Synthesis and Spectral Investigation of Some Transition Metal Complexes Containing Pentadentate Macroacyclic <Emphasis Type="Italic">NNNNN</Emphasis>-donor Schiff Base Ligands

A new Schiff base, 2,6-diacetylpyridine bis(2-hydrazinobenzothiazole) (DPHB), has been designed, and synthesized by the condensation of 2,6-diacetylpyridine with 2-hydrazinobenzothiazole, and structurally characterized. Copper(II), cobalt(II), nickel(II), manganese(II), zinc(II), cadmium(II) and oxovanadium(IV) complexes of DPHB have been synthesized for the first time. Their structures have been elucidated on the basis of elemental analyses, conductance measurements, magnetic properties, spectral (i.r., ¹H-n.m.r., u.v.–vis., e.p.r. and FAB-mass) and thermal studies. The complexes exhibit an octahedral geometry around the metal centre. The conductance data of all the complexes suggest them to be 1:1 electrolytes. The X-band e.p.r. spectra of the copper(II) and oxovanadium(IV) complexes in the polycrystalline state at room (300 K) and liquid nitrogen temperature (77 K) were recorded and their salient features are reported. Thermal stabilities of the manganese(II) and zinc(II) complexes have been studied.     

Crystal Structure of 2-thiophene-2-yl-3(thiophene-2-carboxylideneamino)-1, 2-dihydroquinazolin-4(3H)-one and the Synthesis, Spectral and Thermal Studies of its Transition Metal(II) Complexes

The synthesis of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes of a new ligand 2-thiophene-2-yl-3(thiophene-2-carboxylidene-amino)-1,2-dihydroquinazolin-4(3H)-one (TTCADQ) is described. The ligand and metal complexes were characterized by elemental analysis, conductivity measurements, spectral (u.v.–vis., i.r., 1D n.m.r., 2D hetcor and e.p.r.) and thermal studies. The formation of 1,2-dihydroquinazolin-4(3H)-one rather than hydrazone, in the reaction of aromatic aldehyde and o-aminobenzoylhydrazide is proved by single crystal X-ray diffraction and 2D hetcor n.m.r. studies. On the basis of elemental analysis, u.v.–vis.spectroscopy and magnetic moment studies, six coordinate geometry for all the complexes was proposed. The i.r. spectral studies reveal the bidentate behaviour of the ligand.     

A novel and facile iodine(III)-mediated approach for C(5)-acetoxylation of 6-hydroxyflavone and 6-hydroxyflavanones

Oxidation of 6-hydroxyflavone 1 and 6-hydroxyflavanones 2a-c with iodobenzene diacetate (IBD) in acetic acid leads to regioselective acetoxylation, thereby providing a novel and convenient route for the synthesis of 5-acetoxylated products.     

Evolution of titanium(IV) alkoxides and raney nickel for asymmetric reductive amination of prochiral aliphatic ketones

[reaction: see text] A new method for the one-pot asymmetric reductive amination of prochiral aliphatic ketones has been developed. The previously unexplored reagent combination of Ti(O(i)Pr)(4)/Raney Ni/H(2) in the presence of (R)- or (S)-alpha-methylbenzylamine provides good to excellent yield (76-90%) and diastereomeric excess (72-98%). The second step, hydrogenolysis, provides the corresponding primary amine in high yield (88-93%) and with uncompromised enantiomeric excess.     

N-(salicylidene)nitrosophenylglycine Schiff base as NOOO-donor towards transition metal ions

A new tetradentate NOOO-donor ligand, N-(salicylidene)nitrosophenylglycine (H₂snpg) has been designed, synthesized and structurally characterized. Copper(II), nickel(II), cobalt(II), manganese(II) and zinc(II) complexes of H₂snpg have been prepared for the first time. The authenticities of the ligand and its metal complexes have been established on the basis of elemental analyses, molar conductance measurements, magnetic properties, spectral (i.r., ¹H-n.m.r., u.v.–vis. and mass) studies. The i.r. spectral studies of all the complexes exhibit a similar feature about the ligating nature of the ligand to the metal ions and revealed that the ligand has coordinated through the carbonyl oxygen, azomethine nitrogen, nitroso oxygen and deprotonated hydroxyl oxygen. The molar conductance data suggest them to be non-electrolytes. The antimicrobial activity of all the compounds was studied against Escherichia coli, Bacillus cirroflagellosus, Aspergillus niger and Candida albicans. All the complexes have shown a moderate to high fungal activity compared to the ligand.     

