CHLOROSULFONATION OF N-PHENYLMORPHOLINE,BENZOTHIAZOLE, 2-METHYL BENZOTHIAZOLE AND TRIPHENYLOXAZOLE

Abstract

N-Phenylmorpholine (1) reacted with chlorosulfonic acid to give the p-sulfonyl chloride (2), which was characterized as the sulfonamides (3–5). Benzothiazole (6) was converted into the sulfonyl chloride (7) by sequential treatment with hot chlorosulfonic acid and thionyl chloride. Reaction of (7) with amines afforded the derivatives (8–10); NMR spectral analysis of the dimethylamide (8) indicated that it was a mixture of the 4- and 7-isomers. Chlorosulfonation of 2-methylbenzothiazole (11) was achieved by heating with chlorosulfonic acid with or without thionyl chloride. The chloride (12) was converted into amides (13–19). Study of the NMR spectra indicated that mixtures of the 5- and 6-isomers were formed. 2,4,5-Triphenyloxazole (20) reacted with chlorosulfonic acid to give either the mono-(21), bis (23) or bis-tris sulfonylchlorides (23, 34); these were converted into 14 sulfonamides. 2-(p-Nitrophenyl)-4,5-diphenyloxazole (41) reacted with hot chlorosulfonic acid to give the bis-sulfonyl chloride (42), characterized as the dimethylsulfonamide (43). Attempts to form the pure monosulfonyl chloride and to mono nitrate 2,4,5-triphenyloxazole (20) were unsuccessful.     

Some New Pyrazole and Pyrazolopyrimidines: Synthesis and Antimicrobial Evaluation

Novel β‐enaminonitrile of 1‐(6‐phenyl‐pyridazin‐3‐yl)‐pyrazole derivative 2 was formed using (6‐phenyl‐pyridazin‐3‐yl)‐hydrazine ( 1 ) and 2‐ethoxymethylene‐malononitrile. The β‐enaminonitrile derivative 2 was in turn used as precursors for the preparation of 1‐(6‐phenyl‐pyridazin‐3‐yl)‐pyrazoles ( 3 , 9 , 11 ), 1‐(6‐phenyl ‐pyridazin‐3‐yl)‐pyrazolo[3,4‐d]pyrimidines ( 4 , 5 , 6 , 7 , 8 , 13 , 14 , 15 , 16 ) and some of their corresponding N‐acyclic nucleosides ( 17 , 18 ). All synthesized compounds were tested for their antimicrobial evaluation, and compounds 3 , 9 , 17 , and 18 showed more significant activity than the other tested compounds and some known drugs (standers).     

Synthesis of New 1H-indazole derivatives

Reactions of 3-aryl-1-phenyl-2-propen-1-ones IIa-d with ethyl phenylacetate (I) in the presence of sodium ethoxide under reflux for one hour gave only the corresponding 3,5-diaryl-2,4-dibenzoyl-6-phenyl-cyclo-hexanones IIIa-d. The reaction of these compounds with hydrazine hydrate afforded the corresponding 5-benzoyl-4,6-diaryl-3,7-diphenyl-1,4,5,6,7-pentahydro-1H-indazole IVa-d. The structures of the products were established by spectroscopic (ir, uv, nmr and mass spectra), single-crystal X-ray analysis and chemical evidence.     

Precolumn fluorescence labeling method for simultaneous determination of hydroxyzine and cetirizine in human serum

A highly selective and sensitive method was developed for simultaneous determination of the antihistaminic drug hydroxyzine (HZ) and its pharmacologically active metabolite cetirizine (CZ) in human serum using haloperidol as internal standard. The method was based on fluorescence labeling of both drugs with a fluorescent arylboronic acid 4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl boronic acid followed by separation on silica column using a mobile phase consisting of acetonitrile and water (90:10, v/v%) containing triethylamine and acetic acid. The labeling reaction conditions were optimized and the liquid-liquid extraction method was successfully applied to extract the both drugs from serum. The linearity range was 0.025-2.00 microg/mL for HZ and CZ. The limit of detection (S/N = 3) was 10 and 5 ng/mL for HZ and CZ, respectively.     

Measurements of H2O2 in low temperature dimethyl ether oxidation

H₂O₂ is one of the most important species in dimethyl ether (DME) oxidation, acting not only as a marker for low temperature kinetic activity but also responsible for the “hot ignition” transition. This study reports, for the first time, direct measurements of H₂O₂ and CH₃OCHO, among other intermediate species concentrations in helium-diluted DME oxidation in an atmospheric pressure flow reactor from 490 to 750 K, using molecular beam electron-ionization mass spectrometry (MBMS). H₂O₂ measurements were directly calibrated, while a number of other species were quantified by both MBMS and micro gas chromatography to achieve cross-validation of the measurements. Experimental results were compared to two different DME kinetic models with an updated rate coefficient for the H + DME reaction, under both zero-dimensional and two-dimensional physical model assumptions. The results confirm that low and intermediate temperature DME oxidation produces significant amounts of H₂O₂. Peroxide, as well as O₂, DME, CO_, and CH₃OCHO profiles are reasonably well predicted, though profile predictions for H₂/CO₂ and CH₂O are poor above and below ～625 K, respectively. The effect of the collisional efficiencies for the H + O₂ + M = HO₂ + M reaction on DME oxidation was investigated by replacing 20% He with 20% CO₂. Observed changes in measured H₂O₂ concentrations agree well with model predictions. The new experimental characterizations of important intermediate species including H₂O₂, CH₂O and CH₃OCHO, and a path flux analysis of the oxidation pathways of DME support that kinetic parameters for decomposition reactions of HOCH₂OCO and HCOOH directly to CO₂ may be responsible for model under-prediction of CO₂. The H abstraction reactions for DME and/or CH₂O and the unimolecular decomposition of HOCH₂O merit further scrutiny towards improving the prediction of H₂ formation.     

