Sulfuric Acid → 3-Chloro-5-nitrobenzotrifluoride

HRID 2252835Notes

Reaction equation

HRID 2252835 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

56.7 ml of 96% sulphuric acid are added dropwise over 30 min 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 1 h (gas evolution). Stirring is effected for 2.5 h at 75° C., followed by cooling to RT. The reaction mixture is poured onto 1.5 l of ice water and extracted 4 times with diethylether. Washing of the organic phase with 0.1 N HCl, sat. NaHCO3 solution and brine, drying (Na2SO4) and concentrating by evaporation yield a brown oil. Column chromatography (SiO2; hexane) yields 5-chloro-3-trifluoromethyl-nitrobenzene as an oil; 1H-NMR (DMSO-d6) δ 8.62 (m, 1H), 8.46 (m, 2H).

Workup

  1. temperatureby cooling to RT
  2. extractionextracted 4 times with diethylether
  3. washWashing of the organic phase with 0.1 N HCl, sat. NaHCO3 solution and brine
  4. dry with materialdrying (Na2SO4)
  5. concentrationconcentrating by evaporation
  6. customyield a brown oil

Sources & evidence

ORD record
ord-ac08a552d2b64df8ad718759932076ae
Source dataset
uspto-grants-2008_01
Patent number
US07323474B2

Reaction notes

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