A study of the thermal decomposition of allyl t-butyl peroxide and 3-hydroperoxy-1-propene (allyl hydroperoxide) in toluene /|nby Krishnankutty Nair V. G. -- 260 St. Catharines [Ont. : s. n.],

Kinetics and product studies of the decompositions of allyl-t-butyl peroxide and 3-hydroperoxy- l-propene (allyl hydroperoxide ) in tolune were investigated. Decompositions of allyl-t-butyl peroxide in toluene at 130-1600 followed first order kinetics with an activation energy of 32.8 K.cals/mol and a log A factor of 13.65. The rates of decomposition were lowered in presence of the radical trap~methyl styrene. By the radical trap method, the induced decomposition at 1300 is shown to be 12.5%. From the yield of 4-phenyl-l,2- epoxy butane the major path of induced decomposition is shown to be via an addition mechanism. On the other hand, di-t-butYl peroxyoxalate induced decomposition of this peroxide at 600 proceeded by an abstraction mechanism. Induced decomposition of peroxides and hydroperoxides containing the allyl system is proposed to occur mainly through an addition mechanism at these higher temperatures. Allyl hydroperoxide in toluene at 165-1850 decomposes following 3/2 order kinetics with an Ea of 30.2 K.cals per mole and log A of 10.6. Enormous production of radicals through chain branching may explain these relatively low values of E and log A. The complexity of the reaction is indicated a by the formation of various products of the decomposition. A study of the radical attack of the hydro peroxide at lower temperatures is suggested as a further work to throw more light on the nature of decomposition of this hydroperoxide.

Education, sport and myth in the community of Glengarry, Ontario : the athletic career of Roderick R. McLennan. 260 St. Catharines, Ont. : Faculty of Education, Brock University ;

This study examined how the athletic career of Roderick R. McLennan contributed to the popularization and subsequent development of Caledonian games in Ontario during the latter nineteenth century. Initially, the development of Caledonian games during the 1800s was examined to provide a contextual framework for McLennan's career. This investigation revealed that the games emerged from rural athletic events at pioneer working bees in the first quarter of the nineteenth century to regional sporting events by the mid-1800s, and finally into annual federated Caledonian games in 1870. Noteworthy primary source material for this chapter included the John MacGillivray Papers at the National Archives of Canada, the Scottish American Journal (NY) and the files retained by the Glengarry Sport Hall of Fame in Maxville, Ontario. Following the investigation of Caledonian games, McLennan's early athletic career was studied. Analysis of the Roderick and Farquhar McLennan Papers at the Archives of Ontario and the newspapers from the period revealed that McLennan rose to popularity in 1865 through a "Championship of the World" hammer throwing match in Cornwall and two "Starring Tours". The next chapter examined the height of McLennan's career through an investigation of the Roderick McLennan versus Donald Dinnie rivalry of the early .. n 1870s. It was detennined that the rivalry between McLennan and Dinnie, the champion athlete of Highland games in Scotland, was a popular attraction and had an impact on the Toronto and Montreal games of 1870 and the Toronto games of 1872. Finally, the athletic records established by McLennan during the 1860s and 1870s were investigated. These records were examined through the context of a media controversy over McLennan's feats that developed in the early 1880s between two newspapers. This controversy erupted between the Toronto Mail and the Spirit of the Times. Caledonian games in Canada have only been briefly examined and a thorough examination of prominent Canadian figures in this context has yet to be undertaken. This study unearths a prominent Canadian athlete of Scottish decent and details his involvement in the Caledonian games of nineteenth century Ontario.

Elliptical orbital studies of H21 and H2 molecules /|nS. K. Gupta. -- 260 St. Catharines, Ont. : [s. n.],

Calculations are performed on the \S <:Jd ground states of d ' + the H and HC) molecules using a basis set of non-integral ~ ~ I elliptical orbitals. Different variational wavefunctions constructed i- for H~ involved one parameter to three par~~eter variation. In order to l"'educe the ntunber of parameters in most commonly 0- used basis orbitals set, the importance of the term (,+~) Y\ over the term ;u 'Where n is a variational pararneter and the value of cr may be given by boundary condition or cusp condition is outlined in Chapters II and III. It is found that the two parameter -+ and moderate internuclear separations. c;. In order to find out the importance of the term (I +~ ) Y\ over ;U for the two electron problem, the variational energy is computed for the H~ molecule from unrestricted two parameter closed shell wavefunctions including the term U+ft)and from the cusp condition in the second case. In order to take into account in-out correlation partially, open shell calculation for the ground state of the hydrogen molecule for R =1.4 (equilibrium internuclear separation) is perfonaed. The results are excellent.

