Dichloromethane → 4-Methacryloyloxy-4-methyltetrahydropyran

Temperature

3.5 °C

A three-necked flask having an inner volume of 100 mL, which was equipped with a thermometer, was charged with 3.48 g (30.0 mmoles) of 4-hydroxy-4-methyltetrahydropyran and 30.0 g of methylene chloride, and the inside of the flask was purged with nitrogen. This mixed solution was cooled with ice water; 4.40 mL (45.0 mmoles) of methacryloly chloride was subsequently added; and 6.27 mL (45.0 mmoles) of triethylamine was further added dropwise slowly while maintaining the temperature of the reaction solution at 2 to 5° C. After completion of the dropwise addition, stirring was continued at 4 to 5° C. for 3 hours. 20 mL of water and 20 mL of a saturated sodium hydrogencarbonate aqueous solution were successively added slowly to the obtained reaction mixed solution, and after stirring for a while, the mixture was allowed to stand, thereby separating it into an aqueous layer and an organic layer. The aqueous layer was extracted twice with 30 mL of methylene chloride; the extract was combined with the foregoing organic layer; the mixture was washed once with 10 mL of saturated salt water, dried over anhydrous magnesium sulfate and then concentrated in vacuo; and the obtained residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=8/1 (volume ratio)), thereby obtaining 3.03 g (16.45 mmoles) of 4-methacryloyloxy-4-methyltetrahydropyran having the following physical properties as a colorless transparent liquid (purity: 99%, yield: 55%).

1. customA three-necked flask having
2. customan inner volume of 100 mL, which was equipped with a thermometer
3. customthe inside of the flask was purged with nitrogen
4. temperatureThis mixed solution was cooled with ice water
5. addition4.40 mL (45.0 mmoles) of methacryloly chloride was subsequently added
6. additionAfter completion of the dropwise addition
7. additionmixed solution
8. stirringafter stirring for a while
9. customseparating it into an aqueous layer
10. extractionThe aqueous layer was extracted twice with 30 mL of methylene chloride
11. washthe mixture was washed once with 10 mL of saturated salt water
12. dry with materialdried over anhydrous magnesium sulfate
13. concentrationconcentrated in vacuo
14. customand the obtained residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=8/1 (volume ratio))

ORD record

ord-995b875519a64414a668ae385ee0631c

Source dataset

uspto-grants-2011_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07867690B2