The chemistry of some novel nitrogen-containing spirocyclohexadienes

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Southcott, M.R., 1988. The chemistry of some novel nitrogen-containing spirocyclohexadienes. PhD, Nottingham Trent University.

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Abstract

The work described in this thesis involves nitrogen-containing spirocyclohexadienes as isolated products or as reaction intermediates.

In the first Chapter is described the synthesis of a series of 2'-sulphonaitiido-4-hydroxydiphenylainines. Oxidation of these compounds gave novel N-sulphonylphenazinones rather than anticipated spirobenzimidazoles, but one bis-dienone based on the latter system was isolated. An attempt was made to elucidate some acid-base reaction of the bis-dienone and related products.

The following Chapter discusses the preparation of several N-aryl- cyclohexadienimine-4-spirolactones and acetals by the anodic or chemical oxidation of 4-anilinophenoxyacetic or hydrocinnamic acids and corresponding alcohols. The stability of the lactones and acetals is strongly influenced by alkyl substituents in the heterocyclic ring.

In Chapter Three there is reported an investigation of the reaction of t-butyl 4-nitrohydrocinnamate with zinc and trifluoroacetic acid to give directly a cyclohexadienone spirolactone, presumably via a dienimine intermediate. Unsuccessful efforts were made to improve yields in this reaction, and to extend it to more complex substrates, including tetrahydroisoquinoline-l-carboxylate esters. However, the preparation of a spirolactone by acid treatment of an aryl azide shows synthetic promise.

The final Chapter describes application of a Smiles rearrangement in the development of a useful general method for converting phenols to primary or secondary anilines. Reaction of a range of phenols, including electron-rich molecules, with bromoisobutyramide gives aryl ethers, which on treatment with sodium hydride in DMF/DMPU rearrange smoothly to anilides, which can be hydrolysed to anilines. Steric and electronic restraints on the reaction were studied. N-substituted aryloxyisobutyramides, obtained by reacting phenols with secondary bromoisobutyramides or derived- lactams rearranged to give anilides, benzoxazinones, or, surprisingly, N-alkyl anilines directly.

Item Type:

Thesis

Creators:

Southcott, M.R.

Date:

1988

ISBN:

9781369325164

Identifiers: