2-Methyl-3-butyn-2-ol → 4-(1,1-Dimethyl-2-propynyloxy)anisole

温度

0 °C

To a solution of 4-methoxyphenol (15.0 g, 121 mmol) in acetonitrile (75 mL), 1,8-diazabicyclo[5.4.0]undecene (23.9 g, 157 mmol) was added under ice cooling and the resulting mixture was stirred at 0° C. for 30 minutes (Solution 1). To a solution of 2-methyl-3-butyn-2-ol (11.7 g, 139 mmol) in acetonitrile (75 mL), 1,8-diazabicyclo[5.4.0]undecene (23.9 g, 157 mmol) was added under ice cooling, the resulting mixture was stirred at 0° C. for 30 minutes, then trifluoroacetic anhydride (25.4 g, 121 mmol) was added and the resulting mixture was stirred at 0° C. for 30 minutes (Solution 2). Copper (I) chloride (36 mg, 0.36 mmol) was added to Solution 1, and then Solution 2 was added dropwise thereto over 15 minutes. Upon the completion of dropwise addition, the temperature was raised to room temperature, and the mixture was stirred overnight. Upon the completion of the reaction, an aqueous solution of ammonium chloride solution was added to the reaction solution, and the solvent was distilled off under a reduced pressure. An aqeuous solution of 1 mol/L hydrochloric acid was added to the residue, the resulting mixture was extracted with ethyl acetate, the organic phase was washed once with an aqeuous solution of 1 mol/L hydrochloric acid, twice with an aqueous solution of saturated sodium hydrogen carbonate and once with saturated sodium chloride solution. Then, the organic phase was dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was directly used for the subsequent reaction.

1. waitover 15 minutes
2. additionUpon the completion of dropwise addition
3. temperaturethe temperature was raised to room temperature
4. stirringthe mixture was stirred overnight
5. customUpon the completion of the reaction
6. distillationthe solvent was distilled off under a reduced pressure
7. additionAn aqeuous solution of 1 mol/L hydrochloric acid was added to the residue
8. extractionthe resulting mixture was extracted with ethyl acetate
9. washthe organic phase was washed once with an aqeuous solution of 1 mol/L hydrochloric acid, twice with an aqueous solution of saturated sodium hydrogen carbonate and once with saturated sodium chloride solution
10. dry with materialThen, the organic phase was dried over anhydrous magnesium sulfate
11. distillationAfter distilling off the solvent
12. customthe residue was directly used for the subsequent reaction

ORDレコード

ord-7403f6a319a04cea846f0f9d9f80e25e

出典データセット

uspto-grants-2010_01

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US07652008B2