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dc.creatorLorenc, Ljubinka
dc.creatorGašić, Miroslav J.
dc.creatorJuranić, Ivan
dc.creatorDabović, Milan
dc.creatorMinailović, M. Lj.
dc.date.accessioned2019-04-26T16:16:11Z
dc.date.available2019-04-26T16:16:11Z
dc.date.issued1980
dc.identifier.issn1472779X
dc.identifier.urihttp://cer.ihtm.bg.ac.rs/handle/123456789/2709
dc.description.abstractKinetic measurements of the solvolysis of (Z)-3α- and (Z)-3β-, and (E)-3α- and (E)-3β-tosyloxy-5,10-secocholest-1(10)-en-5-ones in buffered aqueous acetone (90 : 10 v/v) reveal that the (Z)-3α-, (E)-3α-, and (E)-3β-tosylates are solvolysed according to a first-order rate law (the relative rates being ca. 1 : 3 : 8), while the (Z)-3β-ester, under the same conditions, reacts at a much slower rate by a complex mechanism, the kinetics of which are best approximated by a second-order law. These data and product analysis indicate that the former three esters are solvolysed with considerable double bond participation [resulting in the case of the (E)-3-esters in intramolecular cyclopropane ring closure], and that this interaction is unimportant for the (Z)-3β-tosylate. On the basis of conformational analysis of the starting tosylates and stereoelectronic requirements for homoallylic interaction, a possible mechanistic pathway for these solvolyses is proposed.
dc.publisherRoyal Society of Chemistry
dc.relationSerbian Republic Research Fund
dc.relationSerbian Academy of Sciences and Arts
dc.rightsrestrictedAccess
dc.sourceJournal of the Chemical Society, Perkin Transactions 2
dc.titleSynthesis, structure, and reactions of secosteroids containing a medium-sized ring. Part 17. Structure-reactivity relationship in the solvolysis of 5,10-secosteroidal 3-tosylates
dc.typearticleen
dc.rights.licenseARR
dcterms.abstractЛоренц, Љубинка; Минаиловић, М. Љ.; Дабовић, М.; Јуранић, Иван; Гашић, М. Ј.;
dc.rights.holderRoyal Society of Chemistry
dc.citation.issue9
dc.citation.spage1356
dc.citation.epage1365
dc.identifier.scopus2-s2.0-37049113652
dc.type.versionpublishedVersion


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