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 pancreatic islet system of the rock bass /|nby Edward Francis Squires. -- 260 St. Catharines, Ont. : [s. n.],

The endocrine pancreas of the rock bass (Ambloplites rupestris) was examined by light and electron microscopy. Two cell types with staining properties similar to mammalian A and B cells, and a third, non-staining cell type were found in the spherical pancreatic islets that were surrounded by a connective tissue capsule and embedded in two small masses of exocrine tissue. From an analysis of the ultrastructure of the A and B cells, a secretory cycle for each of these cell types was proposed. The secretory cycle of the A cell consisted of three well defined stages: (1) A cell production stage: during which A granule formation occurred in the sacs of the Golgi apparatus and the cell was characterized by the presence of numerous secretory granules, some elements of lamellar endoplasmic reticulum, and a homogeneously granular nucleus. The cytoplasm contained few distended cisternae, variable numbers of free ribosomes, microtubules and small vesicles. (2) A cell release stage: during which the release of A granules occurred and the cell usually contained several large distended cisternae and variable numbers of secretory granules. Granule release mechanisms included exocytosis, by which individual granules were released into the extracellular space after their membranes fused with the plasmalemma, and emiocytosis, by which one or more granules were released into a large cisterna whose membrane fused with the plasmalemma and formed a pore through which the cisternal contents passed out of the cell. (3) A cell reorganization stage: during which the changeover from the release stage to the production stage occurred and the reorganization of organelles and membrane structures took place. The cell contained few secretory granules and numerous small endoplasmic reticular cisternae. The cytoplasm exhibited less electron density than either of the other two stages. The A granule after formation underwent a series of morphological changes which were described in four numerically identified phases. The secretory cycle of the B cell consisred of two stages: (1) B cell production stage: during which the B granule formation occurred in the sacs of the Go1gi apparatus. The cell was characterized by an irregular outline, the presence of numerous secretory granules, and an irregularly shaped nucleus which contained variable amounts of clumped chromatin. The cytoplasm contained moderate amounts of lamellar endoplasmic reticulum studded with ribosomes, several small vesicles, and an active Go1gi apparatus. (2) B cell release stage: during which the release of B granules occurred. The cell contained a rounded nucleus with dispersed chromatin, several distended endoplasmic reticular cisternae and a variable number of secretory granules. Granule release occu~ by emiocytosis and exocytosis similar to that found for the A cell.

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.

The Smiles rearrangement in hydrazidic systems and related syntheses /|nG. A. Pawelchak. -- 260 St. Catharines, Ont. : [s. n.],

This research was directed towards the investigation of the Smiles rearrangement in hydrazidic systems and the synthesis of related heterocyclic compounds. The work can be conveniently divided into two main sections. Section 1 of the thesis relates to the synthesis and examination of the O+N migration of phenoxy- derivatives of hydrazidic halides. In general, hydrazidic halides were found to react with 2-nitrophenol and 4-nitrophenol to give corresponding a-nitrophenoxy- compounds. These a-nitrophenoxy- compounds were found to rearrange in warm base to give the corresponding N-benzoyl compounds via a proposed five-membered transition state. Experiments conducted in styrene revealed no radical contribution to the rearrangement. Cross-over product analysis indicated the rearrangement as intramolecular and consistent with the Smiles rearrangement. The preparation of N-a-chlorobenzylidene-N'-2-nitrophenyl- -N'-(2,4-dibromophenyl)hydrazine from N-benzoyl-N'-2-nitrophenyl- N'-(2,4-dibromophenyl)hydrazine was accomplished using phosphorus oxychloride. Examination of this hydrazidic chloride indicated a marked decrease .in reactivity as compared to the N-a-chlorobenzylidene-N'-phenylhydrazine case. Section 2 concerns itself with the preparation of heterocyclic compounds using an analogy of the five-membered transition state present in the Smiles rearrangement of a substituted benzylidene derivatives A new preparation of 2,4-phenyl1,3,4- oxadiazol-S-one using N-benzoyl-N'-phenylhydrazine and ethyl thiochloroformate is reported. Two new preparations of N-a-thiobenzoyl-N'-(2,4-dibromophenylhydrazine are reported using sodium hydrosulfide in conjunction with N-a-bromobenzylidene-N'-(2,4-dibromophenyl)hydrazine in the first, and phosphorus pentasulfide with N-benzoylN'-( 2,4-dibromophenyl)hydrazine in the second. The latter is preferred due to the formation of a sulfide co-product in the former. Two preparations of 2-phenyl-4-(2,4-dibromophenyl)-1,3,4- thiadiazol-S-one are reported using N-thiobenzoyl-N'-(2,4-dibromophenyl) hydrazine and ethyl chloroformate and ethyl thiochloroformate Two rapid and easy preparations of 2-phenyl-4-(2,4-dibromophenyl)- 1,3,4-triazol-S-one are reported using ethyl chloroformate and ethyl thiochloroformate. Sodium cyanate in conjunction with a-aminobenzylidene-N'-(2,4-dibromophenyl)hydrazine also provided 2-phenyl-4-(2,4-dibromophenyl)-1,3,4-triazol-S-one Section 2 concludes with an examination of two possible mechanistic routes to the prepared heterocycles.

