Phosphoric Acid → 11H-Dibenz[b,e]azepine

HRID 741549Notes

Reaction equation

HRID 741549 reaction equation
O=P12OP3(OP(OP(O3)(O1)=O)(=O)O2)=O.OP(O)(O)=O.O=P(Cl)(Cl)Cl.[C:25]1([CH2:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][C:33]=2[NH:38][CH:39]=O)[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1>CC1C=CC(C)=CC=1>[CH:37]1[C:32]2[CH2:31][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=3[CH:39]=[N:38][C:33]=2[CH:34]=[CH:35][CH:36]=1

Participants

6

Reactant 4

HCID 1004Phosphoric AcidHCID 14812Phosphorus oxide (P4O10)HCID 24813Phosphorus oxychlorideHCID 268130n-(2-benzylphenyl)formamide2×

Product 1

HCID 1087801611H-Dibenz[b,e]azepineYield 4.1%

Reagents, catalysts & solvents 1

HCID 7809P-XyleneSolvent

Procedure

P2O5 (516.5 g) was added portionwise to H3PO4 (247.5 ml) and stirred under a N2 flow at room temperature. The mixture was stirred for 2 hours at 120° C., then cooled to 50° C. p-Xylene (1810 ml) was added, and stirring was continued for 15 minutes. POCl3 (83.3 g) was added, and stirring was continued for 10 minutes. N-[2-(phenylmethyl)phenyl]formamide (prepared as described in Helv. Chim. Acta 47(5) 1163-72 (1964)) (37.2 g) was added portionwise. The mixture was stirred for 30 minutes at 60°-70° C. Another portion of N-[2-(phenylmethyl)phenyl]formamide (74.3 g) was added portionwise, and the reaction mixture was stirred overnight at 100° C. The reaction mixture was cooled and the p-xylene layer was removed. Water (990 ml) was added slowly. The mixture was cooled with ice-water. A solution of KOH (1073 g) in water (2200 ml) was added over 2 hours. CH2Cl2 (500 ml) was added dropwise and the mixture was stirred vigorously during 15 minutes. The organic layer was separated. The aqueous layer was extracted twice with CH2Cl2. The combined organic layers were dried with MgSO4, filtered off and the solvent evaporated. The residue was purified by distillation yielding a mixed fraction. The mixed fraction was repurified twice by distillation, yielding 1.4 g of 11H-dibenz[b,e]azepine (interm. 9).

Workup

  1. stirringThe mixture was stirred for 2 hours at 120° C.
  2. additionwas added
  3. stirringstirring
  4. stirringstirring
  5. waitwas continued for 10 minutes
  6. stirringThe mixture was stirred for 30 minutes at 60°-70° C
  7. stirringthe reaction mixture was stirred overnight at 100° C
  8. temperatureThe reaction mixture was cooled
  9. customthe p-xylene layer was removed
  10. additionWater (990 ml) was added slowly
  11. temperatureThe mixture was cooled with ice-water
  12. additionA solution of KOH (1073 g) in water (2200 ml) was added over 2 hours
  13. additionCH2Cl2 (500 ml) was added dropwise
  14. stirringthe mixture was stirred vigorously during 15 minutes
  15. customThe organic layer was separated
  16. extractionThe aqueous layer was extracted twice with CH2Cl2
  17. dry with materialThe combined organic layers were dried with MgSO4
  18. filtrationfiltered off
  19. customthe solvent evaporated
  20. distillationThe residue was purified by distillation
  21. customyielding a mixed fraction
  22. distillationThe mixed fraction was repurified twice by distillation

Sources & evidence

ORD record
ord-cbb2cf470c974667bf173c5cf38ad906
Source dataset
uspto-grants-1996_09
Patent number
US05552399

Reaction notes

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