Cornforth reagent → 4-Hydroxy-4-methyl-1-{4-(methylthio)phenyl}-2-hexyn-1-one

HRID 2298287Notes

Reaction equation

HRID 2298287 reaction equation
[CH3:1][C:2]([OH:17])([CH2:15][CH3:16])[C:3]#[C:4][CH:5]([C:7]1[CH:12]=[CH:11][C:10]([S:13][CH3:14])=[CH:9][CH:8]=1)[OH:6].[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=O.[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1>ClCCl>[OH:17][C:2]([CH3:1])([CH2:15][CH3:16])[C:3]#[C:4][C:5]([C:7]1[CH:8]=[CH:9][C:10]([S:13][CH3:14])=[CH:11][CH:12]=1)=[O:6]

Participants

4

Reactant 2

HCID 2724130Cornforth reagentHCID 183860124-Methyl-1-{4-(methylthio)phenyl}-2-hexyn-1,4-diol

Product 1

HCID 183861674-Hydroxy-4-methyl-1-{4-(methylthio)phenyl}-2-hexyn-1-oneYield 54.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To 9.9 g of 4-methyl-1-{4-(methylthio)phenyl}-2-hexyn-1,4-diol dissolved in 200 ml dichloromethane, were added 15 g of pyridinium dichromate (PDC) and 15 g of celite. The suspension was stirred overnight at room temperature, and then the insoluble material was filtered off through Florisil. The filtrate was purified by column chromatography (hexane/ethylactate=4:1) to give 5.34 g of 4-hydroxy-4-methyl-1-{4-(methylthio)phenyl}-2-hexyn-1-one. NMR: δ1.13 (t, J=7.5 Hz, 3H), 1.62 (s, 3H), 1.85 (q, J=7.8 Hz, 2H), 2.54 (s, 3H), 7.28 (d, J=8.7 Hz, 2H), 8.01 (d, J=8.7 Hz, 2H). IR (cm−1): 3427, 2974, 1588, 1095, 914, 745.

Workup

  1. filtrationthe insoluble material was filtered off through Florisil
  2. customThe filtrate was purified by column chromatography (hexane/ethylactate=4:1)

Sources & evidence

ORD record
ord-594f156c54f84e5d8c48f3a50769f664
Source dataset
uspto-grants-2002_12
Patent number
US06492416B1

Reaction notes

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