An Isolated Nitridyl Radical‐Bridged {Rh(N.)Rh} Complex

Photochemical activation of [(PNNH)Rh(N₃)] (PNNH=6‐di‐(tert‐butyl)phosphinomethyl‐2,2′‐bipyridine) complex 2 produced the paramagnetic (S=1/2), [(PNN)Rh?N^.‐Rh(PNN)] complex 3 (PNN^?=methylene‐deprotonated PNNH), which could be crystallographically characterized. Spectroscopic investigation of 3 indicates a predominant nitridyl radical (^.N^2?) character, which was confirmed computationally. Complex 3 reacts selectively with CO, producing two equivalents of [(PNN)Rh^I(CO)] complex 4 , presumably by nitridyl radical N,N‐coupling.     

Synthesis and Antimicrobial Activities of Novel Series of 3‐(4‐(2‐substituted thiazol‐4‐yl)phenyl)‐2‐(4‐methyl‐2‐substituted thiazol‐5‐yl)thiazolidin‐4‐one Derivatives

In the present investigation, a novel series of 3‐(4‐(2‐substituted thiazol‐4‐yl)phenyl)‐2‐(4‐methyl‐2‐substituted thiazol‐5‐yl)thiazolidin‐4‐one derivatives were synthesized by condensation of 2‐substituted‐4‐methylthiazole‐5‐carbaldehyde with 4‐(2‐substituted thiazol‐4‐yl)benzenamine followed by cyclo‐condensation with thioglycolic acid in toluene. All the newly synthesized compounds were characterized by spectral (IR, ¹H NMR, ¹³C NMR, and Mass) methods. The title compounds were screened for quantitative antibacterial activity (minimal inhibitory concentration). All compounds 7a , 7b , 7c , 7d , 7e , 7f , 7g , 7h and 8a , 8b , 8c , 8d , 8e , 8f , 8g , 8h show moderate to good antimicrobial activity, whereas compounds ( 7a , 7b , 7c , 7d , 7e , 7f , 7g , 7h ) also show moderate antifungal activity.     

Silica Gel Supported Chromium Trioxide: An Efficient Reagent for Oxidative Cleavage of Oximes to Carbonyl Compounds under Mild Condition

A facile, efficient oxidative deblocking of aldoximes and ketoximes to their corresponding aldehydes and ketones have been achieved by using silica gel supported chromium trioxide.     

Synthetic Route to a Benzooxazole Derivative with Heparanase Inhibitory Activity

The synthesis of a benzooxazol-5-yl acetic acid derivative (9) with strong heparanase and angiogenesis inhibitory activity, and thus possible commercial interest, is described in detail.     

Thiamine hydrochloride as a promoter for the efficient and green synthesis of 12-aryl-8,9,10,12 tetrahydrobenzoxanthene-11-one derivatives in aqueous micellar medium

An environmentally benign, three-component, one-pot integrated chemical process has been developed for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzoxanthene-11-one by nucleophilic addition reaction between aldehyde and β-naphthol followed by Michael addition of dimedone, catalyzed by thiamine hydrochloride in aqueous micellar medium with excellent yield. Simple reaction conditions, no requirement of chromatographic separation, short reaction time, ease of isolation, use of inexpensive, easily recoverable and reusable catalyst makes this protocol very interesting from an economic and environmental perspective.     

An efficient synthesis of furano analogs of duocarmycin C1 and C2: seco-iso-cyclopropylfurano[e]indoline-trimethoxyindole and seco-cyclopropylfurano[f]quinoline-trimethoxyindole

seco-Iso-cyclopropylfurano[e]indoline-trimethoxyindole 1 and seco-cyclopropylfurano[f]quinoline-trimethoxyindole 2 are potent cytotoxic agents. Previous synthesis of these compounds was inefficient and the approach required separation of a mixture containing the isomeric indoline and quinoline intermediates 11 and 12, formed from radical cyclization of allylic bromide 10. Reported herein is an efficient and selective synthesis of either intermediate 11 or 12, thus product 1 or 2, as needed. The conditions of the Stobbe condensation, bromination, 5-exo-trig radical cyclization, amine-carboxylic acid coupling, and debenzylation were optimized for multi gram scale. As a result, the reaction times were shortened, the products were readily isolated, and the yields and purity improved.     

Scheduling service in tandem queues attended by a single server

Consider a tandem queue model with a single server who can switch instantaneously from one queue to another. Customers arrive according to a Poisson process with rate λ . The amount of service required by each customer at the i^th queue is an exponentially distributed random variable with rate μ_i. Whenever two or more customers are in the system, the decision as to which customer should be served first depends on the optimzation criterion. In this system all server allocation policies in the finite set of work conserving deterministic policies have the same expected first passage times (makespan) to empty the system of customers from any initial state. However, a unique policy maximizes the first passage probability of empty-ing the system before the number of customers exceeds K, for any value of K, and it stochastically minimizes (he number of customers in the system at any time t > 0 . This policy always assigns the server to the non empty queue closest to the exit     

Ion-isotopic exchange reaction kinetics using Duolite ARA-9366B and Indion-AGR resins

Radiotracer isotopic technique as an effective analytical tool was used to study the kinetics of ion-isotopic exchange reactions in the nuclear- and nonnuclear-grade anion exchange resins Duolite ARA-9366B and Indion-AGR. On the basis of kinetic data, specific reaction rate (per minute), amount of ion exchanged (millimoles), initial rate of iodide ion exchange (millimoles per minute), and log K _d values were calculated for the two resins. It was observed that under identical experimental conditions of 35.0 °C, 1.000 g of ion exchange resins, and 0.002 mol/L of labeled iodide ion solution, the values calculated were 0.200 min^?1, 0.278 mmol, 0.056 mmol/min, and 9.6, respectively, for Duolite ARA-9366B resin, which were higher than 0.102 min^?1, 0.216 mmol, 0.022 mmol/min, and 5.7, respectively, for Indion-AGR resins. An identical trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate that under identical experimental conditions, Duolite ARA-9366B resins show superior performance than Indion-AGR resins. The results of the present experimental work have demonstrated that the radioanalytical technique used here can be successfully applied for the characterization of different ion exchange resins so as to evaluate their performance under various process parameters.     

A new algorithm for minimizing convex functions over convex sets

Let be a convex set for which there is an oracle with the following property. Given any pointz∈ℝ ⁿ the oracle returns a “Yes” ifz∈S; whereas ifz∉S then the oracle returns a “No” together with a hyperplane that separatesz fromS. The feasibility problem is the problem of finding a point inS; the convex optimization problem is the problem of minimizing a convex function overS. We present a new algorithm for the feasibility problem. The notion of a volumetric center of a polytope and a related ellipsoid of maximum volume inscribable in the polytope are central to the algorithm. Our algorithm has a significantly better global convergence rate and time complexity than the ellipsoid algorithm. The algorithm for the feasibility problem easily adapts to the convex optimization problem.