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

HRID 8217

반응식

HRID 8217 반응식
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]

참가 물질

7

반응물 3

HCID 8471Triethylamine2회HCID 137268EthynylpyridineHCID 21992780Ethyl 4-bromoquinoline-2-carboxylate

생성물 1

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

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매2회HCID 6102075Dichlorobis(triphenylphosphine)palladium촉매2회HCID 6342Acetonitrile용매

반응 조건

온도
77.5 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-9dbb6f48418e4ea8ad11976c7e04ceca
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07087626B2

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