1,4-Dioxane → (E)-ethyl 3-(4-((6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)amino)phenyl)acrylate

HRID 332888ノート

反応式

HRID 332888 の反応式
Br[C:2]1[C:3]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][C:4]=2[S:5][C:6]=1[C:7]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[CH:9][CH:8]=1.[NH2:21][C:22]1[CH:34]=[CH:33][C:25]([CH:26]=[CH:27][C:28]([O:30][CH2:31][CH3:32])=[O:29])=[CH:24][CH:23]=1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].O1CCOCC1>CCOC(C)=O>[CH3:20][O:19][C:16]1[CH:17]=[CH:18][C:3]2[C:2]([NH:21][C:22]3[CH:23]=[CH:24][C:25](/[CH:26]=[CH:27]/[C:28]([O:30][CH2:31][CH3:32])=[O:29])=[CH:33][CH:34]=3)=[C:6]([C:7]3[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[CH:9][CH:8]=3)[S:5][C:4]=2[CH:15]=1

参加物

6

反応物 4

HCID 312751,4-DioxaneHCID 62657Potassium Phosphate, TribasicHCID 97826Ethyl 3-(4-aminophenyl)acrylateHCID 8509423-Bromo-6-methoxy-2-(4-methoxyphenyl)-benzo[b]thiophene

生成物 1

HCID 86730674(E)-ethyl 3-(4-((6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)amino)phenyl)acrylate収率 15%

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒

実験手順

To a large microwave vial (10-20 mL) was added 3-bromo-6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophene (350 mg, 1.00 mmol), ethyl 4-aminocinnamate (383 mg, 2.00 mmol) and K3PO4 (425 mg, 2.00 mmol). 1,4-dioxane (6.0 mL) was then added followed by chloro-(2-dicyclohexylphosphino-2′,6′-diisopropoxy-1,1′-biphenyl)[2-(2-aminoethyl)phenyl]palladium(II) methyl-t-butyl ether adduct (RuPhos palladacycle, 73.0 mg, 0.10 mmol) and the reaction was subjected to microwave irradiation at 120° C. for 3 h. Upon completion the reaction mixture was transferred to round bottom flask with EtOAc and concentrated in vacuo. The resulting material was partitioned between water and EtOAc and separated, the aqueous layer was then further extracted with EtOAc (3×) and the combined organic layers were passed through a phase separator to remove water and concentrated in vacuo. The crude material was purified by column chromatography (SiO2, 0-30% EtOAc/heptane) to afford (E)-ethyl 3-(4-((6-methoxy-2-(4-methoxyphenyl)benzo[b]thiophen-3-yl)amino)phenyl)acrylate (69.0 mg, 0.15 mmol, 15% yield) as a white solid. LC/MS (m/z, MH+): 460.3.

後処理

  1. customirradiation at 120° C. for 3 h
  2. concentrationconcentrated in vacuo
  3. customThe resulting material was partitioned between water and EtOAc
  4. customseparated
  5. extractionthe aqueous layer was then further extracted with EtOAc (3×)
  6. customto remove water
  7. concentrationconcentrated in vacuo
  8. customThe crude material was purified by column chromatography (SiO2, 0-30% EtOAc/heptane)

出典と根拠

ORDレコード
ord-fc52f176f3404c188324bdbc212b0d60
出典データセット
uspto-grants-2014_11
特許番号
US08877801B2

反応ノート

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