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.

Some aspects of the chemistry of Reissert compounds / |nDurga Prasad Aysola. -- 260 St. Catharines [Ont. : s. n.],

1-(0- and m-Ohlorobenzoyl)isoquinolines have been synthesized by two routes involving Reissert compounds. One route involves condensation of 2-benzoyl-l,2-dihydroisoquinaldonitrile with the appropriate chlorobenzaldehyde and the second involves rearrangement of the appropriate Z-(chlorobenzoyl)-l,Z-dihydroisoquinaldonitrile under basic conditions. The action of potassamide in anhydrous liquid ammonia on both ketones gave unexpectedly N-(l-isoquinolyl)benzamide (67) as the major product and the use of dibenzo-18-crown-6-ether 98% substantially improved the yd..e.ld in the case of l-chloroketone. This amide (67) exhibits unusual hydrogen bonding. 1-(o-chlorobenzoyl)-6,7-dimethoxyisoquinoline (79) was prepared in very s,amll quantities by the route involving condensation of 2-benzoyll, Z-dihydro-6,7-dimethoxyisoquinaldonitrile with o-chlorobenzaldehyde. The poor yields are due to the instability of the anion of 2-benzoyl1, Z-dihydro-6,7-dimethoxyisoquinaldonitrile. Attempted preparation of the ketone (79) by rearrangement of 2-(o-chlorobenzoyl)-l,2-dihydro6,7- dimethoxyisoquinaldonitrile under basic conditions yielded the start~ng material (Reissert compound) and 6,7-dimethoxyisoquinoline. The action of potassamide in anhydrous liquid ammonia on l-(o-bromo-4,5-dimethoxybenzoyl)isoquinoline (85), which was prepared by the route involving the condensation of 2-benzoyl-l,4-dihydroisoquinaldonitrile with o-bromo-4,5-dimethoxybenzaldehyde, gave two products, which have not yet been identified. The ketone (85) and its precursors are interest~ng in that their 20 eV and 70 eV mass spectra do not show molecular ions.

Some aspects of the chemistry of 1, 3, 4 - Thiadiazolium salts and related compounds

The work described in this thesis has been divided into seven sections. The first section involves the preparation of N'-acyl-N'-arylN- benzothiohydrazides by the acylation of N'-aryl-N-benzothiohydrazides and is followed by a brief discussion of their possible conformation in solution. The second section deals with the preparation of 1,3,4-thiadiazolium salts by the action of perchloric acid/acetic anhydride on N'-acylN'- aryl-N-benzothiohydrazides and also by the reaction of N'-arylN- benzothiohydrazides with nitriles in an acidic medium. The preparation of 2-methylthio-I,3,4-thiadiazolium methosulfate by methylating the corresponding thione is also described. The third section deals with the reaction of 2-phenyl- and 2-methyl-I,3,4-thiadiazolium salts with alcohols in the presence of base. The stability and spectra of these compounds are discussed. Treatment of the 2-methyl-I,3,4-thiadiazolium salt with base was found to give rise to a dimeric anhydrobase and evidence supporting its structure is given. The anhydrobase could be trapped by a variety of acylating and thioacylating agents before dimerization occurred. In the fourth section, the reaction of N'-acyl-N'-aryl-N-benzothiohydrazides with a variety of acid anhydrides is described. These compounds were found to be identical with those obtained by acylating the anhydrobase. The mass spectral fragmentation of these compounds is described and the anomolous product obtained upon thiobenzoylation of 3-methyl-l-phenyl-pyrazal-5-one is also discussed. The fifth section deals with thioacyl derivatives of the anhydrobase which were prepared by the action of phosphorus pentasulfide upon the oxygen analogues and also obtained as the major product of the reaction of thioacetic acid with compounds related to N'-aryl-N-benzothiohydrazides. The mass spectra and p.m.r. spectra of these compounds are discussed. In the sixth section, the reaction of the 2-methylthio-l,3,4- thiadiazolium salt with active methylene compounds to give acyl and diacyl derivatives of the anhydrobase is described. Some aspects of these compounds are discussed. The seventh section describes the synthesis of ncyanine~' type dyes incorporating the l,3,4-thiadiazole ring and their spectra are briefly discussed.

