Sulfur Dioxide → 4'-Methoxybiphenyl-4-sulfonyl chloride

HRID 352400Notes

Reaction equation

HRID 352400 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([O:14][CH3:15])=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.C([Li])CCC.S(=O)=O.COC1C=CC(C2C=CC(S(O)=O)=CC=2)=CC=1.[Li].[S:42](Cl)([Cl:45])(=[O:44])=[O:43]>O1CCCC1>[CH3:15][O:14][C:11]1[CH:12]=[CH:13][C:8]([C:5]2[CH:6]=[CH:7][C:2]([S:42]([Cl:45])(=[O:44])=[O:43])=[CH:3][CH:4]=2)=[CH:9][CH:10]=1

Participants

7

Reactant 5

HCID 1119Sulfur Dioxide2×HCID 24648Sulfuryl chlorideHCID 40340054-Bromo-4'-methoxybiphenylHCID 69743094Lithium 4-(4'-methoxyphenyl)phenylsulfinic acidHCID 178418339Butyllithium

Product 1

HCID 27947504'-Methoxybiphenyl-4-sulfonyl chlorideYield 99.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Part B: 5.2 grams (20 mmol) of 4-(4′-bromophenyl)-anisole was dissolved in 100 mL of anhydrous tetrahydrofuran and placed under nitrogen to cool to −78 C. To this flask was added 8.0 mL of 2.5 molar butyl lithium over 10 minutes. In an adjacent flask was added 100 mL of anhydrous tetrahydrofuran which was cooled to −60 C and a stream of sulfur dioxide was added through a dispersion tube while the system is under nitrogen atmosphere. After the addition of approximately 10 mL of liquid sulfur dioxide the dispersion tube was removed and the cold sulfur dioxide solution was transferred by a cannula to the stirred aryl lithium solution over five minutes. After one hour at −70 C the contents were warmed to room temperature and the solution was concentrated to dryness to yield a crude lithium sulfinate. The crude lithium 4-(4′-methoxyphenyl)phenylsulfinic acid was slurried in 100 mL of dry hexanes under nitrogen atmosphere and cooled to 0 C. To this cooled suspension was added 2.45 grams (18.1 mmol) of sulfuryl chloride and the suspension was allowed to warm to room temperature. The contents were concentrated by rotory evaporation to yield 5.1 grams of crude 4-(4′-methoxyphenyl)phenyl-sulfonyl chloride which was purified by recrystallization from chloroform.

Workup

  1. temperatureto cool to −78 C
  2. temperaturewas cooled to −60 C
  3. customwas removed
  4. concentrationthe solution was concentrated to dryness
  5. customto yield a crude lithium sulfinate
  6. temperaturecooled to 0 C
  7. temperatureto warm to room temperature
  8. concentrationThe contents were concentrated by rotory evaporation

Sources & evidence

ORD record
ord-8e8171dc5ea04f87aa0adcb831b48eb0
Source dataset
uspto-grants-2004_06
Patent number
US06747027B1

Reaction notes

Loading…