Formic Acid → Methyl 8-bromo-1-formyl-1,2,3,4-tetrahydro-1-benzoazocine-5-carboxylate

HRID 1928958Notes

Reaction equation

HRID 1928958 reaction equation
[CH:1](O)=[O:2].C(OC(=O)C)(=O)C.[Br:11][C:12]1[CH:13]=[CH:14][C:15]2[NH:22][CH2:21][CH2:20][CH2:19][C:18]([C:23]([O:25][CH3:26])=[O:24])=[CH:17][C:16]=2[CH:27]=1>C1COCC1>[Br:11][C:12]1[CH:13]=[CH:14][C:15]2[N:22]([CH:1]=[O:2])[CH2:21][CH2:20][CH2:19][C:18]([C:23]([O:25][CH3:26])=[O:24])=[CH:17][C:16]=2[CH:27]=1

Participants

5

Reactant 3

HCID 284Formic AcidHCID 7918Acetic AnhydrideHCID 68650133Methyl 8-bromo-1,2,3,4-tetrahydro-1-benzazocine-5-carboxylate

Product 1

HCID 86595586Methyl 8-bromo-1-formyl-1,2,3,4-tetrahydro-1-benzoazocine-5-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
55 °C

Procedure

Formic acid (5.96 ml) was added to acetic anhydride (12.2 ml) at 0° C. and then the mixture was stirred under nitrogen atmosphere at 55° C. for 2 hours. After cooling to 0° C., THF (150 ml) was added, and further a solution of methyl 8-bromo-1,2,3,4-tetrahydro-1-benzoazocine-5-carboxylate (8.5 g) in THF (100 ml) was added dropwise under nitrogen atmosphere. The mixture was returned to room temperature and stirred for 5 hours, after which the solvent was distilled off under reduced pressure. The reaction material was diluted with ethyl acetate, followed by washing with saturated sodium bicarbonate, water and saturated brine. The resultant was dried with magnesium sulfate, after which the solvent was distilled off under reduced pressure, and the resulting residue was washed with hexane to give methyl 8-bromo-1-formyl-1,2,3,4-tetrahydro-1-benzoazocine-5-carboxylate (8.3 g) as colorless crystals.

Workup

  1. temperatureAfter cooling to 0° C.
  2. customwas returned to room temperature
  3. stirringstirred for 5 hours
  4. distillationafter which the solvent was distilled off under reduced pressure
  5. additionThe reaction material was diluted with ethyl acetate
  6. washby washing with saturated sodium bicarbonate, water and saturated brine
  7. dry with materialThe resultant was dried with magnesium sulfate
  8. distillationafter which the solvent was distilled off under reduced pressure
  9. washthe resulting residue was washed with hexane

Sources & evidence

ORD record
ord-bb53caa7a7594b2782e9696908f9960d
Source dataset
uspto-grants-2012_05
Patent number
US08183273B2

Reaction notes

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