Pyridine, 2,4,6-trichloro- → 2,4-Dichloro-6-(4-isopropoxyphenyl)pyridine

HRID 523139

反応式

HRID 523139 の反応式
Cl[C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[C:4]([Cl:9])[N:3]=1.[CH:10]([O:13][C:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1)([CH3:12])[CH3:11].[O-]P([O-])([O-])=O.[K+].[K+].[K+]>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].C(Cl)Cl>[Cl:9][C:4]1[CH:5]=[C:6]([Cl:8])[CH:7]=[C:2]([C:17]2[CH:18]=[CH:19][C:14]([O:13][CH:10]([CH3:12])[CH3:11])=[CH:15][CH:16]=2)[N:3]=1

参加物

6

反応物 3

HCID 27665Pyridine, 2,4,6-trichloro-HCID 62657Potassium Phosphate, TribasicHCID 36987264-Isopropoxybenzeneboronic acid

生成物 1

HCID 901180792,4-Dichloro-6-(4-isopropoxyphenyl)pyridine

試薬・触媒・溶媒 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 6344Dichloromethane溶媒

実験手順

To a 40 mL vial equipped with a stir bar was added 2,4,6-trichloropyridine (1.00 g, 5.48 mmol), (4-isopropoxyphenyl)boronic acid (1.00 g, 5.56 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (“Pd(dppf)Cl2”, 200 mg, 0.273 mmol), and K3PO4 (3.49 g, 16.4 mmol). The vial was sealed with a septum screwcap and then placed under N2 atmosphere. To the vial was added degassed THF (30 mL). The vial was placed in a 60° C. heating block with stirring for 60 hours. To the mixture was added diatomaceous earth (Celite®). The mixture was filtered and the filtrate was concentrated in vacuo to afford an amber solid residue. This material was subjected to silica gel chromatography (hexanes:CH2Cl2) to afford 2,4-dichloro-6-(4-isopropoxyphenyl)pyridine as a colorless oil that solidified upon standing (710 mg, 46%). 1H-NMR: (400 MHz, CDCl3) δ 7.95-7.90 (m, 2H), 7.58 (d, J=1.5 Hz, 1H), 7.22 (d, J=1.5 Hz, 1H), 6.99-6.93 (m, 2H), 4.64 (spt, J=6.1 Hz, 1H), 1.38 (d, J=6.0 Hz, 6H); MS: MS m/z 281.9 (M++1).

後処理

  1. customTo a 40 mL vial equipped with a stir bar
  2. customThe vial was sealed with a septum screwcap
  3. additionTo the vial was added
  4. customdegassed THF (30 mL)
  5. customwas placed in a 60° C.
  6. temperatureheating block
  7. additionTo the mixture was added diatomaceous earth (Celite®)
  8. filtrationThe mixture was filtered
  9. concentrationthe filtrate was concentrated in vacuo
  10. customto afford an amber solid residue

出典と根拠

ORDレコード
ord-cb74c821ed5e42d094b421c4432bd1ef
出典データセット
uspto-grants-2016_05
特許番号
US09334279B2

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