PAPER
One-Step Preparation of Symmetrical 1,4-Diketones from a-Halo Ketones
1753
MS: m/z = 306 (M+, 10), 139 (100), 111 (33), 75 (23).
IR (film): 3068, 3006, 2962, 2937, 2840, 1679, 1598, 1509, 1259,
1172, 1031, 788 cm–1.
1,4-Bis(2-bromophenyl)butane-1,4-dione (2d)
Yield: 29%; colorless crystals: mp 132 °C (benzene).
1H NMR (200 MHz, CDCl3): d = 7.89 and 6.89 (AA¢XX¢ system, 8
H
arom), 3.91 (s, 4 H, CH2), 3.82 (s, 6 H, OCH3).
IR (film): 3064, 2958, 2925, 2869, 1698, 1587, 1465, 1427, 1355,
1282, 1241, 1025, 755, 593 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.62 (m, 2 H), 7.44 (m, 2 H), 7.32
(m, 4 H), 3.34 (s, 4 H, CH2).
13C NMR (50 MHz, CDCl3): d = 199.05, 135.68, 132.64, 130.90,
130.42, 121.88, 38.46.
13C NMR (50 MHz, CDCl3): d = 198.84, 165.48, 132.58, 132.35,
115.66, 57.47, 34.28.
Anal. Calcd for C18H18O4: C, 72.47; H, 6.08. Found: C, 72.44; H,
6.05.
2,3-Dimethyl-1,4-diphenylbutane-1,4-dione (2j)
Yield: 79%; colorless crystals; mp 79 °C (benzene) (Lit.29 85–86
°C).
Anal. Calcd for C16H12Br2O2: C, 48.52; H, 3.05. Found: C, 48.49;
H, 3.04.
IR (KBr): 3068, 2958, 2925, 2856, 1702, 1589, 1428, 1220, 1027,
987, 796, 698 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.99 (m, 2 H), 7.72 (m, 2 H), 7.48
(m, 6 H), 3.91 (m, 2 H, CH), 1.25 (d, 6 H, CH3).
1,4-Bis(3-bromophenyl)butane-1,4-dione (2e)
Yield: 51%; colorless crystals; mp 168 °C (CHCl3–hexane) (Lit.26
mp 170–172 °C).
IR (KBr): 3081, 3064, 3027, 2962, 2927, 1691, 1675, 1567, 1452,
1288, 1099, 800, 781, 674 cm–1.
1H NMR (200 MHz, CDCl3): d = 8.17 (m, 2 H), 7.96 (m, 2 H), 7.72
(m, 2 H), 7.34 (m, 2 H), 3.42 (s, 4 H, CH2).
13C NMR (50 MHz, CDCl3): d = 198.80, 138.50, 132.34, 130.00,
129.21, 128.86, 124.92, 34.34.
MS: m/z = 396 (M+, 12), 183 (100), 155 (43), 76 (22).
13C NMR (50 MHz, CDCl3): d = 203.02, 149.26, 131.69, 130.55,
127.29, 33.85, 12.91.
Anal. Calcd for C18H18O2: C, 81.17; H, 6.81. Found: C, 81.15; H,
6.84.
1,2,3,4-Tetraphenylbutane-1,4-dione (2k)
Yield: 87% from 1k; 98% from 1l; colorless crystals; mp 157–160
°C (Lit.30 mp 158–162 °C).
1,4-Bis(4-bromophenyl)butane-1,4-dione (2f)
Yield: 96%; colorless crystals; mp 182 °C (CHCl3–hexane) (Lit.27
mp 182–183 °C).
IR (KBr): 3085, 3064, 3031, 2962, 2927, 1695, 1598, 1448, 1272,
1012, 871, 698 cm–1.
1H NMR (200 MHz, CDCl3): d = 8.07 (m, 4 H), 7.53 (m, 4 H), 7.30
(m, 12 H), 4.32 (s, 2 H, CH2).
13C NMR (50 MHz, CDCl3): d = 196.62, 138.71, 136.64, 135.17,
132.95, 132.45, 131.93, 131.52, 131.08, 130.96, 130.89, 130.66,
130.43, 129.38, 129.23, 128.92, 127.91, 47.54.
