Hydrochloric Acid → HCID 22929687, compound

HRID 1295936Notes

Reaction equation

HRID 1295936 reaction equation
[Br:1][C:2]1[C:3]([CH2:15][OH:16])=[CH:4][C:5]([N:12]([CH3:14])[CH3:13])=[C:6]([CH:11]=1)[C:7](OC)=[O:8].[OH-].[Na+].Cl.[CH3:20][NH:21]C.O1CCCC1.ON1C2C=CC=CC=2N=N1.C1(N=C=NC2CCCCC2)CCCCC1>O1CCCC1.CO.C(#N)C>[CH3:20][NH:21][C:7](=[O:8])[C:6]1[CH:11]=[C:2]([Br:1])[C:3]([CH2:15][OH:16])=[CH:4][C:5]=1[N:12]([CH3:14])[CH3:13]

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 10868DicyclohexylcarbodiimideHCID 14798Sodium HydroxideHCID 757711-HydroxybenzotriazoleHCID 22320367Dimethylamine tetrahydrofuranHCID 22929977HCID 22929977, compound

Product 1

HCID 22929687HCID 22929687, compoundYield 103.8%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Procedure

After dissolving the methyl 5-bromo-2-(dimethylamino)-4-(hydroxymethyl)benzoate (1.179 g, 4.1 mmol) in a tetrahydrofuran (10 ml)-methanol (10 ml) mixed solvent, a 1 N sodium hydroxide aqueous solution (9.8 ml, 9.8 mmol) was added and the mixture was heated to reflux for 4 hours. Next, 5 N hydrochloric acid (9.8 ml, 9.8 mmol) was added and the reaction mixture was concentrated under reduced pressure. Acetonitrile was added to the residue and the mixture was concentrated under reduced pressure, and then the same procedure was repeated twice. Acetonitrile (20 ml), a 2.0 M dimethylamine-tetrahydrofuran solution (4.1 ml, 8.2 mmol), 1-hydroxybenztriazole (1.11 g, 8.2 mmol) and dicyclohexylcarbodiimide (1.69 g, 8.2 mmol) were added to the residue in that order and the mixture was stirred at room temperature for 20 hours. The insoluble portion was filtered off, the reaction mixture was concentrated under reduced pressure, ethyl acetate was added and the mixture was filtered through alumina. The filtrate was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (solvent: n-hexane-ethyl acetate) to yield the title compound (1.222 g) as a white solid. (100% yield)

Workup

  1. additionmixed solvent
  2. temperaturethe mixture was heated
  3. temperatureto reflux for 4 hours
  4. concentrationthe reaction mixture was concentrated under reduced pressure
  5. additionAcetonitrile was added to the residue
  6. concentrationthe mixture was concentrated under reduced pressure
  7. filtrationThe insoluble portion was filtered off
  8. concentrationthe reaction mixture was concentrated under reduced pressure, ethyl acetate
  9. additionwas added
  10. filtrationthe mixture was filtered through alumina
  11. concentrationThe filtrate was concentrated under reduced pressure
  12. customthe residue was purified by silica gel column chromatography (solvent: n-hexane-ethyl acetate)

Sources & evidence

ORD record
ord-9b7dbd3403da4eb1982ab43444158c0b
Source dataset
uspto-grants-2007_07
Patent number
US07244730B2

Reaction notes

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