(E)-1-Bromo-4-(2-iodovinyl)benzene → Ethyl 2-(4-bromophenyl)pyrazolo[1,5-a]pyridine-5-carboxylate

HRID 1475934

反応式

HRID 1475934 の反応式
[CH2:1]([O:3][C:4]([C:6]1[CH:11]=[CH:10][N+:9](=[N:12]C(=O)C2C=CC=CC=2)[CH2:8][CH:7]=1)=[O:5])[CH3:2].[Br:21][C:22]1[CH:27]=[CH:26][C:25](/[CH:28]=[CH:29]/I)=[CH:24][CH:23]=1>[Pd](Br)Br.[O-]S(C(F)(F)F)(=O)=O.[Ag+].O1CCOCC1>[Br:21][C:22]1[CH:27]=[CH:26][C:25]([C:28]2[CH:29]=[C:8]3[CH:7]=[C:6]([C:4]([O:3][CH2:1][CH3:2])=[O:5])[CH:11]=[CH:10][N:9]3[N:12]=2)=[CH:24][CH:23]=1

参加物

6

反応物 2

HCID 12051842(E)-1-Bromo-4-(2-iodovinyl)benzeneHCID 867112174-Ethoxycarbonyl-N-benzoyliminopyridinium

生成物 1

HCID 68276034Ethyl 2-(4-bromophenyl)pyrazolo[1,5-a]pyridine-5-carboxylate収率 54%

試薬・触媒・溶媒 3

HCID 76223Silver(I) trifluoromethanesulfonate触媒HCID 83469Palladium bromide (PdBr2)触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
127.5 °C

実験手順

Related procedures are described in Org. Lett. 2010, 12, 516): 4-Ethoxycarbonyl-N-benzoyliminopyridinium ylid (JOC 2003, 68, 7119) (3.50 g, 13.0 mmol), para-tris-methoxyphenylphosphine (686 mg, 1.95 mmol), Palladium (II) bromide (173 mg, 0.65 mmol), silver triflate (8.93 g, 39.0 mmol) and (E)-1-Bromo-4-(2-iodovinyl)benzene (Org. Lett. 2008, 10, 5485) (4.02 g, 13.0 mmol) were placed in a 250 mL round bottom flask equipped a with magnetic stirrer. Dioxane (52 mL) was added. The mixture was degassed by bubbling nitrogen for 10 minutes with vigorous stirring and heated to 125-130° C. for 15-20 h. The mixture was then cooled to room temperature, diluted with CH2Cl2, filtered over Celite. The organic layer was then washed with saturated aqueous sodium bicarbonate and the organic phase was concentrated under reduced pressure. The crude product was triturated with methanol to afford 2.40 g (54%) of the title compound. LCMS m/z 345.0, 347.0 (M+H)+, ret. time=3.05 min.

後処理

  1. customwere placed in a 250 mL round bottom flask
  2. customequipped a with magnetic stirrer
  3. customThe mixture was degassed
  4. customby bubbling nitrogen for 10 minutes
  5. temperatureThe mixture was then cooled to room temperature
  6. additiondiluted with CH2Cl2
  7. filtrationfiltered over Celite
  8. washThe organic layer was then washed with saturated aqueous sodium bicarbonate
  9. concentrationthe organic phase was concentrated under reduced pressure
  10. customThe crude product was triturated with methanol

出典と根拠

ORDレコード
ord-8d9afb91e3aa4b77aed1ebcef3454d46
出典データセット
uspto-grants-2015_04
特許番号
US09018395B2

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