The versatility and utilization of phosphorus based compounds in classic carbon-carbon bond forming and esterification reactions

The phosphonium salt room temperature ionic liquid tetradecyltrihexylphosphonium chloride (THPC) has been employed as an efficient reusable media for the palladium catalyzed Suzuki cross-coupling reaction of aryl halides, including aryl chlorides, under mild conditions. The cross-coupling reactions were found to proceed in THPC containing small amounts ofwater and toluene (single phase) using potassium phosphate and 1% Pd2(dba)3'CHCI3. Variously substituted iodobenzenes, including electron rich derivatives, reacted efficiently in THPC with a variety of arylboronic acids and were all complete within 1 hour at 50°C. The corresponding aryl bromides also reacted under these conditions with the addition of a catalytic amount of triphenylphosphine that allowed for complete conversion and high isolated yields. The reactions involving aryl chlorides were considerably slower, although the addition of triphenylphosphine and heating at 70°C allowed high conversion of electron deficient derivatives. Addition of water and hexane to the reaction products results in a triphasic system, from which the catalyst was then recycled by removing the top (hexanes) and bottom (aqueous) layers and adding the reagents to the ionic liquid which was heated again at 50°C; resulting in complete turnover of iodobenzene. Repetition of this procedure gave the biphenyl product in 82-97% yield (repeated five times) for both the initial and recycled reaction sequences. IL ESTERIFICATIONREACTION A new class oftrialkylphosphorane has been prepared through reaction of a trialkylphosphine with 2-chlorodimethylmalonate in the presence oftriethylamine. These new reagents promote the condensation reaction of carboxylic acids with alcohols to provide esters along with trialkylphosphine oxide and dimethylmalonate. The condensation reaction of chiral secondary alcohols can be controlled to give either high levels of inversion or retention through a subtle interplay involving basicity of the reaction media, solvent, and tuning the electronic and steric nature of the carboxylic acid and stenc nature of the phosphorane employed. A coherent mechanism is postulated to explain these observations involving reaction via an initial acyloxyphosphonium ion.

ESL students' off-line and on-line texts : differences and similarities /

This study was undertaken to investigate any textual differences and similarities within essays written with a word processing program and an e-mail editor by non-native writers. It arose from many contradictions and a paucity of empirical research within the field of second language learning and electronic technology. To further explore these contradictory observations, 3 classes of intermediate level ESL (English as a Second Language) students v^ote 6 essays, alternating between a word processing program and an e-mail editor. Prior to the data collection, students read brief texts and responded to questions that focused upon three formal topics: immigration, economics, and multiculturalism. Data were examined for (a) the differences in the frequency counts of 12 cohesive devices, (b) sentence complexity, which focused upon the occurrences of simple and complex sentences, (c) the number of words within the writings, (d) the method of contextualization preferred by writers, and (e) any variations in the final grades of the students' texts that resulted from holistic rating. Results of analysis indicated that there were no statistically significant differences in the frequency counts of the linguistic features. Sentence complexity did not vary within the off-line and on-line essays. The average number of words found within the off-line essays was approximately 20% greater than within on-line essays. Contextualization methods were not different within word-processed or e-mailed essays. Finally, there was no difference in the quality of the texts when holistically rated.