A potential industrial process is profitable only if it is successfully implemented by the continuously developing chemical industry. Throughout last decades heterogeneous catalysis has opened doors to the creation of various know-how products which previously were considered unfeasible. Moreover, the use of heterogeneous catalysts allows improving existing processes to shift towards more ecological and cost efficient practices. In particular, polymer or fuel compounds could be eco-friendly produced from wood extractives, as an alternative to the conventional oil resources. This goal becomes even more attractive in light of the upcoming peak-oil. In the Nordic pulping industry turpentine is widely available as a tonnage by-product. Despite its interesting properties and promising application possibilities this fraction is commonly burned in the recovery boilers for energy. Although the chemical composition of turpentine depends strongly on the specific pulping process, α-pinene is the predominant compound and as such most studied. The general message of this thesis is the successful implementation of the heterogeneous catalysts in one-pot value-added upgrading of crude turpentine and specific terpenes, particularly α-pinene. Concepts allowing the production of fragrances, resins, plastics and pharmaceutical compounds are presented in the current study. Both commercial (Amberlyst 70) and self-prepared (Me/Al-SBA-15 or TiO2) catalysts were studied in several reactions including: acetoxylation, isomerization, dehydroisomerisation and oxidation. Both commercially purified α-pinene and crude thermo-mechanical turpentine were used as raw materials in the catalytic one-pot synthesis of value-added compounds. The experiments were performed in both batch and continuous reactor systems depending on the studied reaction. Successful results were obtained in case of several reactions. As an example, upon acetoxylation of α-pinene valuable fragrances – α-terpinyl and bornyl acetates – were produced with yields of 35 and 40 wt-%, respectively. Furthermore, in the dehydroisomerisation reaction of α-pinene, a yield of around 80 wt-% of an important fragrance, solvent and plastics precursor, ρ-cymene, was obtained. In the last case, thermo-mechanical turpentine was also successfully utilized. Still, some α-pinene oxidation tests leading to α-pinene oxide and verbenone fragrances were also carried out. Upon this study, further oxidation of ρ-cymene lead to the formation of ρ-methyl-acetophenone, a product essential for perfumery, pharmaceutical and pesticide industry as well as a potent polymer precursor. In addition, isomerization reactions were performed. Additionally, the catalytic materials were thoroughly characterized and analyzed.

iv, 210 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, 1985

Thesis (Ph. D.)--Virginia Commonwealth University, 2007. / Prepared for: Dept. of Chemistry. Bibliography: leaves 120-134. Available online via the Internet.

Thesis (Ph.D.)--University of Melbourne, Dept. of Chemistry, 2006. / Typescript. Includes bibliographical references (leaves 245-289).

Thesis (Ph. D.)--University of Hong Kong, 2009. / Includes bibliographical references. Also available in print.

Thesis (Ph. D.)--New York University, 1933. / Bibliography: p. 50-51.

Thesis (M.S.)--University of Wisconsin--Madison, 1971. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Hong Kong, 1999. / Includes bibliographical references (leaves 145-152).

A series of optically active tertiary phosphorus ligands, [special characters omitted] (R = bornyl, menthyl, or isopinocamphyl; n = 1, 2, or 3, 1 – 9), containing chiral alkoxy groups derived from natural terpene alcohols, menthol, borneol, and isopinocampheol, are synthesized and characterized by various spectroscopic techniques. The reactions of these ligands with iron and cobalt carbonyl complexes are carried out, giving monomeric mono- and di-substituted iron(0) and dimeric di-substituted cobalt carbonyl complexes [special characters omitted]. The characterization of these complexes by IR and NMR spectrometries is discussed. Results of preliminary studies on hydroformylation reaction under oxo conditions catalysed by several cobalt complexes are presented. Pyrazolyl bridged di-iridium(I) systems, [special characters omitted], are prepared as diastereomers with unequal thermodynamic distribution. The X-ray crystal structure of 41 shows cocrystallization of the two diastereomers in the same unit cell, which provides 1:1 kinetic distribution of the two isomers. Kinetic studies of the interconversion from the kinetic ratio to the thermodynamic ratio of the two diastereomers in 41 indicates the existence of a slow inversion process of the six-membered central metallocycle in 41. Oxidative addition of Mel to 41 generates a pair of diastereomeric adducts (43) in kinetic distribution, which is slowly converted to its thermodynamic distribution, implying a very slow reductive elimination of Mel. Oxidative additions of exo- and endo-norbornyl iodide to [special characters omitted] results in same product (44). Possible mechanisms for this process are discussed. Bisdiphenylphosphinoalkylsilane containing chiral menthoxy group [special characters omitted] is prepared and characterized. Its four-coordinate square planar platinum complex [special characters omitted] and five-coordinate iridium(I) complex [special characters omitted] are synthesized. Isomerizations of 49 and its CO adducts, [special characters omitted] (55 and 56), are studied in relation to their methyl analogues. / Graduate

CURRENTLY UNDER EMBARGO UNTIL THE 26/4/2019: Type 2 diabetes is a metabolic disorder characterised by inflammation, insulin resistance and the inability of pancreatic β-cells to secrete enough insulin to produce a physiological effect. Obesity and high levels of triacylglycerol’s are associated with the development of Type 2 diabetes. Adipose tissue is an active endocrine organ that secretes various protein and peptide hormones, known as adipokines, which mediate important metabolic functions. In an insulin resistant and hyperglycaemic state, levels of anti-inflammatory adipokines, adiponectin, are reduced, whereas levels of pro-inflammatory cytokines, interleukin-6 and interleukin-1β, are elevated; this results in a shift from an anti- to a pro-inflammatory state that is accompanied by dysfunction and apoptosis of the pancreatic β-cells. Cannabis sativa L. has been traditionally used as an anti-inflammatory agent in Southern Africa, specifically treating snakebites, fever and malaria. Δ9-tetrahydrocannabinol is the main psychoactive compound derived from C. sativa, whereas the other major cannabinoids, cannabinol and cannabidiol, have shown anti-inflammatory and sedative properties respectively. Marrubiin is a compound derived from the plant Leonotis leonurus L. and has been traditionally used as an anti-inflammatory and anti-diabetic agent. To determine the effects of these compounds in a hyperglycaemic state, pre- and differentiated mouse adipocytes (3T3-L1 cells) were exposed for seven and fourteen days to the following treatments: Δ9-tetrahydrocannabinol, cannabidiol, cannabinol, marrubiin, anandamide (an endogenous endocannabinoid) and cannabis extract, individually and in combination, under normal glucose and hyperglycaemic conditions. Levels of adiponectin, interleukin-6, leptin, tumour-necrosis factor-α and interleukin-1β were quantified using mouse enzyme-linked immunosorbent assay kits and Oil Red O staining was carried out to determine lipid distribution and lipid droplet characteristics. Results indicate that various cannabinoids, in combination, mediate an anti-inflammatory effect by decreasing the expression of various pro-inflammatory cytokines, which may have allowed for a shift from a pro- to an anti-inflammatory state by these compounds, and may also contribute to the reduction of lipid, which may be used as a supplementary option to current diabetic treatment regimes.