Hydrochloric Acid → 9-Acetyl-8-methoxy-1,2-dihydro-6-(3-dimethylaminopropyl)-cyclopenta[c]carbazole-3-one

HRID 514796Notes

Reaction equation

HRID 514796 reaction equation
[H-].[Na+].[C:3]([C:6]1[C:18]([O:19][CH3:20])=[CH:17][C:16]2[NH:15][C:14]3[CH:13]=[CH:12][C:11]4[C:21](=[O:24])[CH2:22][CH2:23][C:10]=4[C:9]=3[C:8]=2[CH:7]=1)(=[O:5])[CH3:4].[H][H].Cl.[CH3:28][N:29]([CH3:34])[CH2:30][CH2:31][CH2:32]Cl.Cl>C(Cl)Cl>[C:3]([C:6]1[C:18]([O:19][CH3:20])=[CH:17][C:16]2[N:15]([CH2:32][CH2:31][CH2:30][N:29]([CH3:34])[CH3:28])[C:14]3[CH:13]=[CH:12][C:11]4[C:21](=[O:24])[CH2:22][CH2:23][C:10]=4[C:9]=3[C:8]=2[CH:7]=1)(=[O:5])[CH3:4]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 943083-(Dimethylamino)propyl chloride hydrochlorideHCID 711790429-Acetyl-8-methoxy-1,2-dihydro-6H-cyclopenta[c]carbazole-3-oneHCID 178418361HCID 178418361, compound

Product 1

HCID 453808019-Acetyl-8-methoxy-1,2-dihydro-6-(3-dimethylaminopropyl)-cyclopenta[c]carbazole-3-oneYield 84.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

NaH (6.88 g of 60%, 171.95 mmol, 2.5 eq) was added to a suspension of 9-acetyl-8-methoxy-1,2-dihydro-6H-cyclopenta[c]carbazole-3-one (83) (26 g, 68.78 mmol, 1 eq) in dry CH2Cl2 (300 mL), and the mixture was stirred at room temperature for 20-30 min until the evolution of hydrogen ceased. 3-Dimethylaminopropylchloride hydrochloride (16.3 g, 103.16 mmol, 1.5 eq) was added portionwise under nitrogen. The reaction mixture was stirred for 30 min at room temperature, then at 60° C. for 24 h and poured into ice water (4 L). The aqueous solution was acidified to pH about 2 with conc. HCl and the unreacted starting material extracted with EtOAc/THF=3/1 mixture. Upon adjusting the pH of the water layer to about 9, the product was extracted with 1:1 EtOAc:THF mixture (10×500 mL). The combined extracts were washed with brine, dried over Na2SO4 and solvent evaporated out to afford 22 g (68%) of crude carbazole (84), reasonable pure by LC/MS. It was used in the next step without further purification.

Workup

  1. waitat 60° C. for 24 h
  2. extractionextracted with EtOAc/THF=3/1 mixture
  3. extractionthe product was extracted with 1:1 EtOAc
  4. washThe combined extracts were washed with brine
  5. dry with materialdried over Na2SO4 and solvent
  6. customevaporated out

Sources & evidence

ORD record
ord-85382d8316cb42839341bf5272606fd3
Source dataset
uspto-grants-2015_08
Patent number
US09108916B2

Reaction notes

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