NMR studies of mixed tetrahaloborates and some related boron trihalide complexes /|nGary John Schrobilgen. -- 260 St. Catharines, Ont. : [s. n.],

Nuclear magnetic resonance spectroscopy has been used to study donor-acceptor complexes of boron trifluoride with several ureas, tetramethylthiourea, tetramethylselenourea, and tetramethylquanidine as well as adducts of tetramethyl- -urea with BF2Cl, BFC1 2 , and BC1 3 - A large number of mixed tetrahaloborate ions, including some of the ternary ones such as BF2CIBr-,have been obtained by ligand exchange reactions and studied by NMR techniques. The bonding in these ions is of the same inherent interest as the bonding in the isoelectronic tetrahalomethanes which have been the subject of many detailed studies and have been involved in a controversy concerning the existence of and the nature of "fluorine hyperconjugation" or C-F P1T- Pn bonding_ Ligand exchange reactions also gave rise to the difluoroboron cation, (TMU)20BF2+o The difluoroboron cation has been observed in solutions of TMU-BF3 , and has been proposed as a possible intermediate for fluorine exchange reactions in BF3 adducts.

Reactions of some non-enolisable chloroketones with amide ion and a new synthesis of acridones /|nGuo-shyoung John Chen. -- 260 St. Catharines, Ont. : [s. n.],

This research was directed mainly towards the investigation of the reacti.ons of· substituted chlorobenziophenones under strongly basi,c conditions. The work 'can be divided into two main sections. The Introduction deals mainly with historical studies on aryne chemistry and the Haller-Bauer reaction. Secti.on I i.s concerned with syntheses of 2-benzamido-2'chlorobenzophenone and 2-benzamido~3'-chlorobenzophenone,and with thei,r respective reactions wi.th potassium amide in ammonia. o-Chlorophenylacetic acid was converted to the acid chloride and then by Friedel-Craftsreaction with benzene to w-(o-chlorophenyl)acetophenone. Reaction wi.th phenylhydrazine and Fischer cyclization gave 3- (0chlorophenyl)- 2-phenylindole, which was ozonized to 2-benzamido-2'chlorobenzophenone. The isomeric 3' -chlor,..o ke: tone was similarly synthesised from m-chlorophenylacetic acid. Both the 2'- and 3' -ch.loroketones gave N-benzoylacridone on treatment with potassium amide in ammonia; an aryne mechanism is involved for the 3'-chloroketone but aryne and nucleophilic substitution mechanisms are possible for the 2'-chloroketone. Hydrolysis of the 2'- and 3'-chloroketones gave 2-amino-2'chlorobenzophenone and 2-amino-3'-chlorobenzophenone respectively. A second new acridone synthesis is given in the Appendix involving reactions of these two ketones with potassium t-butoxide in t-butylbenzene. i Section 2 deals with the investigation of the reaction of some tricyclic ch1orobenzophenones with potassium amide in liquid ammonia. These were 1-ch1orof1uorenone; which was pr~pared in several steps from f1uoranthene, and 1- and 2-ch1oroanthraquinones. 1-Ch1orof1uorenone gave 1-aminof1uorenone ; 1-ch1oroanthraquinone gave 1- and 2-aminoanthraquinones; 2-ch1oroanthraquinone was largely recovered from the attempted reaction.

Reduced local energy calculations on X¹Sigmaâ ½gHâ and 1¹S He /|nGerald F. Thomas. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,

The one-electron reduced local energy function, t ~ , is introduced and has the property < tL)=(~>. It is suggested that the accuracy of SL reflects the local accuracy of an approximate wavefunction. We establish that <~~>~ <~2,> and present a bound formula, E~ , which is such that where Ew is Weinstein's lower bound formula to the ground state. The nature of the bound is not guaranteed but for sufficiently accurate wavefunctions it will yield a lower bound. ,-+ 1'S I I Applications to X LW Hz. and ne are presented.

