Potassium Carbonate → 4-(4-Chloro-2-methoxyphenyl)pyridine 1-oxide

HRID 1020668ノート

反応式

HRID 1020668 の反応式
Cl[C:2]1[CH:7]=[CH:6][N+:5]([O-:8])=[CH:4][CH:3]=1.[CH3:9][O:10][C:11]1[CH:16]=[C:15]([Cl:17])[CH:14]=[CH:13][C:12]=1B(O)O.C([O-])([O-])=O.[K+].[K+]>CS(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Cl:17][C:15]1[CH:14]=[CH:13][C:12]([C:2]2[CH:7]=[CH:6][N+:5]([O-:8])=[CH:4][CH:3]=2)=[C:11]([O:10][CH3:9])[CH:16]=1

参加物

6

反応物 3

HCID 11430Potassium CarbonateHCID 707244-chloropyridine N-oxideHCID 3858606(4-Chloro-2-methoxyphenyl)boronic acid

生成物 1

HCID 579502904-(4-Chloro-2-methoxyphenyl)pyridine 1-oxide収率 74.2%

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 679Dimethyl Sulfoxide溶媒

反応条件

温度
120 °C

実験手順

4-Chloropyridine-N-oxide (500 mg, 3.85 mmol), 2-methoxy-4-chlorophenylboronic acid (862 mg, 4.63 mmol) and K2CO3 (1.59 g, 11.55 mmol) were suspended in DMSO (5 mL) and PdCl2(dppf) (314 mg, 0.385 mmol) was added. The reaction mixture was placed under vacuum for 20 min and flushed with N2. This process was repeated, and the reaction mixture was heated at 120° C. for 3 h. The reaction mixture was cooled to 25° C. and partitioned between methylene chloride and 5% lithium chloride. The aqueous phase was removed, and the organic phase was washed with brine, dried over Na2SO4, filtered and concentrated to dryness under reduced pressure. Flash chromatography (ISCO 40 g column, methylene chloride/MeOH 100:0 to 90:10) provided the title compound (673 mg, 74%) as a tan solid: 1H NMR (300 MHz, CD3OD) δ 8.21 (dd, J=5.4, 1.8 Hz, 2H), 7.47 (dd, J=5.6, 1.6 Hz, 2H), 7.26 (d, J=8.2 Hz, 1H), 7.06 (dd, J=8.3, 2.4 Hz, 1H), 7.00 (d, J=1.7 Hz, 1H), 3.87 (s, 3H); ESI MS m/z 235 [M+H].

後処理

  1. customflushed with N2
  2. temperatureThe reaction mixture was cooled to 25° C.
  3. custompartitioned between methylene chloride and 5% lithium chloride
  4. customThe aqueous phase was removed
  5. washthe organic phase was washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated to dryness under reduced pressure

出典と根拠

ORDレコード
ord-df9685f28a304f059b9ccfb2ce52dbdf
出典データセット
uspto-grants-2014_05
特許番号
US08716308B2

反応ノート

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