Water → 2-Methoxy-8-hydroxy-11,12-dihydro-5H-benzo[b]naphtho[2,1-d]pyran-5-one

HRID 1709

反応式

HRID 1709 の反応式
[C:1]([CH:5]1[C:14]2[C:9](=[CH:10][C:11]([O:15][CH3:16])=[CH:12][CH:13]=2)[CH2:8][CH2:7][C:6]1=O)([O:3][CH3:4])=[O:2].[C:18]1([CH:25]=C[CH:23]=[C:21](O)[CH:20]=1)[OH:19].P(Cl)(Cl)(Cl)=O.O>C1(C)C=CC=CC=1>[CH3:16][O:15][C:11]1[CH:10]=[C:9]2[C:14](=[CH:13][CH:12]=1)[C:5]1[C:1](=[O:2])[O:3][C:4]3[CH:25]=[C:18]([OH:19])[CH:20]=[CH:21][C:23]=3[C:6]=1[CH2:7][CH2:8]2

参加物

6

反応物 4

HCID 962WaterHCID 5054ResorcinolHCID 24813Phosphorus oxychlorideHCID 109554821-Carbomethoxy-6-methoxy-2-tetralone

生成物 1

HCID 106614352-Methoxy-8-hydroxy-11,12-dihydro-5H-benzo[b]naphtho[2,1-d]pyran-5-one収率 70.8%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
80 °C

実験手順

To a solution of 1-carbomethoxy-6-methoxy-2-tetralone (see, Colvin, Martin, and Shroot, Chemistry and Industry, 2130 (1966)) (18.0 g, 76.8 mmol) and resorcinol (8.9 g, 80.7 mmol) stirring at ambient temperature in toluene (450 mL) was added phosphorus oxychloride (12.0 g, 7.3 mL, 18.3 mmol) dropwise, and the mixture warmed to 80° C. for 12 h. After cooling to room temperature, the mixture was poured into water (500 mL) and filtered, rinsing the precipitate with ether. The filtrate layers were separated, the aqueous layer was extracted with ethyl acetate (3×500 mL), and the combined organic layers were dried (sodium sulfate) and concentrated. Recrystallization of the residue from methanol provided 16.0 g of the title compound as a yellow solid, mp 244-249 d°C.: 1 H NMR (300 MHz, DMSO-d6) d 10.55 (br s, 1H), 8.24 (d, J=8.6 Hz, 1H), 7.75 (d, J=8.7 Hz, 1H), 6.6-7.0 (m, 4H), 3.76 (s, 3H), 2.8-3.0 (m, 4H); 13C NMR (125 MHz, DMSO-d6) d 170.3, 160.3, 158.3, 158.1, 153.3, 147.7, 137.5, 127.4, 125.8, 122.5, 114.5, 112.6, 112.4, 110.9, 101.4, 54.6, 26.3, 22.7; IR (KBr) 3250, 1676, 1618 cm-1 ; MS (FD+) m/e 294 (M+); Anal. calc'd. for C18H14O4 : C, 73.45; H, 4.80. Found: C, 73.15; H, 4.86.

後処理

  1. temperatureAfter cooling to room temperature
  2. filtrationfiltered
  3. washrinsing the precipitate with ether
  4. customThe filtrate layers were separated
  5. extractionthe aqueous layer was extracted with ethyl acetate (3×500 mL)
  6. dry with materialthe combined organic layers were dried (sodium sulfate)
  7. concentrationconcentrated
  8. customRecrystallization of the residue from methanol

出典と根拠

ORDレコード
ord-2e1c1509e9854bccbce85b7561bd70a2
出典データセット
uspto-grants-1998_03
特許番号
US05726186

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