2-Thiocresol → 2-methylphenyl 2-methyl-N-phenyl-3-(phenylthio)-2-propenimidothioate

HRID 2061011Notes

Reaction equation

HRID 2061011 reaction equation
[CH3:1]/[C:2](=[CH:12]\[S:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)/[C:3]([NH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)=O.S(Cl)(Cl)=O.[CH3:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=1[SH:31].[H-].[Na+]>CN(C=O)C.O.C1(C)C=CC=CC=1>[CH3:1][C:2](=[CH:12][S:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[C:3]([S:31][C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][C:25]=1[CH3:24])=[N:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

9

Reactant 4

HCID 87122-ThiocresolHCID 24386Thionyl ChlorideHCID 24758Sodium hydrideHCID 59498330(E)-2-methyl-N-phenyl-3-(phenylthio)-2-propenamide

Product 1

HCID 675434062-methylphenyl 2-methyl-N-phenyl-3-(phenylthio)-2-propenimidothioateYield 82.5%

Reagents, catalysts & solvents 4

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

A mixture of 0.5 g (1.85 mmol) of (E)-2-methyl-N-phenyl-3-(phenylthio)-2-propenamide, 0.4 ml of thionyl chloride, 5 mg of DMF, and 10 ml of toluene was refluxed for 1 hour and then concentrated. The residue was dissolved in 5 ml of DMF and cooled to 0° C. To a solution of 277 mg (2.23 mmol) of 2-methylthiophenol in 5 ml of DMF was added 90 mg of sodium hydride (60% in oil) under ice cooling and stirred for 5 minutes. The solution was added portionwise to the above-described DMF solution of the residue under ice cooling and stirred at room temperature for 1 hour. The reaction mixture was poured into water and extracted with tert-butyl methyl ether (three times). The combined organic layer was washed sequentially with water and a saturated NaCl solution, dried over anhydrous MgSO4, and concentrated. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=20/1) to obtain 573 mg of 2-methylphenyl 2-methyl-N-phenyl-3-(phenylthio)-2-propenimidothioate (hereinafter referred to as the present compound 21).

Workup

  1. temperaturewas refluxed for 1 hour
  2. concentrationconcentrated
  3. dissolutionThe residue was dissolved in 5 ml of DMF
  4. stirringstirred at room temperature for 1 hour
  5. extractionextracted with tert-butyl methyl ether (three times)
  6. washThe combined organic layer was washed sequentially with water
  7. dry with materiala saturated NaCl solution, dried over anhydrous MgSO4
  8. concentrationconcentrated
  9. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=20/1)

Sources & evidence

ORD record
ord-d1475a81b191440fb986fcb2204ccfb1
Source dataset
uspto-grants-2012_10
Patent number
US08278473B2

Reaction notes

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