IR (film): 3091, 3062, 3035, 2954, 2896, 1671, 1583, 1392, 1324,
1189, 1072, 1000, 848, 784, 761 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.88 and 7.64 (AA¢BB¢ system, 8
Harom), 3.41 (s, 4 H, CH2).
13C NMR (50 MHz, CDCl3): d = 199.43, 137.46, 133.94, 131.61,
130.37, 34.46
MS: m/z (%) = 390 (M+,5), 372 (100), 267 (34), 105 (11), 77 (8).
3,4-Diacetylhexane-2,5-dione (2l)
MS: m/z (%) = 396 (M+, 8), 183 (100), 155 (24), 76 (15).
Yield: 68%; colorless crystals; mp 188 °C (Lit.31 mp 192–193 °C).
1,4-Bis(2-methoxyphenyl)butane-1,4-dione (2g)
Yield: 26%; colorless crystals; mp 98–102 °C (benzene) (Lit.28 mp
102–104 °C).
IR (KBr): 3064, 3031, 2962, 2931, 1685, 1598, 1448, 1319, 1288,
1209, 1176, 698 cm–1.
1H NMR (200 MHz, CDCl3): d = 5.48 (s, 2 H, CH), 2.11 (s, 12 H,
CH3).
13C NMR (50 MHz, CDCl3): d = 195.88, 62.08, 19.42.
MS: m/z (%) = 198 (M+, 7), 182 (34), 91 (100), 65 (12).
IR (film): 3072, 3002, 2960, 2937, 2046, 1930, 1673, 1463, 1292,
1180, 1024, 788 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.41 (m, 2 H), 7.21 (m, 2 H), 6.99
(m, 4 H), 3.90 (s, 6 H, OCH3), 3.77 (s, 4 H, CH2).
13C NMR (50 MHz, CDCl3): d = 199.14, 160.94, 135.75, 132.36,
123.24. 122.54, 113.59, 57.50, 33.92.
Acknowledgment
Anal. Calcd for C18H18O4: C, 72.47; H, 6.08. Found: C, 72.43; H,
6.11.
The authors are indebted to the Department of Chemistry at Gazios-
manpaa University for its financial support (Grant Nr. 2002/13 Ga-
ziosmanpaa University Science Research Fund). Furthermore, we
thank Dr. Hamdullah Kilic for his assistance with the GC/MS spec-
tra and elemental analyses.
1,4-Bis(3-methoxyphenyl)butane-1,4-dione (2h)
Yield: 60%; colorless crystals; mp 128 °C (CHCl3–hexane).
IR (KBr): 3062, 3027, 2960, 2929, 2871, 1963, 1911, 1816, 1677,
1596, 1448, 1272, 1211, 1072, 1000, 919, 875, 755, 696 cm–1.
1H NMR (200 MHz, CDCl3): d = 7.68 (m, 2 H), 7.56 (m, 2 H), 7.40
(m, 2 H), 7.16 (m, 2 H), 3.85 (s, 6 H, OCH3), 3.42 (s, 4 H, CH2).
13C NMR (50 MHz, CDCl3): d = 200.44, 161.86, 140.19, 131.57,
122.88, 121.68, 114.36, 57.45, 34.78.
MS: m/z (%) = 298 (M+, 5), 105 (100), 77 (31).
References
(1) Ellison, R. A. Synthesis 1973, 397.
(2) Bosshard, P.; Eugster, C. H. Adv. Heterocycl. Chem. 1966,
77, 377.
(3) Hoeve, W. T.; Wynberg, H.; Havinga, E. E.; Meijer, E. W.
J. Am. Chem. Soc. 1991, 113, 5887.
(4) Sato, T.; Okazaki, H.; Otera, J.; Nozaki, H. J. Am. Chem.
Soc. 1988, 110, 5209.
(5) Severin, T.; Koenig, D. Chem. Ber. 1974, 107, 1499.
(6) Ballini, R.; Bartoli, G. Synthesis 1993, 965.
1,4-Bis(4-methoxyphenyl)butane-1,4-dione (2i)
Yield: 32%; colorless crystals; mp 155–159 °C (benzene) (Lit.25 mp
153–155 °C).
Synthesis 2004, No. 11, 1750–1754 © Thieme Stuttgart · New York