Thiophenol → S-phenyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanethioate

HRID 893208Notes

Reaction equation

HRID 893208 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:14])[CH2:10][C:11]([OH:13])=O)=[C:4]([CH3:15])[CH:3]=1.[C:16]1([SH:22])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C1(N=C=NC2CCCCC2)CCCCC1.BrC1C=CC(NC(=O)CC(N(C2CCCCC2)C(NC2CCCCC2)=O)=O)=C(C)C=1>O1CCCC1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([NH:8][C:9](=[O:14])[CH2:10][C:11](=[O:13])[S:22][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[C:4]([CH3:15])[CH:3]=1

Participants

6

Reactant 4

HCID 7969ThiophenolHCID 10868DicyclohexylcarbodiimideHCID 129348693-[(4-Bromo-2-methylphenyl)amino]-3-oxopropanoic acidHCID 190968861-(3-[(4-Bromo-2-methylphenyl)amino]-3-oxopropanoyl)-1,3-dicyclohexylurea

Product 1

HCID 86745928S-phenyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanethioateYield 40%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred mixture of 5.44 grams (0.02 mole) of 3-[(4-bromo-2-emthylphenyl)amino]-3-oxopropanoic acid prepared in Example V (Compound No. 97) and 2.31 grams (0.02 mole) of thiophenol in approximately 100 milliliters of dry tetrahydrofuran in an oven-dried reaction flask was fed a solution of 4.13 grams (0.02 mole) of 1,3-dicyclohexylcarbodiimide in about 25 milliliters of dry tetrahydrofuran, while cooling the reaction mixture in an ice-water bath. On completing the feed the ice bath was removed and the mixture stirred for about one hour following which the precipitated 1,3-dicyclohexylurea by-product (2.5 grams) was removed by filtration. Vacuum stripping the filtrate gave a solid which was recrystallized from acetone to give a compound, melting point 184° C.-187° C., which proved to be 1-(3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoyl)-1,3-dicyclohexylurea. The filtrate from this was concentrated and flash chromatographed (7:3 hexane:ethylacetate, silica column) to give 2.83 grams (0.008 mole) of S-phenyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanethioate having a melting point of 133° C.-135° C.

Workup

  1. temperaturewhile cooling the reaction mixture in an ice-water bath
  2. customwas removed
  3. customwas removed by filtration
  4. customgave a solid which
  5. customwas recrystallized from acetone
  6. customto give a compound, melting point 184° C.-187° C., which
  7. concentrationThe filtrate from this was concentrated
  8. customflash chromatographed (7:3 hexane:ethylacetate, silica column)

Sources & evidence

ORD record
ord-620cbe0cb7cc49fab35c7dc69e4d1607
Source dataset
uspto-grants-1992_06
Patent number
US05123951

Reaction notes

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