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

HRID 612738

반응식

HRID 612738 반응식
[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

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 1140Toluene용매

반응 조건

온도
80 °C

실험 절차

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 aulfate) and concentrated. Recrystallization of the residue from methanol provided 16.0 g of the title compound as a yellow solid, mp 244-249d° C.: 1H 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.

후처리

  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 aulfate)
  7. concentrationconcentrated
  8. customRecrystallization of the residue from methanol

출처 및 근거

ORD 기록
ord-81e861405e724be9ae146c3e36bac5ea
출처 데이터셋
uspto-grants-1999_12
특허 번호
US06004971

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