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 → 9-Bromo-4-methoxycarbonylmethyl-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid methyl ester

HRID 575123ノート

反応式

HRID 575123 の反応式
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]2/[C:8](=[CH:20]/[C:21]([O:23][CH3:24])=[O:22])/[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]>CCOC(C)=O.[Pd]>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]2[CH:8]([CH2:20][C:21]([O:23][CH3:24])=[O:22])[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

4

反応物 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

生成物 1

HCID 866931499-Bromo-4-methoxycarbonylmethyl-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid methyl ester収率 85.6%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
50 °C

実験手順

To a stirred solution of 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 (70 mg, 0.17 mmol) in EtOAc (15 mL), 10% Pd/C (1% H2O) (30 mg) was added. The reaction mixture was degassed with H2. The mixture was stirred at 50° C. under 50 Psi of H2 overnight. Then the mixture was filtered thought Celite, and the filtrate was concentrated in vacuo, and purified by flash column chromatography to afford 9-Bromo-4-methoxycarbonylmethyl-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene-2-carboxylic acid methyl ester (60 mg, 85%) as a light yellow solid. 1H NMR (400 MHz, CDCl3): δ 8.75 (d, J=2.5 Hz, 1H), 7.38 (dd, J1=8.6 Hz, J2=2.5 Hz, 1H), 6.98 (d, J=8.6 Hz, 1H), 4.62 (dd, J1=12.2 Hz, J2=3.7 Hz, 1H), 4.07 (m, 1H), 4.04 (s, 3H), 3.98 (m, 1H), 2.79 (s, 3H), 2.88 (m, 1H); LC-MS (ESI & APCI): 414.4 (M+2).

後処理

  1. customThe reaction mixture was degassed with H2
  2. filtrationThen the mixture was filtered
  3. concentrationthe filtrate was concentrated in vacuo
  4. custompurified by flash column chromatography

出典と根拠

ORDレコード
ord-02f206ad67a146618e1de4e4c28479a7
出典データセット
uspto-grants-2015_05
特許番号
US09034866B2

反応ノート

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