2-Methyl-2-butanol → Acetoacetic Acid

HRID 1735823Notes

Reaction equation

HRID 1735823 reaction equation
[K].CC([OH:7])(CC)C.[CH3:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][C:14]([C:17]1[CH:18]=[C:19]([OH:35])[C:20]2[C@H:26]3[CH2:27][C:28]([CH2:31][OH:32])=[CH:29][CH2:30][C@@H:25]3[C:24]([CH3:34])([CH3:33])[O:23][C:21]=2[CH:22]=1)([CH3:16])[CH3:15]>C1C=CC=CC=1>[CH3:22][C:21]([CH2:20][C:19]([OH:35])=[O:7])=[O:23].[CH3:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][C:14]([C:17]1[CH:18]=[C:19]([OH:35])[C:20]2[C@H:26]3[CH2:27][C:28]([CH2:31][OH:32])=[CH:29][CH2:30][C@@H:25]3[C:24]([CH3:34])([CH3:33])[O:23][C:21]=2[CH:22]=1)([CH3:15])[CH3:16]

Participants

6

Reactant 3

HCID 64052-Methyl-2-butanolHCID 107778DexanabinolHCID 5462222Potassium

Product 2

HCID 96Acetoacetic AcidHCID 107778Dexanabinol

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Potassium (1 g) was added to 2-methyl-2-butanol (16 ml) under a nitrogen atmosphere. The mixture was warmed, at 80°, until all the metal had reacted. The excess alcohol was removed by vacuum distillation and the dry residue was dissolved in dry benzene (45-ml). Two ml of this solution were added to HU-211- (30 mg, 0.78 mmoles) dissolved in dry benzene (30 ml). The solution was stirred, under a nitrogen atmosphere, for 2 hrs., then it was washed with a dilute HCl solution (1N), followed by a sodium bicarbonate solution (1N) and then with water. The organic layer was dried over MgSO4, and evaporated. The oil obtained was chromatographed on silica gel (15 gr.) Elution with ether:petroleum ether (1:10) gave the diacetate of HU-211 (99 mg) followed by traces of the monoacetate (on the allylic alcohol moiety), eluted with ether:petroleum ether (2:10), followed by the monoacetate (4c), 150 mg, identified by the I.R. peak at 1760 cm-1 ; 1H NMR δ 2.28 (3H, s, OCOCH3), 2.98 (1H, dd, C-2 equat. H), 4.02 (2H, q, C-7H), 5.72 (1H, d, C-6H), 6.52, 6.66 (atom. H).

Workup

  1. temperatureThe mixture was warmed, at 80°, until all the metal
  2. customhad reacted
  3. customThe excess alcohol was removed by vacuum distillation
  4. dissolutionthe dry residue was dissolved in dry benzene (45-ml)
  5. wash, then it was washed with a dilute HCl solution (1N)
  6. dry with materialThe organic layer was dried over MgSO4
  7. customevaporated
  8. customThe oil obtained
  9. customwas chromatographed on silica gel (15 gr.) Elution with ether:petroleum ether (1:10)

Sources & evidence

ORD record
ord-258571b996aa41f08ec31c3b7f456d18
Source dataset
uspto-grants-1996_07
Patent number
US05538993

Reaction notes

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