Chloroform → HCID 54212508, compound

HRID 1885733Notes

Reaction equation

HRID 1885733 reaction equation
[N:1]#CBr.C(N(C(C)C)CC)(C)C.C(Cl)(Cl)Cl.[CH3:17][N:18]1[C:22]2[CH2:23][CH2:24][C:25]3[C:32]4([CH3:35])[CH:33]([CH3:34])[CH:19]1[CH2:20][C:21]=2[C:26]=3[CH:27]=[CH:28][CH2:29][N:30]=[CH:31]4>C(=O)(O)[O-].[Na+]>[C:17]([N:18]1[C:22]2[CH2:23][CH2:24][C:25]3[C:32]4([CH3:35])[CH:33]([CH3:34])[CH:19]1[CH2:20][C:21]=2[C:26]=3[CH:27]=[CH:28][CH2:29][N:30]=[CH:31]4)#[N:1]

Participants

6

Reactant 4

HCID 6212Chloroform2×HCID 10476Cyanogen BromideHCID 81531DiisopropylethylamineHCID 54133654HCID 54133654, compound

Product 1

HCID 54212508HCID 54212508, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 516892Sodium BicarbonateSolvent

Procedure

To a stirred solution of 6.81 g of cyanogen bromide, 4.7 ml of diisopropylethylamine, and 142 ml of chloroform was added, at room temperature with stirring, a solution of 13.7 g of 1,2,3,4,5,6-hexahydro-3,6,12-trimethyl-2,6-methano-9H-pyrrolo[3,2-h][3]benzazocine and 414 ml of chloroform. The mixture was heated at reflux for 2.6 hr, cooled to room temperature, diluted with aqueous sodium bicarbonate solution, and the layers were separated. The organic layer was washed with sodium bicarbonate solution. The combined aqueous layers were extracted with ether. The combined organic layers were washed with brine, dried over anhydrous potassium carbonate, and filtered. Concentration of the filtrate followed by purification by flash chromatography (silica gel, 2% triethylamine/ethyl acetate) afforded 13.5 g (95%) of 3-cyano-6,12-dimethyl-1,2,3,4,5,6-hexahydro-2,6-methano-9H-pyrrolo[3,2-h][3]benzazocine.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 2.6 hr
  3. customthe layers were separated
  4. washThe organic layer was washed with sodium bicarbonate solution
  5. extractionThe combined aqueous layers were extracted with ether
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over anhydrous potassium carbonate
  8. filtrationfiltered
  9. customConcentration of the filtrate followed by purification by flash chromatography (silica gel, 2% triethylamine/ethyl acetate)

Sources & evidence

ORD record
ord-29a7316a4a4e4e1bb7a0a0b8eb8ee7c5
Source dataset
uspto-grants-1992_09
Patent number
US05145965

Reaction notes

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