Nitric Acid → Methyl 5-chloro-2-nitrobenzeneacetate

HRID 354062

反応式

HRID 354062 の反応式
[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]

参加物

5

反応物 3

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

生成物 2

HCID 10376538Methyl 3-chloro-4-nitrophenylacetate収率 33%HCID 13265167Methyl 5-chloro-2-nitrobenzeneacetate収率 51%

反応条件

温度
0 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-823a3f459fa449e384e68d514017d78a
出典データセット
uspto-grants-2004_06
特許番号
US06756395B2

関連ノート

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