ORDER
REPRINTS
1840
JUNG,MIN,AND PARK
brine two times, respectively. The organic layer was dried over anhydrous
MgSO4 and concentrated to give a pale yellow solid, to which thionyl
chloride (11.0 mmol) and urea (15 mg) in 2.2 mL of anhydrous toluene
were added at 10–15ꢀC. The reaction mixture was heated in an oil bath at
100–110ꢀC for 3 h, then cooled to room temperature. The mixture of diethyl
malonate (10.0 mmol), magnesium (10.1 mmol), ethanol (30.3 mmol), CCl4
(0.1 mL) and anhydrous toluene (20 mL) was refluxed for 1 h and then
cooled to 0–5ꢀC. The former solution was cannulated into the latter. The
resulting reaction mixture was stirred at room temperature for 30 min, and
then cooled to 0–5ꢀC. 10 mL of 1N HCl was added. The organic layer was
washed with brine, dried and concentrated under reduced pressure.
Diethyl
2-{hydroxy[3-methyl-2-(acetoxy)phenyl]methylene}malonate
(4a). Rf ¼ 0.45 (hexane/ethyl acetate ¼ 3/1); 91% yield; IR (ꢀmax, KBr)
1
3420, 2978, 1732, 1680, 1216 cmꢁ1; H NMR (CDCl3) d 13.58 (br s, 1 H),
7.62 ꢂ 7.18 (m, 3 H), 4.32 (q, J ¼ 7.13 Hz, 2 H), 4.24 (q, J ¼ 7.12 Hz, 2H),
2.28 (s, 3 H), 2.19 (s, 3H), 1.35 (t, J ¼ 7.13 Hz, 3 H), 1.24 (t, J ¼ 7.12 Hz, 3 H);
13C NMR (CDCl3) d 174.91, 171.12, 168.66, 164.82, 148.24, 135.95, 133.06,
129.31, 126.89, 125.80, 101.77, 62.35, 61.47, 20.64, 16.23, 14.07, 13.65
Diethyl 2-{hydroxy[3-methoxy-2-(acetoxy)phenyl]methylene}malonate
(4b). Rf ¼ 0.41 (hexane/ethyl acetate ¼ 3/1); 87% yield; IR (ꢀmax, KBr)
1
3389, 2990, 1728, 1652, 1108 cmꢁ1; H NMR (CDCl3) d 13.56 (br s, 1 H),
7.41 ꢂ 7.06 (m, 3 H), 4.25 (q, J ¼ 7.14 Hz, 2 H), 4.11 (q, J ¼ 7.14 Hz, 2 H),
3.83 (s, 3 H), 2.04 (s, 3 H), 1.36 (t, J ¼ 7.14 Hz, 3 H), 1.25 (t, J ¼ 7.14 Hz,
3 H); 13C NMR (CDCl3) d 174.24, 171.08, 168.22, 164.66, 151.59, 137.32,
126.43, 121.38, 116.92, 114.35, 102.08, 62.36, 60.38, 56.18, 20.70, 14.20, 13.48
Diethyl 2-{hydroxy[5-methoxy-2-(acetoxy)phenyl]methylene}malonate
(4c). Rf ¼ 0.46 (hexane/ethyl acetate ¼ 3/1); 90% yield; IR (ꢀmax, KBr)
1
3426, 2966, 1730, 1648, 1210 cmꢁ1; H NMR (CDCl3) d 13.55 (br s, 1 H),
7.66 ꢂ 7.21 (m, 3 H), 4.36 (q, J ¼ 7.14 Hz, 2 H), 4.27 (q, J ¼ 7.12 Hz, 2 H),
3.79 (s, 3 H), 2.28 (s, 3H), 1.36 (t, J ¼ 7.14 Hz, 3 H), 1.27 (t, J ¼ 7.12 Hz, 3 H);
13C NMR (CDCl3) d 176.28, 172.36, 169.59, 165.72, 151.69, 139.51, 126.50,
121.36, 117.81, 115.64, 101.08, 61.24, 60.12, 57.61, 19.88, 14.10, 13.16
Diethyl 2-{hydroxy[5-chloro-2-(acetoxy)phenyl]methylene}malonate (4d).
Rf ¼ 0.33 (hexane/ethyl acetate ¼ 5/1); 86% yield; IR (ꢀmax, KBr) 3316,
1
2986, 1722, 1688, 1180 cmꢁ1; H NMR (CDCl3) d 13.72 (br s, 1 H), 8.08
(dd, J ¼ 2.61 Hz, J ¼ 2.64 Hz, 1 H), 7.58 (dd, J ¼ 2.79 Hz, J ¼ 2.62 Hz, 1 H),
7.09 (dd, J ¼ 8.93 Hz, J ¼ 8.62 Hz, 1 H), 4.22 (q, J ¼ 7.14 Hz, 2 H), 4.13 (q,
J ¼ 7.13 Hz, 2 H), 2.36 (s, 3 H), 1.38 (t, J ¼ 7.14 Hz, 3 H), 1.29 (t, J ¼ 7.13 Hz,
3 H); 13C NMR (CDCl3) d 174.62, 168.46, 165.80, 162.77, 150.22, 136.41,
135.88, 129.81, 122.56, 118.11, 99.85, 61.23, 60.89, 20.04, 14.22, 13.89
Diethyl 2-{hydroxy[5-bromo-2-(acetoxy)phenyl]methylene}malonate (4e).
Rf ¼ 0.36 (hexane/ethyl acetate ¼ 5/1); 90% yield; IR (ꢀmax, KBr) 3378,