O-(propan-2-yl)hydroxylamine hydrochloride → methyl (2E)-2-(3-chloro-4-methylsulfonylphenyl)-2-propan-2-yloxyiminoacetate

HRID 600952ノート

反応式

HRID 600952 の反応式
[CH3:1][O:2][C:3](=[O:17])[C:4]([C:6]1[CH:11]=[CH:10][C:9]([S:12]([CH3:15])(=[O:14])=[O:13])=[C:8]([Cl:16])[CH:7]=1)=O.Cl.[CH:19]([O:22][NH2:23])([CH3:21])[CH3:20]>CO>[CH3:1][O:2][C:3](=[O:17])/[C:4](/[C:6]1[CH:11]=[CH:10][C:9]([S:12]([CH3:15])(=[O:14])=[O:13])=[C:8]([Cl:16])[CH:7]=1)=[N:23]/[O:22][CH:19]([CH3:21])[CH3:20]

参加物

4

反応物 2

HCID 12696235O-(propan-2-yl)hydroxylamine hydrochlorideHCID 67482571(3-Chloro-4-methanesulfonyl-phenyl)-oxo-acetic acid methyl ester

生成物 1

HCID 87416843methyl (2E)-2-(3-chloro-4-methylsulfonylphenyl)-2-propan-2-yloxyiminoacetate

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
70 °C

実験手順

(3-Chloro-4-methanesulfonyl-phenyl)-oxo-acetic acid methyl ester (prepared as in Example 1, 1.30 g, 4.70 mmol) was stirred in methanol (9.5 mL) and warmed in a 70° C. oil bath. O-Isopropyl-hydroxylamine hydrochloride (786 mg, 7.04 mmol) was added. After 7 h, the reaction mixture was allowed to cool and concentrated in vacuo. The residue was dissolved in ethyl acetate (100 mL) and washed with 0.2 M aqueous potassium bisulfate solution (50 mL), 50% aqueous sodium bicarbonate solution (50 mL) and brine (50 mL). The organic phase was dried over magnesium sulfate and concentrated in vacuo. Purification by flash column chromatography (Merck silica gel 60, 40-63 μm; 20% ethyl acetate/hexanes to 33% ethyl acetate/hexanes) afforded (E)-(3-chloro-4-methanesulfonyl-phenyl)-isopropoxyimino-acetic acid methyl ester as a faintly yellow oil contaminated with an unknown impurity (645 mg, <41%): LC-MS (ESI) m/e calcd for C13H16ClNO5S [M+] 333.04, found 334 [M+H+].

後処理

  1. temperatureto cool
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in ethyl acetate (100 mL)
  4. washwashed with 0.2 M aqueous potassium bisulfate solution (50 mL), 50% aqueous sodium bicarbonate solution (50 mL) and brine (50 mL)
  5. dry with materialThe organic phase was dried over magnesium sulfate
  6. concentrationconcentrated in vacuo
  7. customPurification by flash column chromatography (Merck silica gel 60, 40-63 μm; 20% ethyl acetate/hexanes to 33% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-6bf07104eb47450c9ad90dfd1c024eee
出典データセット
uspto-grants-2011_03
特許番号
US07902248B2

反応ノート

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