Water → 2-Nitrobenzaldehyde

HRID 1973199Notes

Reaction equation

HRID 1973199 reaction equation
C[O-].[Na+].C(OC(=O)C([O:10][CH2:11][CH3:12])=O)C.[N+:14]([C:17]1C=[CH:21][CH:20]=[CH:19][C:18]=1C)([O-:16])=[O:15].O>C(O)C>[N+:14]([C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][C:12]=1[CH:11]=[O:10])([O-:16])=[O:15]

Participants

6

Reactant 4

HCID 962WaterHCID 69442-NitrotolueneHCID 7268Diethyl OxalateHCID 10942334Sodium Methoxide

Product 1

HCID 111012-Nitrobenzaldehyde

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
40 °C

Procedure

383 g (7.1 mols) of sodium methylate are dissolved in ethanol and 985 g (6.75 mols) of oxalic acid diethyl ester and 925 g (6.75 mols) of 2-nitrotoluene are poured in. The mixture is heated under reflux for 30 minutes and is allowed to cool, 300 ml of ice water are next added cautiously and after the exothermic reaction has subsided 1,600 ml of water are added. After boiling additionally for 90 minutes under reflux, the mixture is steam-distilled until two phases no longer pass over. The organic phase is separated from the distillate and 310 g of 2-nitrotoluene are recovered from it. The residual aqueous phase of the distillate is filtered, 600 g of (anhydrous) sodium carbonate and 2,000 ml of toluene are added and the mixture is cooled to +3° C. 650 g of solid potassium permanganate are added over the course of 70 minutes and the reaction temperature is kept at between +2° and +6° C. The mixture is stirred for a further 45 minutes at +5° C and then warmed to 40° C, and 50% strength sulphuric acid is then added dropwise (gas being evolved). The exothermic reaction is kept at 35°- 40° C by cooling. Insoluble material is then filtered off and the toluene phase is separated from the filtrate. The filter residue is washed with hot toluene and the combined toluene phases are extracted by shaking with 15% strength sodium carbonate solution and with water and are then dried with the sodium sulphate. On concentrating the toluene phase in vacuo, 2-nitrobenzaldehyde is obtained as a viscous oil which crystallizes immediately on cooling. Melting point 40°- 41° C.

Workup

  1. temperatureThe mixture is heated
  2. temperatureunder reflux for 30 minutes
  3. temperatureto cool
  4. customafter the exothermic reaction
  5. additionare added
  6. temperatureunder reflux
  7. distillationthe mixture is steam-distilled until two phases
  8. customThe organic phase is separated from the distillate and 310 g of 2-nitrotoluene
  9. customare recovered from it
  10. filtrationThe residual aqueous phase of the distillate is filtered
  11. addition600 g of (anhydrous) sodium carbonate and 2,000 ml of toluene are added
  12. temperaturethe mixture is cooled to +3° C
  13. addition650 g of solid potassium permanganate are added over the course of 70 minutes
  14. customis kept at between +2° and +6° C
  15. addition50% strength sulphuric acid is then added dropwise (gas being evolved)
  16. customThe exothermic reaction
  17. customis kept at 35°- 40° C
  18. temperatureby cooling
  19. filtrationInsoluble material is then filtered off
  20. customthe toluene phase is separated from the filtrate
  21. washThe filter residue is washed with hot toluene
  22. extractionthe combined toluene phases are extracted
  23. stirringby shaking with 15% strength sodium carbonate solution and with water
  24. dry with materialare then dried with the sodium sulphate
  25. concentrationOn concentrating the toluene phase in vacuo

Sources & evidence

ORD record
ord-42461763cd1e4bf586766fde61a71dbf
Source dataset
uspto-grants-1976_12
Patent number
US03996289

Reaction notes

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