Efficient synthesis of carbonyl compounds: oxidation of azides and alcohols catalyzed by vanadium pentoxide in water using tert-butylhydroperoxide

Catalytic amount of vanadium reagent with tert-butylhydroperoxide as the oxidant was found to be an excellent oxidizing agent in aqueous medium. Vanadium pentoxide with aq tert-butylhydroperoxide readily oxidizes primary benzylic azides to the corresponding acids and secondary benzylic azides to the corresponding ketones in excellent yields. Further, vanadium pentoxide and aq tert-butylhydroperoxide combination turned out to be an effective catalyst for the oxidation of alcohols. Using vanadium pentoxide and aq tert-butylhydroperoxide primary alcohols were oxidized to the corresponding acids, whereas secondary alcohols underwent a smooth transformation to furnish corresponding ketones in excellent yields. All the oxidations are performed in water. (C) 2011 Elsevier Ltd. All rights reserved.

River water quality response under hypothetical climate change scenarios in Tunga-Bhadra river, India

Analysis of climate change impacts on streamflow by perturbing the climate inputs has been a concern for many authors in the past few years, but there are few analyses for the impacts on water quality. To examine the impact of change in climate variables on the water quality parameters, the water quality input variables have to be perturbed. The primary input variables that can be considered for such an analysis are streamflow and water temperature, which are affected by changes in precipitation and air temperature, respectively. Using hypothetical scenarios to represent both greenhouse warming and streamflow changes, the sensitivity of the water quality parameters has been evaluated under conditions of altered river flow and river temperature in this article. Historical data analysis of hydroclimatic variables is carried out, which includes flow duration exceedance percentage (e.g. Q90), single low- flow indices (e.g. 7Q10, 30Q10) and relationships between climatic variables and surface variables. For the study region of Tunga-Bhadra river in India, low flows are found to be decreasing and water temperatures are found to be increasing. As a result, there is a reduction in dissolved oxygen (DO) levels found in recent years. Water quality responses of six hypothetical climate change scenarios were simulated by the water quality model, QUAL2K. A simple linear regression relation between air and water temperature is used to generate the scenarios for river water temperature. The results suggest that all the hypothetical climate change scenarios would cause impairment in water quality. It was found that there is a significant decrease in DO levels due to the impact of climate change on temperature and flows, even when the discharges were at safe permissible levels set by pollution control agencies (PCAs). The necessity to improve the standards of PCA and develop adaptation policies for the dischargers to account for climate change is examined through a fuzzy waste load allocation model developed earlier. Copyright (C) 2011 John Wiley & Sons, Ltd.

Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta): New water gas shift (WGS) catalysts

Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) and Ce(0.67)Fe(0.33)O(2-delta) have been synthesized by a new low temperature sonochemical method using diethylenetriamine as a complexing agent. Due to the substitution of Fe and Pt ions in CeO(2), lattice oxygen is activated in Ce(0.67)Fe(0.33)O(2-delta) and Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). Hydrogen uptake studies show strong reduction peaks at 125 C in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) against a hydrogen uptake peak at 420 degrees C in Ce(0.67)Fe(0.33)O(2-delta). Fe substituted ceria, Ce(0.67)Fe(0.33)O(2-delta) itself acts as a catalyst for CO oxidation and water gas shift (WGS) reactions at moderate temperatures. The rate of CO conversion in WGS with Pt free Ce(0.65)Fe(0.33)O(2-delta) is 2.8 mu mol g(-1) s(-1) at 450 C and with Pt substituted Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta) is 4.05 mu mol g(-1) s(-1) at 275 degrees C. Due to the synergistic interaction of the Pt ion with Ce and Fe ions in Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta), the catalyst showed much higher activity for CO oxidation and WGS reactions compared to Ce(0.67)Fe(0.33)O(2-delta). A reverse WGS reaction does not occur over Ce(0.65)Fe(0.33)Pt(0.02)O(2-delta). The catalyst also does not deactivate even when operated for a long time. Nearly 100% conversion of CO to CO(2) with 100% H(2) selectivity is observed in WGS reactions even up to 550 degrees C. (C) 2011 Elsevier B.V. All rights reserved.

An oxidative cross-dehydrogenative-coupling reaction in water using molecular oxygen as the oxidant: vanadium catalyzed indolation of tetrahydroisoquinolines

An aerobic oxidative cross-dehydrogenative coupling reaction between sp(3) C-H and sp(2) C-H bonds is developed by employing a vanadium catalyst (10 mol%) in an aqueous medium using molecular oxygen as the oxidant. This environmentally benign strategy exhibits larger substrate scope and shows high regioselectivity.