Reactions of various aromatic nitro-compounds and anthraquinones with selected bases and nucleophiles

The Introducti on deals mainly with hi storical studies on aryne chemi stry and ring closure via arynes , hydride replacement from aromatic rings by nucleophi les, c l eavage of anthr aquinones in basic medium and the Leuckart reaction . This work can be divided into two main s ect i ons. Section I is concerned with the investigation of t he reaction of some aromatic ni t ro-compounds with potassamide in l iquid ammonia. 3-Amino-4- nitrobenzophenone was obtained from the reacti on of 4-nitrobenzophenone with t his reagent, toge t her with benzoic acid formed in a competing Haller-Bauer reaction. Nitrobenzene under these conditions gave a complex mixture from which 2-phenylphenol was isolated; a reaction i nvolving benzyne may be i nvo l ved. 4-Nitrodiphenyl sulfone gave 4-aminodiphenyl sulfone and 4-nitroani l ine. 4-Ethoxydiphenyl sulfone and 4-ethoxynitrobenzene were isolated when ethanol was used as a co-solvent in the reaction. Oxidative coupling reactions were observed with nitrotoluenes. 4-Nitrotoluene gave 4,4t-dinitrobibenzyl which i n a pro longed reaction gave 4,4t-dinitros t ilbene . 2-Nitrotoluene gave 2 , 2 t-dinitrobibenzyl, but not the corresponding stilbene derivative even after a longer time . A rather i nteresting result was obtained with 1-nitro-2,4,6- trimethylbenzene which gave a stilbene derivative only. Also the corresponding stilbene was obtained from bis-(4-nitrophenyl)-methane in a rather slow r eaction with this reagent . Section II deals wi th (i) the preparation of 5-chloro- 1-N-methyl aminoanthraquinone and a new synthesis of N-methyl acridones and (ii) treatment of chloro-anthraquinones with fo rmamide and a new synthesis of chloro-anthracenes . 5-Chloro-1 -N-methylaminoanthraqui none was synthesised f rom 1,5-dichloroanthraquinone by treatment with N-methylformamide. Treatment of 5-chloro-1-N-methylaminoanthraquinone with potassamide in liquid ammonia or with potassium t-butoxide i n t-butylbenzene gave N-methylacridone-1-carboxylic acid. This pleasing result, t he outcome of r i ng opening and alter native ring closure, is being extended to related ring systems.

Fast atom bombardment and electron impact mass spectrometry studies of some aryltin compounds and ferrocenes

Both El MS and FAB MS behavior of two groups of compounds, aryltin and ferrocene compounds, have been studied. For the aryltin compounds, the effect of substituent group position, substituent group type and ligand type on the El spectra have been explored in the El MS studies. The fragmentation mechanism has been investigated under El with linked scans, such as fragment ion scans(BJE), parent ion scans(B2JE) and constant neutral radical loss scans(B2(1-E)JE2). In the FAB MS studies, matrix optimization experiments have been carried out. The positive ion FAB MS studies focused on the effect of substituent group position, substituent group type and ligand type on the spectra. The fragmentation mechanisms of all the samples under positive ion FAB have been studied by means of the linked scans. The CA positive ion FAB fragmentation studies were also carried out for a typical sample. Negative ion FAB experiments of all the compounds have been done. And finally, the comparison of the El MS and FAB MS has been made. For ferrocenes, the studies concentrated on the fragmentation mechanism of each compound under El with linked scan techniques in the first field-free region and the applicability of positive/negative ion FAB MS to this group of compounds. The fragmentation mechanisms under positive ion FAB of those ferrocenes which can give positive ion FAB MS spectra were studied with the linked scan techniques. The CA +ve F AB fragmentation studies were carried out for a typical sample. Comparison of the E1 MS and FAB MS has been made.

Reactions of polyhalogenated aromatic compounds and related ethers with metal/ammonia solutions

This work contains the results of a series of reduction studies on polyhalogenated aromatic compounds and related ethers using alkali metals in liquid ammonia. In general, polychlorobenzenes were reduced to t he parent aromatic hydrocarbon or to 1 ,4-cyc1ohexadiene, and dipheny1ethers were cleaved to the aroma tic hydrocarbon and a phenol. Chlorinated dipheny1ethers were r eductive1y dechlorinated in the process. For example, 4-chlorodipheny1- ether gave benzene and phenol. Pentach1orobenzene and certain tetrachlorobenzenes disproportionated to a fair degree during the reduction process if no added proton source was present. The disproportionation was attributed to a build-up of amide ion. Addition of ethanol completely suppressed the formation of any disproportionation products. In the reductions of certain dipheny1ethers , the reduction of one or both of the dipheny1ether rings occurred, along with the normal cleavage. This was more prevalent when lithium was the metal used . As a Sidelight, certain chloropheno1s were readily dechlorinated. In light of these results, the reductive detoxification of the chlorinated dibenzo-1,4-dioxins seems possible with alkali metals in l iquid ammonia.

