Dimethylformamide → n-hexyl 2-methyl-N-phenyl-3-(phenylthio)-2-propenimidothioate

HRID 2061015Notes

Reaction equation

HRID 2061015 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.CN(C=O)C>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:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])=[N:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 59498330(E)-2-methyl-N-phenyl-3-(phenylthio)-2-propenamide

Product 1

HCID 67542494n-hexyl 2-methyl-N-phenyl-3-(phenylthio)-2-propenimidothioateYield 12%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A suspension of 1.0 g (3.71 mmol) of (E)-2-methyl-N-phenyl-3-(phenylthio)-2-propenamide, 0.81 ml of thionyl chloride, and 10 mg of DMF in 10 ml of toluene was refluxed for 1 hour and then concentrated under vacuum. The residue was dissolved in 5 ml of DMF and cooled in ice bath. To a solution of 241 mg of n-hexylthiol in 5 ml of DMF was added 90 mg of sodium hydride (60% in oil) under ice cooling and stirred for 5 minutes. The mixture was added portionwise to the above-described DMF solution of the residue under ice cooling and then 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 82 mg of n-hexyl 2-methyl-N-phenyl-3-(phenylthio)-2-propenimidothioate (hereinafter referred to as the present compound 47) and 114 mg of n-hexyl 3-(hexylthio)-2-methyl-N-phenyl-2-propenimidothioate (hereinafter referred to as the present compound 48).

Workup

  1. temperaturewas refluxed for 1 hour
  2. concentrationconcentrated under vacuum
  3. dissolutionThe residue was dissolved in 5 ml of DMF
  4. temperaturecooled in ice bath
  5. additionTo a solution of 241 mg of n-hexylthiol in 5 ml of DMF was added 90 mg of sodium hydride (60% in oil) under ice cooling
  6. additionThe mixture was added portionwise to the above-described DMF solution of the residue under ice cooling
  7. stirringstirred at room temperature for 1 hour
  8. additionThe reaction mixture was poured into water
  9. extractionextracted with tert-butyl methyl ether (three times)
  10. washThe combined organic layer was washed sequentially with water
  11. dry with materiala saturated NaCl solution, dried over anhydrous MgSO4
  12. concentrationconcentrated
  13. customThe residue was purified by silica gel column chromatography (hexane/ethyl acetate=20/1)

Sources & evidence

ORD record
ord-b8a24558bd224a2fbed23c7530c6a919
Source dataset
uspto-grants-2012_10
Patent number
US08278473B2

Reaction notes

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