Hydrochloric Acid → 2-cyano-5-methylbenzenesulfonyl chloride

HRID 442963Notes

Reaction equation

HRID 442963 reaction equation
N[C:2]1[CH:9]=[C:8]([CH3:10])[CH:7]=[CH:6][C:3]=1[C:4]#[N:5].N([O-])=O.[Na+].[S:15](=[O:18])(O)[O-:16].[Na+].O.[ClH:21]>S([O-])([O-])(=O)=O.[Cu+2]>[C:4]([C:3]1[CH:6]=[CH:7][C:8]([CH3:10])=[CH:9][C:2]=1[S:15]([Cl:21])(=[O:18])=[O:16])#[N:5]

Participants

7

Reactant 5

HCID 313Hydrochloric Acid2×HCID 962WaterHCID 28012762-Amino-4-methylbenzonitrileHCID 23665763Sodium BisulfiteHCID 23668193Sodium Nitrite

Product 1

HCID 27798372-cyano-5-methylbenzenesulfonyl chlorideYield 52%

Reagents, catalysts & solvents 1

HCID 24462Copper SulfateCatalyst

Procedure

To a solution of 2-amino-4-methylbenzonitrile (2.65 g, 20 mmol), as prepared in the preceding step, in 30% aqueous HCl (7 mL) was added 40% aqueous sodium nitrite (6 mL) at 0°-5° C. After 15 minute, to the diazo solution were added 30% HCl (15 mL), copper sulfate (100 mg) and 40% aqueous sodium bisulfite (15 mL) at 5°-10° C. The mixture was stirred for 30 minute, then additional water (50 mL) was added. The mixture was extracted into dichloromethane (3×50 mL), and the dichloromethane solution was washed with brine (50 mL) and dried over Na2SO4. After removing the solvent in vacuo, the residue was purified by flash column chromatography (2:1 dichloromethane/hexane) to give the title compound as a white solid (2.1 g, 52%). 1H-NMR (300 MHz, CDCl3) δ 8.03 (s, 1H), 7.87 (d, J=7.8 Hz, 1H), 7.66 (d, J=7.8 Hz, 1H), 2.59 (s, 3H).

Workup

  1. extractionThe mixture was extracted into dichloromethane (3×50 mL)
  2. washthe dichloromethane solution was washed with brine (50 mL)
  3. dry with materialdried over Na2SO4
  4. customAfter removing the solvent in vacuo
  5. customthe residue was purified by flash column chromatography (2:1 dichloromethane/hexane)

Sources & evidence

ORD record
ord-18859a4f891a48c8b10c2b92ac77d925
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

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