Benzo(d)thiazol-2-amine → (2E)-N-(1,3-benzothiazol-2-yl)-2-(3-chloro-4-methylsulfonylphenyl)-2-(2-methylpropoxyimino)acetamide

HRID 600984ノート

反応式

HRID 600984 の反応式
[Cl:1][C:2]1[CH:3]=[C:4](/[C:12](=[N:16]\[O:17][CH2:18][CH:19]([CH3:21])[CH3:20])/[C:13]([OH:15])=O)[CH:5]=[CH:6][C:7]=1[S:8]([CH3:11])(=[O:10])=[O:9].[NH2:22][C:23]1[S:24][C:25]2[CH:31]=[CH:30][CH:29]=[CH:28][C:26]=2[N:27]=1.C(N(CC)C(C)C)(C)C>C(Cl)Cl>[S:24]1[C:25]2[CH:31]=[CH:30][CH:29]=[CH:28][C:26]=2[N:27]=[C:23]1[NH:22][C:13](=[O:15])/[C:12](/[C:4]1[CH:5]=[CH:6][C:7]([S:8]([CH3:11])(=[O:9])=[O:10])=[C:2]([Cl:1])[CH:3]=1)=[N:16]/[O:17][CH2:18][CH:19]([CH3:21])[CH3:20]

参加物

5

反応物 3

HCID 8706Benzo(d)thiazol-2-amineHCID 81531DiisopropylethylamineHCID 87416786(2E)-2-(3-chloro-4-methylsulfonylphenyl)-2-(2-methylpropoxyimino)acetic acid

生成物 1

HCID 59745092(2E)-N-(1,3-benzothiazol-2-yl)-2-(3-chloro-4-methylsulfonylphenyl)-2-(2-methylpropoxyimino)acetamide収率 60%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

(E)-(3-chloro-4-methanesulfonyl-phenyl)-isobutoxyimino-acetic acid (prepared as in Example 24, 104 mg, 0.31 mmol), 2-aminobenzothiazole (47 mg, 0.31 mmol) and N,N-diisopropylethylamine (163 μL, 0.94 mmol) were combined in methylene chloride (1.5 mL) and cooled in an ice bath. O-(7-Azabenzotriazole-1-yl)-N,N,N′N′-tetramethyluronium hexafluoro-phosphate (119 mg, 0.31 mmol) was added and the ice bath was removed. After stirring 2 h, the reaction mixture was evaporated in vacuo. The residue was treated with saturated aqueous sodium bicarbonate solution (1 mL) and extracted with chloroform (2×3 mL). The combined organic phases were dried over sodium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography (Merck silica gel 60, 40-63 μm; 30% ethyl acetate/hexanes) to afford (E)-N-benzothiazol-2-yl-2-(3-chloro-4-methanesulfonyl-phenyl)-2-isobutoxyimino-acetamide (86 mg, 60%) as a white solid after lyophilization from aqueous acetonitrile: LC-MS (ESI) m/e calcd for C20H20ClN3O4S2 [M+] 465.06, found 466 [M+H+]; H1-NMR (400 MHz, CDCl3) δ ppm 0.97 (d, J=6.6 Hz, 6 H, 2×CH3), 2.09 (m, 1 H, CH), 3.32 (s, 3 H, SO2CH3), 4.12 (d, J=6.8 Hz, 2 H, OCH2), 7.35 (brt, J=7.8 Hz, 1H, Ar), 7.48 (brt, J=7.8 Hz, 1H, Ar), 7.63 (dd, Jo=8.2, Jm=1.6 Hz, 1 H, Ar), 7.74 (d, Jm=1.6 Hz, 1 H, Ar), 7.83 (m, 2H, Ar), 8.24 (d, Jo=8.2 Hz, 1 H, Ar), 10.25 (brs, 1 H, NH).

後処理

  1. temperaturecooled in an ice bath
  2. customthe ice bath was removed
  3. customthe reaction mixture was evaporated in vacuo
  4. additionThe residue was treated with saturated aqueous sodium bicarbonate solution (1 mL)
  5. extractionextracted with chloroform (2×3 mL)
  6. dry with materialThe combined organic phases were dried over sodium sulfate
  7. customevaporated in vacuo
  8. customThe residue was purified by flash column chromatography (Merck silica gel 60, 40-63 μm; 30% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-46a8eac5b83a47c4a426426d69972d93
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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