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Title: Cyclopentadienylides
Author: Freeman, Brian Harding
Awarding Body: University of St Andrews
Current Institution: University of St Andrews
Date of Award: 1971
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The thermal decomposition of 2,3,4,5-tetraphenyldiazocyclopentadiene in the presence of carbene acceptors having Group V and VI elements to give 2,3,4,5-tetraphenylcyclopentadienylides has been extended and the first example of a telluronium ylide has been prepared by this method. The procedure has also been extended to other substituted diazo-cyclopentadienes and various new phosphonium, arsonium and sulphonium ylides have been prepared. The reaction of diazocyclopentadienes with triphenylphosphine to give either phosphazines or phosphonium ylides has been studied and the reasons for the difference in reactivity of these diazo-compounds has been clarified to some extent. It has been shown that for phosphazine formation both lack of steric hindrance and the absence of an electron- donating group on the cyclopentadiene ring are required. The thermal reaction of diazocyclopentadienes is assumed to proceed via a carbene-type intermediate which is then attacked by the reagent present to give an ylide. This reaction can be catalysed by the presence of copper-bronze and, in this case, can be effected either under melt conditions or in solution. The stability of the carbenoid intermediate is demonstrated by its preferential reaction with triphenylarsine rather than with benzene, which is present as the solvent. The reaction of 2,5-diphenyldiazocyclopentadiene with triphenylarsine gives a rearranged 2,4-disubstituted product. The carbene-type intermediate in this case is presumed to rearrange before reaction with the triphenylarsine. Some cyclopentadienylidene triphenylphosphazines have been shown to decompose thermally in the presence of triphenylphosphine to give the related triphenylphosphonium ylides. Diazocyclopentadienes have been found to react with either hydrochloric or hydrobromic acid to give the monochloro or monobromo cyclopentadienes. The parent, unsubstituted triphenylarsonium cyclopentadienylide has been prepared by the reaction of triphenylarsine with dibromocyclopentene and basification of the bis-arsonium salt so formed. Its properties and reactions have been studied and are found to be similar to the analogous triphenylphosphonium ylide. The salt method for the preparation of cyclopentadienylides has also been investigated. Triphenylarsine has been shown to react with 5-bromo-1,2,3-triphenylcyclopentadiene in solution at room temperature to give the hydrobromide salt of the ylide. Various sulphides also reacted with the bromo-compound to give, in most cases, unexpected products. The reactions of the cyclopentadienylides prepared with aldehydes have been investigated and the results are in line with previous findings. The cyclopentadienylides also readily undergo electrophilic substitution on the five-membered ring. The reaction proceeds preferentially at the 2(5)-position.
Supervisor: Lloyd, D. M. G. Sponsor: Science Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD400.F8 ; Heterocyclic chemistry