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4-ETHOXYCARBONYL PYRAZOLIN-5-ONE DERIVATIVES
3773
99.49, 62.45, 61.33, 27.57, 14.27, 14.17, 7.79; MS (ESI) (m/z) 217 [M þ H]þ,
161, 133, 104 (base peak); 239 [M þ Na]þ.
Diethyl pivaloylmalonate (2c): Rf ¼ 0.50 (10% ethyl acetate in
1
hexanes); IR (neat, NaCl) 3654, 2978, 1736, 1478, 1038 cmÀ1; H NMR[11c]
(CDCl3) ꢀ 4.83 (br s, 1H), 4.15 (q, J ¼ 7.12, 4H), 1.19 (q, J ¼ 7.12, 6H), 1.10
(s, 9H); 13C NMR (CDCl3) ꢀ 203.88, 165.01, 62.47, 60.05, 45.82, 26.13,
14.22; MS (m/z) 245 [M þ H]þ, 161, 84 (base peak); 267 [M þ Na]þ.
Diethyl cyclopentanecarbonylmalonate (2d): Rf ¼ 0.60 (15% ethyl ace-
tate in hexanes); IR (neat, NaCl) 3583, 2963, 1730, 1601, 1241, 1035 cmÀ1
;
1H NMR[11d] (CDCl3) ꢀ 13.28, 4.52 (br s, br s, total 1H), 4.22–4.23 (m, 4H),
3.05–2.90 (m, 1H), 1.78–1.52 (m, 8H), 1.27–1.18 (m, 6H); 13C NMR (CDCl3)
ꢀ 202.13, 171.43, 165.00, 99.54, 62.49, 61.48, 43.09, 31.34, 29.90, 26.74,
26.32, 14.56, 14.28; MS (ESI) (m/z) 257 [M þ H]þ, 202, 115, 96.55 (base
peak); 279 [M þ Na]þ.
Diethylcaproylmalonate (2e): Rf ¼ 0.50 (10% ethyl acetate in hexanes);
IR (neat, NaCl) 3584, 2959, 1734, 1602, 1243, 1040 cmÀ1; 1H NMR (CDCl3)
ꢀ 13.36, 4.43 (br s, br s, total 1H), 4.26–4.19 (m, 4H), 2.58 (t, J ¼ 7.30, 1H),
2.40 (t, J ¼ 7.30, 1H), 1.64–1.57 (m, 2H), 1.30–1.22 (m, 10H), 0.86 (t,
J ¼ 6.76, 3H); 13C NMR (CDCl3) ꢀ 199.37, 171.56, 165.04, 100.08, 62.59,
61.60, 34.11, 31.77, 26.83, 22.69, 14.45, 14.34, 14.21; MS (ESI) (m/z) 259
[M þ H]þ, 180, 135 (base peak); 281 [M þ Na]þ.
Diethyldecanoymlaolnate (2f ):
Rf ¼ 0.30 (15% ethyl acetate in
hexanes); IR (neat, NaCl) 2927, 1735, 1602, 1243, 1037 cmÀ1
;
1H NMR
(CDCl3) ꢀ 13.36, 4.43 (br s, br s, total 1H), 4.28–4.19 (m, 4H), 2.59 (t,
J ¼ 7.29, 1H), 2.41 (t, J ¼ 7.29, 1H), 1.64–1.57 (m, 2H), 1.31–1.21 (m, 18H),
0.86 (t, J ¼ 6.87, 3H); 13C NMR (CDCl3) ꢀ 199.39, 171.58, 165.05, 100.08,
62.61, 61.45, 34.19, 32.22, 29.77, 29.63, 27.17, 25.36, 23.76, 23.02, 14.61,
14.43, 14.33; MS (ESI) (m/z) 315 [M þ H]þ, 202, 161 (base peak); 104; 337
[M þ Na]þ.
Diethylbenzoylmalonate (2g): Rf ¼ 0.45 (20% ethyl acetate in hexanes);
IR (neat, NaCl) 3463, 3063, 1734, 1692, 1294, 1037 cmÀ1 1H NMR[11a]
;
(CDCl3) ꢀ 13.41, 5.28 (br s, br s, total 1H), 7.89–7.42 (m, 5H), 4.23 (q,
J ¼ 7.13, 4H), 1.23 (t, J ¼ 7.13, 6H); 13C NMR (CDCl3) ꢀ 189.36, 165.26,
135.80, 134.41, 129.07, 128.69, 62.75, 61.94, 14.40, 14.03; MS (ESI) (m/z)
265 [MþH]þ, 219, 104 (base peak); 287 [MþNa]þ.
Diethyl4-methoxybenzoyml aolnate (2h): Rf ¼ 0.50 (20% ethyl acetate
in hexanes); IR (neat, NaCl) 3651, 2983, 1735, 1600, 1028 cmÀ1 1H
;
1H NMR (CDCl3) ꢀ 13.35, 5.23 (br s, br s, total 1H), 7.83 (d, J ¼ 8.92,
2H), 6.88 (d, J ¼ 8.92, 2H), 4.20 (q, J ¼ 7.08, 4H), 3.78 (s, 3H), 1.19 (t,
J ¼ 7.08, 6H); 13C NMR (CDCl3) ꢀ 187.78, 165.43, 164.64, 134.33, 131.26,
125.65, 114.50, 62.58, 61.95, 55.90, 14.26; MS (ESI) (m/z) 295 [MþH]þ, 249,
135 (base peak); 317 [MþNa]þ.