Thiophenol → 2-Chloro-4-phenylthioaniline

HRID 841190Notes

Reaction equation

HRID 841190 reaction equation
[Cl:1][C:2]1[CH:8]=[C:7](I)[CH:6]=[CH:5][C:3]=1[NH2:4].[C:10]1([SH:16])[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.C[O-].[Na+]>C(O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:1][C:2]1[CH:8]=[C:7]([S:16][C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[CH:6]=[CH:5][C:3]=1[NH2:4]

Participants

6

Reactant 3

HCID 7969ThiophenolHCID 2829302-Chloro-4-iodoanilineHCID 10942334Sodium Methoxide

Product 1

HCID 222872082-Chloro-4-phenylthioaniline

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolvent

Procedure

Tetrakis(triphenylphosphine)palladium(0) (0.1 15 g) was added to a deoxygenated mixture of 2-chloro-4-iodoaniline (0.507 g), thiophenol (0.214 ml) and sodium methoxide (0.227 g) in ethanol (20 ml). The mixture was further deoxygenated by evacuation and refilling with argon (3 cycles) then heated under reflux with stirring under argon for 18 hours, cooled, diluted with ether (30 ml) and filtered. Volatile material was removed by evaporation and the residue was purified by chromatography on a silica gel Mega Bond Elut column eluting with 10-15% ethyl acetate/hexane to give the title compound (0.443 g) as a solid. M.p. 59-60° C.; NMR: 5.78 (br s, 2H), 6.8 (t, 1H), 7.04 (m, 2H), 7.15 (m, 2H), 7.2-7.35 (m, 3H); EA: C12H10ClNS requires C, 61.1; H, 4.3; N, 5.9; S, 13.6%; found: C, 60.8; H, 4.4; N, 5.7; S, 13.3%.

Workup

  1. customThe mixture was further deoxygenated by evacuation and refilling with argon (3 cycles)
  2. temperaturethen heated
  3. temperatureunder reflux
  4. temperaturecooled
  5. additiondiluted with ether (30 ml)
  6. filtrationfiltered
  7. customVolatile material was removed by evaporation
  8. customthe residue was purified by chromatography on a silica gel Mega Bond Elut column
  9. washeluting with 10-15% ethyl acetate/hexane

Sources & evidence

ORD record
ord-11a6c1f5558c4f74beef4f56f34e74cf
Source dataset
uspto-grants-2002_04
Patent number
US06369273B1

Reaction notes

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