Sodium Hydroxide → Tert-butyl-3,3-dinitroazetidine

HRID 1171923Notes

Reaction equation

HRID 1171923 reaction equation
Cl.[C:2]([N:6]1[CH2:9][C:8](CO)([N+:10]([O-:12])=[O:11])[CH2:7]1)([CH3:5])([CH3:4])[CH3:3].[OH-].[Na+].[N:17]([O-:19])=[O:18].[Na+].S(OOS([O-])(=O)=O)([O-])(=O)=O.[Na+].[Na+]>O.[Fe-4](C#N)(C#N)(C#N)(C#N)(C#N)C#N.[K+].[K+].[K+].[K+]>[C:2]([N:6]1[CH2:7][C:8]([N+:10]([O-:12])=[O:11])([N+:17]([O-:19])=[O:18])[CH2:9]1)([CH3:3])([CH3:4])[CH3:5]

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 62655Sodium PersulfateHCID 19010110N-tert-butyl-3-hydroxymethyl-3-nitroazetidine hydrochlorideHCID 23668193Sodium Nitrite

Product 1

HCID 10954639Tert-butyl-3,3-dinitroazetidineYield 103.3%

Reagents, catalysts & solvents 2

HCID 178511492HCID 178511492, compoundCatalystHCID 962WaterSolvent2×

Procedure

To a solution (60 ml) of N-tert-butyl-3-hydroxymethyl-3-nitroazetidine hydrochloride (13.50 g, 0.060 mol) prepared in the Example 3 in distilled water, 30 ml of aqueous solution of NaOH (7.173 g, 0.179 mol) was added. The resulting yellow solution was stirred for 3 hours at room temperature. The resultant was cooled to 8° C. and a chilled solution (45 ml) of sodium nitrite (NaNO2) (16.5 g, 0.239 mol) and potassium ferrocyanide (K3Fe(CN)6) (1.974 g, 0.060 mol) in distilled water was added slowly. Then, solid sodium persulphate (Na2S2O8) (17.80 g, 0.075 mol) was added in a single portion. The resulting yellow solution was warmed to room temperature as the solution gradually turned into light orange color. The solution was stirred for another 1 hour and then extracted with dichloromethane (CH2Cl2) (150 ml). The organic layer was dried with magnesium sulfate (MgSO4) and the solvent was removed via vacuum evaporation to give N-tert-butyl-3,3-dinitroazetidine (12.583 g, 0.062 mol, yield: 86.66%) as a yellow oil.

Workup

  1. temperatureThe resultant was cooled to 8° C.
  2. temperatureThe resulting yellow solution was warmed to room temperature as the solution
  3. stirringThe solution was stirred for another 1 hour
  4. extractionextracted with dichloromethane (CH2Cl2) (150 ml)
  5. dry with materialThe organic layer was dried with magnesium sulfate (MgSO4)
  6. customthe solvent was removed via vacuum evaporation

Sources & evidence

ORD record
ord-5fe444eb79f642b6bad2631d1dbc467e
Source dataset
uspto-grants-2010_11
Patent number
US07829729B2

Reaction notes

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