Sodium hydride → 9-Bromo-4-[1-methoxycarbonyl-meth-(E)-ylidene]-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid methyl ester

HRID 575122ノート

反応式

HRID 575122 の反応式
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]2[C:8](=O)[CH2:9][O:10][C:11]3[CH:18]=[CH:17][C:16]([Br:19])=[CH:15][C:12]=3[C:13]=2[N:14]=1)=[O:4].[Br-].[CH3:22][O:23][C:24]([CH2:26][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)=[O:25].[H-].[Na+]>C1COCC1>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]2/[C:8](=[CH:26]/[C:24]([O:23][CH3:22])=[O:25])/[CH2:9][O:10][C:11]3[CH:18]=[CH:17][C:16]([Br:19])=[CH:15][C:12]=3[C:13]=2[N:14]=1)=[O:4]

参加物

5

反応物 3

HCID 24758Sodium hydrideHCID 2733211Phosphonium, (2-methoxy-2-oxoethyl)triphenyl-, bromide (1:1)HCID 866930859-Bromo-4-oxo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid methyl ester

生成物 1

HCID 897547389-Bromo-4-[1-methoxycarbonyl-meth-(E)-ylidene]-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid methyl ester収率 43.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
70 °C

実験手順

To a stirred solution of 9-Bromo-4-oxo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid methyl ester (100 mg, 0.28 mmol) in THF (7 mL), was added Methoxycarbonylmethyl(triphenyl)phosphonium Bromide (120 mg, 0.28 mmol), NaH (6.8 mg, 0.28 mmol). The reaction mixture was heated to 70° C. overnight. The mixture was cooled to room temperature and partitioned between EtOAc and H2O. The aqueous layer was extracted with EtOAc (2×10 mL). The combined organic layers were washed with brine, dried over Na2SO4, filtered, concentrated in vacuo, and purified by flash column chromatography to afford 9-Bromo-4-[1-methoxycarbonyl-meth-(E)-ylidene]-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid methyl ester (50 mg, 43%) as a light yellow solid. LC-MS (ESI & APCI): 412.3 (M+2).

後処理

  1. temperatureThe mixture was cooled to room temperature
  2. custompartitioned between EtOAc and H2O
  3. extractionThe aqueous layer was extracted with EtOAc (2×10 mL)
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. custompurified by flash column chromatography

出典と根拠

ORDレコード
ord-4db7007d1ca04f7bbf40987094391164
出典データセット
uspto-grants-2015_05
特許番号
US09034866B2

反応ノート

読み込み中…