1190
C. Peppe, R. Pavão das Chagas
LETTER
1-(4¢-Chlorophenyl)-4-(4¢¢-methoxyphenyl)-butane-1,4-dione (1i):
mp 132–134 °C; lit.10 136 °C. 1H NMR (CDCl3): d = 7.99 (m, 4 H),
7.45 (d, 2 H), 6.95 (d, 2 H), 3.88 (s, 3 H), 3.40 (s, 4 H). 13C NMR
(CDCl3): d = 197.69, 196.97, 163.59, 139.51, 135.18, 130.36,
129.78, 129.53, 128.87, 113.74, 55.45, 32.57, 32.18. DEPT (135):
d = 130.36 (C-H), 129.53 (C-H), 128.87 (C-H), 113.74 (C-H),
55.45 (CH3), 32.57 (CH2), 32.18 (CH2). MS (EI, 70 eV, for 35Cl):
m/z (%) = 302 (3) [M], 135 (100).
(s, v. br., 0.43 H), 4.49 (s, 0.57 H), 4.62 (s, 0.43 H), 5.88 (s, 0.57 H),
6.01 (s, 0.43 H). 13C NMR (CDCl3): d = 18.79, 19.48, 28.16, 29.59,
63.81, 65.77, 76.75, 76.90, 77.46, 78.37, 202.71, 204.00.
Acknowledgment
C.P. is grateful to FAPERGS and CNPq for financial support and
R.P.C. to PIBIC-UFSM-CNPq for the award of a scholarship.
1-(4¢-Chlorophenyl)-4-(4¢¢-methylphenyl)-butane-1,4-dione (1j):
MS (EI, 70 eV, for 35Cl): m/z (%) = 286 (10) [M], 139 (41), 119
(100).
References
1
1-Phenyl-pentane-1,4-dione (lk): yellow oil. H NMR (CDCl3):
(1) (a) Cintas, P. Synlett 1995, 1087. (b) Li, C.-J. Tetrahedron
1996, 52, 5643. (c) Li, C.-J.; Chan, T. H. Tetrahedron 1999,
55, 11149. (d) Ranu, B. C. Eur. J. Org. Chem. 2000, 2343.
(e) Podlech, J.; Maier, T. C. Synthesis 2003, 633.
(2) Chan, T. H.; Yang, Y. J. Am. Chem. Soc. 1999, 121, 3228;
and references therein.
(3) For applications of indium(I) compounds in organic
synthesis see: (a) Barros, O. S. D.; Lang, E. S.; de Oliveira,
C. A. F.; Peppe, C.; Zeni, G. Tetrahedron Lett. 2002, 43,
7921. (b) Nóbrega, J. A.; Gonçalves, S. M. C.; Peppe, C.
Tetrahedron Lett. 2001, 43, 7921. (c) Nóbrega, J. A.;
Gonçalves, S. M. C.; Peppe, C. Tetrahedron Lett. 2000, 43,
5779.
(4) For oxidative insertions of indium monohalides into carbon-
halogen bonds see: (a) Peppe, C.; Tuck, D. G.; Victoriano,
L. J. Chem. Soc., Dalton Trans. 1982, 2165. (b) Khan, M.
A.; Peppe, C.; Tuck, D. G. J. Organomet. Chem. 1985, 280,
17. (c) de Carvalho, A. B.; de Maurera, M. A. M. A.;
Nobrega, J. A.; Peppe, C.; Brown, M. A.; Tuck, D. G.;
Hernandes, M. Z.; Longo, E.; Sensato, F. R.
d = 7.99 (m, 2 H), 7.50 (m, 3 H), 3.21 (t, 2 H, J = 5.8 Hz), 2.81 (t, 2
H, J = 5.8 Hz), 2.19 (s, 3 H). 13C NMR (CDCl3): d = 207.40,
198.52, 136.56, 133.16, 128.56, 128.02, 37.02, 32.38, 30.11. MS
(EI, 70 eV): m/z (%) = 176 (3) [M], 105 (100).
