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

HRID 600952노트

반응식

HRID 600952 반응식
[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]

참가 물질

4

반응물 2

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

생성물 1

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

시약·촉매·용매 1

HCID 887Methanol용매

반응 조건

온도
70 °C

실험 절차

(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+].

후처리

  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)

출처 및 근거

ORD 기록
ord-6bf07104eb47450c9ad90dfd1c024eee
출처 데이터셋
uspto-grants-2011_03
특허 번호
US07902248B2

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