65855-34-7

Upstream product

• 92-83-1 xanthene 
• 126179-52-0 1-benzoyl-2-tert-butyl-2-phenylaziridine 
• 86-73-7 9H-fluorene 
• 613-31-0 9,10-dihydroanthracene 
• 136175-22-9 2-tert-butyl-2-phenyl-1-(4-tolylsulfonyl)aziridine 

Downstream Products

• 136175-22-9 2-tert-butyl-2-phenyl-1-(4-tolylsulfonyl)aziridine 
• 126179-55-3 N-(3,3-dimethyl-2-phenylbutyl)benzamide 
• 136175-25-2 9-<3,3-dimethyl-2-phenyl-2-(4-tolylsulfonamido)butyl>-9,10-dihydroanthracene 
• 126179-52-0 1-benzoyl-2-tert-butyl-2-phenylaziridine 

Relevant academic research and scientific papers

Reactions of N-acylaziridines with sodium metal and sodium naphthalenide. Elimination of olefines

Reactions of N-acylaziridines 1a-g (N-benzoyl except 1d) with sodium or naphthalenide N.- in THF provide a variety of products that usually arise via the aziridino ketyls 2. Homolytic ring opening of 2 generates the amidatoalkyl radicals 3. Only with a very short reaction time were small amounts of benzil or benzoylnaphthalenes obtained indicating a reversible trapping of 2 by dimerization or coupling with N.-. Homolysis of 2 produced always the more stable 3 apart from reactions of monomethylaziridines 1c,d where the primary radical i-3c,d is kinetically favoured. The amides R1CONHCHR4CHR2R3 (9, isopropylamides i-9c,d from 1c,d) were usually the main products. 9 arise from 3 either by H atom abstraction from THF (probably in sodium metal runs) or by reduction of 3 to carbanions 5 that abstract a proton from THF (N.- runs). Addition of 5a (R2-4 = H) to 1a gives finally the ketone 8a. Self reaction of primary radical 3a is dimerization. Self reaction of tertiary or secondary radicals is disproportionation when an allylamide arises. This isomerizes to an enamide unless it is conjugated. R2R3C=CHR4 and R1CONH2 arise (probably) always. The mechanism, possibly a cyclic process of anion 6, is not clear. Johann Ambrosius Barth 1996.

Reactions of Carbanions with two Sterically Demanding 1-Benzoylaziridines: SET, SN2, Carbonyl Attack.

Reactions of 2-phenyl (1a) and 2-benzyl (1b) 1-benzoyl-2-butylaziridines with carbanions X-, AH-, and Fl- of xanthene, dihydroanthracene and fluorene always form N-(2-butylethyl)-benzamides carrying phenyl (9a) or benzyl (9b).This reductive ring opening indicates an SET mechanism with aziridino ketyls 6a,b as intermediates.Nucleophilic ring opening (SNs) is found only with the carbanion of the lowest reducing power: Fl- 5a,b (62percent, 14percent).These two mechanisms cleave different bonds, a finding without precedence in SN2/SET competitions.Carbonyl addition resulting in benzoyl transfer to xanthene, dihydroanthracene or fluorene is usually also observed.It is the main reaction with X- and 1a.The highest yields of 9a,b are obtained with AH- since a special inner-sphere SET is available.

N-S Cleavage Is Faster Than Homolytic Ring Opening in Single-Electron Transfer to Some N-Sulfonylaziridines. Competition between SN2 and SET

The radical anions of the N-sulfonylaziridines, 1a,b and 3 undergo N-S cleavage in place of homolytic ring opening as is demonstrated by reactions with anthracenide A*-.Nucleophilic ring opening of the sulfonylaziridines 1a,b and 3 by the carbanions AH-, X-, and Fl- of dihydroanthracene, xanthene, and fluorene, respectively, proceeds with the expected regioselectivity and is slow enough to allow some competition by a single-electron transfer (SET) initiated N-S cleavage, which provides the desulfonated aziridines and bixanthenyl X-X or bifluorenyl Fl-Fl, respectively.The SET path is favored by light.The competition is in favor of SET to the exclusion of the nucleophilic opening when trityl anion reacts with 1a.The twice-found byproducts 11 and 12 require the azirine intermediate 15, which is, at least formally, generated by elimination of TsH from 1a in a non-SET reaction.