Sulfuric Acid → 3-Chloro-5-nitrobenzotrifluoride

HRID 396217Notes

Reaction equation

HRID 396217 reaction equation
S(=O)(=O)(O)O.N[C:7]1[C:12]([N+:13]([O-:15])=[O:14])=[CH:11][C:10]([C:16]([F:19])([F:18])[F:17])=[CH:9][C:8]=1[Cl:20].N([O-])=O.[Na+].CCCCCC>C(O)C>[Cl:20][C:8]1[CH:9]=[C:10]([C:16]([F:17])([F:18])[F:19])[CH:11]=[C:12]([N+:13]([O-:15])=[O:14])[CH:7]=1

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 8058HexaneHCID 27340812-Chloro-6-nitro-4-(trifluoromethyl)anilineHCID 23668193Sodium Nitrite

Product 1

HCID 502553-Chloro-5-nitrobenzotrifluoride

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
75 °C

Procedure

(see also: EP 0 516 297 A1) 56.7 ml of 96% sulfuric acid are added dropwise over a period of 30 minutes to a brown solution of 90 g (374 mmol) of 4-amino-3-chloro-5-nitro-benzotrifluoride (Maybridge; Tintagel/England) in 500 ml of ethanol (exothermic). After heating to 75° C., 64.53 g (935 mmol) of sodium nitrite are added in portions over a period of one hour (evolution of gas). The mixture is stirred for 2.5 hours at 75° C. and then cooled to room temperature. The reaction mixture is poured onto 1.5 liters of ice-water and extracted four times with ether. Washing the organic phases with 0.1 N HCl, saturated NaHCO3solution and brine, drying (Na2SO4) and concentration by evaporation yield a brown oil. Column chromatography (SiO2; hexane) yields the title compound in the form of an oil: 1H-NMR (DMSO-d6) 8.62 (m, 1H), 8.46 (m, 2H), MS 225 (M)+, 179 (M—NO2)+.

Workup

  1. temperaturecooled to room temperature
  2. extractionextracted four times with ether
  3. washWashing the organic phases with 0.1 N HCl, saturated NaHCO3solution and brine
  4. customdrying
  5. concentration(Na2SO4) and concentration
  6. customby evaporation
  7. customyield a brown oil

Sources & evidence

ORD record
ord-49feda6b86c84729a658ab84827da99a
Source dataset
uspto-grants-2003_08
Patent number
US06608071B2

Reaction notes

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