The vibrational spectra and the normal coordinate analysis of thiocarbonye halides /|nby C. R. Subramaniam. -- 260 St. Catharines, Ont. : [s. n.],

The infrared and the Raman spectra of eSelF has been obtained for the first time and has been analysed to give the in-plane normal vibrational frequencies of the molecule, in the ground state. A normal co-ordinate analysis has been carried out for the molecules CSF2, CSClF and eSel 2 using a Urey-Bradley type of potential function and the elements of the [L] matrix elements, the distribution of the potential energy in Urey-Bradley space, and the displacement vector diagrams for the normal modes of vibration for these molecules, have been obtained. The bond for~e constants obtained through the normal co-ordinate analysis, have given some interesting results. The stretching force constant, Kes ' varies markedly with halogen substitution and the force constants KeF and Keel also vary with substitution.

An Act to authorise the stock held by private parties in the Welland Canal to be purchased on behalf of the Province [Welland Canal Stock Bill], 1841

The bill is a proposal by the government to purchase Welland Canal stock held in private hands. The bill was read for the first time on Wednesday 4 August, 1841, and received second reading on 10th August, 1841. One hundred and fifty copies were printed of the bill. This example was addressed to Samuel Street at the Falls of Niagara, by William Hamilton Merritt, September 1841.

Copies of two dispatches upon the subject of the Welland Canal, 1827-1828

The material is a printed record of two dispatches sent by Sir Peregrine Maitland, Lieutenant Governor of Upper Canada to secretary of state for the colonies, the first in 1827 to Earl Bathurst, the second in 1828 to Right Hon. W. Huskisson. The dispatches concern funding for the canal as well as an introduction of William Hamilton Merritt as managing agent of the Welland Canal Company. It was the intention of the Welland Canal Company to send Mr. Merritt to England to gain further assistance from the government and private investors.

Second Welland Canal - Book 1, Survey Map 3 - Old Lock 2 in Grantham Township

Survey map of the Second Welland Canal created by the Welland Canal Company showing a portion of the Grantham Township near Port Dalhousie. Identified structures associated with the Canal include the new towing path. The surveyors' measurements and notes can be seen in red and black ink and pencil. Features of the First Welland Canal are noted in red ink and include the old Lock 2, old towing path and the original bed of the Twelve Mile Creek. Local area landmarks are also identified and include streets and roads (ex. Side Line and Old Road), four unnamed bridges, and a tree stump along the old towing path. A New Road to Port Dalhousie is featured in red ink. Properties and property owners of note are: Concession 3 Lots 21, 22 and 23, Concession 4 Lots 21, 22 and 23, Jabez Johnson, Adam Gould, Peter Weaver and Samuel Wood.

Second Welland Canal - Book 1, Survey Map 4 - Through Grantham Township

Survey map of the Second Welland Canal created by the Welland Canal Company showing a portion of the Grantham Township. Identified structures associated with the Canal include the floating tow path and the canal itself. The surveyors' measurements and notes can be seen in red and black ink and pencil. Features of the First Welland Canal are noted in red ink and include the old towing path. Local area landmarks are also identified and include streets and roads (ex. Line between Wood and Tenbroeck), an unnamed bridge, a poplar tree and walnut tree along the east shore. Properties and property owners of note are: Concession 4 Lot 22, Samuel Wood, and John R. Tenbroeck.

