Sulfuric Acid → Benzonitrile, 2-(3,4-dichlorophenoxy)-5-(methylsulfonyl)-

HRID 1702822Notes

Reaction equation

HRID 1702822 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:17]=[CH:18][C:19]=1[Cl:20])[O:5][C:6]1[CH:11]=[CH:10][C:9]([S:12]([CH3:15])(=[O:14])=[O:13])=[CH:8][C:7]=1N.S(=O)(=O)(O)O.N([O-])=O.[Na+].[C-:30]#[N:31].[Na+]>O.C(O)(=O)C>[Cl:1][C:2]1[CH:3]=[C:4]([CH:17]=[CH:18][C:19]=1[Cl:20])[O:5][C:6]1[CH:11]=[CH:10][C:9]([S:12]([CH3:15])(=[O:14])=[O:13])=[CH:8][C:7]=1[C:30]#[N:31]

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 8929Sodium CyanideHCID 514872Benzenamine, 2-(3,4-dichlorophenoxy)-5-(methylsulfonyl)-HCID 23668193Sodium Nitrite

Product 1

HCID 514868Benzonitrile, 2-(3,4-dichlorophenoxy)-5-(methylsulfonyl)-Yield 96.1%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent4×

Conditions

Temperature
0 °C

Procedure

A mixture of 5.0 g (0.0151 mole) of 2-(3,4-dichlorophenoxy)-5-(methylsulfonyl)benzenamine (Example 16), 75 ml of glacial acetic acid, 37.5 ml of water and 3.0 g (0.0306 mole) of concentrated sulfuric acid was cooled to 0° C. and 1.5 g (0.0217 mole) of sodium nitrite dissolved in 15 ml of water was added slowly. The mixture was stirred at 0° C. for 20 minutes and then added slowly to a mixture of 7.5 g (0.0838 mole) of cuprous cyanide and 30 g (0.612 mole) of sodium cyanide dissolved in 150 ml of water at 0° C. The mixture was stirred at 0° C. for 45 minutes and allowed to warm to room temperature. The mixture was then heated at 50° C. for 1 hr. The mixture was poured into water and the crystalline product collected by filtration, washed with water and dried, to obtain 4.95 g (96.1% yield) of product. Purification was accomplished by column chromatography using silica gel as the support and chloroform as the eluent followed by recrystallization from ethyl acetate, which gave purified 2-(3,4-dichlorophenoxy)-5-(methylsulfonyl)benzonitrile, mp 162°-163° C.

Workup

  1. additionwas added slowly
  2. stirringThe mixture was stirred at 0° C. for 45 minutes
  3. temperatureto warm to room temperature
  4. temperatureThe mixture was then heated at 50° C. for 1 hr
  5. filtrationthe crystalline product collected by filtration
  6. washwashed with water
  7. customdried

Sources & evidence

ORD record
ord-f9f77be462774aa1a12be0ac293b0dd9
Source dataset
uspto-grants-1982_09
Patent number
US04349568

Reaction notes

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