64398-73-8Relevant academic research and scientific papers
1,3-Dioxolane Formation by Nucleophilic Attack of Diazoalkanes on the Peroxide Bond of 1,2-Dioxetanes
Adam, Waldemar,Treiber, Alexander
, p. 840 - 844 (2007/10/02)
The reaction of the 1,2-dioxetanes 1a-d with the diazoalkanes 2α-η was investigated.The two 3,3-disubstituted (3,3-dimethyl- and 3-(bromomethyl)-3-phenyl) dioxetanes (1a and 1b), trimethyldioxetane (1c) and tetramethyldioxetane (1d) gave with the various diazoalkanes 2 the corresponding 1,3-dioxolanes 3 (insertion products) and/or the dioxetane-derived ketone 4 (fragmentation).Nucleophilic attack by the negatively charged carbon pole of the diazoalkane on the sterically less hindered site of the dioxetane peroxide bond affords the 1,3-dioxolane 3 after cyclization with denitrogenation of the resulting O,N dipole.The O,C dipole, formed by the nucleophilic attack of the negatively charged nitrogen pole on the dioxetane, is proposed as precursor to the ketones 4 through Grob-type fragmentation with regeneration of the diazoalkane.
Reaction of 1,2-dioxetanes with heteroatom nucleophiles: Adduct formation by nucleophilic attack at the peroxide bond
Adam, Waldemar,Heil, Markus
, p. 5591 - 5598 (2007/10/02)
The reactions of 3,3-disubstituted 1,2-dioxetanes 1 with numerous heteroatom nucleophiles, e.g., R2NH, R3N, RSH, R2S, CN-, SCN-, Br-, Cl-, OH-, and O2*-, were investigated. Initial nucleophilic substitution at the sterically less hindered site of the dioxetane peroxide bond leads to addition, deoxygenation, and fragmentation products. The observed SN2 chemistry was substantiated with the dioxetane le because bromide ion displacement by the proximate alkoxide ion site afforded epoxide products. Thus, with anionic nucleophiles the epoxy alcohol 8c was obtained in appreciable amounts, and triethylamine and DABCO gave with 1c exclusively the alkoxyammonium epoxides 4c and 5c. Moreover, the labile alkoxysulfonium epoxide 6c was detected as an intermediate in the deoxygenation of 1c by diphenyl sulfide. From the reaction of 1b-d with secondary amines were isolated the hydroxylamine derivatives 2 and 3, and the cyanide and thiocyanate ions gave with 1c,d five-membered-ring insertion products, namely, the carbonates 9c,d and the cyclic sulfite 10c.
