tert-Butyl hydroperoxide → (2S-trans)-3-Nonyloxirane Methanol

온도

-20 °C

A suspension of 1.00 g of 4a powdered molecular sieves in 50 ml of dry CH2Cl2 was cooled to 0.° C. under argon. To the cooled suspension was added 308 mg (1.09 mmole) of Ti(OiPr)4 and 356 mg (1.52 mmole) of L(+)diisopropyl tartrate via syringe. The mixture was stirred for 15 min and cooled to -20° C. A solution of tert-butyhydroperoxide in isooctane (3.8M, 4.30 ml, 16.4 mmole) was added slowly to the mixture and the catalyst was allowed to "age" for 30 min at -20° C. A solution fo 2.00 g (10.9 mmole) of E-2-dodecen-1-ol in 10 ml of CH2Cl2 was dried over 3A molecular sieves for 15 min before being added to the mixture slowly, with stirring, at -20°. The solution was then placed in the freezer (-30° C.) and allowed to stand for 24 H. The mixture was warmed to 0° C. and poured into a solution of 1.00 g of citric acid and 3.50 g of FeSO4 in 15 ml H2O. The organic layer was separated and the aqueous layer washed twice with 20 ml of CH2Cl2. The CH2Cl2 layers were combined, dried over MgSO4, filtered and evaporated to yield a sticky white solid. Recrystallization from Et2O: petroleum ether afforded 1.98 g of white solid, mp 62°-4° C. 1H NMR δ3.92 (ddd, 1, J=2.5, 6, 12 Hz), 3.63 (ddd, 1, J=4, 7, 12 Hz), 2.95 (m, 2), 1.69 (dd, 1, J=7, 6 Hz), 1.6-1.2 (m, 16), 0.88 (t, 3, J=6 Hz). Mass Spectra: M-31(-CH2OH)(0.4)169, M(100)55.1.

1. temperaturewas cooled to 0.° C
2. waitthe catalyst was allowed to "age" for 30 min at -20° C
3. dry with materialwas dried over 3A molecular sieves for 15 min
4. additionbefore being added to the mixture slowly
5. stirringwith stirring, at -20°
6. customwas then placed in the freezer (-30° C.)
7. temperatureThe mixture was warmed to 0° C.
8. additionpoured into a solution of 1.00 g of citric acid and 3.50 g of FeSO4 in 15 ml H2O
9. customThe organic layer was separated
10. washthe aqueous layer washed twice with 20 ml of CH2Cl2
11. dry with materialdried over MgSO4
12. filtrationfiltered
13. customevaporated
14. customto yield a sticky white solid
15. customRecrystallization from Et2O

ORD 기록

ord-e2cdb271a7f545f0b07fbaca48b4159e

출처 데이터셋

uspto-grants-1993_03

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US05190969