Teachers' perceptions of effects of terminal examinations on teaching and learning at the secondary school level in Zimbabwe

This study was particularly aimed at the examinations and the effect they have on schooling at the secondary school level in Zimbabwe. The views and opinions of teachers on the use of terminal examinations for certification and the influence they are seen to have on teachers' approach to the curriculum were examined. The literature has shown that there is widespread criticism of the justice and effects of terminal examinations. It is argued that they lead to an over-emphasis of that which is measured, knowledge and intellectual ability, at the expense of that kind of education progress which is almost impossible to measure in an end-of-the-course assessment. Three hundred and six secondary school teachers responded to a survey which asked for teachers' perceptions of examinations and the curriculum. The findings of this study indicated that teaching is structured towards examinations. Although teachers are trying to teach and develop reasoning skills and other activities, the pressure of examinations and the importance of doing well in them force teachers to restrict themselves to examination requirements.

Test of Hockman and Oldham's job characteristics model in a post-secondary educational setting

One hundred and seventy-two subj ects participated in this quantitative, correlational survey which tested Hackman and Oldham's Job Characteristics Model in an educational setting. Subjects were Teaching Masters, Chairmen and Deans from an Ontario community college. The data were collected via mailed questionnaire, on all variables of the model. Several reliable, valid instruments were used to test the variables. Data analysis through Pearson correlation and stepwise multiple regression analyses revealed that core job characteristics predicted certain critical psychological states and that these critical psychological states, in turn were able to predict various personal and work outcomes but not absenteeism. The context variable, Satisfaction with Co-workers, was the only consistent moderating variable between core characteristics and critical psychological states; however, individual employee differences did moderate the relationship between critical psychological states and all of the personal and work outcomes except Internal Work Motivation. Two other moderator variables, Satisfaction with Context and Growth Need Strength, demonstrated an ability to predict the outcome General Job Satisfaction. The research suggests that this model may be used for job design and redesign purposes within the community college setting.

The satellite band patterns in the near ultraviolet absorption spectra of isotopic compounds of acetaldehyde

The 3700 A - 3000 A absorption spectra of CH3CHO and its isotopic compounds such as CH3CDO, CD3CHO and CD3CDO were studied in the gas phase at room temperature and low temperatures. The low resolution spectra of the compounds were recorded by a 1.5 m Baush and Lomb grating spectrograph. The high resolution spectra were recorded by a Ebert spectrograph with the Echelle grating and the holographic grating separately. The multiple reflection cells were used to achieve the long path length. The pressure-path length used for the absorption spectrum of CH 3CHO was up to 100 mm Hg )( 91 . 43mo The emission spectrum and the excitation spectrum of CH3CHO were also recorded in this research. The calculated satellite band patterns \vhich were ob-tailied by the method of Lewis were used to compare with the observed near UV absorption spectrum of acetaldehyde. These calculated satellite band patterns belonged to two cases: namely, the barriers-in-phase case and the barriers- out-of-phase case. Each of the calculated patterns corresponded to a stable conformation of acetaldehyde in the excited state . The comparisons showed that the patterns in the observed absorption spectra corresponded to the H-H eclipsed conformations of acetaldehyde in the excited state . The least squares fitting analysis showed that the barrier heights in the excited state were higher than in the ground state. Finally, the isotopic shifts for the isotopic compounds of acetaldehyde were compared to the compounds with the similar deuterium substitution.

Understanding the portfolio in the secondary school classroom

Four secondary school teachers were involved in this case study. Individual interviews, group reflective sessions, and participant portfolios were transcribed verbatim and analyzed. The use of the portfolio in the secondary school classroom was then discussed in relation to emergent themes. These themes included teacher attitude, portfolio structure, portfolio purpose, challenges, effect, and professional development. Teachers were able to individualize the portfolio structure to meet both program and students' needs. The portfolio structure enabled both teachers and students to assume control over the learning process. The portfolio informed teachers about their teaching. This, in tum, challenged them to reflect on their teaching practices and enabled them to redesign curriculum implementation. A collaborative professional development structure fostered a learning environment that enabled teachers to experience success, despite the challenges that they inevitably encountered. These findings were related to contemporary literature. Finally, implications for theory and practice related to portfolio use in the secondary school classroom and professional development for secondary school teachers were considered.

Who expects what from whom? : a gender based study on expectations and secondary school administration

