Bimanes. 6. Reactive Halogen Derivatives of syn- and anfi-l,5-Diazabicyclo[3.3.0]octadienediones (9,10-Dioxabimanes)

Edward M. Kosower*, Barak Pazhenchevsky, Hanna Dodiuk, Hannah Kanety, Dov Faust

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

51 Scopus citations

Abstract

The preparation of reactive halogen derivatives of syn- and anti-1,5-diazabicyclo[3.3.0]octadienediones (9,10-dioxabimanes) is accomplished through the intermediate monobromo- and dibromobimanes previously described. Mono- and dihydroxy compounds are produced from the bromides by reaction with wet sodium trifluoroacetate in CH3CN and Me used to prepMe the (a) monochlorides and dichlorides (SOCl2) and (b) the monofluorides and difluorides (Et2NSF3. Monofunctional halides react with nucleophiles (amines, thiols, CMboxylates) to yield direct substitution products, with some reduction accompanying the thiol reaction. Difunctional halides react with excess nucleophile to give direct disubstitution products. syn-Dihalides react with difunctional nucleophiles (actual or potential, e.g., RNH2, S2-, (CN)2C<) to yield a new series of heterocyclic compounds, the “bridged” 9,10-dioxabimanes. The absorption spectra of both syn- and ontt-(XCH2,CH3)B Me mMkedly affected by the nature of X. Most syn-bromobimanes Me nonfluorescent and Me moderately photosensitive, due to thermally reversible isomerizations and additional irreversible reactions. syn-Chlorobimanes are nonfluorescent to weakly fluorescent. syn-Monofluoro- and difluorobimanes Me strongly fluorescent. At 77 K, the halogenated compounds Me all phosphorescent to some extent and many of the syn derivatives are strongly fluorescent.

Original languageEnglish
Pages (from-to)1666-1673
Number of pages8
JournalJournal of Organic Chemistry
Volume46
Issue number8
DOIs
StatePublished - Apr 1981

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