Dichloromethane → 6-(2,6-Difluorophenyl)-2-methyl-3-nitropyridine

HRID 1529331

反応式

HRID 1529331 の反応式
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([CH3:11])[N:3]=1.[F:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([F:19])[C:14]=1B(O)O.C(Cl)Cl>O1CCOCC1.C([O-])([O-])=O.[Na+].[Na+].CCOC(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]>[F:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([F:19])[C:14]=1[C:2]1[N:3]=[C:4]([CH3:11])[C:5]([N+:8]([O-:10])=[O:9])=[CH:6][CH:7]=1

参加物

8

反応物 3

HCID 6344DichloromethaneHCID 27343362,6-Difluorophenylboronic acid3 回HCID 247280146-Bromo-2-methyl-3-nitropyridine

生成物 1

HCID 679582356-(2,6-Difluorophenyl)-2-methyl-3-nitropyridine収率 56%

試薬・触媒・溶媒 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 8857Ethyl Acetate溶媒HCID 10340Sodium Carbonate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

A suspension of 2-bromo-6-methyl-5-nitropyridine (3 g, 13.82 mmol, Matrix Scientific), 2,6-difluorobenzeneboronic acid (4.37 g, 27.6 mmol, Alfa Aesar) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with DCM (0.564 g, 0.691 mmol, Strem) in Dioxane (60 mL) (degassed with argon for 30 min) and Na2CO3, 2.0 M (20.74 mL, 41.5 mmol) was heated to 100° C. under N2. After 3 h, 2,6-difluorobenzeneboronic acid (4.37 g, 27.6 mmol) was further added. After a total of 7 h, 2,6-difluorobenzeneboronic acid (2.18 g, 13.8 mmol) was further added. After a total of 9 h, the reaction mixture was cooled to 23° C., diluted with EtOAc (400 ml) and washed with brine (200 mL), dried over MgSO4, concentrated in vacuo and purified by silica gel chromatography (eluent: 5-10% EtOAc/hexane), affording 6-(2,6-difluorophenyl)-2-methyl-3-nitropyridine (1.931 g, 56%).

後処理

  1. temperatureAfter a total of 9 h, the reaction mixture was cooled to 23° C.
  2. washwashed with brine (200 mL)
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated in vacuo
  5. custompurified by silica gel chromatography (eluent: 5-10% EtOAc/hexane)

出典と根拠

ORDレコード
ord-07ddec78a2fc438a849269ed09293510
出典データセット
uspto-grants-2015_07
特許番号
US09090593B2

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