.7 Hz, 2H), 7.67 (t, J = 7.7 Hz, 1H), 4.49 (s, 4H); 13C
NMR (100 MHz, CDCl3) d 190.7, 134.8, 134.1, 129.9, 129.5, 30.6;
MS m/z 320 (M+), 225, 147, 118.
1
2-Bromopropiophenone (Table 2, entry 12)24. Colorless oil; H
NMR (400 MHz, CDCl3) d 8.03 (d, J = 7.4 Hz, 2H), 7.60 (t, J =
7.4 Hz, 1H), 7.49 (t, J = 7.4 Hz, 2H), 5.30 (q, J = 6.4 Hz, 1H), 1.91
(d, J = 6.4 Hz, 3H); MS m/z 212 (M+), 105, 77.
2-Bromo-1-phenyl-1-decanone (Table 2, entry 13)25. Colorless
oil; 1H NMR (400 MHz, CDCl3) d 8.02 (d, J = 7.4 Hz, 2H), 7.60
(t, J = 7.4 Hz, 1H), 7.49 (t, J = 7.4 Hz, 2H), 5.13 (t, J = 7.2 Hz,
1H), 2.28–2.03 (m, 2H), 1.60–1.10 (m, 12H), 0.88 (t, J = 7.0 Hz,
3H); MS m/z 310 (M+), 231, 198, 120, 105, 77.
2-Bromoisobutyrophenone (Table 2, entry 14)26. Colorless oil;
1H NMR (400 MHz, CDCl3) d 8.14 (d, J = 7.4 Hz, 2H), 7.53 (t,
J = 7.4 Hz, 1H), 7.44 (t, J = 7.4 Hz, 2H), 2.04 (s, 6H); MS m/z 226
(M+), 105, 77.
2-Bromo-2-phenylacetophenone (Table 2, entry 15)27. Colorless
1
solid; H NMR (400 MHz, CDCl3) d 8.03–7.96 (m, 2H), 7.59–
7.50 (m, 3H), 7.48–7.42 (m, 2H), 7.40–7.29 (m, 3H), 6.38 (s, 1H);
13C NMR (100 MHz, CDCl3) d 191.0, 135.9, 134.1, 133.7, 129.1,
129.0, 128.8, 51.0; MS m/z 195 [(M-Br)+], 105, 77.
22 D. I. Perez, S. Conde, C. Perez, C. Gil, D. Simon, F. Wandosell, F. J.
Moreno, J. L. Gelpi, F. J. Luque and A. Martinez, Bioorg. Med. Chem.,
2009, 17, 6914.
23 H.-B. Wang, J. A. Wisner and M. C. Jennings, Beilstein J. Org. Chem.,
2010, 6, DOI: 10.3762/bjoc.650.
Notes and references
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2 R. C. Larock, Comprehensive, Organic Transformations: A Guide to
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25 S. Mochizuki, S. Fukuzumi and T. Tanaka, Bull. Chem. Soc. Jpn., 1989,
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26 V. K. Aggarwal and S. Warren, J. Chem. Soc., Perkin Trans. 1, 1987,
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27 M. Tiecco, L. Testaferri, M. Tingoli, D. Chianelli and D. Bartoli,
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4704 | Org. Biomol. Chem., 2010, 8, 4701–4704
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