Methyl Acetate → Methyl 5-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]thio]-3-hydroxypentanoate

HRID 1087589Notes

Reaction equation

HRID 1087589 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[C:13]([O:16][CH3:17])(=[O:15])[CH3:14].[CH3:18][C:19]([C:22]1[CH:23]=[C:24]([S:33][CH2:34][CH2:35][CH:36]=[O:37])[CH:25]=[C:26]([C:29]([CH3:32])([CH3:31])[CH3:30])[C:27]=1[OH:28])([CH3:21])[CH3:20].[Cl-].[NH4+]>O1CCCC1.CCCCCC>[CH3:32][C:29]([C:26]1[CH:25]=[C:24]([S:33][CH2:34][CH2:35][CH:36]([OH:37])[CH2:14][C:13]([O:16][CH3:17])=[O:15])[CH:23]=[C:22]([C:19]([CH3:18])([CH3:20])[CH3:21])[C:27]=1[OH:28])([CH3:30])[CH3:31]

Participants

8

Reactant 5

HCID 6584Methyl AcetateHCID 7912DiisopropylamineHCID 25517Ammonium ChlorideHCID 140118163-[[3,5-Bis(1,1-dimethylethyl)-4-hydroxyphenyl]thio]propanal2×HCID 178418339Butyllithium

Product 1

HCID 14390824Methyl 5-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]thio]-3-hydroxypentanoate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 1.5 g of diisopropylamine in 25 ml of tetrahydrofuran (THF), stirred at -78° C. in an atmosphere of nitrogen, was added 6.5 ml of 1.6 M n-butyllithium in hexane. The mixture was stirred at -78° C. for 5 min after which a solution of 1.2 g of methyl acetate in 5 ml of THF was added. The mixture was again stirred at -78° C. for 5 min. Then a solution of 1.75 g of 3-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]thio]propanal, the product of Example 3, in 20 ml of THF was added. The reaction mixture was stirred at -78° C. for 1/2 hr. A saturated solution of ammonium chloride was carefully added, and the resultant mixture was allowed to warm to room temperature. The mixture was extracted with ether. The ether extract was washed with water, dried over anydrous MgSO4, and distilled to dryness under reduced pressure. The residual oil was chromatographed on silica gel. Elution with hexane-ethyl acetate followed by crystallization from aqueous methanol gave the product mp. 77°-80° C.

Workup

  1. additionwas added
  2. stirringThe reaction mixture was stirred at -78° C. for 1/2 hr
  3. temperatureto warm to room temperature
  4. extractionThe mixture was extracted with ether
  5. extractionThe ether extract
  6. washwas washed with water
  7. dry with materialdried over anydrous MgSO4
  8. distillationdistilled to dryness under reduced pressure
  9. customThe residual oil was chromatographed on silica gel
  10. washElution with hexane-ethyl acetate
  11. customfollowed by crystallization from aqueous methanol

Sources & evidence

ORD record
ord-327f274c54ed464e817d45f2168c5a0b
Source dataset
uspto-grants-1991_07
Patent number
US05036105

Reaction notes

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