Nitric Acid → Methyl 5-chloro-2-nitrobenzeneacetate

HRID 354062

Reaction equation

HRID 354062 reaction equation
[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([Cl:11])[CH:6]=1.S(=O)(=O)(O)O.[N+:18]([O-:21])([OH:20])=[O:19]>>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([N+:18]([O-:20])=[O:19])=[C:7]([Cl:11])[CH:6]=1.[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:6]=[C:7]([Cl:11])[CH:8]=[CH:9][C:10]=1[N+:18]([O-:21])=[O:19]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 2733544Methyl 2-(3-chlorophenyl)acetate

Product 2

HCID 10376538Methyl 3-chloro-4-nitrophenylacetateYield 33%HCID 13265167Methyl 5-chloro-2-nitrobenzeneacetateYield 51%

Conditions

Temperature
0 °C

Procedure

To a solution of (3-chloro-phenyl)acetic acid methyl ester (5.0 g, 27.1 mmol, commercially available) in concentrated sulfuric acid (7.5 mL, 140.7 mmol) at 0° C. was added drop-wise nitric acid (2.52 g, 70%, 28.0 mmol). After stirring at 0° C. for two hrs, the reaction mixture was poured into ice water and was extracted into dichioromethane. The organic extract was washed with brine, dried (anhydrous sodium sulfate), filtered and concentrated under reduced pressure. The residue was purified by flash column chromatography over silica gel eluting with 6% ethyl acetate in hexane to give the desired (3-chloro-4-nitro-phenyl)acetic acid methyl ester as an oil (2.1 g,33%), and (5chloro-2-nitro-phenyl)acetic acid methyl ester as an oil (3.2 g, 51%). 1H NMR (CDCl3) δ: 3.69 (s, 2H), 3.74 (s, 3H), 7.33 (dd, 1H, J=8.4 Hz, 1.9 Hz), 7.50 (d, 1H, J=1.8 Hz), 7.87 (d, 1H, J=8.4 Hz.

Workup

  1. extractionwas extracted into dichioromethane
  2. extractionThe organic extract
  3. washwas washed with brine
  4. dry with materialdried (anhydrous sodium sulfate)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by flash column chromatography over silica gel eluting with 6% ethyl acetate in hexane

Sources & evidence

ORD record
ord-823a3f459fa449e384e68d514017d78a
Source dataset
uspto-grants-2004_06
Patent number
US06756395B2

Linked notes

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