Metal-mediated dearomatization leading to 2-azaspiro[4.5]decanes via tandem nucleophilic aromatic addition–Horner–Wadsworth–Emmons olefination–oxidative demetalation sequences

A ruthenium-mediated dearomatization sequence has been developed that delivers structurally intriguing azaspirolactam products in stereoselective fashion. Treatment of (η⁶-arene)Ru(cyclopentadienyl) complexes bearing N-benzyl-β-amido phosphonate side chains with excess NaH results in intramolecular nucleophilic aromatic addition to the ipso position of the coordinated arenes. Subsequent Horner–Wadsworth–Emmons (HWE) reaction with added aldehydes affords olefinated spirolactam cyclohexadienyl ruthenium complexes. Mild oxidation with CuCl₂ or CuBr₂ under CO effects removal and recovery of the CpRu(II) fragment. Substituents present on the cyclohexadienyl skeleton influence the outcome of demetalation and products obtained in this study include functionalized 2-azaspiro[4.5]decanes and tetrahydroisoquinolinones.     

Comparison of Extraction Methods by Soxhlet, Sonicator, and Microwave in the Screening of Pesticide Residues from Solid Matrices

Three types of solvent extraction methods (by soxhlet, sonicator and microwave) for pesticide recoveries in solid matrices were compared and evaluated using the standard addition method. Variables (solvent and extraction time) for the optimization of microwave assisted extraction (MAE) were also studied. Three organochlorine pesticides (BHC, DDE, and Dildrin) were chosen for this particular study because of their great presence in the soil where the samples were collected and their positive association with the risk of breast cancer. Comparison of the results obtained indicates that the efficiency of extraction varies, depending on the matrices and the pesticides analyzed. The study focused on the variation in the extraction quantities of different methods in different matrices. The extraction conditions were optimized for MAE with a single matrix (bark) and applied to the rest in order to study the variability in results. Gas chromatography with an electron capture detector (GC–ECD) was used for analysis of the extracts. The results show that even though the use of MAE improved extraction in some of the matrices studied, the extraction method must be optimized whenever a new matrix is evaluated. A statistical comparison indicated that pesticide recoveries and method reproducibility of microwave extraction compared less favorably with the conventional soxhlet method in some of the matrices, whereas the sonicator method was not found to be as efficient as the others.     

Conformation of (?)/(l)-1,3-Bis(4,6-dimethyl-1H-nicotinonitril-1-yl)1,3-dithioxypropane Stabilized via Intra/Intermolecular Weak Interactions

Abstract  

In solution state, the stable gauche conformation of 1,3-bis(4,6-dimethyl-1H-nicotinonitril-1-yl)1,3-dithioxypropane is predicted by CD spectra. Weak interaction present in the molecule makes it flexible, and due to this reason helicity is observed in it. In solid state, the molecular conformation and packing geometry is stabilized via both intra/inter molecular CH···N, CH···S and π···π interactions.     

Camphor-10-sulfonamide-based prolinamide organocatalyst for the direct intermolecular aldol reaction between ketones and aromatic aldehydes

Prolinamides derived from l-proline and N,N-dialkyl 2-aminocamphor-10-sufonamides have been synthesized and used as organocatalysts in the direct intermolecular aldol reaction. Reactions of several aromatic aldehydes with cyclohexanone, cyclopentanone, 4-oxa and 4-sulfa-cyclohexanones and acetone are investigated employing 1a as an organocatalyst. Very high to excellent selectivities are obtained in these direct aldol reactions.     

Development of a highly sensitive and selective hyphenated technique (molecularly imprinted micro-solid phase extraction fiber-molecularly imprinted polymer fiber sensor) for ultratrace analysis of folic acid

A simple polymerization strategy is reported in this work which allows molecularly imprinted polymeric fiber (monolith) fabrication for direct use in sensing devices. This is advantageous for achieving higher degree of enrichment of target analyte (folic acid) from the complex matrices of real samples, without any surface fouling, cross-reactivity, and non-specific (false-positive) contributions. In order to measure serum folic acid at ultratrace level to detect spina bifida, a neural tube defect in mother, and other acute cases of proteomic diseases, the hyphenation between molecularly imprinted micro-solid phase extraction fiber and a complementary molecularly imprinted polymer-carbon composite fiber sensor has been found quite efficient. The primitive diagnosis of many chronic diseases is feasible by estimating folic acid as biomarker, with the detection limit as low as 0.0036 ng mL⁻¹ (relative standard deviation = 0.13%, signal/noise = 3) in human blood serum.