Nitrogen → 5-Chloromethoxy-4-hydroxy-2-nitrobenzaldehyde

HRID 1982217Notes

Reaction equation

HRID 1982217 reaction equation
[Al+3].[Cl-:2].[Cl-].[Cl-].[CH2:5]1[O:9][C:8]2[CH:10]=[C:11]([N+:16]([O-:18])=[O:17])[C:12]([CH:14]=[O:15])=[CH:13][C:7]=2[O:6]1.N#N.O>ClC(Cl)C>[Cl:2][CH2:5][O:6][C:7]1[C:8]([OH:9])=[CH:10][C:11]([N+:16]([O-:18])=[O:17])=[C:12]([CH:13]=1)[CH:14]=[O:15]

Participants

6

Reactant 4

HCID 947NitrogenHCID 962WaterHCID 128406-Nitro-1,3-benzodioxole-5-carboxaldehydeHCID 6451240Aluminum(III) Chloride

Product 1

HCID 114247525-Chloromethoxy-4-hydroxy-2-nitrobenzaldehydeYield 97%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent2×

Procedure

AlCl3 (6 g) and dry dichloroethane (15 ml) are added to a three-neck round bottom flask, which has been purged with N2, and the dispersion is cooled to -5°. A solution of 6-nitropiperonal (3 g; 0.0154 mol) (available from Aldrich Chemical Co.) in 12 ml dry dichloroethane is added to the dispersion, in one portion, while the temperature and N2 atmosphere are maintained. The reaction mixture is stirred for 1.25 hours, and 100 ml H2O (0°) is added. The emulsion is stirred for 15 minutes, then extracted with 3×100 ml ethyl acetate. The combined organics are washed with saturated NaCl, then dried over Na2SO4. After filtration, the ethyl acetate is removed at reduced pressure. Recrystallization from ethyl acetate gives 3.45 g (97%) of (10): mp 160°-161° C.

Workup

  1. customwhich has been purged with N2
  2. temperaturethe dispersion is cooled to -5°
  3. temperatureare maintained
  4. stirringThe emulsion is stirred for 15 minutes
  5. extractionextracted with 3×100 ml ethyl acetate
  6. washThe combined organics are washed with saturated NaCl
  7. dry with materialdried over Na2SO4
  8. filtrationAfter filtration
  9. customthe ethyl acetate is removed at reduced pressure
  10. customRecrystallization from ethyl acetate

Sources & evidence

ORD record
ord-df8b27b8e1e74d54a1d595e591787cbd
Source dataset
uspto-grants-1986_06
Patent number
US04595765

Reaction notes

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