A new flavonol glycoside and other flavonoids from the aerial parts of Taverniera aegyptiaca

Isolation of flavonoids from the aerial parts of Taverniera aegyptiaca Bioss. (Fabaceae) led to identification of one new flavonol glycoside, isorhamnetin-3-O-α-l-rhamnopyranosyl-(1→2)-α-l-arabinopyranoside (1), along with eleven compounds, which previously have not been isolated from this plant quercetin-3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (2), isorhamnetin-3-O-α-l-arabinopyranoside (3), quercetin-3-O-α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside (4), isorhamnetin-3-O-α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside (7), isorhamnetin 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (8), isorhamnetin 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-glucopyranoside] (9), kaempferol 3-O-α-l-rhamnopyranosyl-(1→2)-[α-l-rhamnopyranosyl-(1→6)-β-d-galactopyranoside] (10), isorhamnetin (11), 4,4′-dihydroxy-2′-methoxychalcone (12), formononetin (13) and calycosin (15)] and some compounds already known from this plant [quercetin-3-O-robinobioside (5), isorhamnetin-3-O-robinobioside (6), afrormosin (14) and odoratin (16)].     

Reductive Amination of Aldehydes and Ketones with Sodium Triacetoxyborohydride. Studies on Direct and Indirect Reductive Amination Procedures(1)

Sodium triacetoxyborohydride is presented as a general reducing agent for the reductive amination of aldehydes and ketones. Procedures for using this mild and selective reagent have been developed for a wide variety of substrates. The scope of the reaction includes aliphatic acyclic and cyclic ketones, aliphatic and aromatic aldehydes, and primary and secondary amines including a variety of weakly basic and nonbasic amines. Limitations include reactions with aromatic and unsaturated ketones and some sterically hindered ketones and amines. 1,2-Dichloroethane (DCE) is the preferred reaction solvent, but reactions can also be carried out in tetrahydrofuran (THF) and occasionally in acetonitrile. Acetic acid may be used as catalyst with ketone reactions, but it is generally not needed with aldehydes. The procedure is carried out effectively in the presence of acid sensitive functional groups such as acetals and ketals; it can also be carried out in the presence of reducible functional groups such as C-C multiple bonds and cyano and nitro groups. Reactions are generally faster in DCE than in THF, and in both solvents, reactions are faster in the presence of AcOH. In comparison with other reductive amination procedures such as NaBH(3)CN/MeOH, borane-pyridine, and catalytic hydrogenation, NaBH(OAc)(3) gave consistently higher yields and fewer side products. In the reductive amination of some aldehydes with primary amines where dialkylation is a problem we adopted a stepwise procedure involving imine formation in MeOH followed by reduction with NaBH(4).     

Synthesis of Some New Heterobicyclic Nitrogen Systems Bearing 7H‐1,2,4‐Triazolo[1,5‐d]tetrazol‐6‐yl Moiety for Biological Interest

Reaction of 6‐mercapto‐7H‐1,2,4‐triazolo[1,5‐d]tetrazole ( 1 ) wtih 1,2‐phenylenediamine afforded N‐{7H‐1,2,4‐triazolo[1,5‐d]tetrazol‐6‐yl}‐1,2‐phenylenediamine which was cyclized to benzimidazolyl‐1,2,4‐triazolo[1,5‐d]tetrazoles using various one‐carbon cyclizing agents. Also, the treatment of 1 with maleic anhydride or phthalic anhydride gave the corresponding thio derivatives followed by hydrazinolysis to afford the thio heterobicyclic systems. Former structures of the products have been established upon elemental and spectral analyses.     

Spectroscopic and quantum chemical studies on the structure of 2-arylquinoline-4(1H)-thione derivatives

The geometries of the title compounds were probed in solution, solid and gas states using spectroscopic methods, X-ray crystallography and quantum chemical techniques. The exclusive existence of the NH-4-thiones in solution (NMR and PCM-B3LYP(MP2)/6-31+G(d) calculations) and solid state (FT-IR and X-ray) is also corroborated by comparison of their spectroscopic data with those of the corresponding 2-aryl-1-methylquinoline-4(1H)-thione derivatives. The co-existence of the quinoline-4-thione and quinoline-4-thiol (4-mercaptoquinoline) isomers in the gas phase is confirmed by mass spectrometry and the preponderance of the 4-thiol is supported by quantum chemical techniques (PM3, MP2 and B3LYP).     

Tailor-made functionalization of silicon nitride surfaces

This communication presents the first functionalization of a hydrogen-terminated silicon-rich silicon nitride (Si3Nx) surface with a well-defined, covalently attached organic monolayer. Properties of the resulting monolayers are monitored by measurement of the static water contact angle, X-ray photoelectron spectroscopy (XPS), and infrared reflection absorption spectroscopy (IRRAS). Further functionalization was performed by reaction of Si3Nx with a trifluoroethanol ester alkene (CH2=CH-(CH2)8CO2CH2CF3) followed by basic hydrolysis to afford the corresponding carboxylic acid-terminated monolayer with hydrophilic properties. These results show that Si3Nx can be functionalized with a tailor-made organic monolayer, has highly tunable wetting properties, and displays significant potential for further functionalization.     

