Sodium Cyanide → 2-Chloro-4-(trifluoromethyl)benzonitrile

HRID 1418027Notes

Reaction equation

HRID 1418027 reaction equation
[Cl:1][C:2]1[CH:8]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:6]=[CH:5][C:3]=1N.N([O-])=O.[Na+].[C-]#N.[Na+].[Cu](C#N)[C:21]#[N:22].C(=O)([O-])O.[Na+]>S(=O)(=O)(O)O.O.O.S([O-])([O-])(=O)=O.[Ni+2]>[Cl:1][C:2]1[CH:8]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:6]=[CH:5][C:3]=1[C:21]#[N:22]

Participants

9

Reactant 5

HCID 8929Sodium CyanideHCID 1620012-Chloro-4-trifluoromethylanilineHCID 516892Sodium Bicarbonate2×HCID 23668193Sodium NitriteHCID 178418260HCID 178418260, compound

Product 1

HCID 27364762-Chloro-4-(trifluoromethyl)benzonitrileYield 391.4%

Reagents, catalysts & solvents 3

HCID 21951433Nickel sulfate hydrateCatalystHCID 962WaterSolvent3×HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
95 °C

Procedure

A suspension of 10 g of 2-chloro-4-trifluoromethylaniline in 18 g of 95% sulphuric acid and 65 ml of water is slowly added at 15° C. to a solution of 3.57 g of sodium nitrite in 7 ml of water. The reaction mixture is stirred at 40°-45° C. for 2 hours and then carefully poured onto the following mixture maintained at 95° C.: 10.77 g of sodium cyanide, 0.51 g of copper cyanide, 25.8 g of sodium hydrogencarbonate and 0.46 g of nickel sulphate hydrate in 30 ml of water. The reaction mixture is stirred at 100° C. for 1 hour and then, after cooling, 30 ml of a saturated aqueous sodium hydrogencarbonate solution are added and extraction is carried out with dichloromethane. The extract is filtered through celite and then successively washed with water, with salted water, dried over sodium sulphate and evaporated to dryness. The residue is purified on a column of silica gel, eluent: 20/1 (v/v) cyclohexane/ethyl acetate, and 3.55 g of 2-chloro-4-trifluoromethylbenzonitrile are obtained in the form of a brown oil. 1H NMR (CDCl3): 7.4 to 7.8 (m, 3H).

Workup

  1. additioncarefully poured onto the following mixture
  2. stirringThe reaction mixture is stirred at 100° C. for 1 hour
  3. temperatureafter cooling
  4. extractionextraction
  5. filtrationThe extract is filtered through celite
  6. washsuccessively washed with water, with salted water
  7. dry with materialdried over sodium sulphate
  8. customevaporated to dryness
  9. customThe residue is purified on a column of silica gel, eluent

Sources & evidence

ORD record
ord-c08c0d39217147f88f984321003a6a69
Source dataset
uspto-grants-1999_03
Patent number
US05880135

Reaction notes

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