Sodium Carbonate → [2-(Methoxy)-3-nitrophenyl]acetaldehyde

HRID 1179617Notes

Reaction equation

HRID 1179617 reaction equation
COC1C([N+]([O-])=O)=CC=CC=1C=O.C1OCCOCCOCCOCCOCCOC1.[Cl-].COC[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C(=O)([O-])[O-].[K+].[K+].[CH3:61][O:62][C:63]1[C:68]([N+:69]([O-:71])=[O:70])=[CH:67][CH:66]=[CH:65][C:64]=1/[CH:72]=[CH:73]/[O:74]C.COC1C([N+]([O-])=O)=CC=CC=1/C=C\OC.C(=O)([O-])[O-].[Na+].[Na+]>C1COCC1.Cl>[CH3:61][O:62][C:63]1[C:68]([N+:69]([O-:71])=[O:70])=[CH:67][CH:66]=[CH:65][C:64]=1[CH2:72][CH:73]=[O:74]

Participants

10

Reactant 7

HCID 10340Sodium CarbonateHCID 11430Potassium CarbonateHCID 2855718-Crown-6HCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 140810742-Methoxy-3-nitrobenzaldehydeHCID 574542632-(methoxy)-1-[(E)-2-(methoxy)ethenyl]-3-nitrobenzeneHCID 684276382-(methyloxy)-1-[(Z)-2-(methyloxy)ethenyl]-3-nitrobenzene

Product 1

HCID 57444344[2-(Methoxy)-3-nitrophenyl]acetaldehydeYield 54%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
60 °C

Procedure

To a stirred solution of 2-(methoxy)-3-nitrobenzaldehyde in THF were added 18-Crown6 (0.2 eq), (methoxymethyl)triphenylphosphonium chloride (2 eq) and potassium carbonate (6.5 eq). The resulting suspension was warmed to 60° C. for 2 hours then cooled to room temperature and filtered. The filtrate was concentrated under vacuum and purified by chromatography on a silica cartridge (eluent cyclohexane-ethyl acetate, 9:1) to give a mixture of 2-(methoxy)-1-[(E)-2-(methoxy)ethenyl]-3-nitrobenzene and 2-(methyloxy)-1-[(Z)-2-(methyloxy)ethenyl]-3-nitrobenzene. The alkene mixture was dissolved in THF and 6N hydrochloric acid (1:1), and stirred for 1 hour. The solution was made basic with aqueous sodium carbonate solution and extracted with DCM. The organic layer was washed (water, brine), dried (sodium sulfate) and concentrated under vacuum to give the title compound (54% overall yield).

Workup

  1. temperaturethen cooled to room temperature
  2. filtrationfiltered
  3. concentrationThe filtrate was concentrated under vacuum
  4. custompurified by chromatography on a silica cartridge (eluent cyclohexane-ethyl acetate, 9:1)
  5. customto give
  6. extractionextracted with DCM
  7. washThe organic layer was washed (water, brine)
  8. dry with materialdried (sodium sulfate)
  9. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-8af01f8160a54e8da9064b98cf545669
Source dataset
uspto-grants-2007_10
Patent number
US07279481B2

Reaction notes

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