Hydrochloric Acid → 4,6-Bis(1,1-dimethylethyl)-2,3-dihydro-2,2-dipentyl-5-benzofuranol

HRID 23803Notes

Reaction equation

HRID 23803 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C([O:10][C:11]1[C:12]([C:34]([CH3:37])([CH3:36])[CH3:35])=[CH:13][C:14]2[O:18][C:17]([CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])([CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[CH2:16][C:15]=2[C:29]=1[C:30]([CH3:33])([CH3:32])[CH3:31])(=O)C.[Cl-].[NH4+].Cl>C(OC)(C)(C)C>[C:30]([C:29]1[C:15]2[CH2:16][C:17]([CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])([CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])[O:18][C:14]=2[CH:13]=[C:12]([C:34]([CH3:35])([CH3:37])[CH3:36])[C:11]=1[OH:10])([CH3:31])([CH3:33])[CH3:32]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 11102070HCID 11102070, compoundHCID 21226445Aluminium lithium hydride

Product 1

HCID 98004724,6-Bis(1,1-dimethylethyl)-2,3-dihydro-2,2-dipentyl-5-benzofuranolYield 99.4%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent2×

Conditions

Temperature
30 °C

Procedure

In an argon atmosphere, 0.27 kg of lithium aluminum hydride was added to 18 L of methyl t-butyl ether and the mixture was heated under reflux for 0.5 hours. The solution was cooled to 30° C. and a solution of 2.8 kg of 5-acetoxy-4,6-di-tert-butyl-2,2-dipentyl-2,3-dihydrobenzofuran in 5 L of methyl t-butyl ether was added dropwise; thereafter, the mixture was stirred for 4.5 hours at 50° C. in an argon atmosphere. The solution was cooled to 10° C. and 1.4 L of a saturated aqueous solution of ammonium chloride was slowly added dropwise. Subsequently, 14 L of 10% aqueous hydrochloric acid was added and the mixture was extracted with 14 L of hexane. The aqueous layer was discarded and the organic layer was washed with 14 L of a saturated aqueous solution of sodium chloride; thereafter, the organic layer was concentrated under reduced pressure and the residue was dissolved in 12.5 L of hexane; 2.5 kg of silica gel was added to the solution which was then stirred for 1 hour. After filtering off the silica gel, the filtrate was concentrated under reduced pressure to give 1.9 kg (99.4% in purity) of 4,6-di-tert-butyl-5-hydroxy-2,2-dipentyl-2,3-dihydrobenzofuran.

Workup

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 0.5 hours
  3. temperatureThe solution was cooled to 10° C.
  4. extractionthe mixture was extracted with 14 L of hexane
  5. washthe organic layer was washed with 14 L of a saturated aqueous solution of sodium chloride
  6. concentrationthereafter, the organic layer was concentrated under reduced pressure
  7. dissolutionthe residue was dissolved in 12.5 L of hexane
  8. addition2.5 kg of silica gel was added to the solution which
  9. stirringwas then stirred for 1 hour
  10. filtrationAfter filtering off the silica gel
  11. concentrationthe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-b7b5df9b39f24c8e9ea458c501570e07
Source dataset
uspto-grants-2005_02
Patent number
US06852867B2

Reaction notes

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