Tin atom → N,N-dimethyl-4-(3-methyl-1H-pyrrolo[3,2-c]pyridin-2-yl)-1-phenylcyclohexanamine

HRID 1095593Notes

Reaction equation

HRID 1095593 reaction equation
[Sn].[CH3:2][N:3]([CH3:26])[C:4]1([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH2:9][CH2:8][C:7]([C:10]2[NH:18][C:17]3[CH:16]=[CH:15][N:14]=[CH:13][C:12]=3[C:11]=2[CH3:19])=[CH:6][CH2:5]1>Br>[CH3:26][N:3]([CH3:2])[C:4]1([C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)[CH2:5][CH2:6][CH:7]([C:10]2[NH:18][C:17]3[CH:16]=[CH:15][N:14]=[CH:13][C:12]=3[C:11]=2[CH3:19])[CH2:8][CH2:9]1

Participants

4

Reactant 2

HCID 5352426Tin atomHCID 57475174N,N-Dimethyl-N-[4-(3-methyl-1H-pyrrolo[3.2-c]pyridin-2-yl)-1-phenylcyclohex-3-enyl]amine

Product 1

HCID 24952602N,N-dimethyl-4-(3-methyl-1H-pyrrolo[3,2-c]pyridin-2-yl)-1-phenylcyclohexanamineYield 4%

Reagents, catalysts & solvents 1

HCID 260Hydrogen BromideSolvent

Procedure

Tin powder (3.00 g, 45 mmol) was added to N,N-Dimethyl-N-[4-(3-methyl-1H-pyrrolo[3.2-c]pyridin-2-yl)-1-phenylcyclohex-3-enyl]amine (525 mg, 1.58 mmol) in HBr/glacial acetic acid (33 per cent strength; 30 ml) in the course of 150 min (vigorous evolution of gas). The reaction mixture became dark brown in colour. The mixture was stirred at room temperature overnight. The reaction mixture was then evaporated to dryness in vacuo and 5 N sodium hydroxide solution (20 ml) was added to the residue. Methylene chloride (20 ml) was added to the pale-coloured suspension and the mixture was stirred for 10 min. Insoluble grey powder was then filtered off. Thereafter, the phases of the filtrate were separated. The aqueous phase was extracted with methylene chloride (2×20 ml) and trichloromethane/ethanol (2×20 ml; 1:1). The combined organic phases were dried with sodium sulfate and the volatile constituents were then removed completely in vacuo. The residue (250 mg of pale yellow powder) was separated by chromatography [silica gel 60 (100 g), ethyl acetate/methanol 1:1 (500 ml); methanol (1,000 ml)]. 20 mg (0.06 mmol; 4%) of N,N-dimethyl-4-(3-methyl-1H-pyrrolo[3,2-c]pyridin-2-yl)-1-phenylcyclohexanamine (non-polar diastereoisomer) and 78 mg (0.41 mmol; 15%) of the polar diastereoisomer were isolated.

Workup

  1. customThe reaction mixture was then evaporated to dryness in vacuo and 5 N sodium hydroxide solution (20 ml)
  2. additionwas added to the residue
  3. additionMethylene chloride (20 ml) was added to the pale-coloured suspension
  4. stirringthe mixture was stirred for 10 min
  5. filtrationInsoluble grey powder was then filtered off
  6. customThereafter, the phases of the filtrate were separated
  7. extractionThe aqueous phase was extracted with methylene chloride (2×20 ml) and trichloromethane/ethanol (2×20 ml; 1:1)
  8. dry with materialThe combined organic phases were dried with sodium sulfate
  9. customthe volatile constituents were then removed completely in vacuo
  10. customThe residue (250 mg of pale yellow powder) was separated by chromatography [silica gel 60 (100 g), ethyl acetate/methanol 1:1 (500 ml); methanol (1,000 ml)]

Sources & evidence

ORD record
ord-8f7259d822d641c390df21505a21ebd9
Source dataset
uspto-grants-2012_03
Patent number
US08138187B2

Reaction notes

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