Hydrochloric Acid → HCID 85431747, compound

HRID 983664Notes

Reaction equation

HRID 983664 reaction equation
[CH:1]([C:3]1[CH:17]=[C:16]([N+:18]([O-:20])=[O:19])[CH:15]=[CH:14][C:4]=1[N:5]([CH2:7][CH2:8][CH2:9][CH2:10][C:11]([OH:13])=[O:12])[CH3:6])=O.[C:21](=O)([O-])[O-].[K+].[K+].CI.CN(C=O)C.C(=O)(OC)OC.C[O-].[Na+].Cl>CN(C=O)C.CO.CCCCCC.C(OCC)(=O)C>[CH3:21][O:13][C:11]([C:10]1[CH2:9][CH2:8][CH2:7][N:5]([CH3:6])[C:4]2[CH:14]=[CH:15][C:16]([N+:18]([O-:20])=[O:19])=[CH:17][C:3]=2[CH:1]=1)=[O:12]

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 12021Dimethyl CarbonateHCID 10942334Sodium MethoxideHCID 11346512HCID 11346512, compoundHCID 86587335iodomethane DMF

Product 1

HCID 85431747HCID 85431747, compoundYield 78%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6228DimethylformamideSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

To a solution of 5-(2-formyl-4-nitro-N-methylanilino)pentanoic acid (3.0 g) in DMF (8.1 ml), potassium carbonate (1.6 g) and a solution of methyl iodide/DMF (1.8 g/1 ml) were added at room temperature, and the resulting mixture was stirred further for 2 hours. To the mixture, dimethyl carbonate (18 ml) and subsequently a solution of 28% sodium methoxide in methanol (5.0 g) were added and the resulting mixture was stirred at 50° C. for 2.5 hours. The mixture was allowed to cool to room temperature, and neutralized with 1N hydrochloric acid. After ethyl acetate extraction, the organic layer was washed with saturated salt water, dried over anhydrous sodium sulfate, and concentrated. The concentrate was redissolved in hot isopropyl alcohol [IPA], and the solution was allowed to cool to room temperature, stirred at room temperature further for 1 hour, and at ice temperature for 0.5 hours. The precipitated crystal was collected by filtration, and washed with IPA. The crystal was purified by silica gel column chromatography (n-hexane/ethyl acetate=2/1 to 1/1), and subsequent concentration of the appropriate eluate gave yellow crystal of 8-nitro-1-methyl-1,2,3,4-tetrahydro-1-benzazocin-5-carboxylic acid methylester (2.3 g, yield 78%).

Workup

  1. stirringthe resulting mixture was stirred at 50° C. for 2.5 hours
  2. extractionAfter ethyl acetate extraction
  3. washthe organic layer was washed with saturated salt water
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated
  6. dissolutionThe concentrate was redissolved in hot isopropyl alcohol [IPA]
  7. temperatureto cool to room temperature
  8. stirringstirred at room temperature further for 1 hour
  9. waitat ice temperature for 0.5 hours
  10. filtrationThe precipitated crystal was collected by filtration
  11. washwashed with IPA

Sources & evidence

ORD record
ord-5608770b2e5d4485b54660b3e1679a46
Source dataset
uspto-grants-2005_03
Patent number
US06864367B2

Reaction notes

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