Hydrochloric Acid → methyl N-[2-chloro-5-(3-methoxy-3-methyl-1-butynyl)benzyl]carbamate

HRID 427249Notes

Reaction equation

HRID 427249 reaction equation
[Cl:1][C:2]1[CH:13]=[CH:12][C:11]([C:14]#[C:15][C:16]([OH:19])([CH3:18])[CH3:17])=[CH:10][C:3]=1[CH2:4][NH:5][C:6](=[O:9])[O:7][CH3:8].[Cl-].[Ca+2].[Cl-].Cl.[CH3:24][O-].[Na+]>C1(C)C=CC=CC=1.CO.[Cu]I.[Cu].O>[Cl:1][C:2]1[CH:13]=[CH:12][C:11]([C:14]#[C:15][C:16]([O:19][CH3:24])([CH3:17])[CH3:18])=[CH:10][C:3]=1[CH2:4][NH:5][C:6](=[O:9])[O:7][CH3:8]

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 5284359Calcium ChlorideHCID 10942334Sodium MethoxideHCID 15483920methyl N-[2-chloro-5-(3-hydroxy-3-methyl-1-butynyl)benzyl]carbamate

Product 1

HCID 15483922methyl N-[2-chloro-5-(3-methoxy-3-methyl-1-butynyl)benzyl]carbamateYield 82.6%

Reagents, catalysts & solvents 5

HCID 23978CopperCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 887MethanolSolventHCID 962WaterSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

0.60 g of methyl N-[2-chloro-5-(3-hydroxy-3-methyl-1-butynyl)benzyl]carbamate was dissolved in 10 ml of toluene. This solution was added at 0° C. to a mixture comprising 0.12 g of calcium chloride, 0.08 g of copper(I) iodide, 0.01 g of copper and 10 ml of concentrated hydrochloric acid, followed by stirring at 0° C. for 5 hours. This solution was poured into water and extracted with ethyl acetate, followed by drying over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was dissolved in 10 ml, of methanol. To this solution, 0.50 g of sodium methylate (28 wt % methanol solution) was added at room temperature, followed by stirring at room temperature for 24 hours. The reaction mixture was poured into water and extracted with ethyl acetate, followed by drying over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified with silica gel column chromatography to obtain 0.52 g of methyl N-[2-chloro-5-(3-methoxy-3-methyl-1-butynyl)benzyl]carbamate as a brown viscous liquid.

Workup

  1. extractionextracted with ethyl acetate
  2. dry with materialby drying over anhydrous magnesium sulfate
  3. distillationThe solvent was distilled off under reduced pressure
  4. customthe obtained crude product
  5. stirringby stirring at room temperature for 24 hours
  6. extractionextracted with ethyl acetate
  7. dry with materialby drying over anhydrous magnesium sulfate
  8. distillationThe solvent was distilled off under reduced pressure
  9. customthe residue was purified with silica gel column chromatography

Sources & evidence

ORD record
ord-295b57c1a31a45b8be65cd46c174eb80
Source dataset
uspto-grants-2001_11
Patent number
US06313071B1

Reaction notes

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