2-Nitrobenzaldehyde → HCID 18999062, compound

HRID 2260797Notes

Reaction equation

HRID 2260797 reaction equation
C([Li])CCC.Br[C:7]1[CH:8]=[CH:9][C:10]([O:13][CH3:14])=[N:11][CH:12]=1.[N+:15]([C:18]1[CH:25]=[CH:24][CH:23]=[CH:22][C:19]=1[CH:20]=[O:21])([O-:17])=[O:16].[K+].[Br-]>O1CCCC1.CCCCCC>[N+:15]([C:18]1[CH:25]=[CH:24][CH:23]=[CH:22][C:19]=1[CH:20]([C:7]1[CH:12]=[N:11][C:10]([O:13][CH3:14])=[CH:9][CH:8]=1)[OH:21])([O-:17])=[O:16]

Participants

7

Reactant 4

HCID 111012-NitrobenzaldehydeHCID 253877Potassium BromideHCID 27348955-Bromo-2-methoxypyridineHCID 178418339Butyllithium

Product 1

HCID 18999062HCID 18999062, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-85 °C

Procedure

n-Butyllithium (6.7 ml of a 1.6M hexane solution) was added dropwise to a stirred, cooled (-100° C.) solution of 5-bromo-2-methoxypyridine (2.0 g, Eur. J. Med. Chem. 1977, 12, 531) in anhydrous tetrahydrofuran (60 ml), under a nitrogen atmosphere. After 20 minutes a solution of 2-nitrobenzaldehyde (1.61 g) in anhydrous tetrahydrofuran (30 ml)was added dropwise and the reaction mixture was stirred whilst maintaining the temperature between -90° and -100° C. for 2 hours. The reaction mixture was warmed to -85° C. then quenched with saturated aqueous ammonium chloride solution then allowed to warm to room temperature. The organic layer was separated and the aqueous extracted with ethyl acetate (3×100 ml). The combined organics were dried (magnesium sulphate) then evaporated to give a gum which was purified by column chromatography on silica using ethyl acetate/petroleum ether (60-80) (1:4) to afford an oil which solidified to give a low melting solid on standing (1.42 g). Rf =0.30 in 33% ethyl acetate/petroleum ether (60-80) on silica plates; 1H NMR (360 MHz, CDCl3) δ 2.60 (1H, broad s), 3.91 (3H, s), 6.43 (1H, s), 6.70 (1H, d, J=9 Hz), 7.48 (1H, dd, J=1 and 8 Hz), 7.53 (1H, dd, J=3 and 9 Hz), 7.67 (1H, dd, J=1 and 8 Hz), 7.83 (1H, d, J=8 Hz), 7.96 (1H, dd, J=1 and 8 Hz), 8.11 (1H, d, J=3 Hz); MS, m/z 261 for (M+H)+ ; IR (KBr) 3300 cm-1 (v. broad).

Workup

  1. temperaturewhilst maintaining the temperature between -90° and -100° C. for 2 hours
  2. customthen quenched with saturated aqueous ammonium chloride solution
  3. temperatureto warm to room temperature
  4. customThe organic layer was separated
  5. extractionthe aqueous extracted with ethyl acetate (3×100 ml)
  6. dry with materialThe combined organics were dried (magnesium sulphate)
  7. customthen evaporated
  8. customto give a gum which
  9. customwas purified by column chromatography on silica
  10. customto afford an oil which
  11. customto give a low melting solid

Sources & evidence

ORD record
ord-05ed6fb54e8742c5911b2c61d3bcfa16
Source dataset
uspto-grants-1995_12
Patent number
US05478933

Reaction notes

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