Trifluoroacetic acid → methyl 9-bromo-2,3,4,5-tetrahydro-1H-1-benzoazonin-6-carboxylate

HRID 402280Notes

Reaction equation

HRID 402280 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[N:13](CC3C=CC(OC)=CC=3)[CH2:12][CH2:11][CH2:10][CH2:9][C:8]([C:23]([O:25][CH3:26])=[O:24])=[CH:7][C:6]=2[CH:27]=1.FC(F)(F)C(O)=O>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:13][CH2:12][CH2:11][CH2:10][CH2:9][C:8]([C:23]([O:25][CH3:26])=[O:24])=[CH:7][C:6]=2[CH:27]=1

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 68650162methyl 9-bromo-1-(4-methoxybenzyl)-2,3,4,5-tetrahydro-1H-1-benzoazonin-6-carboxylate

Product 1

HCID 68649852methyl 9-bromo-2,3,4,5-tetrahydro-1H-1-benzoazonin-6-carboxylateYield 82.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of methyl 9-bromo-1-(4-methoxybenzyl)-2,3,4,5-tetrahydro-1H-1-benzoazonin-6-carboxylate (12.5 g) in toluene (62.5 ml) was added trifluoroacetic acid (62.5 ml) and the mixture was stirred under nitrogen atmosphere at 80° C. for 7 hours. After distilling off the solvent under reduced pressure, water was added at 0° C. and the mixture was neutralized with potassium carbonate, and extracted with ethyl acetate. After washing the organic layer with aqueous saturated sodium bicarbonate solution and saturated brine, the resultant was dried with magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (hexane-ethyl acetate=9:1) and recrystallized from hexane:ethyl acetate to give methyl 9-bromo-2,3,4,5-tetrahydro-1H-1-benzoazonin-6-carboxylate (7.4 g) as yellow crystals.

Workup

  1. distillationAfter distilling off the solvent under reduced pressure, water
  2. additionwas added at 0° C.
  3. extractionextracted with ethyl acetate
  4. washAfter washing the organic layer with aqueous saturated sodium bicarbonate solution and saturated brine
  5. dry with materialthe resultant was dried with magnesium sulfate
  6. distillationThe solvent was distilled off under reduced pressure
  7. customthe resulting residue was purified by silica gel column chromatography (hexane-ethyl acetate=9:1)
  8. customrecrystallized from hexane

Sources & evidence

ORD record
ord-12f1ec4218d84aff9c4f3b69d26a4381
Source dataset
uspto-grants-2014_06
Patent number
US08741943B2

Reaction notes

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