Phenyl isocyanate → HCID 22401502, compound

HRID 260465Notes

Reaction equation

HRID 260465 reaction equation
C[C:2]1[NH:3][C:4]2[C:9]([C:10]=1[S:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[CH:8][CH:7]=[CH:6][CH:5]=2.[CH2:18]([Li])CCC.C([Li])(C)(C)C.[C:28]1([N:34]=[C:35]=[O:36])[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>O1CCCC1.CCCCCC.O>[C:28]1([N:34]([C:2]2[NH:3][C:4]3[C:9]([C:10]=2[S:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)=[CH:8][CH:7]=[CH:6][CH:5]=3)[C:35](=[O:36])[CH3:18])[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

Participants

8

Reactant 4

HCID 7672Phenyl isocyanateHCID 668282HCID 668282, compoundHCID 178418306HCID 178418306, compoundHCID 178418339Butyllithium

Product 1

HCID 22401502HCID 22401502, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

2-Methyl-3-phenylthioindole (0.50 g, 2.1 mmol) (prepared according to the procedure described by Atkinson, J. G., et al., Synthesis, p. 480-481 (1988), was dissolved in dry tetrahydrofuran and cooled under nitrogen to -78° C. A solution of n-butyllithium in hexane (0.83 mL, 2.5M) was added via syringe. Carbon dioxide was bubbled into the reaction mixture over a period of several minutes; unreacted carbon dioxide was removed by freezing the reaction at liquid nitrogen temperature under high vacuum and warming to -78° C. A solution of t-butyllithium in hexane was added (1.35 mL, 1.7M) and the reaction stirred for 20 min. Phenylisocyanate (0.23 mL, 2.1 mmol) in tetrahydrofuran (1.5 mL) was added and the reaction stirred at 20° C. overnight. The reaction was diluted with water and extracted with ethyl acetate. The organic phase was washed with saturated brine and dried over magnesium sulfate. Filtration and evaporation of solvent left an amber oil. The crude products were chromatographed on silica gel eluting successively with 15%, 20%, and 40% ether in hexane. 2-(N-Phenylacetamido)-3-phenylthioindole was isolated as a solid, mp 66°-68° C. Anal. Calc. for C22H18N2OS: C, 72.98; H, 5.01; N, 7.73. Found: C, 72.99; H, 4.87; N, 7.52 . Later fractions contained 2-(N-phenylacetamido)-1-(phenylcarbamoyl)-3-phenylthioindole, mp 123°-125° C. Anal. Calc. for C29H23N3O2S: C, 70.28, H, 4.67, N, 8.47. Found: C, 70.37, H, 4.61; N, 8.34.

Workup

  1. custom, et al., Synthesis, p
  2. customCarbon dioxide was bubbled into the reaction mixture over a period of several minutes
  3. customunreacted carbon dioxide was removed
  4. customthe reaction at liquid nitrogen temperature under high vacuum
  5. temperaturewarming to -78° C
  6. stirringthe reaction stirred at 20° C. overnight
  7. extractionextracted with ethyl acetate
  8. washThe organic phase was washed with saturated brine
  9. dry with materialdried over magnesium sulfate
  10. filtrationFiltration and evaporation of solvent
  11. waitleft an amber oil
  12. customThe crude products were chromatographed on silica gel eluting successively with 15%, 20%, and 40% ether in hexane

Sources & evidence

ORD record
ord-953e9caaecb8416cb527c872eb854385
Source dataset
uspto-grants-1996_06
Patent number
US05527819

Reaction notes

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