This chapter deals with ’activated amides’, i.e. saltlike compounds, imino derivatives of carboxylic acids as well as compounds which formally arise by complete esterification or amidation of carboxylic orthoacids.

Synthesis of Iminium Salts, Orthoesters and Related Compounds

Oxime carbonates have been synthesised and their potential studied as a new class of radical precursor A general synthetic route, avoiding laboratory use of phosgene, was developed Alkyl or aryl 1H-imidazole-1-carboxylates were prepared from the corresponding alcohols and 1,1-carbonyldiimidazole, then reacted with oximes in the presence of base UV photolyses of oxime carbonates released particular N- and O-centred radicals suitable for spectroscopic examination Spiro-cyclisations of alkoxycarbonyloxyl radicals onto aromatic acceptors and 5-exo cyclisations onto alkene acceptors were studied by EPR spectroscopy EPR data also provided insight to the loss of CO2 from alkoxycarbonyloxyl radicals The conformational preferences of 2-oxo-1,3-dioxolan-4-yl-methyl and related radicals were established Modest yields of cyclic carbonates were obtained from preparative scale photolyses

An all-purpose preparation of oxime carbonates and resultant insights into the chemistry of alkoxycarbonyloxyl radicals

A mild, expedient, one-pot trifluoromethanesulfonic anhydride mediated synthesis of N-arylimidates

This chapter presents pyrolysis of nitro and nitroso compounds, hydroxylamines, oxyamines, N-alkoxyammonium hydroxide derivatives, oximes and oxime derivatives, amine N-oxides and nitrones, hydrazines and hydrazones, azo, diazo, azoxy derivatives, and azides derivatives. Among the compounds with pyrolysis presented in more detail are nitromethanes, various other nitroalkanes, nitrobenzene, nitroaromatic compounds with additional functionalities, nitro derivatives of heterocycles, several nitroso compounds, amine N-oxides, nitrones, several hydrazines, and hydrazones.

Pyrolysis of Other Nitrogen-Containing Compounds

A new Cu-catalyzed efficient protocol is described for the transformation of oximes to the corresponding carbonate derivatives. Diisopropyl azodicarboxylate acted as a selective new precursor for the synthesis of oxime carbonates in high yields. The O–H bond cleavage and O–C bond formation occur in the presence of a copper catalyst providing a synthetically useful process, which tolerates a wide range of functional groups.

A copper-catalyzed reaction of oximes with diisopropyl azodicarboxylate: an alternative method for the synthesis of oxime carbonates.

Aryl ketoxime carbonates have been found to undergo decompositions at temperatures ranging from 180–200°C to give carbon dioxide and aryl imino ethers (imidates). This pyrolysis could prove to be a...

P. E. Titus

Papers

Pyrolysis of benzophenone oxime carbonates: a potential route to aryl imino ethers (aryl imidates)

Pyrolysis of benzophenone oxime carbonates- a potential route to aryl imino ethers (aryl imidates)