Free radical reactions of allylic and propargylic derivatives

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dc.contributor.advisor Glen A. Russell
dc.contributor.author Wu, Yuh-Wern
dc.contributor.department Chemistry
dc.date 2018-08-15T06:37:57.000
dc.date.accessioned 2020-07-02T06:13:42Z
dc.date.available 2020-07-02T06:13:42Z
dc.date.copyright Mon Jan 01 00:00:00 UTC 1990
dc.date.issued 1990
dc.description.abstract <p>Addition of tert-butyl radical, generated from t-BuHgCl, to allyl or propargyl derivatives forms adduct radicals which can undergo [beta]-elimination with substituents such as halogen, PhS, PhSO[subscript]2 to form the alkyl-substituted propene or allene and an eliminated radical which regenerates the tert-butyl radical by displacement from t-BuHgCl. With [beta]-oxy substituents, such as O[subscript]2CR, OP(O)(OEt)[subscript]2, O[subscript]3SAr, the adduct radical can displace the alkyl radical from alkylmercurial to yield the [beta]-substituted alkylmercurials which spontaneously, or in the presence of nucleophiles, undergo an elimination reaction to yield the alkene or allene. Relative reactivities towards tert-butyl radical attack, such as k(allyl chloride) / k(propargyl chloride) ≅ 10, have been determined. A similar relative reactivity is observed in reaction with (t-Bu)[subscript]2CuLi, implicating attack by tert-butyl radical. With propargyl iodide, radical attack leads to iodine atom abstraction. Reaction of propargyl iodide with t-BuHgCl / h[upsilon], (t-Bu)[subscript]2CuLi, or (t-Bu)[subscript]3ZnLi leads to a mixture of hydrocarbons in which tert-butylallene is present in only trace amounts. Benzene is an important reaction product which seems to be formed via the cyclodimerization of two "propargyl" (C[subscript]3H[subscript]3•) radicals in the presence of metal ion. The pseudo-unimolecular rate constants, k[subscript] obs, of allyl derivatives with excess t-BuHgCl have been determined and the plot of log k[subscript] obs vs. [sigma][subscript] m gives a straight line with correlation coefficient of 0.994 and [rho] value of 3.24. Addition of t-Bu• to 1,3-butadiene epoxide in the presence of DABCO gives a 53% yield of t-BuCH[subscript]2CH=CHCHO with very high regio- and stereoselectivity. The reaction is thought to involve the loss of a proton from the intermediate t-BuCH[subscript]2CH=CHCH[subscript]2O•, followed by electron transfer from the ketyl radical anion to t-BuHgCl.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/rtd/9473/
dc.identifier.articleid 10472
dc.identifier.contextkey 6360007
dc.identifier.doi https://doi.org/10.31274/rtd-180813-11194
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath rtd/9473
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/82576
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/rtd/9473/r_9101384.pdf|||Sat Jan 15 02:33:26 UTC 2022
dc.subject.disciplines Organic Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Organic chemistry
dc.title Free radical reactions of allylic and propargylic derivatives
dc.type article
dc.type.genre dissertation
dspace.entity.type Publication
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
thesis.degree.level dissertation
thesis.degree.name Doctor of Philosophy
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