Intramolecular carbenoid insertions : the reactions of [alpha]-diazoketones derived from furanyl, thienyl, benzofuranyl and benzothienyl acetic acids with rhodium (II) acetate /

A number of synthetically useful ring systems can be prepared via the intramolecular insertion of a metal-stabilized carbenoid into a heteroaromatic systems. The chemical outcome of these reactions are dependent not only on the nature of the heteroatom but also on the length of the aliphatic tether linking the carbenoid moiety with the aromatic fragment. Our work with furanyl and thienyl systems containing a single methylene tether have allowed for some rather atypical chemistry. For example, treatment of l-diazo-3-(2-thienyl)-2-propanone (6) with catalytic rhodium (II) acetate yields 5,6- dihydro-4^-cyclopenta[Z>]thiophen-5-one (3) while, the isomeric l-diazo-3-(3-thienyl)-2- propanone(15) gives a spiro-disulphide (20). Novel chemistry was also exhibited in the analogous furanyl systems. While treatment of l-diazo-3-(3-furanyl)-2-propanone (52) with Rh2(OAc)4 resulted in the expected 2-(4-Oxo-2-cyclopentenyliden)acetaldehyde (54), isomeric l-diazo-3-(2- furanyl)-2-propanone (8) undergoes vinylogous Wolff rearrangement to give a mixture of 6a-methyl-2,3,3a,6a-tetrahydrofuro[2,i-^>]furan-2-one (44) and 2-(2-methyl-3-furyl)acetic acid (43). Rhodium acetate catalyzed decomposition of l-diazo-3-(3-benzofuranyl)-2- propanone (84) and l-diazo-3-(2-benzofuranyl)-2-propanone (69)also allows for vinylogous Wolff rearrangement, a chemistry unseen in benzofuranyl systems with longer tethers. A number of interesting products were isolated from the trapping of intermediate ketenes. Decomposition of l-diazo-3-(3-benzothienyl)-2-propanone (100) resulted in the formation of 2,3-dihydro-l//-benzo[^]cyclopenta[^thiophen-2-one (102). However, in addition to (102), a dimer was also generated from the decomposition of l-diazo-3-(2- benzothienyl)-2-propanone (109). The insight into the mechanistic underpinnings of the above reactions are provided by molecular modeling at a PM3 level.

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.

Demographic and genetic attributes of dispersing and resident individuals of an enclosed Microtus pennsylvanicus population

A dispersal polymorphism may exist in emigrants from cyclic populations of Microtus '~nnsylvanicus biasing trap-revealed movements of unenclosed animals in favour of sedentary or colonizing individuals. The dispersal tendency of emigrants from an enclosed population was investigated by releasing animals via tubes into one of two adjacent enclosures, one vacant and one inhabited. Individuals from the enclosed population were monitored for age, sex, weight and electrophoretically detectable serum transferrin genotype in an intensive live-trapping program. In 1973 the minimum number alive in the introduced enclosed study population reached approximately l67/ha when breeding stopped in October. In 1974 intensive breeding increased the population density to 333/ha by mid-July when a long decline in numbers and breeding intensity began without an intervening plateau. An adjacent unenclosed area had a much lower density and longer breeding season in 1974. The growth rate of young males in the enclosed population tended to be lowest during the decline period in 1974. Survival of the enclosed population was high throughout but was lowest during the decline phase in both sexes, especially males. Low transferrin heterozygote survival during the decline coincided with a significant heterozygote deficiency in females whereas in males genotype frequencies did not depart from Hardy-Weinberg equilibrium values throughout th.e study. Twenty-nine suitable ani.mals were released during the decline in five periods from July to November 1974. The proportions of males and transferrin heterozygotes in the released graun were generally greater than in the source population~ In the test enclosures 21% of the released animals continued their movement through the vacant area while 41% (no significant difference) moved through the inhabited enclosure. In the vacant test area, females had a greater tendency than males to continue dispersal whereas no difference was noted in the inhabited area. Low frequency of captures in the tubes, predator disturbances and cold weather forced the termination of the study. The role of dispersal as a population regulating mechanism was further substantiated. The genetic differences between emigrant and resident animals lend support to Howard's hypothesis that a genetic polymorphism influences the tendency to disperse. Support is also given to Myers' and Krebs' contention that among dispersers an additional density dependent polymorphism influences the distance dispersed.

