Studies of nucleophilic attack on tris (pentafluorophenyl) phosphine and its oxides

The reaction of tris(pentafluorophenyl)phosphine [5] with the nucleophiles dimethyl formamide (DMF), hexamethylphosphoric triamide (HMPA), diethyl formamide (DEF), hexaethylphosphoric triamide (HEPA), hydrazine, N,N-dimethyl hydrazine (in presence and/or absence of KF), phenylhydrazine, ammonium hydroxide, formamide, aniline, sodium hydrogen sulfide, and hexaethylphosphorous triamide was investigated. The reaction of [5] with DMF and HMPA gave the same product, namely tris-[4-(N,N-dimethylamino)-2,3,5,6-tetrafluorophenyl]phosphine [12] but in higher yield in the case of HMPA. Compound (5] also reacted with DEF to give tris[4-(N,N-diethylamino)-2,3,5,6-tetrafluorophenyl] phosphine [14]. When [51 was treated with HEPA, it gave a mixture of bis(pentafluorophe~yl)-(N,N-diethylamino-tetrafluorophenyl)phosphine, pentafluorophenyl-bis-(N,N-diethylamino-tetrafluorophenyl)phosphine and tris (N,N-diethylamino-tetrafluorophenyl)phosphine. Treatment of [5] with aqueeus hydrazine solution in excess ethanol gave tris(4-hydrazo-2,3,4,6-tetrafluorophenyl)phosphine [1s1 in high yield while reaction with aqueous hydrazine led to C-P cleavage and production of tetrafluorophenyl hydrazine. With N,N-dimethyl hydrazine, [5] gave tris(4-N,N-dimethylhydrazine-2,3,5,6-tetrafluorophenyl) phosphine {20j. The latter could be obtained in higher yield and shorter reaction time, by the addition of KF. The reaction of compound {51 with phenylhydrazine in THF gave bis(pentafluorophe~yl)-4-S-phenylhydrazino- 2,3,5,6-tetrafluorophenyl phosphine [22] in low yield. Reaction of [5] with ammonium hydroxide in THF at high pressure in the presence of KF gave tris-~4-amino-2,3,5,6-tetrafluorophenyl)phosphine [25]. Similarly, formamide led to a mixture of (C6F4NHZ)3P, (C6F4NHZ)ZPC6FS, (C6F4NHZ)ZPC6F4NHCHO, and C6F4NHZP(C6Fs)(C6F4NHCHO). When [5] was treated with aniline, a mixture of mono-, di-, and tri-substituted products was obtained. Sodium hydrogen sulfide in ethylene glycol/ pyridine led to C-P cleavage and the isolation of pentafluorobenzene and tetrafluorothiophenol. Reaction of [5] and its oxide [35] with different alkoxides in the corresponding alcohols led mainly to C-P bond cleavage products, with the exception of one case where sodium methoxide was used in ether, and which led to tris-(4-methoxy-2,3,9,6-tetrafluorophenyl)phosphine [37]. On the basis of various spectroscopic data, it was concluded that the para position in compound [5] was generally the favoured site of attack.

The effect of schooling on student self-concept /|nRonald S. Cowley. -- 260 St. Catharines [Ont. : s. n.],

