Sodium Chloride → 1,3-Dibromo-5-(methylsulfanyl)benzene

HRID 653622Notes

Reaction equation

HRID 653622 reaction equation
C([Li])CCC.[Br:6][C:7]1[CH:12]=[C:11](Br)[CH:10]=[C:9]([Br:14])[CH:8]=1.[CH3:15][S:16]SC.[Cl-].[Na+]>CCOCC.O1CCCC1.C(OCC)(=O)C>[Br:6][C:7]1[CH:12]=[C:11]([S:16][CH3:15])[CH:10]=[C:9]([Br:14])[CH:8]=1

Participants

8

Reactant 4

HCID 5234Sodium ChlorideHCID 12232Dimethyl DisulfideHCID 122791,3,5-TribromobenzeneHCID 178418339Butyllithium

Product 1

HCID 190104071,3-Dibromo-5-(methylsulfanyl)benzene

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A 2.5M solution of n-butyllithium (42 mL; 0.105M) was added over 25 mins. to a vigorously stirred suspension of 1,3,5-tribromobenzene (31.5 G; 0.1M) in 1.6 L of anhydrous ether and 400 mL of anhydrous tetrahydrofuran under nitrogen at -78°. After stirring the mixture 30 minutes, 2 equivalents of dimethyldisulfide was added dropwise. The resulting mixture was stirred at R.T. overnight. 150 mL of sat'd sodium chloride solution was cautiously added. 500 mL of ethyl acetate was added. The organic phase was separated, and dried over anhyd. magnesium sulfate. Solvent removal gave a crude product, which was purified on silica gel using hexane as solvent. The desired product was isolated and distilled at 107°-110°/~1 mm to give 18 G of 3,5-dibromothioanisole as a colorless liquid, which slowly solidified on standing.

Workup

  1. additionwas added dropwise
  2. customThe organic phase was separated
  3. customdried over anhyd
  4. customSolvent removal
  5. customgave a crude product, which
  6. customwas purified on silica gel

Sources & evidence

ORD record
ord-4124a0cc7c534584a11046d859077aba
Source dataset
uspto-grants-1992_07
Patent number
US05128335

Reaction notes

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