SHORT PAPER
Synthesis of -Keto Esters
319
Methyl 3-(2,4-Dichlorophenyl)-3-oxopropanoate (2d)
Recrystallized from hexane;white solid; mp 70 °C; yield: 0.50 g
(68%).
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IR (KBr): 3448, 3088, 3008, 2960, 1656, 1632, 1584, 1552, 1476,
1448, 1392, 1368, 1280, 1244, 1204, 1112, 1008, 880, 848, 824,
800, 736, 568, 432 cm–1.
1H NMR (CDCl3): = 12.40 (s, 0.4 H, OH in enol form), 7.20–7.70
(m, 3 H, H-3,5,6), 5.59 (s, 0.4 H, =CH in enol form), 4.04 (s, 1.2 H,
CH2), 3.82 (s, 1.2 H, CO2CH3 in enol form), 3.75 (s, 1.8 H, CO2CH3
in keto form).
MS: m/z (%) = 247 (M+, 4), 213 (31), 211 (75), 177 (25), 175 (92.5),
173 (100), 147 (21), 145 (38), 108 (29), 75 (26), 69 (27), 59 (18), 50
(12).
Anal. Calcd for C10H8Cl2O3 (247.1): C, 48.61; H, 3.26, Cl, 28.70.
Found: C, 48.93, H, 3.43, Cl, 28.86.
Methyl 3-(2,3-Dihydro-1,4-benzodioxin-6-yl)-3-oxopropanoate
(2e)
Purified on a silica gel column (eluent: hexane–CH2Cl2, 1:5); white
crystals; mp 66 °C; yield: 0.62 g (88%).
IR (KBr): 2936, 2848, 1744, 1672, 1608, 1584, 1504, 1432, 1328,
1296, 1248, 1152, 1128, 1064, 1020, 928, 912, 896, 880, 856, 832,
812, 704, 656, 624 cm–1.
1H NMR (CDCl3): = 12.52 (s, 0.05 H, OH in enol form), 7.5 (m,
1 H, H-7), 7.3 (m, 1 H, H-5), 6.9 (m, 1 H, H-8), 5.58 (s, 0.05 H, =CH
in enol form), 4.3–4.4 (m, 2 H, H-2,3), 3.95 (s, 1.9 H, CH2), 3.80 (s,
0.15 H, CO2CH3 in enol form), 3.76 (s, 2.85 H, CO2CH3 in keto
form).
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Org. Synth. 1962, 42, 28. (h) Moriconi, E. J.; White, J. G.;
Franck, R. W.; Jansing, J.; Kelly, J. F.; Salomone, R. A.;
Shimakawa, Y. Tetrahedron Lett. 1970, 27.
(7) (a) Colguhoun, H. M.; Thompson, D. J.; Twigg, M. V.
Carbonylation. Direct Synthesis of Carbonyl Compounds;
Plenum Press: New York, 1991. (b) Parshall, G. W.; Itell, S.
D. Homogeneous Catalysis, The Applications and Chemistry
of Catalysis by Soluble Transition Metal Complexes; Wiley-
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Chem. Rev. 1989, 58, 117.
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1986, 5, 911.
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1989, 1706.
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325.
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1973, 52, 431.
MS: m/z (%) = 236 (M+, 20), 204 (11.5), 164 (23), 163 (100), 135
(13), 107 (8), 79 (11), 77 (7), 69 (4), 51 (10).
Anal. Calcd for C12H12O5 (236.2): C, 61.02; H, 5.12. Found: C,
60.74, H, 5.35.
References
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Synthesis 2002, No. 3, 317–319 ISSN 0039-7881 © Thieme Stuttgart · New York