Formaldehyde → 2,2-Dinitropropanol

HRID 1981958Notes

Reaction equation

HRID 1981958 reaction equation
[OH-:1].[Na+].[N+:3]([CH2:6][CH3:7])([O-:5])=[O:4].[CH2:8]=O.[N:10]([O-:12])=[O:11].[Na+].S(OOS([O-])(=O)=O)([O-])(=O)=O.[Na+].[Na+]>O.[Fe-3](C#N)(C#N)(C#N)(C#N)(C#N)C#N.[K+].[K+].[K+]>[N+:3]([C:6]([N+:10]([O-:12])=[O:11])([CH3:8])[CH2:7][OH:1])([O-:5])=[O:4]

Participants

8

Reactant 5

HCID 712FormaldehydeHCID 6587Nitroethane2×HCID 14798Sodium HydroxideHCID 62655Sodium PersulfateHCID 23668193Sodium Nitrite

Product 1

HCID 701942,2-DinitropropanolYield 65.8%

Reagents, catalysts & solvents 2

HCID 178511488HCID 178511488, compoundCatalystHCID 962WaterSolvent4×

Procedure

To a stirred solution of 2.66 g (66.5 mmoles) of sodium hydroxide in 15 ml of water at 20° was added 5.0 g (66.5 mmoles) of nitroethane. When all the nitroethane dissolved, the solution was cooled to 5°-7° in an ice-water bath and 5.4 g of 37% aqueous formaldehyde (66.5 mmoles) was then added. The cooling bath was removed and the mixture was stirred for 2 hours before the ice-water bath was replaced and 25 ml of ether was added. A solution of 18.3 g of sodium nitrite (0.265 mole) in 30 ml of water was then added followed by solutions of 15.8 g (66.3 mmoles) of sodium persulfate in 30 ml of water and 4.4 g (13.4 mmoles) of potassium ferricyanide in 15 ml of water. The reaction temperature rose from 14° to 35°. The mixture was then stirred at ambient temperature for 1 hour and phases were separated. The aqueous phase was extracted twice with ether and the combined ether extracts were washed with brine and dried. The product was distilled in a short path distillation apparatus to give 6.57 g (65% yield) of 2,2-dinitropropanol.

Workup

  1. temperaturethe solution was cooled to 5°-7° in an ice-water bath
  2. customThe cooling bath was removed
  3. addition25 ml of ether was added
  4. customrose from 14° to 35°
  5. stirringThe mixture was then stirred at ambient temperature for 1 hour
  6. customphases were separated
  7. extractionThe aqueous phase was extracted twice with ether
  8. washthe combined ether extracts were washed with brine
  9. customdried
  10. distillationThe product was distilled in a short path distillation apparatus

Sources & evidence

ORD record
ord-64a49d91d6f744618e4e709100bcd193
Source dataset
uspto-grants-1986_06
Patent number
US04594430

Reaction notes

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