This study is about expectations and aspirations of secondary school teachers. It is an investigation of why some teachers aspire to become administrators and why some teachers do not. My research compares expectations and existing attltudes regarding aspirations toward administration which are held by three distinct groups within the secondary school system: 1) principals/vice-principals, 2) aspiring teachers, and 3) non-aspiring teachers. This study questions why, in the late 60's, secondary school administration is still predominated by men. The conclusions and recommendations were based on interviews with thirty men and women in the Hamilton Secondary School System. In addltion, Mr. Keith Rielly, Superintendent of Operations, made valuable contributions to my work. The interviews revealed experiences and percept ions of men and women in di scourse about f amil y re lat i onshi ps, educational choices and perceived internal and external barriers which inhiblted or enhanced their decision to aspire to secondary school administration. Candidates spoke about their personal and professional Hves wlth respect to encouragement, perceived images of an administrator, netWOrking and the effect of marriage and children on their careers. Historically, women have not accepted the challenge of administration and It would appear as if this is still the case today. My research suggests that women are under-represented in secondary school administration because of internal and external barriers which discourage many women from aspiring. I conclude that many of women's internal barrlers are reinforced by external roadblocks which prevent women from aspiring to secondory school administration. Thus. many women who do not envision a future in educational administration establish priorities outside the general realm of education. I recommend that males and females recognize that women make valuable contributions to educational theory and design based on their experiences which may be "differene from mole experiences. but just as significant. Mole and female representation in secondary school administration represents a balance between attitudes and behaviours which can not be accomplished when an administrative offlce is dominated by on all ma1e or all female staff.

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.

A study of ethical decision-making in hypothetical scenarios by secondary school principals /

The purpose of the study,was to investigate the ways in which secondary school principals make decisions that have an ethical dimension, and the reasons they use to justify their choices. The ethical principles and concepts, as well as the scenarios, were adapted from The Ethics ofSchool Administration by Strike, Haller, and Soltis (1998). In this study, 32 secondary principals from a school board in Ontario were asked to complete a descriptive survey which was designed to have principals make administrative decisions in response to 5 hypothetical scenarios. The open-ended questions were expected to elicit responses that were reflective of the principals' actual decision-making strategies. The survey also required them to justify and explain their reasons for each decision. The data were analyzed and 4 major categories ofjustifications emerged: pedagogy, legalism, moral code, and democracy. The results indicate that the decisions made by principals are grounded in various perspectives. While the data did not indicate any explicit knowledge of ethical principles and concepts, the principals' responses suggest sound and valid reasoning for their decision making, addressing the principles and concepts from a variety of viewpoints and using diverse justifications.

A conceptual analysis of research literature on teachers' ideology and literacy practices: extending the dialogue through a secondary analysis of high school English as an additional language contexts /

This thesis provides a conceptual analysis of research literature on teachers' ideology and literacy practices as well as a secondary analysis of three empirical studies and the ways in which the ideologies of the English as an Additional Language (EAL) (Street, 2005) teachers in these contexts impact the teaching of literacy in empowering/disabling ways. Several major theoretical components of Cummins (1996, 2000), Gee (1996, 2004) and Street (1995, 2001) are examined and integrated into a conceptual triad consisting of three main areas: power and ideology, validation of students ' cultural and linguistic backgrounds, and teaching that empowers. This triad provides the framework for the secondary analysis of three empirical studies on the ideologies of secondary EAL teachers. Implications of the findings from the conceptual and secondary analyses are examined in light of the research community and secondary school teachers of EAL.

Miss-understand-ing: design education in Ontario secondary schools : an exploration of the issues with stakeholders and recommendations for change /

For most people design is a mystery. The products of design are integrated into our daily lives to the point that design has become invisible to us. However. what is subsumed in design practice is a creative problem-solving process that is applicable as a teaching strategy as well as a method for teaching the subject of design. The purpose of this study was to inquire into the current classroom practice of Ontario Visual Arts and Technological Education teachers, understand the goals of Ontario government curriculum developers, and explore the position held by the professional design community on secondary school design education. Data for this study were collected from: (a) a textual analysis of 4 Ministry curriculum documents; (b) interviews with JO stakeholders; (c) unobtrusive observations and informal conversations conducted at 7 secondary school open house events; and (d) observation of 2 sessions of an AQ course for Design and Technology. The research design modeled the design process and was divided into 2 parts: a discovery or problem-finding phase and a discussion or problem-solving phase. The results showed that design is misunderstood and misused; it has become lost between visual arts and technology where neither program holds responsibility for its delivery; students mistake working on computers for design practice; and while there is a desire within the professional community to have a voice in secondary school design education. there is no forum for participation. The technology-driven paradigm shift taking place in society today calls for a new framework for tellching and practicing dcsign. Further research is required; howcvcr. in the meantime. secondary school educators might benefit from professional development and classroom support from the professional dcsign community.

