Ethyl Acetate → HCID 13407681, compound

Temperature

-78 °C

47.3 g (0.17 mole) of titanium (IV) isopropoxide and 19 g (0.17 mole) of dimethylethylvinylsilane were placed in a 500 ml three-neck round bottom flask cooled to −78° C., and 0.34 mole of an isopropylmagnesium chloride Grignard solution was gradually added thereto for 2 hours. The reaction solution thus obtained was warmed to −50° C. and then vigorously stirred for 2 hours. 14.7 g (0.17 mole) of ethyl acetate was gradually added over 30 min, while the reaction solution was maintained at −50° C. The reaction solution was warmed to −20° C., vigorously stirred for 1 hour, warmed to 0° C., and then vigorously stirred for another 1 hour. Finally, the reaction solution was warmed to room temperature and 60 mL of saturated brine was added to the solution. The resulting solution was filtered through Celite which was then thoroughly washed once more with 100 mL of ether. The filtrate thus obtained was dried over anhydrous magnesium sulfate (MgSO4), and was concentrated by the evaporation of solvent under reduced vacuum at a low temperature of 30° C. or less. The resulting concentrate was distilled under vacuum (40-65° C./0.1 mmHg) to obtain 14.6 g (0.092 mole, yield: 54%) of 1-methyl-1-hydroxy-2-(trimethylsilyl)cyclopropane as a mixture of trans and cis isomers in a ratio of about 3:1. Although they may be used directly without any further purification, the trans and cis isomers were separated by silica gel chromatography and their structures were confirmed.

1. customThe reaction solution thus obtained
2. temperaturewas warmed to −50° C.
3. temperaturewas maintained at −50° C
4. temperatureThe reaction solution was warmed to −20° C.
5. stirringvigorously stirred for 1 hour
6. temperaturewarmed to 0° C.
7. stirringvigorously stirred for another 1 hour
8. temperatureFinally, the reaction solution was warmed to room temperature
9. filtrationThe resulting solution was filtered through Celite which
10. washwas then thoroughly washed once more with 100 mL of ether
11. customThe filtrate thus obtained
12. dry with materialwas dried over anhydrous magnesium sulfate (MgSO4)
13. concentrationwas concentrated by the evaporation of solvent under reduced vacuum at a low temperature of 30° C. or less
14. concentrationThe resulting concentrate
15. distillationwas distilled under vacuum (40-65° C./0.1 mmHg)

ORD record

ord-73c304c9296d4051abe0163487ab26b8

Source dataset

uspto-grants-2012_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08314051B2