Browsing by Author "Lewis, Edward S."

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    Identity and near identity rates and equilibria for methyl group transfers between arenesulfonate ions
    (1984) Hu, Daniel David; Lewis, Edward S.; Billups, W. Edward; Stanbury, David M.
    Rates and equilibria were measured for the reaction of methyl arenesulfonates with arenesulfonates in sulfolane. The identity rates for a series of arenesulfonates were measured at a variety of temperatures; a Hammett P was obtained. A Hammett P of ~22.9 was obtained for nonidentity equilibria. Arrhenius plots are inconclusive due to large error limits. The transition state for the identity reaction lies near the area predicted by Albery and Kreevoy. Using the identity rates and measured mixed case equilibrium constants, a test of the Marcus equation with and without the quadratic term was conducted. The test suggests that the Marcus equation is a decent predictive tool for the rate of methyl transfers in solution. The Marcus equation was used to estimate an identity rate for methyltriflate.
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    Indole alkaloid synthesis
    (1983) Simmons, Dana Philip; Wenkert, Ernest; Lewis, Edward S.; Storck, Roger L.
    Indole acetic acid and methyl 1,4,5,6-tetrahydronicotinylacetate obtained by hydrogenation of methyl nicotinylacetate were combined in the presence of base to yield methyl 1-(3-indoleacetyl)-1,4,5,6-tetrahydronicotinylacetate in 45% yield. This, upon heating in polyphosphoric acid, yielded in 73% 2-deethyl-5,17-diketo-2,16-dihydrovincadifformine with complete stereospecific formation of all five chiral centers. Reduction of the two keto functions led to 2-deethyl-2,16-dihydrovincadifformine, whereas reduction of the lactam and oxidation of the 2,16 carbon-carbon bond yielded 2-deethyl-16-ketovincadifformine. 16 ketopseudovincadifformine was prepared in the same manner starting from methyl 5-ethyl-nicotinylacetate.
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    Reactions of [Alpha]-Acyl-[Alpha] Diazoacetaldeydes
    (1980) Ananthanarayan, T. P.; Wenkert, Ernest; Lewis, Edward S.; Fukuyama, Tohru
    The copper-catalyzed thermolysis of ethyl diazoformylacetate and diazomalonaldehyde in n-butyl vinyl ether has been shown to produce ethyl 5-n-butoxy-4,5-dihydrofuran-3-carboxylate and 2-n-butoxy-2,3-dihydro-4-pyrone, respectively.
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    Synthesis of functionalized naphthalenes
    (1983) Lewis, Linda Kay; Billings, W. E.; Engel, Paul S.; Lewis, Edward S.
    1,2 and 2,3-disubstituted naphthalenes were synthesized by carbene addition to substituted indenes. The indene precursors were formed by two methods: Grignard addition to indanones with elimination and by the reaction of indanones with phosphorus pentahalide. The carbene addition to indene was facilitated fcy the use of a micellar phase transfer catalyst, hexadecyltrimethyl ammonium branide. This catalyst allowed carbene addition to double bonds with both electron donating and withdrawing substituents. The naphthalenes formed by this method include: 2-chloro-3-methylnaphthalene, 2-chloro-3-phenylnaphthalene, 1,2-dichloronaphthalene, 2-chloro-l-phenylnaphthalene, 2-brano-3chloronaphthalene and 2,3-dichioronaphthalene.