Allyl bromide → HCID 86757345, compound

HRID 1595004Notes

Reaction equation

HRID 1595004 reaction equation
C([O:5][N:6]=[O:7])(C)(C)C.[CH2:8](Br)[CH:9]=[CH2:10].[N+:12]([C:15]1[CH:16]=[C:17]([CH:19]=[C:20]([N+]([O-])=O)[CH:21]=1)N)([O-:14])=[O:13]>CC#N>[N+:6]([CH:10]=[CH:9][CH2:8][C:17]1[CH:16]=[C:15]([N+:12]([O-:14])=[O:13])[CH:21]=[CH:20][CH:19]=1)([O-:7])=[O:5]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 10906Tert-Butyl nitrite2×HCID 120683,5-Dinitroaniline2×

Product 1

HCID 86757345HCID 86757345, compoundYield 93%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of t-butylnitrite (84.6 ml, 0.71 mol) and allylbromide (530 ml, 6.15 mol) in 25 ml CH3CN, 3,5-dinitroaniline (75 g, 0.41 mol) was added spoonwise, so that the temperature was maintained between 11 and 15° C. During the addition of the final ½ of 3,5-dinitroaniline, more t-butylnitrite (21 ml, 0.18 mol) was added. The reaction mixture was then stirred at room temperature for 1 h. Excess t-butylnitrite, allylbromide and CH3CN was distilled from the reaction mixture at reduced pressure and the residue was dissolved in toluene (500 ml). The solution was filtered through two Al2O3 pads. The toluene was distilled off at reduced pressure and to the remaining residue 3,3,5-trimethylpentane (200 ml) was added. The mixture was heated to 60° C. and stirred for ½ h and then cooled to −60° C. The pentane phase was decanted and the mixture was crystallized from 2,2,4-trimethylpentane at −50° C. The crystals were then triturated twice with 2,2,4-trimethylpentane at −50° C. The remaining pentane was then removed at reduced pressure, to give 78.7 g (93%) of 3,5-dinitroallylbenzene as yellow oil containing approximately 4% of 3,5-dinitrobromo benzene.

Workup

  1. temperaturewas maintained between 11 and 15° C
  2. additionwas added
  3. distillationExcess t-butylnitrite, allylbromide and CH3CN was distilled from the reaction mixture at reduced pressure
  4. dissolutionthe residue was dissolved in toluene (500 ml)
  5. filtrationThe solution was filtered through two Al2O3 pads
  6. distillationThe toluene was distilled off at reduced pressure and to the remaining residue 3,3,5-trimethylpentane (200 ml)
  7. additionwas added
  8. temperatureThe mixture was heated to 60° C.
  9. stirringstirred for ½ h
  10. temperaturecooled to −60° C
  11. customThe pentane phase was decanted
  12. customthe mixture was crystallized from 2,2,4-trimethylpentane at −50° C
  13. customThe crystals were then triturated twice with 2,2,4-trimethylpentane at −50° C
  14. customThe remaining pentane was then removed at reduced pressure

Sources & evidence

ORD record
ord-4278d59c78444009b1a077e71898ccf9
Source dataset
uspto-grants-2001_09
Patent number
US06284894B1

Reaction notes

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