Iodine → HCID 131711668, compound

HRID 1448151Notes

Reaction equation

HRID 1448151 reaction equation
[CH3:1][N:2]([CH3:7])[CH2:3][CH2:4][CH2:5][Cl:6].[Mg].II.[Cl:11][C:12]1[C:17]2[CH:18]=[N:19][N:20]([CH2:21][CH3:22])[C:16]=2[N:15]=[C:14]2[C:23](=[O:32])[C:24]3[CH:31]=[CH:30][CH:29]=[CH:28][C:25]=3[CH2:26][CH2:27][C:13]=12>C(I)C.O1CCCC1>[ClH:6].[Cl:11][C:12]1[C:17]2[CH:18]=[N:19][N:20]([CH2:21][CH3:22])[C:16]=2[N:15]=[C:14]2[C:23]([CH2:5][CH2:4][CH2:3][N:2]([CH3:7])[CH3:1])([OH:32])[C:24]3[CH:31]=[CH:30][CH:29]=[CH:28][C:25]=3[CH2:26][CH2:27][C:13]=12

Participants

7

Reactant 4

HCID 807IodineHCID 669603-Chloro-N,N-dimethyl-1-propanamine2×HCID 5462224MagnesiumHCID 203820734-chloro-1-ethyl-5,6-dihydrobenzo[5,6]-cyclohepta[1,2-b]pyrazolo[4,3-e]pyridin-11(1H)-one

Product 1

HCID 131711668HCID 131711668, compound

Reagents, catalysts & solvents 2

HCID 6340IodoethaneCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

12.3 g. of freshly distilled and absolutely dry 3-(dimethylamino)propyl chloride (0.1 mol.) are added slowly with stirring and gentle heating to 2.4 g. of magnesium turnings in 70 ml. of dry tetrahydrofuran. A crystal of iodine and a few drops of ethyl iodide are employed as initiator. After all of the 3-(dimethylamino)propyl chloride is added, the reaction mixture is refluxed for two to three hours. To this Grignard reagent a solution of 10.8 g. of 4-chloro-1-ethyl-5,6-dihydrobenzo[5,6]cyclohepta[1,2-b]pyrazolo[4,3-e]pyridin-11(1H)-one (0.035 mol.), from example 1(e), in 70 ml. of dry tetrahydrofuran is added. The mixture is heated under reflux for 5 hours after which the solvent is evaporated and the residue treated with 150 ml. of water and 60 ml. of ammonium chloride solution (20%). The mixture is extracted with ether and the ethereal extract is washed with water and dried with Na2SO4. Then the etheral solution is allowed to stand over night in a refrigerator to separate unreacted starting material (2.6 g. of oil). The decanted solution is charcoaled, filtered and 8 ml. of ethereal hydrochloric acid (195 g./l.) are added. Stirring is continued for 40 minutes. The precipitated hydrochloride salt is filtered off, washed with ether, and recrystallized from ethyl acetate/ether (1:5) to yield 8.3 g. (55%) of 4-chloro-11-[3-(dimethylamino)propyl]-1-ethyl-1,5,6,11-tetrahydro[5,6]cyclohepta[1,2-b]pyrazolo[4,3-e]pyridin-11-ol, hydrochloride (1:1); m.p. 172°-176° (dec.).

Workup

  1. distillationof freshly distilled
  2. temperaturegentle heating to 2.4 g
  3. temperaturethe reaction mixture is refluxed for two to three hours
  4. temperatureThe mixture is heated
  5. temperatureunder reflux for 5 hours after which the solvent
  6. customis evaporated
  7. additionthe residue treated with 150 ml
  8. extractionThe mixture is extracted with ether
  9. extractionthe ethereal extract
  10. washis washed with water
  11. dry with materialdried with Na2SO4
  12. waitto stand over night in a refrigerator
  13. customto separate unreacted
  14. filtrationfiltered
  15. additionof ethereal hydrochloric acid (195 g./l.) are added
  16. stirringStirring
  17. filtrationThe precipitated hydrochloride salt is filtered off
  18. washwashed with ether
  19. customrecrystallized from ethyl acetate/ether (1:5)
  20. customto yield 8.3 g

Sources & evidence

ORD record
ord-b914818eb748457aa8ee4d2e5fe58f38
Source dataset
uspto-grants-1979_12
Patent number
US04179564

Reaction notes

Loading…