Carbon Dioxide → 4,4-Dimethyl-3,5,8-trioxabicyclo[5.1.0]octane

To an ice-cold (0°-5° C.), stirred solution of the dioxepin (150.0 g, 1.18 mole) in a mixture of t-butanol (250 ml) and water (150 ml) was added, during 1 hr, powdered calcium hypochlorite (59%; 150 g, 0.62 mole), portionwise, with continuous bubbling of carbon dioxide through the solution. After 30 min, aqueous 50% sodium hydroxide (160 g, 2 moles) was added and the suspension was refluxed, with stirring, using an oil bath (100°) for 1.5 hr. The mixture was filtered and the organic layer of the filtrate was separated. The aqueous layer was extracted once with t-butanol (50 ml) and the combined organic layers were washed with brine (3×20 ml). The combined washings were re-extracted once with t-butanol (50 ml). The solvent was removed from the organic layer in a Rotovapor at 70° and 100 mm. The residue was subject to fractional distillation and the product (III) was isolated as a colorless oil. (116.1 g, 68% yield) b.p. 65°-67°/5 mm.

1. additionwas added, during 1 hr
2. temperaturethe suspension was refluxed
3. custom(100°)
4. customfor 1.5 hr
5. filtrationThe mixture was filtered
6. customthe organic layer of the filtrate was separated
7. extractionThe aqueous layer was extracted once with t-butanol (50 ml)
8. washthe combined organic layers were washed with brine (3×20 ml)
9. extractionThe combined washings were re-extracted once with t-butanol (50 ml)
10. customThe solvent was removed from the organic layer in a Rotovapor at 70°
11. distillationThe residue was subject to fractional distillation

ORD record

ord-b14bd3bba56648689ba487e0acb864f7

Source dataset

uspto-grants-1984_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04439613