1,10-Phenanthroline → 4-(2,4-dichlorobenzyloxy)pyridin-2(1H)-one

HRID 882052

반응식

HRID 882052 반응식
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[CH2:9][OH:10].Cl[C:12]1[CH:17]=[C:16](I)[CH:15]=[CH:14][N:13]=1.C([O-])([O-])=[O:20].[Cs+].[Cs+].N1C2C(=CC=C3C=2N=CC=C3)C=CC=1>C1(C)C=CC=CC=1.[Cu]I.C(O)=O.O>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[CH2:9][O:10][C:16]1[CH:15]=[CH:14][NH:13][C:12](=[O:20])[CH:17]=1

참가 물질

8

반응물 4

HCID 13181,10-PhenanthrolineHCID 10796Cesium carbonateHCID 156842,4-Dichlorobenzyl alcoholHCID 15165112-Chloro-4-iodopyridine

생성물 1

HCID 580922344-(2,4-dichlorobenzyloxy)pyridin-2(1H)-one수율 24%

시약·촉매·용매 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 1140Toluene용매HCID 18673298Formic acid--water (1/1)용매

반응 조건

온도
105 °C

실험 절차

A suspension of (2,4-dichlorophenyl)methanol (4.10 g, 23.2 mmol), 2-chloro-4-iodopyridine (5.05 g, 21.1 mmol), Cs2CO3 (8.94 g, 27.4 mmol), CuI (4.01 g, 21.1 mmol) and 1,10-phenanthroline (760 mg, 4.22 mmol) in toluene (20 mL) was degassed by bubbling N2 through the suspension for 15 min. The suspension was put under N2, and heated at 105° C. for 18 h. The suspension was cooled, EtOAc (50 mL) was added, and the resulting suspension was passed through a plug of SiO2. The resulting solution was concentrated under reduced pressure. Flash chromatography on silica gel (hexanes/(1:1 EtOAc/hexanes), 100:0 to 0:100) afforded a white solid. A suspension of the white solid and NH4OAc (6.13 g, 79.5 mmol) in 1:1 HCO2H/H2O (40 mL) was heated at reflux with stirring for 4 d. The solution was cooled and concentrated under reduced pressure. The resulting residue was made basic with saturated NaHCO3 solution and the resulting suspension was filtered. The solid was washed with H2O and dried under reduced pressure. Flash chromatography on silica gel ((1:1 EtOAc/hexanes)/(9:0.9:0.1 CH2Cl2/MeOH/NH4OH), 100:0 to 0:100) afforded 1.36 g (24%) of the title compound as a white solid: 1H NMR (300 MHz, DMSO-d6) δ 11.16 (br s, 1H), 7.71 (d, J=2.1 Hz, 1H), 7.61 (d, J=8.1, 1H), 7.50 (dd, J=8.4, 2.1 Hz, 1H), 7.26 (d, J=7.2 Hz, 1H), 5.91 (dd, J=7.5, 2.7 Hz, 1H), 5.81 (d, J=2.4 Hz, 1H), 5.10 (s, 2H).

후처리

  1. customwas degassed
  2. customby bubbling N2 through the suspension for 15 min
  3. temperatureThe suspension was cooled
  4. additionEtOAc (50 mL) was added
  5. concentrationThe resulting solution was concentrated under reduced pressure
  6. customFlash chromatography on silica gel (hexanes/(1:1 EtOAc/hexanes), 100:0 to 0:100) afforded a white solid
  7. temperaturewas heated
  8. temperatureat reflux
  9. temperatureThe solution was cooled
  10. concentrationconcentrated under reduced pressure
  11. filtrationthe resulting suspension was filtered
  12. washThe solid was washed with H2O
  13. customdried under reduced pressure

출처 및 근거

ORD 기록
ord-6de36ab8ef1c46bda02b172509fdddfd
출처 데이터셋
uspto-grants-2015_03
특허 번호
US08993765B2

연결된 노트

불러오는 중…