The following research paper was a study into change in student academic and general self-concept with increase in grade level and age# The majority of literature found by this researcher dealt with self-concept and its relationship to achievement and interactions with others, Review, then, was in these two areas-particularily within the academic setting, but outside of it as well. It wrs hypothesized that there would be a decrease in both academic and general student self-concept with increase in grade level and age. Self-Appraisal inventories, measuring general and academic selfconcept, and Inferential Self-Reports, measuring only academic selfconcept, were the instruments used* Subjects were students, Trade 1 to 13, and ranging in age from 5 to 21„ Although al] Self-Appraisal inventories and all Self-1?eports were very similar, they differed according to three Grade levels: Primary (Grades 1 to 3)> Intermediate (Grades L to 8), and Secondary (Grades 9 to 13) • Students in the Primary division received only their respective Self-Appraisal inventory, while others v/ere administered both inventories designed for their grade level. Scores on the inventories were computed to percents and then mean percents were arrived at for epch grade, each of the three grade levels, each age, and each of three age intervals. In all of these instances Spearman1 s rank order coefficients (!lpff) were calculated and significance, at the *05 level, was determined by referring to a table of critical values for one-tailed tests* Similarily fftff scores were computed, but only for individual grades and ages, and significance was determined at the *0b level* In only one instance, the General Dimension for individual grades, was significance of overall decrease found* Consequently the hypotheses put forth did not gain support* The fltff scores, however, revealed some isolated significant changes for the Academic Dimension, which were generally decreases in mean percents from the last grade of one level to the first grade of the next* For age mean percents, significant changes generally took place at early (5 or 6) and late (20 or 21) ages* A number of reasons for the results were presented and were generally based upon the studentfs encounters, or lack of encounters, with achievement or success* No definite conclusions, relevant to the hypotheses stated^ could be made, although a number of isolated ones were drawn on the basis of significant fltff scores* As well, mention was made of the possible trends or tendencies that were revealed by the results, but that could not, or were not, proven significant by "t's11 or "p's"* Teaching methods stressing improvement in academic, as well as socially related, situations, were recommended and a model teaching approach was presented in Appendix B#

The impact of a training program in phonological awareness on children's early writing

This study examined the effects that a training program in phonological awareness had on the early writing skills of children in a Grade One class in the Lincoln County Separate school system. The intent of the training program was to provide consistent and systematic practice in the manipulation of the phonological structure of language. The games and activities of the training program were related to a framework of developmental phonological skills and practised in a group setting during an unstructured period of the regular classroom schedule. The training program operated three days in a six-day cycle for approximately twenty minutes a day, from November until mid-March. All children were tested at the outset and conclusion of the study to determine level of functioning in letter identification, word recognition, verbal intelligence, phonological awareness and spelling. Results of the pre-tests and post-tests were compared to determine differences between the experimental and control groups over time. In addition, a systematic analysis of the children's writing looked at the development of the spelling of regular and irregular words. The results of this study provided strong support for the hypothesis that the treatment group would progress through the stages of early writing development more quickly than children without such training. On the basis of differences between the groups over time, it was evident that training in phonological awareness had a direct positive effect on the spelling of regular words for children during the early stages of writing. The training program did not have a significant effect on the spelling of irregular words. Test results evaluating phonological awareness indicated a significant difference within each group over time but no significance between the groups during the experimental period. It would appear that the results of these tests reflect maturational changes in the child rather than causal effects of the training program. Nor did the effects of the training program transfer significantly to other aspects of language. Although some of the hypotheses considered were not supported by the study, the results do indicate that children during the early stages of writing development can benefit from a training program in phonological awareness. The theoretical direction for effective programming as a result of this study is discussed. The educational implications of training phonological awareness concurrent to beginning efforts in writing are considered.

Effects of credit rating change on risk-taking

This thesis investigates whether there are changes in risk-taking behavior following an upgrade or downgrade in credit ratings. Research on effects of rating changes on capital markets is well-documented but the literature on how rating changes may affect firm behavior is sparse. Following, a downgrade in credit rating, managers may increase risk-taking to improve their overall performance or reduce risk-taking following upgrades to ensure that their performance is assessed more on the basis of what they may deem success in the form of an upgrade. Using a sample of firms trading in the U.S from 1994-2013, we find evidence of change in risk-taking behavior. We use cross-sectional regressions and matching using propensity scores and Barber and Lyon (1997) methodology to measure changes in risk-taking and we do find evidence of changes in managerial risk-taking behavior. Furthermore, we find that the direction of change (increase or decrease) in some cases is dependent on the type of measure rather than the type of rating change.