Tungsten(VI) Oxide-Chlorosulfuric Acid

WO3-ClSO3H
(WO3)

[1314-85-8]  · O3W  · Tungsten(VI) Oxide-Chlorosulfuric Acid  · (MW 231.85) (ClSO3H)

[7790-94-5]  · ClHO3S  · Tungsten(VI) Oxide-Chlorosulfuric Acid  · (MW 116.53)

(induces the coupling of a-hydroxy peroxides and epoxides, forming 1,2,4-trioxane derivatives1)

Alternate Name: tungsten(VI) oxide-chlorosulfonic acid.

Physical Data: WO3: mp 1473 °C; d 7.16 g cm-3; yellow crystals. ClSO3H: bp 151-152 °C/755 mmHg; d 1.753 g cm-3.

Solubility: WO3: sol hot alkali; slightly sol HF. ClSO3H: sol CHCl3, CH2Cl2; reactive to many organic functional groups.

Form Supplied in: WO3: yellow solid. ClSO3H: neat liquid.

Handling, Storage, and Precautions: ClSO3H: reacts violently with water and alcohols; an oxidizer; corrosive.

Synthesis of 1,2,4-Trioxane Derivatives.

Coupling of a-hydroxy peroxides and epoxides in the presence of tungsten(VI) oxide and Chlorosulfonic Acid catalyst leads to the synthesis of 1,2,4-trioxane derivatives, accompanied by the ketone derived from the hydroperoxide (eq 1).1 Overall yields of 1,2,4-trioxane derivative are generally in the range of 30-60%. Epoxides tested in this reaction include cyclohexene oxide, styrene oxide, and 1,1-diphenylethylene oxide. The a-hydroxy peroxides are generated from carbonyl compounds and 30% Hydrogen Peroxide, and used without further purification. Examples tested include a-hydroxy hydroperoxides derived from decanal, benzaldehyde, and cyclohexanone. For a listing of other preparations of 1,2,4-trioxane derivatives, see Jefford et al.2


1. Miura, M.; Nojima, M.; Kusabayashi, S. CC 1981, 581.
2. Jefford, C. W.; Currie, J.; Richardson, G. D.; Rossier, J.-C. HCA 1991, 74, 1239.

James W. Herndon

University of Maryland, College Park, MD, USA



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