A kinetic study of the suprafacial [1,5]-sigmatropic phenyl rearrangements of 3,4-bis- (para-substituted)-1,2,5-triphenyl-2,4- cyclopentadien-1-ols to 3,4-bis-(para-substituted)-2, 2,5-triphenyl-3-cyclopenten-1-ones, where the substituent were, t-butyl, methyl, hydrogen, chloro and bromo, has been performed at 180, 190, 200 and 210 ± 0.2° in tetraethylene glycol. The rearrangement was observed to be first order throughout the temperature range investigated, and the rate constants (k) at the temperatures used were found to be 8.057, 2.143, 2.930 and 6.456 x 10⁻⁴ sec⁻¹ for the t-butyl substituent; 4 7.700, 2.110, 3.434, and 6.581 x 10⁻⁴ sec⁻¹ for the methyl substituent; 0.909, 2.166, 3.678 and 6.448 x 10⁻⁴ sec⁻¹ for the unsubstituted alcohol; 1.469, 2.992, 5.989 and 11.12 x 10⁻⁴ sec⁻¹ for the chloro substituent; and 1.955, 3.215, 6.215 and 13.01 x 10⁻⁴ sec⁻¹ for the bromo substituent, respectively. . Calculations of the activation energy of this phenyl [1,5]-sigmatropic shift from the Arrhenius equation give values of 28.71, 30.31, 28.01, 29.38 and 27.49 kcal·mol⁻¹ for the above substituents respectively, while ΔH^‡ these phenyl migrations were 27.78, 29.39, 27.93, 28.45 and 26.56 kcal·mol⁻¹ respectively. ΔS^‡ values were also calculated to be -16.6, -13.1, -16.1, -14.0 and -17.8 eu, respectively for a mean temperature range of 453-483 ± 0.2°K. The isokinetic temperature was calculated to be 320°. Calculated rho (ρ) values for the sigmatropic migrations were -0.813, -0.400, -0.690 and -0.658 at 180, 190, 200 and 210 ± 0.2°C. These results are used to discuss both the mechanism of this rearrangement and the transition state for rearrangements in the pentaphenylcyclopentadienol system. Ina much broader sense these results and the results of previously documented sigmatropic rearrangements exhibiting electronic influences were used to formulate a general scheme to predict the outcome of those sigmatropic rearrangements that entail an electronic effect as seen in the rates of the above reactions. This scheme used as its basis the transition state approach invoking inductive and mesomeric arguments to rationalize the observed rates of the sigmatropic rearrangements of this dissertation, those of previously documented sigmatropic rearrangements and finally to predict a relative rate of rearrangements in general. Finally a mass spectral investigation of the fragmentation patterns of 1-para-phenylsubstituted 2,3,4,5-tetraphenyl-2,4-cyclopentadien-l-ols and 3,4-bis(para-substituted phenyl)-1,2,5-triphenyl-2,4- cyclopentadien-1-ols was undertaken. A continuum of two super imposable pathways with the choice of the major decomposition mode being determined by the electron donating or withdrawing ability of the substit- vent was established. Linear free energy relationships for mass spectral decomposition were presented as well as a justification for this behavior. / Ph. D.

This dissertation focuses on the development of cyclopentadienes as an emerging class of compounds for use in catalysis. Previous work in the Lambert group had established pentacarboxycyclopentadienes (PCCPs) as a promising class of Brønsted acids capable of being used as catalysts in acid-promoted reactions. The ease of their synthesis distinguished them from the comparable BINOL-derived phosphoric acids, and their unique mode of enantioinduction created opportunities for their use in enantioselective reactions. Initial efforts were focused on the synthesis of leading to the development of two complementary methods for their synthesis. Chapter 2 details the improvements made to the transesterification of penta(methoxycarbonyl)cyclopentadiene, which allowed for sterically encumbered alcohols to be used. Further, a new method for accessing the penta-acyl chloride intermediate was developed, leading to the ability for a wide array of electron-deficient PCCPs to be synthesized. The second half of the dissertation examines the use of electrophilic silicon reagents and their use as Lewis acids. Given our ability to access highly electron-deficient cyclopentadienes, the silyl cyclopentadienes were targeted as potential Lewis acids. Chapter 4 details the synthesis of these species, and their characterization. Having established a convenient route to silyl mono(carboxy)tetracyanocyclopentadienides, we examined their use as catalysts in halide abstraction reactions. Benzylic bromides could be activated and subsequently allylated, or arylated with a nucleophilic arene using allyltrimethylsilane as a sacrificial silyl source.

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Thesis (Ph. D.)--University of Chicago, Department of Chemistry, 2002. / Includes bibliographical references. Also available on the Internet.

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Typescript (photocopy) / 199 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1982

Thesis (Ph.D.) -- University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1982. / Typescript (photocopy).

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No description available.

