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.

Kinetic and product studies for the oxidtion of organic sulfides and sulfoxides in the presence of transition metal complexes

Rates and products of the oxidation of diphenyl sulfide, phenyl methyl sulfide, p-chlorophenyl methyl sulfide and diphenyl sulfoxide have been determined. Oxidants included t-Bu02H alone, t-Bu02H plus molybdenum or vanadium catalysts and the molybdenum peroxo complex Mo0(02)2*HMPT. Reactions were chiefly carried out in ethanol at temperatures ranging from 20° to 65°C. Oxidation of diphenyl sulfide by t-Bu02H in absolute ethanol at 65°C followed second-order kinetics with k2 = 5.61 x 10 G M~1s"1, and yielded only diphenyl sulfoxide. The Mo(C0)g-catalyzed reaction gave both the sulfoxide and the sulfone with consecutive third-order kinetics. Rate = k3[Mo][t-Bu02H][Ph2S] + k^[Mo][t-Bu02H][Ph2S0], where log k3 = 12.62 - 18500/RT, and log k^ = 10.73 - 17400/RT. In the absence of diphenyl sulfide, diphenyl sulfoxide did not react with t-Bu02H plus molybdenum catalysts, but was oxidized by t-Bu02H-V0(acac)2. The uncatalyzed oxidation of phenyl methyl sulfide by t-Bu02H in absolute ethanol at 65°C gave a second-order rate constant, k = 3.48 x 10~"5 M^s""1. With added Mo(C0)g, the product was mainly phenyl methyl sulfoxide; Rate = k3[Mo][t-Bu02H][PhSCH3] where log k3 = 22.0 - 44500/RT. Both diphenyl sulfide and diphenyl sulfoxide react readily with the molybdenum peroxy complex, Mo0(02)2'HMPT in absolute ethanol at 35°C, yielding diphenyl sulfone. The observed features are mainly in agreement with the literature on metal ion-catalyzed oxidations of organic compounds by hydroperoxides. These indicate the formation of an active catalyst and the complexation of t-Bu02H with the catalyst. However, the relatively large difference between the activation energies for diphenyl sulfide and phenyl methyl sulfide, and the non-reactivity of diphenyl sulfoxide suggest the involvement of sulfide in the production of an active species.

Investigations on the production of long chain fatty acids in Choanephora cucurbitarum (Berk.

The fatty acid composition of the total cellular lipids of Choanephora cucurbitarum incubated for 96 hrs on either glucose-ammonium sulfate or malt-weast extract media was determined. The major fatty acids were palmitic, palmitoleic, stearic and linoleic acids. The saturated fatty acid possessing the longest acyl chain was stearate (C 18:0). The presence of glutamic acid (2.0 x 10-1% or 1.36 x la-2M) in either of the above growth media resulted in increase in percent of 1f-linolenic acid, decrease in percent of linoleic ~iCid and appearance of a new series of fatty acid> C ~8 e.g. C ",,,,'V' C2k:O, C26,O. The addition of glutamic acid had no effect on the lipid yield but slightly decreased the degree of unsaturation. Compounds which duplicated the effect of glutamic acid were acetate, malate, citrate, succinate, 0( -ketoglutarate, prOline, -y -aminobutyric acid and glucose (3%) but not aspartic acid or alanine. ~o correlation was found between glutamic acid pool concentration and the presence in the growth medium of those compounds which stimulate long chain fatty acid production. Four hours of incubation with 27 JJ 1-1 glutamate supported the production of long chain fatty acids. This stimulation is inhibited if 272 .u M isophthalic acid is added with 27 AJ M glutamate. But, long chain fatty acids were detected when 27 JJ M eX -ketoglutarate is also present in the incubation mixture. Five hours of incubation with 100 ,Mg/ml of cycloheximide resulted in over 9CY/o inhibition of cytoplasmic :protein synthesise Glutamate (27 .uM) enhanced the synthesis of long chain fatty acids under these conditions. These findings are discussed in an attempt to provide a plausible explanation COmmon to compounds that support the production of long chain fatty acids.