Sodium Phosphate, Dibasic → Benzenemethanol, 4-(1,1-dimethylethyl)-α-methyl-, acetate, (-)-

HRID 1494521Notes

Reaction equation

HRID 1494521 reaction equation
P([O-])([O-])(O)=O.[Na+].[Na+].[C:8]([O:11][CH:12]([CH3:23])[C:13]1[CH:18]=[CH:17][C:16]([C:19]([CH3:22])([CH3:21])[CH3:20])=[CH:15][CH:14]=1)(=[O:10])[CH3:9]>CC(C)=O>[C:8]([O:11][CH:12]([CH3:23])[C:13]1[CH:14]=[CH:15][C:16]([C:19]([CH3:22])([CH3:21])[CH3:20])=[CH:17][CH:18]=1)(=[O:10])[CH3:9].[C:19]([C:16]1[CH:15]=[CH:14][C:13]([CH:12]([OH:11])[CH3:23])=[CH:18][CH:17]=1)([CH3:20])([CH3:21])[CH3:22]

Participants

5

Reactant 2

HCID 24203Sodium Phosphate, DibasicHCID 13648726Benzenemethanol, 4-(1,1-dimethylethyl)-α-methyl-, acetate, (-)-

Product 2

HCID 2607311-(4-tert-Butylphenyl)ethanolYield 34%HCID 13648726Benzenemethanol, 4-(1,1-dimethylethyl)-α-methyl-, acetate, (-)-Yield 62%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

In 400 ml of 0.2 M aqueous solution of disodium hydrogenphosphate was suspended 22.6 g of (-)-p-tert.-butyl-α-methylbenzyl acetate of [α]D25 -36.9° (C=1, C6H12) and optical purity 35.6% e.e. obtained in Synthesis Example 6, and 1.33 g of chicken liver acetone powder was added thereto. The resulting mixture was subjected to reaction at 25° C. for 67 hours. The reaction liquid was extracted twice with 400 ml each of ethyl acetate (insoluble matter was removed by Celite filtration). The ethyl acetate layer was dried over anhydrous sodium sulfate and freed of solvent by distillation. The resulting pale yellow oily residue was subjected to column chromatography (on 200 g of silica gel, wherein p-tert.-butyl-α-methylbenzyl acetate was eluted with a benzene/ethyl acetate 50/1 (V/V) mixture and then p-tert.-butyl-α-methylbenzyl alcohol was eluted with benzene/ethyl acetate 10/1 (V/V) mixture and, thereafter, the solvent in each elute was distilled away). Thus were obtained 14.01 g (yield: 62%) of (-)-p-tert.-butyl-α-methylbenzyl acetate of [α]D25 -85.5° (C=1.07, C6H12), optical purity 82.6% e.e. and 6.25 g (yield 34%) of (+)-p-tert.-butyl-α-methylbenzyl alcohol of [α]D25 +23.1° (C=1.07, C6H12), optical purity 47.2% e.e.

Workup

  1. additionwas added
  2. customThe resulting mixture was subjected to reaction at 25° C. for 67 hours
  3. customThe reaction liquid
  4. extractionwas extracted twice with 400 ml each of ethyl acetate (insoluble matter was removed by Celite filtration)
  5. dry with materialThe ethyl acetate layer was dried over anhydrous sodium sulfate
  6. distillationfreed of solvent by distillation
  7. washwas eluted with a benzene/ethyl acetate 50/1 (V/V) mixture
  8. washp-tert.-butyl-α-methylbenzyl alcohol was eluted with benzene/ethyl acetate 10/1 (V/V) mixture
  9. distillationthe solvent in each elute was distilled away)

Sources & evidence

ORD record
ord-ee6a952a25bd440690ef534c7695edaf
Source dataset
uspto-grants-1991_06
Patent number
US05026850

Reaction notes

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