This dissertation describes a new platform for the synthesis of thermally reversible polymers, based on Diels-Alder reactions of bis-cyclopentadienes (bis-CPDs) and bis-maleimides (bis-MIs), that meets two main objectives. First, the bis-CPD must resist characteristic self-coupling. Second, the CPD-MI adducts should undergo the retro-Diels-Alder (rDA) reaction (i.e., thermal depolymerization) in a temperature regime that is comparable or slightly higher than that of the freely reversible bis-furan/bis-MI polymers (rDA between 80 °C and 130 °C) but much lower than that of bis-CPD homopolymers (rDA above 160 °C). Structure-reactivity relationships gleaned from the literature and from related but as yet unpublished work in our own laboratories led to our main hypothesis that a CPD moiety bearing one sterically encumbering substituent such as isopropyl (𝑖Pr) or tert-butyl (𝑡Bu) and one electronwithdrawing substituent such as perfluoroaryl would have the desired reactivity and adduct stability in combination with an 𝑁-substituted maleimide. Synthetic considerations led to a bisCPD monomer design in which two alkylcyclopentadiene groups (alkyl = 𝑖Pr or 𝑡Bu) are connected by an octafluorobiphenylene linker. As an initial fundamental step (Chapter 3), 1-(nonafluorobiphenyl-4’-yl)-4-tertbutylcyclopentadiene (1) was synthesized to provide a monofunctional model for the proposed difunctional CPD monomer. Reactions of 1 and 𝑁-(4-fluorophenyl)maleimide (FMI) afforded up to five regio- and stereo-isomeric adducts (of fourteen possible). Variable-temperature reactivity studies combined with NMR spectroscopic analysis, X-ray crystallography, and computational modeling enabled product distributions to be understood according to a conventional kinetic-vs- iii thermodynamic framework. These studies also predicted the microstructure of polymers derived from the proposed bis-CPD monomer, which is structurally analogous to 1, and bis-MIs. Moreover, 1 does not undergo DA self-coupling under ordinary conditions (T < 180 °C). Thermolysis studies of the major adducts revealed that the rDA becomes observable on a laboratory timescale (hours) at about 140 °C, which is at the upper end of the temperature range reported for furan+MI adducts but well below that of CPD+CPD adducts. In contrast, adducts formed from either of the analogous monosubstituted cyclopentadienes (𝑡BuC₅H₅ and C₆F₅C₅H₅) do not undergo rDA below 180 °C. These results strongly support the proposed bis-CPD monomer design. In a second fundamental step (Chapter 4), the hypothesis that an electron-withdrawing CPD substituent would destabilize a CPD-MI adduct was further tested by reacting 𝑁-(4- fluorophenyl)maleimide with a series of triarylated cyclopentadienes (1,2,3-Ar₃C₅H₃ and 1,2,4- Ar₃C₅H₃, Ar = C₆F₅, C₆F₄CF₃, and Ar = C₅F₄N). The perfluorophenyl- and perfluorotolylsubstituted compounds were previously reported, but the perfluoropyridyl-substituted cyclopentadienes were prepared for this study using SNAr reactions of pentafluoropyridine and sodium cyclopentadienide. The least electron deficient cyclopentadiene in each series (Ar = C₆F₅) reacted the most quickly and with the highest ultimate equilibrium binding constant, confirming the electron-effects hypothesis as well as the underlying presumption that DA reactions of even relatively electron-poor CPDs with MI would behave according to normal-electron-demand principles. In the main section of this dissertation (Chapter 5) the proposed bis(cyclopentadiene)s reacted with a series of previously reported bis(maleimides) to form linear polymers having molecular weights (Mn) up to 40 kDa. Relationships among the length and flexibility of the bis-MI linker (C₆H₁₂, C₁₂H₂₄, C₆H₄OC₆H₄, and (C₂H₄O)₂), the identity of the CPD alkyl substitutent (CHMe₂, CMe₃ and CMe₂Ph) and the glass transition temperature (Tg) as measured by differential scanning calorimetry (DSC) were understood in terms of a general model of local segmental mobility and free volume. Solution thermolysis of a model polymer system (bis-MI linker = C₆H₁₂ (7), CPD alkyl substituent = 𝑡Bu) showed a rapid decrease in molecular weight at 160 °C as determined by size exclusion chromatography (SEC). Solution thermolysis in the presence of excess FMI (as a trap for free CPD moieties) revealed that the onset temperature for rDA on a laboratory time scale (hours) was as low as 120 °C. In the bulk, thermolysis above 250 °C under vacuum led to recovery of a small portion of the bis-CPD monomer, but bulk thermolysis at 200 °C did not reveal a change in molecular weight as determined by SEC. The current interpretation of these observations is that limited mobility in these glassy polymers prohibits retro-DA decoupling. These findings largely validate the main hypothesis of this dissertation. / Ph. D.