Comparative electron impact and fast atom bombardment mass spectrometric studies of some HMPA adducts of phenyltin and phenyllead halides and studies of strong hydrogen bonding by FAB-MS

The fragmentation patterns and mass spectra of some phenyl tin and -lead halide adducts with hexamethylphosphoramide are compared by subjecting them t~ electron impact and fast atom bombardment ionization in a mass spectrometer. This comparison is restricted to the metal-containing ions. Ligand-exchange mechanisms of some of the metal-containing species are explored by FAB-MS. Several moisturesensitive organo-metallics and H-bonded systems have been examined by FAB for attempted characterization, but without any success. Scavenging and trapping of water molecules by complex aggregates in solutions of quaternary ammonium fluorides and hydroxides are investigated by FAB to complement previous NMR-studies.

NMR studies of strong hydrogen bond to fluoride ion

Systems such as MF/diol (M = alkali metal) and }1F/carboxylic acid were subjected to IH, I9F and 13C nmr study to investigate the nature of the very strong H-bonding of fluoride ions with these systems. Evidence indicates a strong H-bond in diol-fluoride systems (~H ~ -(56) kJ mol-I) which is stronger than most 'typical' H-bonds (~H = -(12-40) kJ mol-I), but weaker than that reported for carboxylic acid-fluoride systems (~H ~ -(120) kJ mol-I). Approximate fluoride H-bonded shifts (o(OH)OHF) were evaluated for MF/diol systems from IH chemical shift measurements. No direct correlation was observed between I9F chemical shift and H-bond strength. Thermodynamic parameters were calculated from temperature dependent IH and 19F shifts. Preliminary studies of BUn 4NF-acetylacetone by I9F nmr were conducted at low temperatures and a possible Jmax (ca. 400 Hz) is reported for the fluoride ion H-bonded to acetylacetone. Highfield shift for non-protonated carbons and downfield shift for protonated carbons were observed in carboxylic acid/KF systems. Significant decreas$in I3C TI due to strong H-bonding to fluoride ions were also detected in both diol and carboxylic acid systems. Anomalous results were obtained, such as increasing NOE with increasing temperature in neat 1,2-ethanediol (values above the theoretical maximum of 1.988) and in 1,2-ethanediol/KF. The large 13C NOE's for carboxy carbons in neat carboxylic acids which are. further enhanced by the addition of KF are also unusual.

Strong hydrogen bonding in organic synthesis

The preparation of phenacyl and para-phenylphenacyl esters, the reactions of carboxylic acids, phenols, 2-nitropropane and alcohols with alkyl halides in the presence of fluoride anion are described. The reactions are thought to be accelerated by the formation of hydrogen bonds between the fluoride anion and the organic electron acceptor. The fluoride ,carboxylic acids, fluoride-phenols and fluoride-2-nitropropane are better reaction systems than the fluoride-alcohol. The source of the fluoride anion and the choice of solvents are also discussed.

Reactions of steroidal epoxides with strong organic bases and an investigation into the syntheses of some labelled pregnane derivatives

Reactions of 5,6- and 4,5-epoxycholestane derivatives with strong bases were investigated. Epoxidation of 3a-acetoxycholest-5-ene also gave a new compound along with the anticipated epoxides. Interconversions of the latter were observed. Some possible mechanisms of its formation and rearrangements have been pIioposed. No reaction was observed with any of the 5,6- and 4,5-steroidal epoxides employed in the present study, using potassium tertiary butoxide under refluxing conditions. n-Butyllithium reacted only with 5,6-epoxycholestanes bearing a ketal moiety at the C3 carbon. Opening of the ketal group was observed with n-butyllithium in the case of a ~-epoxide. The reaction was also investigated in the absence of epoxide functionality. A possible mechanism for the opening of ketal group has been proposed. Lithium diethylamide (LDEA) was found effective in rearranging 5,6- and 4,5-epoxides to their ~orresponding allylic alcohols. These rearrangements presumably proceed via syn-eliminations, however the possibility of a corresponding anti-elimination has not been eliminated. A substituent effect of various functional groups (R = H, OH, OCH2CH20) at C3 has-been observed on product distribution in the LDEApromoted rearrangements of the corresponding epoxides. No reaction of these epoxides was observed with lithium diisopropylamide (LDA) • In the second part of the project, several attempts were made towards the sYRthesis of deoxycorticoste~one~17,2l,2l~d3' a compound desirable for the 2l-dehydroxylation studies of deoxycorticosterone. Several routes were investigated, and some deuterium labelled pregnane derivatives were prepared in this regard. Microbial 21-hydroxylation of progesteronel7,21,21,2l- d4 by ~ niger led to loss of deuterium from C21 of the product. An effort was made to hydroxylate progesterone microbially under neutral condtions.

