Hydrochloric Acid → Benzonitrile, 4,4'-thiobis-

HRID 263532Notes

Reaction equation

HRID 263532 reaction equation
Cl.[S:2]([C:10]1[CH:16]=[CH:15][C:13](N)=[CH:12][CH:11]=1)[C:3]1[CH:9]=[CH:8][C:6](N)=[CH:5][CH:4]=1.N([O-])=O.[Na+].C(=O)([O-])[O-].[Na+].[Na+].[Cu][C:28]#[N:29].[C-:30]#[N:31].[K+]>C(OCC)(=O)C.O.C1C=CC=CC=1>[C:30]([C:6]1[CH:8]=[CH:9][C:3]([S:2][C:10]2[CH:16]=[CH:15][C:13]([C:28]#[N:29])=[CH:12][CH:11]=2)=[CH:4][CH:5]=1)#[N:31]

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 87654,4'-ThiodianilineHCID 9032Potassium CyanideHCID 10340Sodium CarbonateHCID 23668193Sodium NitriteHCID 178418546HCID 178418546, compound

Product 1

HCID 616861Benzonitrile, 4,4'-thiobis-Yield 49.4%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 22272175Benzene--water (1/1)Solvent

Procedure

Concentrated hydrochloric acid (45 ml) and ice were added to 21.7 g of 4,4'-thiodianiline to which, with ice-cooling, was subsequently added dropwise 50 ml of aqueous solution of 15.2 g sodium nitrite spending 30 minutes. Five minutes thereafter, the reaction mixture was neutralized with sodium carbonate and added dropwise to 250 ml of ice-cooled water-benzene (3:2) solution containing 22.4 g of copper (I) cyanide and 38.2 g of potassium cyanide. The reaction mixture was stirred for 2 hours while ice-cooling and then mixed with ethyl acetate to remove insoluble materials by filtration. The resulting organic layer was washed with saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The solvent was evaporated under a reduced pressure, and the resulting residue was subjected to silica gel chromatography and to obtain 11.7 g of bis(4-cyanophenyl) sulfide from fractions of chloroform elution.

Workup

  1. temperaturecooling
  2. customFive minutes
  3. temperaturecooling
  4. customto remove insoluble materials
  5. filtrationby filtration
  6. washThe resulting organic layer was washed with saturated sodium chloride aqueous solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. customThe solvent was evaporated under a reduced pressure

Sources & evidence

ORD record
ord-dd545de5ae9248b8ad8349de4a045129
Source dataset
uspto-grants-1997_07
Patent number
US05643931

Reaction notes

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