Sodium Hydroxide → 3,3-Dinitrooxetane

HRID 1165577Notes

Reaction equation

HRID 1165577 reaction equation
[N+:1]([CH:4]1[CH2:7][O:6][CH2:5]1)([O-:3])=[O:2].[OH-].[Na+].[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+].C(Cl)Cl>[N+:1]([C:4]1([N+:10]([O-:12])=[O:11])[CH2:7][O:6][CH2:5]1)([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 14798Sodium HydroxideHCID 62655Sodium PersulfateHCID 131539093-NitrooxetaneHCID 23668193Sodium Nitrite

Product 1

HCID 131539103,3-DinitrooxetaneYield 75%

Reagents, catalysts & solvents 3

HCID 178511488HCID 178511488, compoundCatalystHCID 962WaterSolvent3×HCID 6344DichloromethaneSolvent

Procedure

A solution of 1.5 g (14.5 mmoles) of 3-nitrooxetane and 0.87 g (22 mmoles) of sodium hydroxide in 10 mL of water was stirred for 10 minute and 10 mL of methylene chloride was added. Then, a solution of 4.0 g (58 mmoles) of sodium nitrite in 10 mL of water was added, followed by 3.5 g of solid sodium persulfate and a solution of 0.96 g (2.9 mmoles) of potassium ferricyanide in 5 mL of water. A cold water bath was used to moderate the slightly exothermic reaction. After 30 minutes, the phases were separated and the aqueous layer extracted with two 30 mL portions of ether. The combined etheral extracts were washed with brine, dried and concentrated. Care was taken not to lose the very volatile product in this concentration step. The crude material was purified by sublimation at 120°-140° C. at atmospheric pressure to give 1.6 g (75% yield) of 3.3-dinitrooxetane, m.p. 70°-71° C. Its IR was identical with that of an authentic sample. 'H NMR (CDCl3): & 5.20 (s, 4H).

Workup

  1. customA cold water bath was used
  2. customthe slightly exothermic reaction
  3. customthe phases were separated
  4. extractionthe aqueous layer extracted with two 30 mL portions of ether
  5. washThe combined etheral extracts were washed with brine
  6. customdried
  7. concentrationconcentrated
  8. concentrationin this concentration step
  9. customThe crude material was purified by sublimation at 120°-140° C. at atmospheric pressure

Sources & evidence

ORD record
ord-499440cfbad44cc0b97dc9d000b2a31d
Source dataset
uspto-grants-1990_03
Patent number
US04910322

Reaction notes

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