Mass spectrometric studies on aryltin compounds and alkali halides /

The fragmentation behavior of aryltin compounds [(p-ThAnis)nSnPh4.n (n=l-4); (p-ThAnis)3SnX (X=C1, Br, I); (o-CH30C6H4)3SnCl; Ph3Sn(o-pyr)] have been studied comparatively under EI and FAB ionization modes. Alkali halides were run under FAB mode. For the aryltin compounds, the effect of ligand type on the spectra have been explored in both EI and FAB modes. The fragmentation mechanisms have been examined with linked scans, such as fragment ion scans (B/E) and parent ion scans (B^/E). Ab Initio molecular orbital calculations were used to determine the structures of the fragments by comparing their relative stabilities. In the EI MS studies, negative ion EI mode has also been used for some of the aryltin compounds, to examine the possible ion molecule reactions under low pressures at 70eV. In the positive ion FAB MS studies, matrix optimization experiments have been carried out. Negative ion FAB experiments of all the compounds have been done in two different ways. Finally, the comparison of the two methods, EI MS and FAB MS, have been made.For alkali halides, the studies focused on the FAB MS behavior under different conditions. The intensities of cluster ions were reported, and the anomalies in the intensity distribution was also discussed.

Baroreflex sensitivity and developmental coordination disorder

Developmental coordination disorder (DCD) is a motor coordination disorder that is characterized by impairment of motor skills which leads to challenges with performing activities of daily living. Children with DCD have been shown to be less physically active and have increased body fatness. This is an important finding since a sedentary lifestyle and obesity are risk factors for cardiovascular disease. One indicator of cardiovascular health is baroreflex sensitivity (BRS), which is a measure of short term BP regulation that is accomplished through changes in HR. Diminished BRS is predictive of cardiovascular morbidity and mortality. The purpose of this study was to investigate BRS in 117 children aged 12 to 13 years with probable DCD (pOCO) and their matched controls with normal coordination. Following 15 minutes of supine rest, five minutes of continuous beat-by-beat blood pressure (Finapres) and RR interval were recorded (standard ECG). Spectral indices were computed using Fast Fourier Transform and transfer function analysis was used to compute BRS. High frequency and low frequency power spectral areas were set to 0.15-0.6 Hz and 0.04-0.15 Hz, respectively. BRS was compared between groups with an independent t-test and the difference was not significant. It is likely that a difference in BRS was not seen between groups since the difference in BMI between groups was small. As well, differences in BRS may not have manifested yet at this early age. However, the cardiovascular health of this population still deserves attention since differences in body composition and fitness were found between groups.

Elucidation of odour-potent compounds and sensory profiles of Vidal blanc and Riesling icewines from the Niagara Peninsula : effect of harvest date and crop level

I t was hypothesized that the freeze/thaw cycles endured by icewine grapes would change their chemical composition, resulting in unique chemical fingerprint and sensory properties, and would be affected by harvest date (HD) and crop level (CL). The objectives were: 1) to identify odour-active compounds using gas chromatographic and sensory analysis; 2) to determine the effect of CL and HD on these compounds; 3) to determine the icewine sensory profiles; 4) to correlate analytical and sensory results for an overall icewine profile. CharmAnalysis™ determined the Top 15 odour-potent compounds in Vidal and Riesling icewine and table wines; 24 and 23 compounds, respectively. The majority of the compounds had the highest concentrations in the icewines compared to table wines. These compounds were used as the foundation for assessing differences in icewine chemical profiles from different HD and CL. Vidal and Riesling icewine were made from grapes picked at different HD; HI : 19 December; H2: 29 December; H3: 18 January; H4: 11 February (Vidal only). HI wines differed from H3 and H4 wines in both Vidal and Riesling for aroma compounds and sensory profiles. - Three·CL [control (fully cropped), cluster thin at fruit set to one basal cluster/shoot (TFS), and cluster thin at veraison to one basal cluster/shoot (TV)] were evaluated for Riesling and Vidal cultivars over two seasons. Vidal icewines had the highest concentration of aroma compounds in the control and TV icewines in 2003 and in TFS icewines in 2004. In Riesling, most aroma compounds had the highest concentration in the TV icewines and the lowest concentration in the TFS wine for both years. The thinned treatments were associated with almost all of the sensory attributes in both cultivars, both years. HD and CL affected the chemical variables, aroma compounds and sensory properties of Vidal and Riesling icewines and freeze/thaw events changed their sensory profile. The most odour-potent compounds were p-damascenone, cis-rose oxide, 1- octen-3-ol, 4-vinylguaiacol, ethyl octanoate, and ethyl hexanoate. The role of Pdamascenone as a marker compound for icewine requires further investigation. This research provides a strong foundation for the understanding the odour-active volatiles and sensory profiles important to icewine.

