Water → N-cyclopropyl-10,11-dihydro-5H-dibenzo-[a,d]cyclohepten-5-imine

HRID 1076070Notes

Reaction equation

HRID 1076070 reaction equation
[CH:1]1[C:11]2[CH2:10][CH2:9][C:8]3[CH:12]=[CH:13][CH:14]=[CH:15][C:7]=3[C:6](=O)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[CH:17]1([NH2:20])[CH2:19][CH2:18]1.O>CN(C)P(N(C)C)(N(C)C)=O.C1C=CC=CC=1.[Ti](Cl)(Cl)(Cl)Cl>[CH:17]1([N:20]=[C:6]2[C:5]3[CH:4]=[CH:3][CH:2]=[CH:1][C:11]=3[CH2:10][CH2:9][C:8]3[CH:12]=[CH:13][CH:14]=[CH:15][C:7]2=3)[CH2:19][CH2:18]1

Participants

7

Reactant 3

HCID 962WaterHCID 14589DibenzosuberoneHCID 69828Cyclopropylamine

Product 1

HCID 21541754N-cyclopropyl-10,11-dihydro-5H-dibenzo-[a,d]cyclohepten-5-imine

Reagents, catalysts & solvents 3

HCID 24193Titanium TetrachlorideCatalystHCID 241BenzeneSolvent2×HCID 12679HexamethylphosphoramideSolvent

Procedure

To a solution of 5 g of 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one and 20 g of cyclopropylamine in 25 ml of hexamethylphosphoramide is added, with cooling, during 30 minutes, a solution of 1.7 ml of titanium tetrachloride in 10 ml of anhydrous benzene. After stirring at room temperature for 2 weeks, benzene (50 ml) and water (50 ml) are added, with cooling. The mixture is filtered, the layers of the filtrate are separated, and the aqueous phase is extracted with 50 ml of benzene. The combined aqueous phases are washed with 5% aqueous sodium bicarbonate solution (25ml) and water (3 × 25 ml) and dried with magnesium sulfate. The solvent is removed, and the residue is shortpath distilled at a bath temperature of 145°-150° (0.3 micron) to give N-cyclopropyl-10,11-dihydro-5H-dibenzo-[a,d]cyclohepten-5-imine as a solid. Nmr spectrum (in CDCl3): multiplets at τ 2.3-3.0 (8H) 6.6-7.2 (5H) and 8.2-9.4 (4H).

Workup

  1. temperaturewith cooling, during 30 minutes
  2. temperaturewith cooling
  3. filtrationThe mixture is filtered
  4. customthe layers of the filtrate are separated
  5. extractionthe aqueous phase is extracted with 50 ml of benzene
  6. washThe combined aqueous phases are washed with 5% aqueous sodium bicarbonate solution (25ml) and water (3 × 25 ml)
  7. dry with materialdried with magnesium sulfate
  8. customThe solvent is removed
  9. distillationthe residue is shortpath distilled at a bath temperature of 145°-150° (0.3 micron)

Sources & evidence

ORD record
ord-e3c5274115914f15bcc558d7898fa0bd
Source dataset
uspto-grants-1976_05
Patent number
US03954865

Reaction notes

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