Sulfuric Acid → 4,4-Dimethyl-3,5,8-trioxabicyclo[5.1.0]octane

To an ice-cold (5°), stirred solution of the dioxepin (II) (12.81 g, 0.1 mole) in aqueous t-butanol (50%; 50 ml) adjusted to pH 6.0 with dilute sulfuric acid, was added t-butyl hypochlorite (11.3 g, 0.105 mole), while the pH was maintained at 6.0. The reaction mixture was allowed to rise to room temperature and stirred for 4 hrs with protection from light. Sodium bisulfite (200 mg) was added to the reaction mixture, followed by 50% aqueous sodium hydroxide to bring the pH to 12. The reaction mixture was heated at 100° for 1 hr and then cooled. The upper t-butanol layer was separated and the aqueous layer was extracted with t-butanol (3×20 ml). The combined organic layers were dried (Na2CO3). Solvent removal, followed by fractional distillation, gave the epoxide product (III) as a colorless oil in ≃80% yield.

1. temperaturewhile the pH was maintained at 6.0
2. customto rise to room temperature
3. temperatureThe reaction mixture was heated at 100° for 1 hr
4. temperaturecooled
5. customThe upper t-butanol layer was separated
6. extractionthe aqueous layer was extracted with t-butanol (3×20 ml)
7. dry with materialThe combined organic layers were dried (Na2CO3)
8. customSolvent removal
9. distillationfollowed by fractional distillation

ORD record

ord-aa741b80156c4fc4b34cf1c2cc2cf44e

Source dataset

uspto-grants-1984_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04439613