Bimanes. 23. The Synthesis and Properties of Vinyl-9,10-dioxabimanes

Edward M. Kosower*, David Zbaida, Michel Baud'huin, Daniele Marciano, Israel Goldberg

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Syntheses and useful reactions of syn-vinylbimanes are reported. The precursors are syn-(ethyl, methyl)bimane (4,6-diethyl-3,7-dimethyl-1,5-diazabicyclo[3.3.0]octa-3,6-diene-2,8-dione) (syn-(CH3CH2,CH3)B) (2) and iyn-(ethyl, chloro)bimane (4,6-diethyl-3,7-dichloro-1,5-diazabicyclo[3.3.0]octa-3,6-diene-2,8-dione) (syn-(CH3CH2,Cl)B) (4). Bromination of 2 yields the 1-bromoethyl derivative (syn-(CH3CHBr, CH3)(CH3CH2,CH3)B) and both diastereomers of the bis-1-bromoethyl derivative (syn-(CH3CHBr, CH3)B) (Radkowsky; Kosower; Eisenberg; Goldberg J. Am. Chem. Soc. 1986,108,4532-4541). Elimination of HBr (Et3N/CH3CN) leads to monovinylbimane (syn-(CH2=CH, CH3)(CH3CH2,CH3)B) and divinylbimane {syn-(CH2=CH, CH3)B), respectively. syn-(CH3CH2,CH3)(CH3,CH3)B may be converted to syn-(CH2=CH, CH3)(CH3,CH3)B. Vinylbimanes can also be prepared via 2-hydroxyethylbimanes from paraformaldehyde and the anion of syn-(CH3,CH3)B. The novel reaction of pure bromine with syn-(ethyl, chloro)bimane (4) or syn-(methyl, chloro)bimane (13) yields monobromo or dibromo derivatives in high yields. The (1-bromoethyl, chloro)bimanes are converted into (vinyl, chloro)bimanes via phenyl thioethers, oxidation to sulfoxides, and thermal elimination. The synthesis of bimane precursors, chloropyrazolinones, is improved through removal of HC1 with f-BuOH and dry MgSO4. Vinylbimanes are stable, with UV absorption maxima similar to those of the corresponding ethylbimanes; the fluorescence maxima are at longer wavelengths, showing that excited state interaction of vinyl groups with the bimane ring is greater than in the ground state. Nucleophiles (water, chloride, amines, and bisulfite ion) add to give good yields of 2-adducts. The sulfonate (sulfite adduct) and Vilsmeier reagent ((CH3)2N+=CHC1,C1-) react to form the sulfonyl chloride. The latter reacts with amines to yield fluorescent derivatives useful for identification. Tricyclic bimanes with an eight-membered ring, are readily obtained by bis addition of bifunctional nucleophiles (CH3NH2,S2-). Dialkyl malonate anions yield both tricyclic monoadducts and bisadducts. The crystal structure of M-(2-thiatrimethylene)-syn-(methylene, methyl)-9,10-dioxabimane is reported.

Original languageEnglish
Pages (from-to)7305-7314
Number of pages10
JournalJournal of the American Chemical Society
Issue number20
StatePublished - Dec 1990


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