F. Gavina

Non concerted pathways in the generation of dehydroarenes by thermal decomposition of diaryliodonium carboxylates.

Abstract 1,3-Dehydrobenzene, 1,4-dehydrobenzene and 2,3-dehydronaphthalene are generated in the thermal decomposition of appropriate diaryliodonium carboxylates as demonstrated by the use of the three phase test. Intermediate species C6H4CO2 for m- and p-benzyne and C10H6CO2 for 2,3-naphthalyne have been unambiguously trapped in the same way, showing how non-concerted processes are the main pathway for generation of arynic intermediates from those iodonium salts.

Arynic species; effect of substituents on the reactivity of monosubstituted dehydrobenzenes

Abstract Evidence is presented demonstrating the existence of free dehydrobenzenes in the thermal decomposition of diaryliodonium-2-carboxylates, and that o-benzyne itself and its 4-methyl-, 4-chloro-,4-bromo- and 4-nitro-derivatives are generated from insoluble polymer-bound precursors and trapped by a second solid phase in Diels-Alder reactions. Lifetimes for these elusive species are determined.

1,1-Di-iodoalkenes from aldehydes and triphenylphosphine-carbon tetraiodide

The Wittig-like transformation of aliphatic and aromatic aldehydes into 1,1-di-iodoalkenes can be achieved with triphenylphosphine–carbon tetraiodide.

Arynic species II: Tosyl and triazene as leaving group in the generation of arynes from polymer-bound reagents

Abstract o-Benzyne and its 4-methyl, 4-chloro and 4-bromo-derivatives were generated in the thermal decomposition of two new kinds of polymer-bound precursors: 1(2-carboxyaryl)triazenes and 2-carboxyaryl-sulphonates. New kinds of trapping polymers for these elusive species are also presented.

Generation of an unsaturated β-lactam intermediate from a polymeric precursor☆

Abstract A polymeric phase able to generate 1-azetin-4-one was prepared. The free existence of the reactive intermediate was demonstrated by trapping it with a nucleophilic polymeric agent. The mechanism of this reaction was established.

Evidence for the formation of 1,3- and 1,4-dehydrobenzenes in the thermal decomposition of diaryliodonium-carboxylates

Abstract Abstract: Generation of m- and p-benzynes in decomposition of diaryliodonium- 3- and 4-carboxylates is demonstrated by three-phase method.

Generation of monosubstituted o-benzynes from polymeric reagents via heterolytic fragmentations

Abstract Generation of four 4-substituted o-benzynes by heterolytic — fragmentation reactions is demonstrated.

Thermogravimetric studies of polymeric reagents: a polymeric o-benzyne precursor

Abstract Thermogravimetry for the study of polymeric reagents is described and used to demonstrate the thermic behavior of a polymeric o-benzyne precursor

Enhanced transport through binding cooperativity in a circulating system

Abstract Allosteric cooperativity in a multiphase circulating system is shown to enhance ion transport when long contact times are involved.

Polymer-bound precursors of diimine: Pericyclic reactions☆

Abstract Diimine has been generated from two insoluble polymeric precursors: polymer-bound sulfonyl hydrazine and poly(phenylsulfonyllactic) hydrazide. The reducing behaviour of these resins is presented. Pericyclic ene- and Diels-Alder reactions of the produced diimine were also studied.