1-Chloro-4-nitrobenzene → Pyridine, 4-[(4-nitrophenoxy)methyl]-

HRID 1993509Notes

Reaction equation

HRID 1993509 reaction equation
[OH:1][CH2:2][C:3]1[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=1.[OH-].[K+].Cl[C:12]1[CH:17]=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][CH:13]=1>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-]>[N+:18]([C:15]1[CH:16]=[CH:17][C:12]([O:1][CH2:2][C:3]2[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=2)=[CH:13][CH:14]=1)([O-:20])=[O:19]

Participants

5

Reactant 3

HCID 74741-Chloro-4-nitrobenzeneHCID 114724-HydroxymethylpyridineHCID 14797Potassium Hydroxide

Product 1

HCID 19576801Pyridine, 4-[(4-nitrophenoxy)methyl]-

Reagents, catalysts & solvents 1

HCID 21218Trioctylmethylammonium chlorideCatalyst

Procedure

4-hydroxymethyl-pyridine (2.23 g, 20 mmol) is added to a suspension of KOH (1.32 g, 20 mmol) and Aliquat 336 (0.937 mL). After stirring for 5 min at rt, 1-chloro-4-nitro-benzene (2.68 g, 16.7 mmol) is added. The resulting reaction mixture is further stirred at rt for 5 min and then at 80° C. for 2 h. The reaction mixture is filtered over silica gel (15 g), concentrated under reduced pressure, and flash chronatographed (silica gel, 3×50 cm, acetone/CH2Cl2=5:95→15:85) to give the title compound as a yellow solid: M+H=231.0; 1H-NMR (400 MHz, DMSO-d6): 8.58 (d, 6.5 Hz, 2H, pyrimidinyl), 8.22 (d, 8.5 Hz, 2H, phenyl-NO2), 7.44 (d, 6.5 Hz, pyrimidinyl), 7.21 (d, 8.5 Hz, 2H, phenyl-NO2), 5.34 (s, 2H, CH2); Rf (acetone/CH2Cl2=15:85): 0.32; HPLC (System 1): 3.40 min.

Workup

  1. customThe resulting reaction mixture
  2. stirringis further stirred at rt for 5 min
  3. waitat 80° C. for 2 h
  4. filtrationThe reaction mixture is filtered over silica gel (15 g)
  5. concentrationconcentrated under reduced pressure, and flash

Sources & evidence

ORD record
ord-937dabfad7d84ef7ac716f250fdb0c1c
Source dataset
uspto-grants-2010_01
Patent number
US07652022B2

Reaction notes

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