Benzyl Alcohol → 2-benzyloxy-5-nitro-pyridine

HRID 1173443Notes

Reaction equation

HRID 1173443 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1.[CH2:11]([OH:18])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[OH-].[K+].C([O-])([O-])=O.[K+].[K+].COCCOCCN(CCOCCOC)CCOCCOC>C1(C)C=CC=CC=1.O>[N+:8]([C:5]1[CH:6]=[CH:7][C:2]([O:18][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[N:3][CH:4]=1)([O-:10])=[O:9]

Participants

8

Reactant 5

HCID 244Benzyl AlcoholHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 783082-Chloro-5-nitropyridineHCID 112414Ethanamine, 2-(2-methoxyethoxy)-N,N-bis[2-(2-methoxyethoxy)ethyl]-

Product 1

HCID 2956762-benzyloxy-5-nitro-pyridineYield 69.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

To a mixture of 2-chloro-5-nitropyridine (3.28 g, 20.0 mmol), benzyl alcohol (3.09 mL, 30.0 mmol), KOH (4.49 g, 80.0 mmol), and K2CO3 (2.76 g, 20.0 mmol) in toluene (100 mL) at rt was added tris[2-(2-methoxyethoxy)ethyl]amine (0.646 g, 2.00 mmol). The mixture was stirred for 20 min, poured into water, and the layers were separated. The aqueous layer was adjusted to pH 7 by addition of solid KHSO4, and extracted with EtOAc (×3). Combined organics were washed (H2O, brine), dried over Na2SO4, filtered and concentrated in vacuo. The residue was recrystallized from EtOH/H2O, affording 3.18 g of the title compound as tan needles: 1H NMR (400 MHz, CDCl3) δ 9.10 (dd, J=2.9, 0.6 Hz, 1H), 8.37 (dd, J=9.1, 2.9 Hz, 1H), 7.48-7.44 (m, 2H), 7.42-7.33 (m, 3H), 6.88 (dd, J=9.1, 0.6 Hz, 1H), 5.49 (s, 2H).

Workup

  1. customthe layers were separated
  2. additionThe aqueous layer was adjusted to pH 7 by addition of solid KHSO4
  3. extractionextracted with EtOAc (×3)
  4. washCombined organics were washed (H2O, brine)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was recrystallized from EtOH/H2O

Sources & evidence

ORD record
ord-2c63b0fe57924256ab1d104586ca5741
Source dataset
uspto-grants-2010_11
Patent number
US07834063B2

Reaction notes

Loading…