Is Brand Equity an Asset or a Liability in Brand Harm Crisis? Buffering and Amplifying Effects and Contingent Conditions

Brand harm crisis often result in negative consumer responses. This thesis addresses the buffering and amplifying theoretical perspectives of brand equity effects. We theorize that brand equity may interplay with the nature of brand-harm crisis in shaping consumer reactions. Results from focus group studies provide interesting insights into the amplifying and buffering effects. Moreover, research findings from two experiment studies show that brand equity amplifies consumer negative responses in a performance-related crisis but only when the crisis is extremely severe. When the crisis becomes less severe, the amplifying effect diminishes from outset. However, in a value-related crisis, the amplifying effect of brand equity is pervasive regardless of the level of crisis severity. The current thesis adds to the extant literature by demonstrating that brand equity can have very complex effects on consumer responses, which are contingent on the severity and domain of a crisis. Theoretical and managerial implications are discussed.

The National Hockey League (NHL) Entry Draft: An Examination of the Impact of Brand Associations Attached to the Russian Hockey Players

This research was conducted to investigate whether negative brand associations attached to Russian hockey players impact their draft rankings during the National Hockey League (NHL) Entry Draft. A quantitative analysis based on various regression model specifications was used to test whether Russian players were drafted relatively equally to their counterparts in the NHL Entry Draft. The data consisted of the NHL draft picks between 1993 and 2013 and their performance statistics and physical characteristics. The results suggested that Russian players were drafted relatively equal to their counterparts from other countries. Meanwhile, Russian players who played in the CHL before the draft are actually drafted better than Canadians who played in the same league. Hence, the negative brand associations attached to Russians were unlikely to impact their draft rankings. This study redefined the so-called “Russian Factor” from a notion that allegedly damages Russian players’ rankings to one that enhances their rankings.

Brand Associations of Minor Hockey Tournaments: Understanding the Rep Hockey Parents' Perspective

Tournaments and other hockey-related activities have been calculated to be a significant driver of tourist dollars for many regions across Canada. The competition to attract teams to participate in tournaments, which benefit the tournament organizers and the communities in which they reside, is significant. Consequently, the purpose of the study was to assess the brand associations that representative (rep) minor hockey parents from Ontario’s Greater Golden Horseshoe Region perceive as relevant when considering ideal tournaments for their child to participate in. Brand associations have been classified as the attributes, benefits, or attitudes one uses to develop a perception of a product or service. To investigate the current study, 30 interviews were conducted using a laddering interview technique. Findings indicate that there are seven attributes and nine benefits that impact a tournament’s brand association including: competition, tournament operations, accommodations, bonding, fun, parity, and time management. The interrelationship between the identified attributes and benefits is discussed while recommendations and directions for future research are presented.

Alleviating Negative Spillover of a Brand-Harm Crisis: Sensegiving vs. Sensehiding in a Competitor’s Denial Response Strategy

A brand-harm crisis not only affects the scandalized brand, but may also influence competing brands. Thus, marketers of competing brands need to develop response strategies for reducing negative spillover effects. This research takes a competitor’s perspective and introduces two types of response strategies used to convey a sense of denial: sensegiving and sensehiding. It also investigates how the effects of response strategies are contingent upon brand relatedness and individual thinking styles. The results from three experimental studies show that using a sensegiving strategy reduces negative spillover effects more than using a sensehiding strategy. Additionally, the studies suggest that the observed difference in the effects of response strategy tends to be greater when the level of brand relatedness is high than when it is low. However, individual thinking styles (holistic vs. analytic) seem to have little impact on consumers’ responses to the two denial strategies. This research contributes to the brand-harm crisis literature and provides novel insights into a competitor’s response to potential negative spillover effects.