Synthesis and properties of some 4H-1, 3, 4 benzothiadiazines /|nby Darko J. Vukov. -- 260 St. Catharines, Ont. : [s. n.],

The work herein has been divided into five sections. In the first section, a new method of converting N-aroyl- hydrazines to hydrazidic halides is described. The second section deals with the products of reaction of hydrazidic halides with thioacetate ion in acetonitrile at room temperature. A number of new acetylthiohydrazides has been isolated together with corresponding hyclrazidic sulphides. Examination of x-ray data for bis-[~ -(2,6- dibromophenylhydrazono) - benZYl] sulphide revealpd the symmetrical structure as the most probable. In the third section, which consists of the three subsections, the synthesis of the 4H-l,3,4 benzothiadiazine ring system has been extended to 4H-l,3,4 benzothiadiazines with substituents in the 5 and 6-positions. Extension of synthesis also involves 4H-l,3,4 benzothiadiazines with mora than one substituent. Nuclear magnetic resonance spectra of 5 and 6 substituted 4H-l,3,4 benzothiadiazines have been ,. recorded. The section ends with a discussion of the mass spectra of some 4H-l.3,4 benzothiadiazines. In the fourth section, which is divided into two sub- -sections, preparation of 7-nitro substituted 4H-l,3,4 benzothiadiazine from N-thiobenzoyl hydrazine and2,4-dinitro -fluorobenzene is found to be satisfactory. Thiohydrazides react with acetic anhydride, in some cases, to give products identical with acetylthiohydrazides obtained from the hydrazidic halides with thioacetate ion at room temperature. In most of the cases thiohydrazides are found to give anomalous products on reaction with acetic anhydride and mechanisms for their formation are discussed. In the fifth section, which forms three subsections, the 4H-l,3,4 benzothiadiazine ring system with a halogen substituent in the 7-position undergoes electrophilic attack preferentially in 5-posi tion. \fuen the 5-posi tion is occupied by a halogen atom, electrophilic substitution occurs at the 7-position of 4H-l,3,4 benzothiadiazine ring system. Substitution at the 4-nitrogen atom in 4H w l,3,4 benzo- -thiadiazine is extremely slow, probably due to delocalisa- -tion of the nitrogen lone pair in the system. Oxidation of 4H-l,3,4 benzothiadiazines occurs at the sulphur atom under relatively mild conditions. t The Appendix deals with the reaction of N-benzoyl-N - -(2,5-dibromophenyl)hydrazine with p-nitrothiophenol~ The proposed p-nitrothiophenoxy - intermediate may undergo benzothiadiazine formation in a proton exchange system.

The application of gas liquid chromatography to the simultaneous analysis of sugars and sugar phosphates in biological samples /|nby David J. LeBlanc. -- 260 St. Catharines [Ont. : s. n.],

A study was undertaken' to determine the applicability of gas liquid chromatography to the simultaneous analysis of sugars and sugar phosphates from biological samples. A new method of silylation involving dimethylsulfoxide, hexamethyldisilazane, trimethylchlorosilane and cyclohexane (1:0.2:0.1:1) which rapidly silylated sugars and sugar phosphates was developed. Subsequent chromatography on a 5% SE-52 column gave good resolution of the sugar and sugar phosphate samples. Sugar phosphates decomposed during chromatography and were lost at the 7 x 10-3 ~mole level. Acidic ethanol extraction of yeast samples revealed background contamination from the yeast sample, the culture medium and the silylation reagents which would further limit the level of detection obtainable with the glc for sugars in biological samples to the 3 x 10-4 ~mole level.

The crystal and molecular structure of thiamine hydroiodide /|nWilliam Edward Lee. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,

The x-ray crystal structure of thiamine hydroiodide,C1ZH18N40S12' has been determined. The unit cell parameters are a = 13.84 ± 0.03, o b = 7.44 ± 0.01, c = 20.24 ± 0.02 A, 8 = 120.52 ± 0.07°, space group P2/c, z = 4. A total of 1445 reflections having ,2 > 2o(F2), 26 < 40° were collected on a Picker four-circle diffractometer with MoKa radiation by the 26 scan technique. The structure was solved by the heavy atom method. The iodine and sulphur atoms were refined anisotropically; only the positional parameters were refined for the hydrogen atoms. Successive least squares cycles yielded an unweighted R factor of 0.054. The site of protonation of the pyrimidine ring is the nitrogen opposite the amino group. The overall structure conforms very closely to the structures of other related thiamine compounds. The bonding surrounding the iodine atoms is distorted tetrahedral. The iodine atoms make several contacts with surrounding atoms most of them at or near the van der Waal's distances A thiaminium tetrachlorocobaltate salt was produced whose molecular and crystal structure was j~dged to be isomorphous to thiaminium tetrachlorocadmate.

