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

HRID 990589

Reaction equation

HRID 990589 reaction equation
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]

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 74861,4-DiisopropylbenzeneSolvent

Procedure

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 (MgSO4) 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).

Workup

  1. customin high yield
  2. customThe cooled reaction mixture
  3. washwashed with water
  4. dry with materialsaturated sodium bicarbonate, dried (MgSO4)
  5. customthen evaporated under reduced pressure
  6. customrecrystallization from ethanol, 79.9 grams
  7. additionof mixed 6

Sources & evidence

ORD record
ord-4c787a78ad644f9cb4b310af8ba3cc45
Source dataset
uspto-grants-2002_10
Patent number
US06461567B1

Linked notes

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