Kinetic and product studies for the oxidtion of organic sulfides and sulfoxides in the presence of transition metal complexes

Rates and products of the oxidation of diphenyl sulfide, phenyl methyl sulfide, p-chlorophenyl methyl sulfide and diphenyl sulfoxide have been determined. Oxidants included t-Bu02H alone, t-Bu02H plus molybdenum or vanadium catalysts and the molybdenum peroxo complex Mo0(02)2*HMPT. Reactions were chiefly carried out in ethanol at temperatures ranging from 20° to 65°C. Oxidation of diphenyl sulfide by t-Bu02H in absolute ethanol at 65°C followed second-order kinetics with k2 = 5.61 x 10 G M~1s"1, and yielded only diphenyl sulfoxide. The Mo(C0)g-catalyzed reaction gave both the sulfoxide and the sulfone with consecutive third-order kinetics. Rate = k3[Mo][t-Bu02H][Ph2S] + k^[Mo][t-Bu02H][Ph2S0], where log k3 = 12.62 - 18500/RT, and log k^ = 10.73 - 17400/RT. In the absence of diphenyl sulfide, diphenyl sulfoxide did not react with t-Bu02H plus molybdenum catalysts, but was oxidized by t-Bu02H-V0(acac)2. The uncatalyzed oxidation of phenyl methyl sulfide by t-Bu02H in absolute ethanol at 65°C gave a second-order rate constant, k = 3.48 x 10~"5 M^s""1. With added Mo(C0)g, the product was mainly phenyl methyl sulfoxide; Rate = k3[Mo][t-Bu02H][PhSCH3] where log k3 = 22.0 - 44500/RT. Both diphenyl sulfide and diphenyl sulfoxide react readily with the molybdenum peroxy complex, Mo0(02)2'HMPT in absolute ethanol at 35°C, yielding diphenyl sulfone. The observed features are mainly in agreement with the literature on metal ion-catalyzed oxidations of organic compounds by hydroperoxides. These indicate the formation of an active catalyst and the complexation of t-Bu02H with the catalyst. However, the relatively large difference between the activation energies for diphenyl sulfide and phenyl methyl sulfide, and the non-reactivity of diphenyl sulfoxide suggest the involvement of sulfide in the production of an active species.

The effects of the menstrual cycle and hormonal contraceptives on the central thermoeffector threshold temperatures and width of the interthreshold zone

Basal body temperature (BBT) and thermoeffector thresholds increase following ovulation in many women. This study investigated if solely central thermoregulatory alterations are responsible. Seven females in a non-contraceptive group (NCG) were compared with 5 monophasic contraceptive users (HCG) on separate accounts: pre-ovulation (Trial I; d 2-5) and post-ovulation (Trial 2; 4-8 d post-positive ovulation) for NCG, and active phase for HCG (d 2-5, d 18-21). During immersion in 28°C water to the axilla, participants exercised for 20-30 min on an underwater ergometer. After steadily sweating, immersion continued until metabolism increased two-fold due to shivering. Rectal (Tre) BBT was not different between trials for neither NCG (1: 37.34±0.16°C; 2: 37.35±0.27°C) nor HCG. At exercise termination, Tre forehead sweating cessation increased (P<0.05) in trial 2 irrespective of group (1: 37.55±0.39°C; 2: 37.90±0,46°C). Tre shivering onset did not increase (P>0.05) in trial 2 (1: 36.91±0.50°C; 2: 37.07±0,45°C). The widths of the interthreshold zone increased (P<0.05) in trial 2 (1: 0.64±0.22°C; 2: 0.82±0.37°C) due to the increased sweating threshold only. HCG cooled quicker (1: -l.15±0,43°C; 2: -1.00±0.50°C) than NCG participants (1: - 0.58±0.22°C; 2: -0.52±O.29°C), and tympanic (Tty) sweat thresholds were significantly (P<0.05) decreased (1: 34.76±0.54°C; 2: 35.39±0.61°C) versus NCG (l: 35.57±0.77°C; 2: 35.89±1.04°C). Lastly, Tre and Tty thresholds were significantly different (P

The Effects of Perceived Product-Association Incongruity on Consumption Experiences

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Le modèle de convergence vu selon l'approche de Dan, Ben-David: une vérification empirique par rapport au 8e cycle du GATT; le cas de l'ALENA versus l'Union Européenne (période 1970-2000).

Rapport de recherche

La centrale à cycle combiné du Suroît est-elle la meilleure solution pour éviter une pénurie prochaine d'électricité?

Rapport de recherche

International Transmission of the Business Cycle in a Multi-Sector Model.

Multi-country models have not been very successful in replicating important features of the international transmission of business cycles. Standard models predict cross-country correlations of output and consumption which are respectively too low and too high. In this paper, we build a multi-country model of the business cycle with multiple sectors in order to analyze the role of sectoral shocks in the international transmission of the business cycle. We find that a model with multiple sectors generates a higher cross-country correlation of output than standard one-sector models, and a lower cross-country correlation of consumption. In addition, it predicts cross-country correlations of employment and investment that are closer to the data than the standard model. We also analyze the relative effects of multiple sectors, trade in intermediate goods, imperfect substitution between domestic and foreign goods, home preference, capital adjustment costs, and capital depreciation on the international transmission of the business cycle.

Top-Cycle Rationalizability

We identify necessary and sufficient conditions for the choice set from every subset A of a (finite) universal set X to coincide with the top cycle in A of some fixed tournament on X.

Solidarity in Choosing a Location on a Cycle

We study the implications of two solidarity conditions on the efficient location of a public good on a cycle, when agents have single-peaked, symmetric preferences. Both conditions require that when circumstances change, the agents not responsible for the change should all be affected in the same direction: either they all gain or they all loose. The first condition, population-monotonicity, applies to arrival or departure of one agent. The second, replacement-domination, applies to changes in the preferences of one agent. Unfortunately, no Pareto-efficient solution satisfies any of these properties. However, if agents’ preferred points are restricted to the vertices of a small regular polygon inscribed in the circle, solutions exist. We characterize them as a class of efficient priority rules.

Analysis of HIV-1 Vpr determinants responsible for cell growth arrest in Saccharomyces cerevisiae

Affiliation: Département de microbiologie et immunologie, Faculté de médecine, Université de Montréal

La profitabilite des fusions et acquisitions dans le contexte du cycle de vie de l'entreprise.

Rapport de recherche

Implementing the Precautionary Principle through Stakeholder Engagement for Product and Service Development

Section des étudiants