The effects of cultural conditions and parasitism on the lipid composition of choanephora cucubitarum (Berk. Rav.) thaxter /|nJohn M. Deven. -- 260 St. Catharines [Ont. : s. n.],

The fatty acid composition of the total, neutral, sterol, free fatty acid and polar-lipid fractions in the mycelium of Choanephora cucurbitarum was determined. The major fatty acids in all lipid fractions were palmitic, oleic, linoleic and y-linolenic acid. Different lipid fractions did not show any particular preference for any individual fatty acid; however, the degree of unsaturation was different in various lipid fractions. Addition of glutamic acid to the malt-yeast extract medium resulted in the biosynthesis of a number of long-chain fatty acids beyond y-linolenic acid. These fatty acids, e.g. C22~1' C24:0 and C26=Q were never observed to be present in the fungus when grown on a malt-yeast extract medium without glutamic acid. Furthermore, thin-layer chromatographic analysis showed a larger and denser spot of diphosphatidyl glycerol from the mycelium grown on the glutamic acid medium than from the control mycelium. Various cultural conditions such as temperature, age, pH, light and carbon:nitrogen ratio in the growth medium used in this study did not alter the qualitative profile of fatty acids normally present in the organism. Neither did these conditions stimulate the production of further long-chain fatty acids (C20 - C26) beyond y-linolenic acid as observed in growth media containing glutamic acid. These cultural conditions influenced the degree of unsaturation, this being due mainly to changes in the concentration of y-linolenic acid. The fatty acid pattern of the lipid fractions though the same qualitatively, differed quantitatively due to the variation in the y-linolenic acid content under different cultural conditions. The degree of unsaturation of various lipid fractions decreased with increases in temperature, light intensity and pH, but within each treatment the same pattern of decreasing degree of unsaturation with increasing age was observed. The cultural conditions, used in this study, are also known to influence the degree and rate of development of the parasite, Piptocephalis virginiana. A direct correlation was observed between the levels of y-linolenic acid in C. cucurbitarum during the early stages of growth (24 h) and the degree of parasitism of P. virginiana. The amount of y-linolenic acid present in the host mycelium was found to be unrelated to either the dry weight of the mycelium or to the total lipid contents. K. virginiana is confined to host species which produce y-linolenic acid in their mycelium. The lipid profile of the host, C. cucurbitarum, did not show a significant qualitative or quantitative change in the lipid profile as a result of infection by the parasite, P. virginiana,e However, an increase in the total lipid was observed in the infected host mycelium. The significance of these results is discussed.

The electronic spectra and the determination of the excited state geometry of 3A" propynal /|nby Chhiu-Tsu Lin. -- 260 St. Catharines, Ont. : [s. n.],

Impurity free eluission spectra of HCCCHO and DCCCHO have been rephotographed using the electronic-energy-exchange method with benzene as a carrier gas. The near ultraviolet spectra of ReeCHO and DCCCHO were photographed in a sorption under conditions of high resolution with absorption path lengths up to 100 meters. The emission and absorption spectra of Propynal resulting from 3 n 1 t 1\ - A excitation has been reanalyzed in som.e detail. Botrl of the eH out-of-plane wagging modes were found to have negative anharmonicity. A barrier height of 56.8/0.0 cm- 1 and a nonplanar oft , , equilibrium angle of 17 3 /30 are calculated for the V 10/ lJ 11 modes. The in-plane and out-of-plane v1. brational modes in the 3A." and 1a~. ' elec ronic states of Propynal were subjected to a normal coordinate treatment in the approximat :on of tIle Urey-Bradley force field. From the relative oscillator strengths of the trans1·t1·0ns connect i ng t he v ibrat1•0n1ess lA' , state and t,he V1· bron1·C 3· if levels of the A state, the differences in equilibrium configuration were evaluated from an approximate Franck-Condon analysis based on the ground state normal coordinates. As this treatment gave 512 possible geometrical structures for the upper state, it 4 was necessary to resort to a comparison of the observed and calculated moments of inertia along with chemical intuition to isolate the structure. A test of the correctness of the calculated structure change and the vibrational assignment was raade by evaluating the intensities of the inplane and out-oi-plane fundarnental, sequence, and cross sequellce transitions y the exact Franck-Condon method.

The kinetics and mechanism of the thermal decomposition of sec-Butyl peroxide in liquid phase /|nby Sandor Szilagyi. -- 260 St. Catharines, Ont. : [s. n.],