1-(4¢-Bromophenyl)-pentane-1,4-dione (ll): mp 71–73 °C. 1H NMR
(CDCl3): d = 7.84 (m, 2 H), 7.60 (m, 2 H), 3.22 (t, 2 H, J = 6.4 Hz),
2.88 (t, 2 H, J = 6.4 Hz), 2.25 (s, 3 H). 13C NMR (CDCl3):
d = 207.03, 197.46, 135.37, 131.87, 129.54, 128.87, 36.96, 32.28,
30.00. MS (EI, 70 eV, for 79Br): m/z (%) = 254 (5) [M], 183 (100).
3-(4¢-Chlorophenyl)-2-chloro-3-hydroxy-1-phenyl-propan-1-one
(5a): mp 100–103 °C. 1H NMR (CDCl3): d = 3.47 (s, 0.6 H), 3.64
(s, 0.4 H), 4.97 (d, J = 8.4 Hz, 0.6 H), 5.09 (d, J = 5.2 Hz, 0.4 H),
5.13 (d, J = 8.4 Hz, 0.6 H), 5.22 (d, J = 5.2 Hz, 0.4 H), 7.16–7.90
(m, 9 H). Anal. Calcd for C15H12Cl2O2: C, 61.04; H, 4.10. Found: C,
61.73; H, 4.46.
2-Chloro-3-hydroxy-3-(4¢-methoxyphenyl)-1-phenyl-propan-1-
one (5b): yellowish oil. 1H NMR (CDCl3): d = 2.70 (s, v. br.), 3.66
(s, 1.2 H), 3.72 (s, 1.8 H), 5.03 (d, J = 8.4 Hz, 0.6 H), 5.14 (d, J = 8.4
Hz, 0.6 H), 5.15 (d, J = 6.0 Hz, 0.4 H), 5.21 (d, J = 6.0 Hz, 0.4 H),
6.67–7.95 (m, 9 H).
Organometallics 1999, 18, 99. (d) dos Santos, J. E.; Peppe,
C.; Brown, M. A.; Tuck, D. G. Organometallics 1996, 15,
2201.
4-(4¢-Chlorophenyl)-3-chloro-4-hydroxy-butan-2-one (5c): yellow-
ish oil. 1H NMR (CDCl3): d = 2.22 (s, 1.29 H), 2.27 (s, 1.71 H), 2.72
(s, v. br.), 4.19 (d, J = 8.0 Hz, 0.57 H), 4.30 (d, J = 4.4 Hz, 0.43 H),
4.92 (d, J = 8.0 Hz, 0.57 H), 5.14 (d, J = 4.4 Hz, 0.43 H), 7.26 (m,
4 H). Anal. Calcd for C10H10Cl2O2: C, 51.53; H, 4.32. Found: C,
52.55; H, 4.81.
(5) Araki, S.; Hirashita, T.; Shimizu, K.; Ikeda, T.; Butsugan, Y.
Tetrahedron 1996, 52, 2803.
(6) Yasuda, M.; Tsuji, S.; Shibata, I.; Baba, A. J. Org. Chem.
1997, 62, 8282.
(7) Selvamurugan, V.; Aidhen, I. S. Tetrahedron 2001, 57,
6065; and references therein.
(8) Kel’in, A. V.; Kulinkovich, O. G. Synthesis 1996, 330.
(9) Takahashi, K.; Matsuzaki, M.; Ogura, K.; Iida, H. J. Org.
Chem. 1983, 48, 1909.
3-Chloro-5,5-dichloro-4-hydroxy-4-methyl-pentan-2-one
(5d):
yellowish oil. 1H NMR (CDCl3): d = 1.44 (s, 1.71 H), 1.48 (s, 1.29
H), 2.36 (s, 1.71 H), 2.37 (s, 1.29 H), 3.28 (s, v. br., 0.57 H), 3.53
Synlett 2004, No. 7, 1187–1190 © Thieme Stuttgart · New York