TY - JOUR
T1 - Bimanes. 23. The Synthesis and Properties of Vinyl-9,10-dioxabimanes
AU - Kosower, Edward M.
AU - Zbaida, David
AU - Baud'huin, Michel
AU - Marciano, Daniele
AU - Goldberg, Israel
PY - 1990/12
Y1 - 1990/12
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=11944268610&partnerID=8YFLogxK
U2 - 10.1021/ja00176a034
DO - 10.1021/ja00176a034
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AN - SCOPUS:11944268610
SN - 0002-7863
VL - 112
SP - 7305
EP - 7314
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 20
ER -