New reactions of phenyl(trihalomethyl)mercury compounds. Dihalocarbene addition to azodicarboxylate esters

Synthesis and Reactivity of C-Heteroatom-Substituted Aziridines

“…Organomercury esters and organomercury halides serve as precursors of fluoroethoxycarbonyl and dihalocarbenes, respectively. These intermediates react with the carbon−nitrogen double bond of aryl and alkylcarbonimidoyl chlorides 168 and 171 to form C -halogenated aziridines 169 , 170 , and 172 (Schemes −54). − Recently, KF/Al 2 O 3 is reported to promote the generation of dichlorocarbene. A number of 2,2-dichloroaziridines have been synthesized from the reactions of N -benzylideneamines with chloroform in aqueous acetonitrile (Scheme ) …”

Ylide formation from the reaction of carbenes and carbenoids with heteroatom lone pairs

“…Ylides which are not substituted with stabilizing groups frequently cyclize to form episulfides. One of the earliest examples of episulfide formation involve the use of hexafluoropropene oxide (283) as a source of difluorocarbene. 137 Treatment of this material with thiocarbonyl fluoride gave rise to the transient thiocarbonyl ylide 284 which spontaneously cyclized to produce tetrafluorothiirane (285).…”

“…Treatment The decomposition of phenyl(bromodichloromethyl)mercury in the presence of azodicarboxylate ester gave a compound which was identified as structure 650. 283 The formation of this material seemingly involves azomethine ylide generation followed by cyclization producing intermediate 649 4-Azahomoadamantane derivatives are known as potential biologically active compounds and several synthetic routes to this skeleton have been reported. 284 The reaction of 5-methyl-4-azahomoadamant-4-ene (651) with dichlorocarbene resulted in the formation of 4-formyl-5-methylene-4-azahomoadamantane (654) in 66% yield.…”

Haloaziridines. 2. Synthesis and pyrolysis of some gem-dichloroaziridines

“…13 Recently, Seyferth et al have reported the use of these reagents for the addition of dichlorocarbene to the C=N, C=S, C=0, and N=N. 14 Seyferth reported the reaction of benzylideneaniline(la) withphenyl(bromodichloromethyl)mercury lead to tar formation in benzene15 and a trace of 2a and tar in carbon tetrachloride. 5 The inability of this reagent to convert the imine to the gem-dichloroaziridine was attributed by Seyferth to nucleophilic attack of the imine ni- trogen at mercury giving rise to tar formation.…”