Acetonitrile → HCID 21249781, compound

HRID 1531625Notes

Reaction equation

HRID 1531625 reaction equation
[N+](C1C=C(C(N=[N+]=[N-])=O)C=C([N+]([O-])=O)C=1)([O-])=O.C(#N)C.[N+:21]([C:24]1[CH:25]=[C:26]([N:33]=[C:34]=[O:35])[CH:27]=[C:28]([N+:30]([O-:32])=[O:31])[CH:29]=1)([O-:23])=[O:22].[CH3:36][CH:37]([CH3:44])[C:38]([O:40][CH2:41][CH2:42][OH:43])=[O:39]>ClCCl.O>[C:38]([O:40][CH2:41][CH2:42][O:43][C:34](=[O:35])[NH:33][C:26]1[CH:25]=[C:24]([N+:21]([O-:23])=[O:22])[CH:29]=[C:28]([N+:30]([O-:32])=[O:31])[CH:27]=1)(=[O:39])[CH:37]([CH3:44])[CH3:36]

Participants

7

Reactant 4

HCID 6342Acetonitrile2×HCID 813662-Hydroxyethyl isobutyrateHCID 1940873,5-Dinitrophenyl isocyanate2×HCID 2794485HCID 2794485, compound

Product 1

HCID 21249781HCID 21249781, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

19.5 g (0.0822 mol) of 3,5-dinitrophenyl carbonyl azide was placed, in a nitrogen current, in a 0.3-l four-necked flask equipped with a nitrogen inlet tube, a dropping funnel, a reflux condenser, a thermometer and a mixing blade. Thereto was added acetonitrile for dissolution and the total amount was made 50 ml. The flask contents were heated for refluxing to obtain 50 ml of an acetonitrile solution containing 3,5-dinitrophenyl isocyanate (compound 7). While the flask was being cooled with ice water, 12.0 g (0.0909 mol) of 2-hydroxyethyl 2-methylpropionate was dropwise added to the flask contents with stirring. After the dropwise addition, stirring was conducted at room temperature for 2 hours; 50 ml of water was added; and stirring was conducted for several minutes. Then, dichloromethane was added. All the flask contents were transferred into a separating funnel for separation of the aqueous layer. The organic layer taken out was returned to the separating funnel. Thereto was added a 5% aqueous sodium carbonate solution, followed by mixing. The lower layer (organic layer) was taken out and dried over anhydrous magnesium sulfate. From the dried solution was removed dichloromethane by distillation by the use of an evaporator, whereby a solid was separated. The solid was recrystallized from butanol to obtain 2-(3,5-dinitrophenylcarbamoyloxy)ethyl isobutyrate (compound 8) as a yellow powder. Yield: 14.4 g (50%) Melting point: 94-95° C.

Workup

  1. customequipped with a nitrogen inlet tube, a dropping funnel, a reflux condenser
  2. dissolutionfor dissolution
  3. temperatureThe flask contents were heated
  4. temperaturefor refluxing
  5. additionwas dropwise added to the flask contents
  6. additionAfter the dropwise addition
  7. stirringstirring
  8. stirringand stirring
  9. waitwas conducted for several minutes
  10. customAll the flask contents were transferred into a separating funnel for separation of the aqueous layer
  11. additionThereto was added a 5% aqueous sodium carbonate solution
  12. additionby mixing
  13. dry with materialdried over anhydrous magnesium sulfate
  14. customFrom the dried solution was removed dichloromethane
  15. distillationby distillation
  16. customby the use of an evaporator, whereby a solid
  17. customwas separated
  18. customThe solid was recrystallized from butanol

Sources & evidence

ORD record
ord-b02f27adfb104c899db7dbe1807f8835
Source dataset
uspto-grants-2001_03
Patent number
US06200831B1

Reaction notes

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