Optimization of the reaction conditions for the preparation of 99mTc-celecoxib and its biological evaluation

Celecoxib was labelled effectively with ^99mTc. The labeling yield was found to be influenced by the amount of celecoxib, the amount of stannous chloride dihydrate, the reaction time, the temperature and the pH of the reaction mixture. The importance of stannous chloride dihydrate arises from its function as a reducing agent for pertechnetate to form complex celecoxib. The suitable amount required to produce high labeling yield of ^99mTc-celecoxib was 500 μg SnCl₂·2H₂O. The pH of the reaction medium was found to play a significant role in this labeling process. The labeling reaction was performed at a neutral medium (pH 7). The labeling reaction proceeds well at room temperature (25 ± 1 °C) and the complex decomposes by heat. The labeled celecoxib (^99mTc-celecoxib) showed a good localization in inflamed foci and a good imaging must be taken 4 h post injection.     

General asymmetric hydrogenation of 2-alkyl- and 2-aryl-substituted quinoxaline derivatives catalyzed by iridium-difluorphos: unusual halide effect and synthetic application

A general asymmetric hydrogenation of a wide range of 2-alkyl- and 2-aryl-substituted quinoxaline derivatives catalyzed by an iridium-difluorphos complex has been developed. Under mild reaction conditions, the corresponding biologically relevant 2-substituted-1,2,3,4-tetrahydroquinoxaline units were obtained in high yields and good to excellent enantioselectivities up to 95%. With a catalyst ratio of S/C = 1000 and on a gram scale, the catalytic activity of the Ir-difluorphos complex was maintained showing its potential value. Finally, we demonstrated the application of our process in the synthesis of compound (S)-9, which is an inhibitor of cholesteryl ester transfer protein (CETP).     

A fully Galerkin method for the damped generalized regularized long‐wave (DGRLW) equation

In this article, a fully discrete Galerkin scheme based on a nonlinear Crank–Nicolson method to approximate the solution of the DGRLW equation is constructed. Some a priori bounds are proved as well as error estimates. Then, a linearized modification scheme by an extrapolation method is discussed. The two schemes are time second order convergence. The last part is devoted to some numerical results. © 2008 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2009     

Robust general N user authentication scheme in a centralized quantum communication network via generalized GHZ states

Quantum communication provides an enormous advantage over its classical counterpart: security of communications based on the very principles of quantum mechanics. Researchers have proposed several approaches for user identity authentication via entanglement. Unfortunately, these protocols fail because an attacker can capture some of the particles in a transmitted sequence and send what is left to the receiver through a quantum channel. Subsequently, the attacker can restore some of the confidential messages, giving rise to the possibility of information leakage. Here we present a new robust General Nuser authentication protocol based on N-particle Greenberger–Horne–Zeilinger (GHZ) states, which makes eavesdropping detection more effective and secure, as compared to some current authentication protocols. The security analysis of our protocol for various kinds of attacks verifies that it is unconditionally secure, and that an attacker will not obtain any information about the transmitted key. Moreover, as the number of transferred key bits N becomes larger, while the number of users for transmitting the information is increased, the probability of effectively obtaining the transmitted authentication keys is reduced to zero.     

Functionalization of Pasteurized Milk Using Rosemary,Thyme, and Ammoides Aqueous Extracts for Better Microbial Quality and an Improved Antioxidant Activity

This study aimed to evaluate the effects of thyme (Thymus vulgaris L.), rosemary (Rosmarinus officinalis L.), and ammoides (Ammoidespusilla L.) aqueous extracts supplementation on the quality of heat-treated (55, 65, and 75 °C) raw milk (sample lots: A, B, and C) and cold-stored pasteurized milk (lot D). The three herbs have shown rich polyphenol contents (32.65–104.23 mgGAE/g), relevant antioxidant capacity, and high caffeic and rosmarinic acids and catechin contents. A significant reduction in psychrotrophic and total viable bacteria counts (PC and TVC) was attained following milk extract supplementation in both experiments. Monitoring PC and TVC counts in sample lots (A, B, and C) has revealed a significant improvement in extracts’ effectiveness in reducing the TVC count with the increment of temperature. The highest reductions of PC and TVC counts were achieved, respectively, in samples treated with thyme and rosemary in (lots: A, B, and C) and in samples treated with ammoides and thyme in (lot D). Thyme extract showed the highest milk serum DPPH scavenging activity (74.84% at 0.1 mg/mL) and induced a significant Listeria monocytogenes growth inhibition (>1 Log cycle). The sensory evaluation of supplemented milk has shown good consumer acceptability of ammoides-supplemented milk, quite similar to the control sample.