title: Selective synthesis of cyclic peroxides from triketones and H2O2.
abstract: A method for the assembly of tricyclic structures containing the peroxide, monoperoxyacetal, and acetal moieties was developed based on the acid-catalyzed reaction of β,δ-triketones with H(2)O(2). Tricyclic compounds are formed selectively in yields from 39% to 90% by the reactions with the use of large amounts of strong acids, such as H(2)SO(4), HClO(4), or HBF(4), which act both as the catalyst and as the co-solvent. The reaction is unusual in that, despite the diversity of possible peroxidation pathways giving cyclic compounds and oligomers, the reaction proceeds with high selectivity and produces tricyclic peroxides via the monoperoxidation of the carbonyl groups in the β-positions and the transformation of the δ-carbonyl group into the acetal one. The syntheses are scaled up to tens of grams, and the resulting peroxides can be easily isolated from the reaction mixture.
authors.affiliation: N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation. terentev@ioc.ac.ru
authors.forename: Alexander O
authors.initials: AO
authors.lastname: Terent'ev
authors.forename: Ivan A
authors.initials: IA
authors.lastname: Yaremenko
authors.forename: Vladimir V
authors.initials: VV
authors.lastname: Chernyshev
authors.forename: Valery M
authors.initials: VM
authors.lastname: Dembitsky
authors.forename: Gennady I
authors.initials: GI
authors.lastname: Nikishin
mesh_terms: D000080:Acetals / Q000737:chemistry*; D001881:Borates; D001888:Boric Acids / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D006575:Heterocyclic Compounds, 3-Ring / Q000138:chemical synthesis* / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D010472:Perchlorates / Q000737:chemistry; D010545:Peroxides / Q000138:chemical synthesis* / Q000737:chemistry; D012997:Solvents; D013464:Sulfuric Acids / Q000737:chemistry
chemical_list: D000080:Acetals; D001881:Borates; D001888:Boric Acids; D006575:Heterocyclic Compounds, 3-Ring; D007659:Ketones; D010472:Perchlorates; D010545:Peroxides; D012997:Solvents; D013464:Sulfuric Acids; D006861:Hydrogen Peroxide; C098759:fluoroboric acid; C033158:sulfuric acid