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Title: 1-alkyl-1-phenylhydrazines : their synthesis and oxidative rearrangement
Author: Maclean, Lachlan
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1977
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Some historical aspects of the oxidation reactions of 1,1-disubstituted hydrazines are reviewed. In particular, the evidence for the proposed intermediacy of diazenes in these reactions is outlined and the nature of the oxidation products is considered in the broader context of diazene-generating reactions. The synthesis of l-alkyl-l-phenylhydrazines has been examined and several preparative procedures are discussed. The alkylation of the sodium salt of phenylhydrazine with the appropriate alkyl halides was found to be the most successful method; the hydrazines prepared in this way all had substituents of the allylic type. Purification (to remove residual phenylhydrazine) can be achieved by selective recrystallisation of the hydrochloride derivative from benzene. Some limitations of this general method are described. The oxidation studies were carried out using lead tetra-acetate and mercuric oxide. The oxidative rearrangement of 1-allyl-l-phenyltiydrazine to 1-phenylazoprop-2-ene was confirmed, and by regarding this as the model system, formation of particular species from the other hydrazines was envisaged. The outcome of each oxidation study is discussed in detail. The oxidation of 1-(pent-3-en-2-yl)-1-phenylhydrazine was studied in the contextof a proposed method of examining the base-catalysed rearrangement of an optically active azo-compound (formed in the oxidative rearrangement of the optically active hydrazine). Preliminary studies on the racemic hydrazine indicate that the azo compound is obtained in the form of two geometrical isomers. The synthesis of l-phenylazoprop-2-ene by an unambiguous route is described; the method should have wider potential. A proposed method of determining the electronic character of the diazene involved in the oxidative rearrangement of allylic hydrazines, and difficulties encountered in its application are described. The attempted interception of the intermediate diazenes by dimethyl sulphoxide and dimethyl sulphide is described. Oxidation of the hydrazines with cupric chloride was found to give copper-containing solids whose exact composition could not be determined.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available