Sodium Hydroxide → 8-chloro-11-(1-methylpiperidin-4-ylidene)-5,11-dihydro-6H-benzo[5,6]cyclohepta[1,2-b]pyridin-6-one

HRID 21414Notes

Reaction equation

HRID 21414 reaction equation
C[O:2][C:3]1[C:13]2[CH:14]=[C:15]([Cl:18])[CH:16]=[CH:17][C:12]=2[C:11]([CH:20]2[CH2:25][CH2:24][N:23]([CH3:26])[CH2:22][CH2:21]2)(O)[C:6]2=[N:7][CH:8]=[CH:9][CH:10]=[C:5]2[CH:4]=1.FC(F)(F)S(O)(=O)=O.[OH-].[Na+]>S(=O)(=O)(O)O>[Cl:18][C:15]1[CH:16]=[CH:17][C:12]2[C:11](=[C:20]3[CH2:21][CH2:22][N:23]([CH3:26])[CH2:24][CH2:25]3)[C:6]3=[N:7][CH:8]=[CH:9][CH:10]=[C:5]3[CH2:4][C:3](=[O:2])[C:13]=2[CH:14]=1

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 62406Trifluoromethanesulfonic acidHCID 14637759HCID 14637759, compound

Product 1

HCID 146377638-chloro-11-(1-methylpiperidin-4-ylidene)-5,11-dihydro-6H-benzo[5,6]cyclohepta[1,2-b]pyridin-6-oneYield 77.2%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

A mixture of 2.00 g (5.39 mmol) of 6-methoxy-8-chloro-11-(1-methyl-4-piperidinyl)-11H-benzo[5,6]cyclohepta[1,2-b]pyridin-11-ol in 87% aqueous sulfuric acid was stirred at room temperature and under an argon atmosphere. After 30 min 30 mL of trifluoromethanesulfonic acid was added and the mixture was heated to 115° C. One hour later the mixture was cooled to room temperature, poured onto ice, basified with 5% aqueous sodium hydroxide and extracted with methylene chloride (2×). The combined organic portions were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo to give 1.41 g of 8-chloro-5,11-dihydro-11-(1-methyl-4-piperidinylidene)-6H-benzo[5,6]cyclohepta-[1,2-b]pyridin-6-one. The material was recrystallized from ethyl acetate/isopropyl ether to give 1.12 g (61%) of the ketone as a granular solid: mp 181°-183° C.

Workup

  1. temperaturethe mixture was heated to 115° C
  2. temperatureOne hour later the mixture was cooled to room temperature
  3. additionpoured onto ice
  4. extractionextracted with methylene chloride (2×)
  5. washThe combined organic portions were washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-19307dc1c48648ebbb98a857f96b0b68
Source dataset
uspto-grants-1995_06
Patent number
US05422351

Reaction notes

Loading…