85809-29-6

Upstream product

• 21384-58-7 2,2-dimethylaziridin-1-yl-phenylmethanone 
• 14314-91-1 9,10-Dihydroanthracenylanion 
• 120-12-7 anthracene 

Relevant academic research and scientific papers

Aziridines. 76: Neglected aspects of anthracenide (anthracenidyl) chemistry - Reactions with two N-benzoylaziridines

Reaction of anthracenide A.- with N-benzoylaziridines 1a,b forms charged radicals 3a,b by single electron transfer and homolytic ring opening. Reactions follow that are known or expected as e.g. coupling with position 9 of A.- forming dihydroanthracene anions 9a,b that yield amidoethylated dihydroanthracenes 10a,b, or react with 1a,b giving finally 9,10-bis-amidoethylated dihydroanthracenes 11a,b. Results depend on experimental conditions and on the counter ions Na+ or Li+. Coupling is not regiospecific: contributions by positions 2 and 1 reach 29% or 4%, respectively, of total coupling with the primary radical 3a; much higher contributions are possible with Li. Product 21s (probably 3,3′-disubstituted tetrahydrobianthryl) may arise by hydrogen detachment from the first intermediate (29) of coupling with position 2 and dimerization of the formed 2-substituted A.- (30). Coupling products may be fully aromatized or may be hydroxylated in one of the benzylic positions. With counter ion Li+ a non-SET reaction of 1a with the dimer of A.- is indicated by the isolation of 9-benzoyl-dihydroanthracene 15 and by 19% yield of 16a (aromatized 10a). Reaction of 3b with anthracene is indicated by 10,10′-disubstituted tetrahydrobianthryl 37. Wiley-VCH Verlag GmbH, 2000.

Highly Regioselective Ring Cleavage of N-Acylaziridines by "Anthracene Hydride" (Anion of 9,10-Dihydroanthracene). Intermediacy of a Carbonyl Adduct. Influence of Nitrogen Inversion on the Ring Opening?

Anthracene hydride AH- reacts with N-acylaziridines by reductive opening of the aziridine ring and/or amidoethylation of AH-.When the two aziridine carbons are differently substituted, in both reactions only that bond is broken which can form the more stable carbon radical quite in accord with the intermediacy of a radical anion (ketyl) 14 and with the known homolytic cleavage of 14 forming the radical 15.The extra electron in 14 is provided by AH- being oxidized to the radical AH., which can react with 15 either by radical combination or by hydrogen transfer.The reaction of AH- with N-aroylaziridines can be interrupted at the stage of the carbonyl adduct 5 as is shown by the isolation of the ketones 7a,b.So, 5 (R4 = aryl) is considered to be in equilibrium with the radical pair AH./14.The conversion of 5 into the final products progresses as expected from its structure apart from the observed retardation by a phenyl substituent in the aziridine ring (3a, 4a).This retardation is tentatively explained by a hypothesis assuming ring opening of 14 to occur in the transition state of nitrogen inversion.The anion X- of xanthene resembles AH- in its reactivity.Both carbanions react with N-sulfonylaziridines as expected from an SN2 mechanism.

NUCLEOPHILIC CLEAVAGE OF 2,2-DIMETHYLAZIRIDINES: COMPETITION BETWEEN SN2 AND POSTULATED "SET" MECHANISM.

Regioselectivity of nucleophilic attack on 2,2-dimethylaziridines depends on the degree of leaving group activation: in highly activated aziridines it occures at the methylene carbon and in less activated at the tertiary carbon.This latter abnormal ring opening is explained by an SET mechanism.