Acts of incorporation and amendments of the Niagara Falls Suspension Bridge Co'y and the Niagara Falls International Bridge Co'y, also articles of association, leases, agreements, etc. (1900)

Contains "Acts of Parliament of Province of Canada and Acts of Parliament of Dominion of Canada."

Printed blank from Frank Pearce and Co. Shipping and Insurance Agents

Printed blank from Frank Pearce and Co. Shipping and Insurance Agents regarding the bill of landing for the porcelain cask, Oct. 26, 1876.

Receipt from Arthur Jukes and Co., Druggists and Dispensing Chemists, St. Catharines for soap

Receipt from Arthur Jukes and Co., Druggists and Dispensing Chemists, St. Catharines for soap, Dec. 1, 1886.

Receipt from Foley, Fitzgerald and Co., Bakers and Confectioners, St. Catharines

Receipt from Foley, Fitzgerald and Co., Bakers and Confectioners, St. Catharines for baked goods, Feb. 29, 1888.

The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halide molecules /

TITLE: The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halides. AUTHOR: J. L. Brema SUPERVISOR: Dr. D. C. Moule NUMBER OF PAGES: 89 ABSTRACT: The vibrational assignment of the five-in-plane fundamental modes of CSClBr has been made on the basis of infrared gas phase and liquid Raman spectral analyses to supplement our earlier vibrational studies. Even though the one out-of-plane fundamental was not observed spectroscopically an attempt has been made to predict its frequency. The vibrational spectra contained impurity bands and the CSClBr assignment was made only after a thorough analysis of the impurities themselves. A normal co-ordinate analysis calculation was performed assuming a Urey-Bradley force field. This calculation yielded the fundamental frequencies in good agreement with those observed after refinement of the originally transferred force constants. The theoretical frequencies are the eigenvalues of the secular equation and the calculation also gave the corresponding eigenvectors in the form of the very important LLj matrix. The [l] matrix is the transfoirmation between internal co-ordinates and normal co-ordinates and it is essential for Franck-Condon calculations on electronically excited molecules and for infrared Integrated band intensity studies. Using a self-consistent molecular orbital calculation termed "complete neglect of differential overlap" (CNDO/2) , theoretical values of equilibrium bond lengths and angleswere calcuted for a series of carbonyl and thlocarbonyl molecules. From these calculations valence force field force constants were also determined but with limited success. With the CNIX)/2 method theoretical dipole moment derivatives with respect to symmetrized internal co-ordinates were calculated and the results should be useful in a correlation with experimentally determined values.

The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

Biotransformation of polycylic aromatic compounds by fungi and an investigation into the oxidation of alkylbenzenes by Mortierella isabellina NRRL 1757

Incubations of several polycyclic heteroaromatic compounds and two polycyclic aromatic hydrocarbons with a series of common fungi have been performed. The fungi Cunninghamella elegans ATCC 26269, Rhizopus arrhizus ATCC 11145, and Mortierella isabellina NRRL 1757 were studied in this regard. Of the aza heteroaromatics, only dibenzopyrrole gave a ring hydroxylated product following the incubation with C. elegans. From the thio heteroaromatics studied, dibenzothiophene was metabolized by all the three fungi and thioxanthone by C. elegans and M. isabellina giving sulfones and sulphoxides. Thiochromanone was metabolized stereoselectively to the corresponding sulphoxide by C. elegans. Methyl substituted thioxanthones on incubation with C. elegans produced oxidative products, arising from S -oxidation and hydroxylation at the methyl group. Of the cyclic ketones studied, only fluorenone was reduced to hydroxyfluorene and this metabolism is compared with that reported with cytochrome P-450 monooxygenases of hepatic microsomes. A series of para-substituted ethylbenzenes has been transformed stereoselectively to the 1-phenylethanols by incubation with M. isabellina. Comparisons of the enantiomeric purities obtained from products with their respective para substituent of the same steric size but different electronic properties indicate that the stereoselectivity of hydroxylation at benzylic carbon may be susceptible to electron donating or withdrawing factors in some cases, but that observation is not va lid in all the comparisons. The stereochemistry of the reaction is discussed in terms of three possible steps, ethylbenzene ---) 1-phenylethanol ---) acetophenone ---) 1-phenylethanol. This metabolic pathway could account for the inconsistencies observed in the comparisons of optical purities and electronic character of para substituents. Furthermore, formation of 2-phenylethanol (in some cases), l-(p-acetylphenyl)ethanol from p-diethylbenzene, and N-acetylation of p-ethylaniline was observed. n-Propylbenzene was also converted to optically active 1-phenylpropanol. Acetophenone, p-ethylacetophenone, and o(,~,~-trifluoroacetophenone were transformed to 1-phenylethanol, l-(p-ethylphenyl)ethanol, and 1-phenyl-2,2,2-trifluoroethanol, respectively, with high chemical and excellent optical yields. The 13 C NMR spectra of several substrates and metabolic products have been reported and assigned for the first time.

