Ammonia → HCID 20455130, compound

HRID 1446997Notes

Reaction equation

HRID 1446997 reaction equation
Cl([O-])(=O)(=O)=O.[CH2:6]([C:8]1([CH2:25][CH2:26][C:27]([O:29][CH3:30])=[O:28])[C:17]2[C:16]3[NH:18][C:19]4[C:24]([C:15]=3[CH2:14][CH2:13][N+:12]=2[CH2:11][CH2:10][CH2:9]1)=[CH:23][CH:22]=[CH:21][CH:20]=4)[CH3:7].N.[Br:32]Br>ClCCl>[CH3:27][O-:28].[CH2:6]([C:8]1([CH2:25][CH2:26][C:27]([O:29][CH3:30])=[O:28])[C:17]2[C:16]3[NH:18][C:19]4[C:24]([C:15]=3[CH2:14][CH2:13][N+:12]=2[CH2:11][CH2:10][CH2:9]1)=[CH:23][C:22]([Br:32])=[CH:21][CH:20]=4)[CH3:7]

Participants

5

Reactant 3

HCID 222AmmoniaHCID 24408BromineHCID 13241182HCID 13241182, compound

Product 1

HCID 20455130HCID 20455130, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

4.39 g. (10 mmoles) of 1-ethyl-1-(2'-methoxycarbonylethyl)-1,2,3,4,6,7-hexahydro-12H-indolo[2,3-a]quinolizin-5-ium perchlorate are shaken with a mixture of 5 ml of 10% aqueous ammonia and 50 ml. of dichloromethane. The phases are separated, the organic phase is dried over 10 g. of solid anhydrous sodium sulfate, and then filtered. 0.5 g. of dry gaseous hydrochloric acid are introduced into the filtrate, thereafter 50 ml of glacial acetic acid are added, and dichloromethane, is distilled off in vacuo. 0.67 ml. (2.08 g., 13 mmoles) of elemental bromine are added dropwise, under vigorous stirring, to the residue at 25° C. The reaction mixture is stirred at room temperature for 3 hours, the separated product is filtered off, and suctioned well to remove the residue of acetic acid. The still wet product is suspended in 40 ml. of dichloromethane, the dilute suspension is rendered alkaline with 14 ml. of 10% aqueous ammonia, and the phases are separated from each other. The organic phase is dried over 10 g. of solid anhydrous sodium sulfate, filtered off, and the filtrate is evaporated. The obtained oily residue is triturated with 10 ml. of methanol, whereupon the product separates in crystalline form containing lattice-bound methanol. In this way 3.15 g. (70%) of 1-ethyl-1-(2'-methoxycarbonylethyl)-9-bromo-1,2,3,4,6,7-hexahydro-12H-indolo[2,3-a]-quinolizin-5-ium methoxide are obtained; m.p.: 140°-142° C. The NMR spectrum of the product is identical with that given in Example 7.

Workup

  1. customThe phases are separated
  2. customthe organic phase is dried over 10 g
  3. filtrationof solid anhydrous sodium sulfate, and then filtered
  4. additionof dry gaseous hydrochloric acid are introduced into the filtrate
  5. addition50 ml of glacial acetic acid are added
  6. distillationdichloromethane, is distilled off in vacuo
  7. filtrationthe separated product is filtered off
  8. customto remove the residue of acetic acid
  9. customof 10% aqueous ammonia, and the phases are separated from each other
  10. customThe organic phase is dried over 10 g
  11. filtrationof solid anhydrous sodium sulfate, filtered off
  12. customthe filtrate is evaporated
  13. customThe obtained oily residue is triturated with 10 ml
  14. additioncontaining lattice-bound methanol

Sources & evidence

ORD record
ord-786e7a9fb73c402586d232126ef6b6bd
Source dataset
uspto-grants-1982_02
Patent number
US04315011

Reaction notes

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