Phosgene → (S)-[6-bromo-5-(o-chlorophenyl)-2,3-dihydro-1,3-dimethyl-2-oxo-1H-1,4-benzodiazepin-7-yl]isocyanate

HRID 1632172Notes

Reaction equation

HRID 1632172 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]([CH3:12])[C:10](=[O:13])[C@H:9]([CH3:14])[N:8]=[C:7]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=3[Cl:21])[C:6]=2[C:22]=1[Br:23].[C:24](Cl)(Cl)=[O:25]>ClCCCl.C1(C)C=CC=CC=1.ClC(Cl)C>[Br:23][C:22]1[C:6]2[C:7]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=3[Cl:21])=[N:8][C@@H:9]([CH3:14])[C:10](=[O:13])[N:11]([CH3:12])[C:5]=2[CH:4]=[CH:3][C:2]=1[N:1]=[C:24]=[O:25]

Participants

6

Reactant 2

HCID 6371PhosgeneHCID 53936752(S)-7-amino-6-bromo-5-(o-chlorophenyl)-1,3-dihydro-1,3-dimethyl-2H-1,4-benzodiazepin-2-one

Product 1

HCID 53715566(S)-[6-bromo-5-(o-chlorophenyl)-2,3-dihydro-1,3-dimethyl-2-oxo-1H-1,4-benzodiazepin-7-yl]isocyanate

Reagents, catalysts & solvents 3

HCID 111,2-DichloroethaneSolventHCID 1140TolueneSolventHCID 63651,1-DichloroethaneSolvent

Procedure

50 g (0.127 mol) of (S)-7-amino-6-bromo-5-(o-chlorophenyl)-1,3-dihydro-1,3-dimethyl-2H-1,4-benzodiazepin-2-one are dissolved in 700 ml of 1,2-dichloroethane while warming and the still hot solution is added dropwise while stirring and cooling to a mixture of 90 ml (0.173 mol) of a 20 percent solution of phosgene in toluene and 500 ml of dichloroethane in such a manner that the temperature does not exceed 10°. The mixture is subsequently heated to boiling under reflux while stirring for 1 hour, 500 ml of 1,2-dichloroethane are distilled off, the solution is cooled to 10°, made basic with triethylamine and evaporated, there being obtained (S)-[6-bromo-5-(o-chlorophenyl)-2,3-dihydro-1,3-dimethyl-2-oxo-1H-1,4-benzodiazepin-7-yl]isocyanate as a foam which can be stored for several days in a refrigerator with the exclusion of moisture.

Workup

  1. temperaturewhile warming
  2. additionthe still hot solution is added dropwise
  3. customdoes not exceed 10°
  4. temperatureThe mixture is subsequently heated
  5. temperatureunder reflux
  6. stirringwhile stirring for 1 hour
  7. distillation500 ml of 1,2-dichloroethane are distilled off
  8. temperaturethe solution is cooled to 10°
  9. customevaporated

Sources & evidence

ORD record
ord-2d285191ec08483caca71e2be82ffdc9
Source dataset
uspto-grants-1984_10
Patent number
US04474777

Reaction notes

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