tert-Butanol → HCID 20063323, compound

HRID 1084453Notes

Reaction equation

HRID 1084453 reaction equation
[CH3:1][CH:2]([CH3:14])[C:3]([C:5]1[CH:13]=[CH:12][CH:11]=[CH:10][C:6]=1[C:7]([OH:9])=[O:8])=[O:4].C(O)(C)(C)C.CC(C)([O-])C.[K+].Br[CH:27]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[C:28]([O:30][CH2:31][CH3:32])=[O:29]>C(O)C>[CH2:31]([O:30][C:28]([C:27]1([C:33]([O:35][CH2:36][CH3:37])=[O:34])[C:3]([OH:4])([CH:2]([CH3:1])[CH3:14])[C:5]2[C:6](=[CH:10][CH:11]=[CH:12][CH:13]=2)[C:7](=[O:8])[O:9]1)=[O:29])[CH3:32]

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 69637Diethyl bromomalonateHCID 3167392-(2-methylpropanoyl)benzoic acidHCID 23665647Potassium tert-butoxide

Product 1

HCID 20063323HCID 20063323, compoundYield 94.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A stirred mixture of 2-(2-methylpropanoyl)benzoic acid (44.27 g) and tert-butanol (300 ml) was treated portionwise with potassium tert-butoxide (28.14 g) over 5 minutes at room temperature and the reaction mixture stirred for a further 10 minutes and then treated dropwise over 10 minutes with a solution of diethyl bromomalonate (55.1 g) in ethanol (200 ml). The stirred mixture was refluxed for 18 hours and then evaporated to dryness. The residue was treated with diethyl ether (400 ml) and washed with water (400 ml). The aqueous phase was re-extracted with diethyl ether (200 ml) and the combined ethereal extracts washed with water (200 ml), saturated aqueous sodium hydrogen carbonate solution (200 ml) and water (200 ml), dried over magnesium sulphate and evaporated to give crude 3,3-bis(ethoxycarbonyl)-4-hydroxy-4-isopropyl-3,4-dihydroisocoumarin (76 g) as an amber oil.

Workup

  1. temperatureThe stirred mixture was refluxed for 18 hours
  2. customevaporated to dryness
  3. additionThe residue was treated with diethyl ether (400 ml)
  4. washwashed with water (400 ml)
  5. extractionThe aqueous phase was re-extracted with diethyl ether (200 ml)
  6. washthe combined ethereal extracts washed with water (200 ml), saturated aqueous sodium hydrogen carbonate solution (200 ml) and water (200 ml)
  7. dry with materialdried over magnesium sulphate
  8. customevaporated

Sources & evidence

ORD record
ord-fcc87bbbdb96499681acd2431c0a0fcd
Source dataset
uspto-grants-1991_04
Patent number
US05004747

Reaction notes

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