Nitric Acid → 3-Chloro-6-nitrotoluene

HRID 1773573Notes

Reaction equation

HRID 1773573 reaction equation
[N+:1]([O-:4])([OH:3])=[O:2].[Cl:5][C:6]1[CH:7]=[C:8]([CH3:12])[CH:9]=[CH:10][CH:11]=1.S(=O)(=O)(O)O>C(O)(=O)C>[Cl:5][C:6]1[CH:7]=[C:8]([CH3:12])[CH:9]=[CH:10][C:11]=1[N+:1]([O-:4])=[O:2].[Cl:5][C:6]1[CH:11]=[CH:10][C:9]([N+:1]([O-:3])=[O:2])=[C:8]([CH3:12])[CH:7]=1

Participants

6

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 79313-Chlorotoluene

Product 2

HCID 793293-Chloro-6-nitrotolueneYield 39%HCID 1234783-Chloro-4-nitrotolueneYield 14%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Concentrated nitric acid (16 mL) was slowly added, at 0° C., to a solution of 3-chlorotoluene (3 mL, 25.4 mmol) and concentrated sulfuric acid (6 mL) in glacial acetic acid (20 mL) and the resulting mixture was stirred for 24 hours allowing the temperature to rise until room temperature. The reaction mixture was then poured into ice-water and partitioned between water and diethyl ether. The aqueous phase was separated and extracted twice with diethyl ether; the combined organic extracts were washed with water and brine, dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The yellow oily residue was purified on a silica gel plug and twice by flash chromatography to give 1.22 g (14% yield) of 2-chloro-4-methyl-1-nitro-benzene as a yellow oil and 3.39 g (39% yield) of 4-chloro-2-methyl-1-nitro-benzene.

Workup

  1. customto rise until room temperature
  2. custompartitioned between water and diethyl ether
  3. customThe aqueous phase was separated
  4. extractionextracted twice with diethyl ether
  5. washthe combined organic extracts were washed with water and brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. customThe yellow oily residue was purified on a silica gel plug and twice by flash chromatography

Sources & evidence

ORD record
ord-dc4775633c1d4cd497d84368ba7831d2
Source dataset
uspto-grants-2016_02
Patent number
US09255110B2

Reaction notes

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