Formic Acid → Methyl (3-chloro-4-formylphenyl)acetate

HRID 1162512

反応式

HRID 1162512 の反応式
[CH3:1][O:2][C:3](=[O:14])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]#N)=[C:7]([Cl:13])[CH:6]=1.C(O)=[O:16]>>[CH3:1][O:2][C:3](=[O:14])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([CH:11]=[O:16])=[C:7]([Cl:13])[CH:6]=1

参加物

3

反応物 2

HCID 284Formic AcidHCID 3564186Methyl 2-(3-chloro-4-cyanophenyl)acetate

生成物 1

HCID 59520437Methyl (3-chloro-4-formylphenyl)acetate

反応条件

温度
110 °C

実験手順

A solution of (3-chloro-4-cyano-phenyl)acetic acid methyl ester 13 (7.4 g, 35.3 mmol) in 88% formic acid (100 mL) is combined with Raney-alloy (9.0 g) and heated to reflux for 10 hours at 110° C. After cooling to room temperature, the alloy is removed by filtration over Celite. The filtrate is concentrated to ˜10% of the original volume and diluted with EtOAc (250 mL) and washed three times with water (80 mL). The organic layer is dried (MgSO4), filtered and concentrated to afford crude product, which is purified by silica gel chromatography using an EtOAc/hexane gradient to give (3-Chloro-4-formyl-phenyl)-acetic acid methyl ester 14 as a wax-like solid. Another amount of product 14 is collected by reesterification of saponified byproduct (3-Chloro-4-formyl-phenyl)-acetic acid: 1H-NMR (400 MHz, CDCl3) δ=10.31 (s, 1H), 7.84 (d, J=8.0 Hz, 1H), 7.58 (s, 1H), 7.45 (d, J=8.0 Hz, 1H), 3.86 (s, 3H), 3.64 (s, 2H). MS calculated for C10H10ClO3 (M+H+) 213.0, found 213.3.

後処理

  1. temperatureheated
  2. temperatureAfter cooling to room temperature
  3. customthe alloy is removed by filtration over Celite
  4. concentrationThe filtrate is concentrated to ˜10% of the original volume
  5. additiondiluted with EtOAc (250 mL)
  6. washwashed three times with water (80 mL)
  7. dry with materialThe organic layer is dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto afford crude product, which
  11. customis purified by silica gel chromatography

出典と根拠

ORDレコード
ord-d2bbdbb85910429bbc057a4e7fb8425c
出典データセット
uspto-grants-2010_10
特許番号
US07820705B2

関連ノート

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