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.
","abstract_html":"<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>","abstract_has_math":false,"creators":["Wu, Yuh-Wern"],"institution":null,"degree_name":"Doctor of Philosophy","degree_level":"dissertation","degree_discipline":null,"degree_department":"Department of Chemistry","school":null,"contributors":[],"advisors":["Glen A. Russell"],"committee_chairs":[],"committee_members":[],"year":1990,"date_issued":"1990","date_published":"1990","updated_at":"2026-07-24T02:37:16Z","subjects":[],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.31274/rtd-180813-11194"],"render_values":[{"text":"https://doi.org/10.31274/rtd-180813-11194","href":"https://doi.org/10.31274/rtd-180813-11194","code":true}]},{"key":"dc:identifier","label":"Identifier","values":["archive/lib.dr.iastate.edu/rtd/9473/"],"render_values":[{"text":"archive/lib.dr.iastate.edu/rtd/9473/","href":null,"code":true}]}]},"links":{"outbound_url":"https://dr.lib.iastate.edu/handle/20.500.12876/82576","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Glen A. 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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.
"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Free radical reactions of allylic and propargylic derivatives"]}]}],"canonical_facts":{"dc:contributor.advisor":["Glen A. Russell"],"dc:contributor.department":["Department of Chemistry"],"dc:creator":["Wu, Yuh-Wern"],"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.issued":["1990"],"dc:description.abstract":["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.
"],"dc:format.mimetype":["application/pdf"],"dc:identifier":["archive/lib.dr.iastate.edu/rtd/9473/"],"dc:identifier.doi":["https://doi.org/10.31274/rtd-180813-11194"],"dc:identifier.uri":["https://dr.lib.iastate.edu/handle/20.500.12876/82576"],"dc:language.iso":["en"],"dc:title":["Free radical reactions of allylic and propargylic derivatives"],"dc:type":["dissertation"],"thesis:degree_level":["dissertation"],"thesis:degree_name":["Doctor of Philosophy"]},"updated_at":"2026-07-24T02:37:16Z"}