Chloroform → 8-(beta-Chloroallyl)-7-butyroxy-4-methylcoumarin

HRID 2081372

Reaktionsgleichung

Reaktionsgleichung von HRID 2081372
ClC(=C)CO[C:5]1[CH:14]=[C:13]2[C:8]([C:9](C)=[CH:10][C:11](=[O:15])[O:12]2)=[CH:7][CH:6]=1.[C:18]([O:23][C:24](=[O:28])[CH2:25][CH2:26][CH3:27])(=O)[CH2:19][CH2:20][CH3:21].C(Cl)(Cl)[Cl:30]>C(C1C=CC(C(C)C)=CC=1)(C)C>[Cl:30][C:6](=[CH2:7])[CH2:5][C:14]1[C:13]([O:12][C:11](=[O:15])[CH2:10][CH2:9][CH3:8])=[CH:21][CH:20]=[C:19]2[C:18]=1[O:23][C:24](=[O:28])[CH:25]=[C:26]2[CH3:27]

Komponenten

5

Edukt 3

HCID 6212ChloroformHCID 7798Butyric anhydrideHCID 11215917-(beta-Chloroallyloxy)-4-methylcoumarin

Produkt 1

HCID 234469868-(beta-Chloroallyl)-7-butyroxy-4-methylcoumarin

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 74861,4-DiisopropylbenzeneLösungsmittel

Versuchsvorschrift

Rearrangement of CAMC was accomplished in high yield by refluxing the allyl ether from Step 2 (143.5 gm; 0.55 mole) in a mixture of p-diisopropylbenzene (Aldrich, 1000 ml) and butyric anhydride (96 ml, 92.8 gm; 0.59 mol, Aldrich) under argon for 18 hours. The cooled reaction mixture was diluted with chloroform, washed with water and then saturated sodium bicarbonate, dried (MgSO<) then evaporated under reduced pressure. Following recrystallization from ethanol, 79.9 grams of mixed 6 and 8-(β-chloroallyl)-7-butyroxy-4-methylcoumarin (BCAMC,15) were obtained. HPLC analysis (Beckman; C18-ODS reverse phase column, isocratic elution with 60% CH3OH/40% H2O) showed the mixture to contain 85.7% of the desired 8-substituted isomer, of which a sample was purified by column chromatography (60-200 mesh silica gel, elution with CH2Cl2). The structures of the two isomers were confirmed by NMR. NMR (CDCl3) d 7.56 (1H, d), 7.11 (1H, d), 6.26 (1h, d), 5.05-5.19 (2H, m), 3.84 (2H, m), 2.55-2.62 (2H, m), 2.43 (3H, d), 1.78-1.82 (2H, m), 1.01-1.09 (3H, t).

Aufarbeitung

  1. customin high yield
  2. customThe cooled reaction mixture
  3. washwashed with water
  4. dry with materialsaturated sodium bicarbonate, dried (MgSO<)
  5. customthen evaporated under reduced pressure
  6. customrecrystallization from ethanol, 79.9 grams
  7. additionof mixed 6

Quellen und Nachweise

ORD-Eintrag
ord-e3d89d4b716f440b91c71872fa526e6c
Quelldatensatz
uspto-grants-1993_02
Patentnummer
US05184020

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