Cornforth reagent → HCID 18386051, compound

HRID 2298299Notes

Reaction equation

HRID 2298299 reaction equation
[CH2:1]([C:3]([OH:18])([CH2:16][CH3:17])[C:4]#[C:5][CH:6]([C:8]1[CH:13]=[CH:12][C:11]([S:14][CH3:15])=[CH:10][CH:9]=1)[OH:7])[CH3:2].[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=O.[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1>ClCCl>[CH2:1]([C:3]([OH:18])([CH2:16][CH3:17])[C:4]#[C:5][C:6]([C:8]1[CH:13]=[CH:12][C:11]([S:14][CH3:15])=[CH:10][CH:9]=1)=[O:7])[CH3:2]

Participants

4

Reactant 2

HCID 2724130Cornforth reagentHCID 18386011HCID 18386011, compound

Product 1

HCID 18386051HCID 18386051, compoundYield 71.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred suspension of celite (20 g) and 4-ethyl-1-{4-(methylthio)phenyl}-2-hexyn-1,4-diol (11 g) in 300 ml dichloromethane, was added 25 g of pyridinium dichromate at 0° C. Then the reaction mixture was stirred for 12 hours at room temperature. The insoluble and metallic substances were removed by filtration through Florisil. The filtrate was extracted with dilute aqueous HCl and dichloromethane (150 ml×3). The organic layer was then washed with brine and dried over anhydrous magnesium sulfate. The organic layer was concentrated in vacuo and the resulting crude product was recrystallized from 5:1 hexane and ethylacetate to yield 7.8 g of 4-ethyl-4-hydroxy-1-{4-(methylthio)phenyl}-2-hexyn-1-one as a low-melting solid. mp: 49-50° C. NMR: δ1.12 (t, J=7.5 Hz, 6H), 1.83 (q, J=7.5 Hz, 4H), 2.15 (br s, 1H), 2.54 (s, 3H), 7.28 (d, J=8.7 Hz, 2H), 8.02 (d, J=8.7 Hz, 2H). IR (cm−1): 3432, 2970, 2208, 1636, 1588, 1285, 1095.

Workup

  1. customThe insoluble and metallic substances were removed by filtration through Florisil
  2. extractionThe filtrate was extracted with dilute aqueous HCl and dichloromethane (150 ml×3)
  3. washThe organic layer was then washed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. concentrationThe organic layer was concentrated in vacuo
  6. customthe resulting crude product was recrystallized from 5:1 hexane and ethylacetate

Sources & evidence

ORD record
ord-9caf762b68414eb2bd0c98b45b18b7c6
Source dataset
uspto-grants-2002_12
Patent number
US06492416B1

Reaction notes

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