Gas chromatographic electron capture negative ionization mass spectrometric (GC/ECNI/MS) determination of unique fluorinated compounds in the sediments of Lake Ontario and the effect of high-boiling alcohols (as injection solvents) on chromatographic behaviour of polycyclic aromatic hydrocarbons in gas chromatography

Part I - Fluorinated Compounds A method has been developed for the extraction, concentration, and determination of two unique fluorinated compounds from the sediments of Lake Ontario. These compounds originated from a common industrial landfill, and have been carried to Lake Ontario by the Niagara River. Sediment samples from the Mississauga basin of Lake Ontario have been evaluated for these compounds and a depositional trend was established. The sediments were extracted by accelerated solvent extraction (ASE) and then underwent clean-up, fractionation, solvent exchange, and were concentrated by reduction under nitrogen gas. The concentrated extracts were analyzed by gas chromatography - electron capture negative ionization - mass spectrometry. The depositional profile determined here is reflective of the operation of the landfill and shows that these compounds are still found at concentrations well above background levels. These increased levels have been attributed to physical disturbances of previously deposited contaminated sediments, and probable continued leaching from the dumpsite. Part II - Polycyclic Aromatic Hydrocarbons Gas chromatography/mass spectrometry is the most common method for the determination of polycyclic aromatic hydrocarbons (PAHs) from various matrices. Mass discrimination of high-boiling compounds in gas chromatographic methods is well known. The use of high-boiling injection solvents shows substantial increase in the response of late-eluting peaks. These solvents have an increased efficiently in the transfer of solutes from the injector to the analytical column. The effect of I-butanol, I-pentanol, cyclopentanol, I-hexanol, toluene and n-octane, as injection solvents, was studied. Higher-boiling solvents yield increased response for all PAHs. I -Hexanol is the best solvent, in terms of P AH response, but in this solvent P AHs were more susceptible to chromatographic problems such as peak splitting and tailing. Toluene was found to be the most forgiving solvent in terms of peak symmetry and response. It offered the smallest discrepancies in response, and symmetry over a wide range of initial column temperatures.

Ligand design for molecule-based magnetic and/or conducting materials

Work in the area of molecule-based magnetic and/or conducting materials is presented in two projects. The first project describes the use of 4,4’-bipyridine as a scaffold for the preparation of a new family of tetracarboxamide ligands. Four new ligands I-III have been prepared and characterized and the coordination chemistry of these ligands is presented. This project was then extended to exploit 4,4’-bipyridine as a covalent linker between two N3O2 macrocyles. In this respect, three dimeric macrocycles have been prepared IV-VI. Substitution of the labile axial ligands of the Co(II) complex IV by [Fe(CN)6]4- afforded the self-assembly of the 1-D polymeric chain {[Co(N3O2)H2O]2Fe(CN)6}n•3H2O that has been structurally and magnetically characterized. Magnetic studies on the Fe(II) complexes V and VI indicate that they undergo incomplete spin crossover transitions in the solid state. Strategies for the preparation of chiral spin crossover N3O2 macrocycles are discussed and the synthesis of the novel chiral Fe(II) macrocyclic complex VII is reported. Magnetic susceptibility and Mössbauer studies reveal that this complex undergoes a gradual spin crossover in the solid state with no thermal hysteresis. Variable temperature X-ray diffraction studies on single crystals of VII reveal interesting structural changes in the coordination geometry of the macrocycle accompanying its SCO transition. The second project reports the synthesis and characterization of a new family of tetrathiafulvalene derivatives VIII – XII, where a heterocyclic chelating ligand is appended to a TTF donor via an imine linker. The coordination chemistries of these ligands with M(hfac)2.H2O (M( = Co, Ni, Mn, Cu) have been explored and the structural and magnetic properties of these complexes are described.