Second Welland Canal - Book 1, Survey Map 5 - Through Grantham Township

Survey map of the Second Welland Canal created by the Welland Canal Company showing a portion of the Grantham Township near Port Dalhousie. Identified structures associated with the Canal include the tow path and floating tow path. The surveyors' measurements and notes can be seen in red and black ink and pencil. Features of the First Welland Canal are noted in red ink and include the old towing path, the Old Canal, two unnamed bridges traversing the Old Canal, and the bed of the Twelve Mile Creek. Local area landmarks are also identified and include streets and roads (ex. Old Road, Side Line, Road to Port Dalhousie), Samuel Wood's house, Peter Weaver's house, J. R. Tenbroeck's house, a poplar and walnut tree along the east shore, an oak and hickory tree along the west shore, and a walnut tree stump along the west shore. Properties and property owners of note are: Concession 3 Lots 21, 22, and 23, Concession 4 Lots 21, 22, and 23, Adam Gould, Samuel Wood, Peter Weaver, and John R. Tenbroeck.

Second Welland Canal - Book 2, Survey Map 8 - Little Deep Cut in Thorold

Survey map of the Second Welland Canal created by the Welland Canal Company showing the canal in Thorold South. Identified structures associated with the Canal include the Little Deep Cut and the towing path. The surveyors' measurements and notes can be seen in red and black ink and pencil. Local area landmarks are also identified and include streets and roads (ex. Road to Beaverdams and Road to Allanburgh), two unnamed bridges, the Spoil Bank, a pond, and the Back Water. Properties and property owners of note are: Lots 29 and 30, Jacob Keefer, John Brown, William Bouck, C. Gisso, and a property reserved for Bridge Tender.

Second Welland Canal - Book 2, Survey Map 9 - Back Water Bodies in Thorold

Survey map of the Second Welland Canal created by the Welland Canal Company showing the Back Water bodies in Thorold Township. The surveyors' measurements and notes can be seen in red and black ink and pencil. A number of trees along the shores presumably used in the measurements are labelled. Local area landmarks are also identified and include streets and roads(ex. Road to Beaverdams), Shriner's Dwelling Home, a barn, and the Back Water bodies. Properties and property owners of note are: Lots 27, 28, and 29, W. Bouck, D. Shriner, and Rev. T. B. Fuller.

Second Welland Canal - Book 2, Survey Map 10 - Through Thorold

Survey map of the Second Welland Canal created by the Welland Canal Company showing the canal in Thorold Township. Identified structures associated with the Canal include the towing path. The surveyors' measurements and notes can be seen in red and black ink and pencil. Local area landmarks are also identified and include streets and roads (ex. Road to Allanburgh), an unnamed bridege, several barns, a structure labelled Bridge Tender, and a dwelling. Properties and property owners of note are: Lots 30, 31, 32, 48, 49, and 50, Robert Booth, Hiram Marlatt, George Keefer, John Kelly, Isaac Kelly, John Brown, Thomas Lee, and the Board of Works.

Second Welland Canal - Book 2, Survey Map 11 - Marlatts Bridge in Thorold

Survey map of the Second Welland Canal created by the Welland Canal Company showing the canal in Thorold Township. Identified structures associated with the Canal include the towing path. The surveyors' measurements and notes can be seen in red and black ink and pencil. Local area landmarks are also identified and include streets and roads(ex. Road to Allanburgh), Marlatt's Bridge, Marlatt's Culvert, Marlatt's Dwelling House, Willson's Dwelling House, Willson's Tannery, a flume, a bridge house, a covered drain, and a creek. Properties and property owners of note are: Lots 49, 50, and 51, Hiram Marlatt, Willson, John Kelley, and E. Hopkins.

Second Welland Canal - Book 2, Survey Map 12 - Through Thorold

Survey map of the Second Welland Canal created by the Welland Canal Company showing the canal in Thorold Township. Identified structures associated with the Canal include the towing path. The surveyors' measurements and notes can be seen in red and black ink and pencil. Local area landmarks are also identified and include streets and roads (ex. Road to Allanburgh), Higgins Flume, Spoil Bank, a creek, a pond, a culvert, and a barn. Properties and property owners of note are: Lots 73, 74, and 75, G. Keefer Sr., James Gibson, Malum Swayze, Henry Higgins, S. Merithew, and Robert Smith.