Triethylamine → 4-Pyridin-2-ylethynyl-quinoline-2-carboxylic Acid Ethyl Ester

HRID 8217

反応式

HRID 8217 の反応式
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[N:5]=[C:4]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:3]=1.C(N(CC)CC)C.[C:24]([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=1)#[CH:25]>CC#N.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I>[CH2:15]([O:14][C:12]([C:4]1[CH:3]=[C:2]([C:25]#[C:24][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][N:27]=2)[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[N:5]=1)=[O:13])[CH3:16]

参加物

7

反応物 3

HCID 8471Triethylamine2 回HCID 137268EthynylpyridineHCID 21992780Ethyl 4-bromoquinoline-2-carboxylate

生成物 1

HCID 693649014-Pyridin-2-ylethynyl-quinoline-2-carboxylic Acid Ethyl Ester収率 50.3%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒2 回HCID 6102075Dichlorobis(triphenylphosphine)palladium触媒2 回HCID 6342Acetonitrile溶媒

反応条件

温度
77.5 °C

実験手順

A mixture of ethyl 4-bromoquinoline-2-carboxylate (2.80 g, 10.0 mmol, J. Org. Chem. 1947, 12, 456), triethylamine (1.7 mL, 12 mmol), bis(triphenylphosphine)-palladium(II)chloride (0.561 g, 0.80 mmol), CuI (0.114 g, 0.60 mmol), and 2-ethynylpyridine (1.11 g, 10.8 mmol) in CH3CN (80 mL) is heated at 75-80° C. for 18 h in a sealed tube. Additional triethylamine (0.85 ml, 6.1 mmol), bis(triphenylphosphine)palladium (II) chloride (0.23 g, 0.40 mmol), and CuI (0.055 g, 0.29 mmol) is added and the mixture heated for an additional 18 h. The mixture is concentrated in vacuo and partitioned between water and chloroform. The chloroform extracts are washed with brine and evaporated. The residue is chromatographed on SiO2 (50% ethyl acetate/hexanes) to yield 1.52 g (50%) of a yellow solid. Precipitation from ethyl acetate gave the title compound as yellow crystals: mp 129-131° C.; MS ES+ m/e 303 (M+1).

後処理

  1. temperaturethe mixture heated for an additional 18 h
  2. concentrationThe mixture is concentrated in vacuo
  3. custompartitioned between water and chloroform
  4. washThe chloroform extracts are washed with brine
  5. customevaporated
  6. customThe residue is chromatographed on SiO2 (50% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-9dbb6f48418e4ea8ad11976c7e04ceca
出典データセット
uspto-grants-2006_08
特許番号
US07087626B2

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