Solid phase organic synthesis is a powerful technique to facilitate rapid synthesis and easy purification of organic compounds. The advancement of linkers and cleavage strategies is of paramount importance for the success of this approach. This thesis is concerned with the development of a robust safety catch linker system aimed to allow a broad range of commonly used reagents to be employed in a synthetic sequence carried out on a solid support. Chapter 1 outlines the principles of solid phase organic synthesis, the terminology associated with this approach and the advantages and disadvantages compared to conventional solution phase methods. Common attachment and release strategies for various functional groups are described and the safety catch principle is introduced. Chapter 2 discusses the design features of the linker system. Proof of principle is demonstrated for the attachment and release strategies with a simple solution phase model system. Chapter 3 describes the adaptation of the linker system to the solid phase. Key transformations are modelled with solution phase experiments and subsequently applied to solid phase. The loading determination of the solid phase system is also described. Chapter 4 reports an assessment of the reactivity of the linker system in the coupling transformation of aliphatic alcohols and amines. The chemoselectivity and efficiency of the CAN debenzylation/cyclorelease protocol is also evaluated. Chapter 5 demonstrates the utility of the linker system with the optimisation of a simple synthetic sequence in solution followed by adaptation to the solid phase. The synthesis of a pilot library of aryl alcohols utilizing a Suzuki coupling on solid support is described. The attachment and release of amines is also demonstrated with solid phase examples. Chapter 6 examines the potential of the linker system as an analytical tool to assess the outcome of stereoselective transformations. A chiral auxiliary is attached to the solid phase by aid of the safety catch linker and released into solution. A solution phase model system is developed to aid preliminary investigations in solution prior to adaptation to the solid phase.

Thesis (M.S.)--Florida State University, 2004. / Advisors: Dr. Jeffrey Chanton and Stephen Opsahl, Florida State University, College of Arts and Sciences, Dept. of Oceanography. Title and description from dissertation home page (viewed Jan. 13, 2005). Includes bibliographical references.

Submitted in fulfillment of the requirement for the degree Master of Applied Sciences in Chemistry, Durban University of Technology, Durban, South Africa, 2017. / In this study, molecular modeling was used to investigate the intermolecular interactions between the functional monomer and ketoprofen which is an acidic pharmaceutical that possesses anti-inflammatory and analgesic activities. Ketoprofen is widely employed in medical care for treating musculoskeletal injury. This led to rational design of a molecularly imprinted polymer (MIP) that is selective to ketoprofen. Density functional theory (DFT) at B3LYP/6-31 level was used to investigate the intermolecular interaction between functional monomers and ketoprofen. Binding energy, ΔE, was used as an indication of the strength of the interaction that occurs between functional monomers and ketoprofen. 2-vinylpyridine (2-VP) as one of the functional monomers gave the lowest binding energy when compared to all the functional monomers investigated. Monomer-template interactions were further experimentally investigated using spectroscopic techniques such as Ultraviolet-visible and Fourier transform infrared (FTIR). A selective MIP for ketoprofen was synthesized using 2-vinylpyridine, ethylene glycol dimethacrylate, 1,1’-azobis(cyclohexanecarbonitrile), toluene/acetonitrile (9:1, v/v), and ketoprofen as a functional monomer, cross-linker, initiator, porogenic mixture, and template, respectively. The polymerization was performed at 60 °C for 16 h, and thereafter the temperature was increased to 80 °C for 24 h to achieve a solid monolith polymer. The non-imprinted polymer (NIP) was synthesized in a similar manner with the omission of ketoprofen. Characterization with thermogravimetric analysis (TGA) and powder X-ray diffraction (XRD) showed that the synthesized polymers were thermally stable and amorphous. Morphology of the particles were clearly visible, with MIP showing rough and irregular surface compared to NIP on the scanning electron microscopy (SEM). The characterization of the prominent functional groups on both MIP and NIP were performed using FTIR and nuclear magnetic resonance (NMR). The existence of hydroxyl was observed in the MIP; this was due to the presence of ketoprofen in the cavity. Prominent carbonyl group was an indication of the cross-linker present in both polymers. The synthesized MIP was applied as a selective sorbent in the solid-phase extraction of ketoprofen from the water. The extracted ketoprofen was monitored by high performance liquid chromatography (HPLC) coupled with UV/Vis detector. Several parameters were investigated for maximum recovery of ketoprofen from the spiked deionized water. The optimum method involved the conditioning of 14 mg MIP sorbent with 5 mL of methanol followed by equilibrating with 5 mL of deionized water adjusted to pH 2.5. Thereafter, 50 mL sample (pH 5) was loaded into the cartridge containing MIP sorbent followed by washing and eluting with 1% TEA/H2O and 100% methanol, respectively. Eluted compounds were quantified with HPLC. MIP was more selective to ketoprofen in the presence of other structural related competitors. The analytical method gave detection limits of 0.23, 0.17, and 0.09 mg L-1 in wastewater influent, effluent, and deionized water, respectively. The recovery for the wastewater influent and effluent spiked with 5 µg L-1 of ketoprofen was 68%, whereas 114% was obtained for deionized water. The concentrations of ketoprofen in the influent and effluent samples were in the ranges of 22.5 - 34.0 and 1.14 - 5.33 mg.L-1, respectively. The relative standard deviation (RSD) given as ± values indicates that the developed analytical method for the analysis of ketoprofen in wastewater was rapid, affordable, accurate, precise, sensitive, and selective. / M

Please read the abstract in the section 00front of this document / Thesis (PhD (Chemistry))--University of Pretoria, 2005. / Chemistry / unrestricted

Thesis (M.S.)--State University of New York at Binghamton, Department of Chemistry, 2006. / Includes bibliographical references.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 151-159). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 151-159). Also available on the Internet.