Iodobenzene → N-(1,1-dimethylethyl)-2-(methylthio)-6-phenylbenzenesulfonamide

HRID 34869Notes

Reaction equation

HRID 34869 reaction equation
[CH3:1][C:2]([NH:5][S:6]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[S:15][CH3:16])(=[O:8])=[O:7])([CH3:4])[CH3:3].C([Li])CCC.I[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.[OH-].[NH4+]>O1CCCC1.C(OCC)(=O)C.C(O)(=O)C>[CH3:4][C:2]([NH:5][S:6]([C:9]1[C:14]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[CH:13][CH:12]=[CH:11][C:10]=1[S:15][CH3:16])(=[O:7])=[O:8])([CH3:1])[CH3:3]

Participants

8

Reactant 4

HCID 11575IodobenzeneHCID 14923Ammonium HydroxideHCID 13670364N-(1,1-dimethylethyl)-2-(methylthio)benzenesulfonamideHCID 178418339Butyllithium

Product 1

HCID 13670365N-(1,1-dimethylethyl)-2-(methylthio)-6-phenylbenzenesulfonamideYield 68.4%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 11.3 g (0.0436 mol) N-(1,1-dimethylethyl)-2-(methylthio)benzenesulfonamide in 300 ml tetrahydrofuran (THF) was treated with 60.5 ml (0.096 mol) 2M n-butyllithium in hexanes at -30° under a nitrogen atmosphere. The mixture was stirred for 1 hour at ambient temperature then recooled to -20° and treated with 8.3 g (0.0436 mol) of cuprous iodide (anhydrous). After 10 minutes at -15°, 4.9 ml (0.0438 mol) iodobenzene was added and the mixture was then heated to reflux overnight. Acetic acid (10 ml) was added after cooling the mixture to 15°, then 200 ml concentrated ammonium hydroxide plus 200 ml ethyl acetate was introduced and the mixture was stirred vigorously in the presence of air to facilitate removal of the copper salts. The aqueous phase was separated, extracted with more ethyl acetate and the combined organic extracts were washed successively with concentrated ammonium hydroxide, water and brine, then dried (MgSO4) and evaporated to an oil. The product crystallized from ether/hexanes to afford 10 g of material, m.p. 162°-165°.

Workup

  1. customthen recooled to -20°
  2. waitAfter 10 minutes at -15°
  3. temperaturethe mixture was then heated
  4. temperatureto reflux overnight
  5. temperatureafter cooling the mixture to 15°
  6. stirringthe mixture was stirred vigorously in the presence of air
  7. customremoval of the copper salts
  8. customThe aqueous phase was separated
  9. extractionextracted with more ethyl acetate
  10. washthe combined organic extracts were washed successively with concentrated ammonium hydroxide, water and brine
  11. dry with materialdried (MgSO4)
  12. customevaporated to an oil
  13. customThe product crystallized from ether/hexanes

Sources & evidence

ORD record
ord-ec1eade7d6bd4b7d8bf0561849d4cd2f
Source dataset
uspto-grants-1988_08
Patent number
US04764204

Reaction notes

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