ESI-MS[n] of anticancer pt[iv] organoamido complexes and their interactions with DNA-model compounds /

The general solution behaviour and" the major fragmentation pathways of the anticanceractive PtIV coordination complexes, trans, trans, cis, cis-[PtCIOH{N(pFC6F4) CH2h(pY)2] (1), trans, cis, cis-[Pt(OH)2{N(p-FC6F4)CH2h(Py)2] (2), trans, cis, cis-[Pt(OH)2{N(p-HC6F4)CH2h(Py)2] (3), trans, trans, cis, cis-[PtCIOH{N(pHC6F4) CH2h(Py)2] (4), and trans, trans, cis, cis-[PtOH(OCH3){N(p-HC6F4)CH2h(PY)2] (5) (Py = pyridine) have been deduced by positive-ion tandem-in-time ESI-MS. Overall, the acquired full-scan, positive-ion ESI-MS spectra of 2, 3, and 5 were characterized by the presence of relatively low-intensity [M+Nar and [M+Kt mass spectral peaks, whereas those of 1 and 4 were dominated by extremely intense [M+Hr peaks. Complexes 2 and 3 were also noted to form [2M+Ht and [2M+Nat dilneric cations. The source of Na + and K+ ions is believed to be the sample, the solvent systems used or the transport line carrying the sample solutions into the ES ion source. Further, the fragmentation pathway of all complexes studied was found to be almost identical with concurrent loss of py and H20 molecules, loss of a {N(p-YC6F4)CH2} (Y = F, H) group and/or concomitant release of the latter group and a py ligand being the most conunon. The photochemical degradation behaviour of 1 and 2 was also investigated using either fluorescent or ultraviolet light and some products of that degradation were positively identified. Altogether, light irradiation of solutions of both complexes resulted in cation cationisation, reductive-elimination, ligand-release, ligand-exchange and ligand-addition reactions. Finally, positive- and negative-ion ESI-MSn spectra of 5' -GMP, guanosine, inosine and products of their reactions with 1, 2,3, and 4 were also recorded. On the whole, full-scan ESI-MS spectra of the pure nucleobases revealed the presence of cationic and anionic species that are highly reflective of both their solution ionic composition and their propensity t9 form polymeric clusters. Analyses of mass spectra acquired from their reaction solutions with the aforementioned platinum complexes indicated very slow kinetics. However, all complexes investigated formed, to various degrees, Pt-nucleobase adducts with guanosine and inosine, but not with 5'-GMP. The products included species having coordination numbers of III, IV, V, and VI, among which the first-time· observed, coordinatively saturated, jive-coordinate PtlI-nucleobase complexes were of most interest. The latter complexes are presumably stabilized by 7tback- donation involving the filled d orbitals of the PtII centre and the empty pz· orbital of MeCN. All products, whose peaks appeared inlull-scan ESI-MS spectra, are believed to represent solution species rather than artifacts of gas-phase processes. Finally, negativeion ESI-MSn spectra recorded in reaction solutions of 1 and 4 with guanosine and of the latter complex with inosine revealed the negative-ion-ESI-MS first-time observed, noncovalent, nucleoside-chloride adducts, with the source of chloride anion being complexes 1 and 4 theillselves. In contrast, no such adducts were observed to form with Na25'-GMP or its protonated fonn. Few suggestions are offered for the possible cause(s) behind the absence of such adduct ions.

Phospha-adamantane ligands and phosphorous ionic liquids for palladium-catalyzed cross-coupling reactions /

New and robust methodologies have been designed for palladiumcatalyzed cross-coupling reactions involving a library of novel tertiary phosphine ligands incorporating a phospha-adamantane framework. The secondary phosphine, l,3,5,7-tetramethyl-2,4,8-trioxa-6-phospha-adamantane was converted into a small library of tertiary phosphine derivatives and the ability of these tertiary phosphaadamantanes to act as effective ligands in the palladium-catalyzed amination reaction and p-alkyl-Suzuki cross-coupling was examined. l,3,5,7-Tetramethyl-6- phenyl-2,4,8-trioxa-6-phosphaadamantane (PA-Ph) used in combination with Pd2(dba)3 CHCI3 facilitated the reaction of an array of aryl iodides, bromides and chlorides with a variety secondary and primary amines to give tertiary and secondary amines respectively in good to excellent yields. 8-(2,4-Dimethoxyphenyl)- l,3,5,7-tetramethyl-2,4,6-trioxa-8-phospha-tricyclo[3.3.1.1*3,7*]decane used in combination with Pd(0Ac)2 permitted the reaction of an array of alkyl iodides, and bromides with a variety aryl boronic acids and alkyl 9-BBN compounds in good to excellent yields. Subsequent to this work, the use of phosphorous based ionic liquids, specifically tetradecyltrihexylphosphonium chloride (THPC), in the Heck reaction provided good to excellent yields in the coupling of aryl iodides and bromides with a variety of olefins.