4-Nitrophenyl phenyl sulfide → Aniline, p-(phenylthio)- (6CI,7CI,8CI)

HRID 2105308Notes

Reaction equation

HRID 2105308 reaction equation
[BH4-].[Na+].[C:3]1([S:9][C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-])=O)=[CH:12][CH:11]=2)[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1>CO.C1COCC1.O.O.O.O.O.O.[Ni](Cl)Cl>[C:3]1([S:9][C:10]2[CH:15]=[CH:14][C:13]([NH2:16])=[CH:12][CH:11]=2)[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1

Participants

6

Reactant 2

HCID 137204-Nitrophenyl phenyl sulfideHCID 4311764Sodium borohydride

Product 1

HCID 96081Aniline, p-(phenylthio)- (6CI,7CI,8CI)

Reagents, catalysts & solvents 3

HCID 11791229Dichloronickel;hexahydrateCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Nickel chloride hexahydrate (41 g, 172.5 mmol), then sodium borohydride (19.5 g, 0.516 mmol) were added to a solution of 4-nitrophenyl phenyl sulfide Compound 161a (20 g, 86.5 mmol) in a mixture of MeOH (200 mL) and THF (75 mL) at 0° C. under nitrogen over a period of 1 hr. The mixture was stirred for 30 mins at 0° C. and the reaction was quenched slowly with aqueous 10% NH4Cl, neutralized with ammonium hydroxide and partitioned between ethyl acetate and water. The organic layer was dried (Na2SO4), then filtered and the solvent evaporated in vacuo to yield 4-phenylsulfanyl-phenylamine Compound 161b (15.08 g, 87%), as a solid. MS (ES+) m/z 202.1 (M+H+). 1H NMR (400 MHz, CDCl3) δ 7.32-7.29 (2H, m), 7.22-7.18 (2H, m), 7.13-7.09 (3H, m), 6.68-6.66 (2H, m), 3.79 (2H, br s)

Workup

  1. customthe reaction was quenched slowly with aqueous 10% NH4Cl
  2. custompartitioned between ethyl acetate and water
  3. dry with materialThe organic layer was dried (Na2SO4)
  4. filtrationfiltered
  5. customthe solvent evaporated in vacuo

Sources & evidence

ORD record
ord-d7b80506733f4d4ea864ac8b62c25b5a
Source dataset
uspto-grants-2009_08
Patent number
US07579356B2

Reaction notes

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