The nesting biology of Ceratina (Hymenoptera: Apidae) in the Niagara Region : new species, nest site selection and parasitism

One of the most common bee genera in the Niagara Region, the genus Ceratina (Hymenoptera: Apidae) is composed of four species, C. dupla, C. calcarata, the very rare C. strenua, and a previously unknown species provisionally named C. near dupla. The primary goal of this thesis was to investigate how these closely related species coexist with one another in the Niagara ~ee community. The first necessary step was to describe and compare the nesting biologies and life histories of the three most common species, C. dupla, C. calcarata and the new C. near dupla, which was conducted in 2008 via nest collections and pan trapping. Ceratina dupla and C. calcarata were common, each comprising 49% of the population, while C. near dupla was rare, comprising only 2% of the population. Ceratina dupla and C. near dupla both nested more commonly in teasel (Dipsacus sp.) in the sun, occasionally in raspberry (Rubus sp.) in the shade, and never in shady sumac (Rhus sp.), while C. calcarata nested most commonly in raspberry and sumac (shaded) and occasionally in teasel (sunny). Ceratina near dupla differed from both C. dupla and C. calcarata in that it appeared to be partially bivoltine, with some females founding nests very early and then again very late in the season. To examine the interactions and possible competition for nests that may be taking place between C. dupla and C. calcarata, a nest choice experiment was conducted in 2009. This experiment allowed both species to choose among twigs from all three substrates in the sun and in the shade. I then compared the results from 2008 (where bees chose from what was available), to where they nested when given all options (2009 experiment). Both C. dupla and C. calcarata had the same preferences for microhabitat and nest substrate in 2009, that being raspberry and sumac twigs in the sun. As that microhabitat and nest substrate combination is extremely rare in nature, both species must make a choice. In nature Ceratina dupla nests more often in the preferred microhabitat (sun), while C. calcarata nests in the preferred substrate (raspberry). Nesting in the shade also leads to smaller clutch sizes, higher parasitism and lower numbers of live brood in C. calcarata, suggesting that C. dupla may be outcompeting C. calcarata for the sunny nesting sites. The development and host preferences of Ceratina parasitoids were also examined. Ceratina species in Niagara were parasitized by no less than eight species of arthropod. Six of these were wasps from the superfamily Chalcidoidea (Hymenoptera), one was a wasp from the family Ichneumonidae (Hymenoptera) and one was a physogastric mite from the family Pyemotidae (Acari). Parasites shared a wide range of developmental strategies, from ichneumonid larvae that needed to consume multiple Ceratina immatures to complete development, to the species from the Eulophidae (Baryscapus) and Encyrtidae (Coelopencyrtus), in which multiple individuals completed development inside a single Ceratina host. Biological data on parasitoids is scarce in the scientific literature, and this Chapter documents these interactions for future research.

Synthesis of cytochrome P450 inhibitors of vitamin E metabolism

Please consult the paper edition of this thesis to read. It is available on the 5th Floor of the Library at Call Number: Z 9999 C54 O46 2007

Letter to S.D. Woodruff from William Colburn with the letterhead “Office of Detroit Bridge and Iron Works”

Letter to S.D. Woodruff from William Colburn with the letterhead “Office of Detroit Bridge and Iron Works” regarding stating that he closed up the business with Dewey’s. He states that “we” now have “warranty deeds” from them for exclusive rights for all time for hunting, shooting and trapping, Mar. 20, 1884.