tert-Butyl mercaptan → Benzene, ((1,1-dimethylethyl)thio)-

HRID 2084591Notes

Reaction equation

HRID 2084591 reaction equation
CC([O-])(C)C.[Na+].[C:7]1(I)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[SH:14][C:15]([CH3:18])([CH3:17])[CH3:16]>CC([O-])=O.CC([O-])=O.[Pd+2].C1(C)C=CC=CC=1>[C:7]1([S:14][C:15]([CH3:18])([CH3:17])[CH3:16])[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

6

Reactant 3

HCID 6387tert-Butyl mercaptanHCID 11575IodobenzeneHCID 23676156Sodium t-butoxide

Product 1

HCID 137798Benzene, ((1,1-dimethylethyl)thio)-Yield 29%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Procedure

In the drybox, 52.0 mg (0.184 mmol) of (Me2CH)PH(O)(2,4-(MeO)2C6H3) from Example 34, 34.0 mg (0.151 mmol) of Pd(OAc)2 and 14.0 ml of toluene were loaded into a reactor (20 ml) equipped with a magnetic stir bar. The resulting mixture was stirred at room temperature for 1 h. Next, 576.0 mg (6.0 mmol) of NaOtBu, 816.0 mg (4.0 mmol) of PhI and 360 mg (4.0 mmol) of HS-t-Bu were added into the mixture above, The resulting mixture was refluxed for 3 days. The reaction mixture was then cooled to room temperature, chromatographed on silicon gel using ethyl acetate/hexane (5% volume ratio) as eluant. The eluate was concentrated by rotary evaporation followed by high vacuum to yield 190 mg (29% yield) of t-butyl phenyl sulfide. It was >95% pure by 1H NMR and GC/MS. 1H NMR (500 MHz, CDCl3): δ7.43-7.42 (m, 2H), 7.22-7.19 (m, 3H), 1.17 (s, 9H) ppm. 13C NMR (125 MHz, CDCl3): δ137.4, 132.7, 128.5, 128.3, 30.9 ppm.

Workup

  1. custom(20 ml) equipped with a magnetic stir bar
  2. temperaturewas refluxed for 3 days
  3. temperatureThe reaction mixture was then cooled to room temperature
  4. customchromatographed on silicon gel
  5. concentrationThe eluate was concentrated by rotary evaporation

Sources & evidence

ORD record
ord-f06a21f37bc348ceb208b719302791cc
Source dataset
uspto-grants-2004_04
Patent number
US06716984B2

Reaction notes

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