A convenient synthesis of 2‐Arylidene‐5H‐thiazolo[2,3‐b]quinazo‐line‐3,5[2H]‐diones and their benzoquinazoline derivatives

Various 5H‐thiazolo[2,3‐b]quinazoline‐3,5[2H]‐diones (7a,b), 2‐arylidene‐5H‐thiazolo[2,3–b]quin‐azoline‐3,5[2H]‐diones ( 9a‐o ) and 2‐arylidene‐5H‐thiazolo[2,3‐b]benzoquinazoline‐3,5[2H]‐diones ( 12a,b ) have been synthesized via simple and efficient methods.     

Thermal decomposition study on mixed ligand thymine complexes of divalent nickel(II) with dianions of some dicarboxylic acids

Thermal decomposition of mixed ligand thymine (2,4-dihydroxy-5-methylpyrimidine) complexes of divalent Ni(II) with aspartate, glutamate and ADA (N-2-acetamido)iminodiacetate dianions was monitored by TG, DTG and DTA analysis in static atmosphere of air. The decomposition course and steps of complexes [Ni(C₅H₆N₂O₂)(C₄H₅NO₄)²⁻(H₂O)₂]·H₂O, [Ni(C₅H₆N₂O₂)(C₅H₇NO₄)²⁻(H₂O)₂]·H₂O and [Ni(C₅H₆N₂O₂)(C₆H₈N₂O₅)²⁻(H₂O)₂]·1.5H₂O were analyzed. The final decomposition products are found to be the corresponding metal oxides. The kinetic parameters namely, activation energy (E*), enthalpy (ΔH*), entropy (ΔS*) and free energy change of decomposition (ΔG*) are calculated from the TG curves using Coats–Redfern and Horowitz–Metzger equations. The stability order found for these complexes follows the trend aspartate > ADA > glutamate.     

Modeling of iron adsorption on HTTA-loaded polyurethane foam using Freundlich,Langmuir and D-R isotherm expressions

The sorption of Fe(III) at low pH range from 1 to 4.5 on open cell polyether type HTTA-loaded polyurethane foam has been carried out using batch technique. The optimum shaking time for 2.5· 10^–4M solution of Fe(III) was found to be 30 minutes. The concept of macropore and micropore nature of polyurethane foam sorbent offers unique advantages of adsorption. Freundlich and Langmuir adsorption isotherms are followed at low concentration range from 1·10^–4 to 3·10^–4M solution of Fe(III). The Freundlich constant (1/n=0.46±0.013 andK=9.16±1.39 mg·g^–1) and Langmuir isotherm constants(M=21.78 mg·g^–1 andb=88.41±9.731·g^–1) were established. The sorption mean free energyE=12.22±0.09 kJ·mol^–1 and loading capacityC _m =145.21±6.1 mg·g^–1 were evaluated using Dubinin-Radushkevich isotherm, which suggested that the adsorption mechanism was chemisorption.     

Quantitative determination of organochlorine pesticides in sewage sludges using soxtec,soxhlet and pressurized liquid extractions and ion trap mass–mass spectrometric detection

A new analytical method is described for the determination of organochlorine pesticides (OCPs) in sewage sludges using GC-ion trap-MS–MS. In this work, 16 organo-chlorine pesticides (OCPs) listed by the US Environmental Protection Agency (US EPA) as priority pollutants were separated and quantified. Sludge samples from three of Kuwaits wastewater treatment plants (WWTPs) were analyzed for organochlorine pesticides (OCPs). Spiked sludge samples were extracted with a mixture of (1:1 v/v) dichloromethane (DCM)/hexane. The extracts were cleaned on a silica/aluminum oxide column, then transferred to a gel permeation chromatography (GPC) column, before undergoing further silica/aluminum oxide clean-up; the presence of OCPs was then confirmed by GC-ion trap-MS–MS. Three extraction techniques, soxtec, soxhlet, and pressurized liquid extractions were utilized, compared and validated using the spiked sludge samples. The methods were validated in term of accuracy (recovery) and precision (RSD). The method recovery values varyied from 76.1 to 92.9% for the three extraction techniques.     

Heck reactions of 2-substituted enol ethers with aryl bromides catalysed by a tetraphosphine/palladium complex

cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C₃H₅)]₂ efficiently catalyses the Heck reaction of β-substituted enol ethers with aryl bromides. Employing β-methoxystyrene, 3-ethoxyacrylonitrile or methyl 3-methoxyacrylate, the regioselective α-arylation of these enol ethers was observed in all cases, and mixtures of Z and E isomers were generally obtained, which in many cases yielded a single ketone product after acid treatment. The stereoselectivity of this reaction depends on steric and electronic factors, and better stereoselectivities in favour of Z isomers were observed with electron-rich or sterically congested aryl bromides. Better yields were obtained for this reaction with electron-rich or sterically congested aryl bromides than with electron-poor aryl bromides. This observation suggests that with these β-substituted enol ethers the rate-limiting step of the catalytic cycle is not the oxidative addition of the aryl bromide to the palladium complex.