Re~tes artd pJ~oducts of tllerma]. d,ecom.position of sec-butyl peroxide at 110 - 150°C i.n four solvents h,ave been determined. The d,ecompos i tion vJas sb.o\'\Tn to be tlnlmolecl.llar wi tho energies of activation in toluene, benzene, and cyclohexane of 36 .7-+ 1.0, 33.2 +- 1..0, 33.t~) +.. 1.0 I'(:cal/mol respectively. The activation energy of thermal decomposition for the d,et.1terated peroxide was found to be 37.2 4:- 1.0 KC8:1/1TIol in toluene. A.bo1J.t 70 - 80/~ ol~ tJJ.e' pl~od.1..1CtS could, be explained by kn01rJ11 reactions of free allcoxy raclicals J and very littJ...e, i.f allY, disPl"Opox~tiol'lation of tll10 sec-butoxy radica.ls in t116 solvent cage could be detected. The oth,er 20 - 30% of the peroxide yielded H2 and metb.:'ll etb..yl 1{etol1e. Tl1.e yield. o:f H2 "'lIas unafJ:'ected by the nature or the viscosity of the solvent, but H2 was not formed when s-t1U202 lrJaS phctolyzed. in tolttene at 35°C nor 'tl!Jrl.en the peroxide 1;'JaS tl1.ermally o..ecoJnposed. in the gas p11ase. ~pC-Dideutero-~-butYlperoxide was prepared and decomposed in toluene at 110 - 150°C. The yield of D2 was about ·•e1ne same 248 the yield. of I{2 from s-Bu202, bU.t th.e rate of decomposition (at 135°C) 1iJas only 1/1.55 as fast. Ivlecl1.anisms fOl') J:1ydrogen produ.ction are discussed, but none satisfactorily explains all the evidence.

The kinetics and mechanism of the thermal decomposition of bis diphenyl methyl and related peroxides in liquid phase /|nby C. Thankachan. -- 260 St. Catharines, Ont. : [s. n.],

Rates and products have been determined for the thermal decomposition of bis diphenyl methyl peroxide and diphenyl methyl tert* butyl peroxide at 110@~145@C* The decomposition was uniformly unimolecular with activation energies for the bis diphenyl methyl peroxide in tetrachloroethylene* toluene and nitrobenzene 26,6* 28*3f and 27 Kcals/mole respectively. Diphenyl methyl tert* butyl peroxide showed an activation energy of 38*6 Kcals/mole* About 80-90% of the products in the case of diphenyl methyl peroxide could be explained by the concerted process, this coupled with the negative entropies of activation obtained is a conclusive evidence for the reaction adopting a major concerted path* All the products in the case of diphenyl methyl peroxide could be explained by known reactions of alkoxy radicals* About 80-85% of tert butanol and benzophenone formed suggested far greater cage disproportionation than diffusing apart* Rates of bis triphenyl methyl peroxide have been determined in tetrachloroethylene at 100-120@C* The activation energy was found to be 31 Kcals/mole*

The preparation and reactions of some 1, 2-dipolar species /|nI. D. Brindle. -- 260 St. Catharines, Ont. : [s. n.],

This research was directed mainly towards the investigation of the reactions of allylic amineimides. The work can be divided into two main sections. Section 1 of the thesis deals mainly with thermolysis studies of amineimides. Sections 1a and 1b represent a comprehensive survey of amineimide literature up to 1971. N-A1ly1-N,N-dirnethylarnine-benzirnide was prepared and rearranged at 1400 to l-allyl-1-benzoyl-2,2-dimethylhydrazine. A tentative mechanism involving an initial migration to the carbonyl oxygen was disproved by incorporating the amineimide system into a five-membered ring. N,N~Dimethyl-N-propargylamine-benzimidedid not rearrange on heating; but the hydrobromide, on heating, disproportionated to give 1-benzoyl~2,2,2-trimethylhydraziniumbromide and I-benzoyl-2,2~ dimethylhydrazine. l-Ally'l--l, I-dimethyl-2-benzoy-lhydrazinium bromide and 1~benzoy-1-2,2, 2-trimethy-lhydrazinium iodide both disproportionated to give l~benzoyl-2,2-dimethylhydrazine. Section 1 concludes with a discussion of the mechanisms of ally'lic migrations in amineimides proposed by J. E. Baldwin. Section 2 deals with the formation of five-membered heterocyclic compounds from amineimides by bromination. 1,1-Dimethyl-2benzoyl- 4-bromopyrazolidinium bromide was formed from N-allyl-N,Ndime thy-lamtne-benzimide , 1,1-dimethyl-2-benzoyl-4-bromopyrazol-3enium bromide from N,N~dimethyl-N-propargylamine~benzimidevia the unusual acetylenic "bromonium" ion. Hydrogenolysis of both heterocyclic compounds gave the same product. The preparation was extended by forming 2,2-dimethyl-4-bromoisoxazolinium bromide from N-allylN, N-dimethylamine-N-oxide. Sections 3 and 4 cover a number of unsuccessful attempts to synthesise other amineimides and l,2-dipolar species.