Preparation and isolation of dithiolene thiophosphoryl molecules as stable, protected forms of dithiolene ligands

The reaction of P4S10 with acyloins, RC(O)CH(OH)R, in refluxing dioxane, followed by the addition of alkylating agents, forms dithiolene thiophosphoryl thiolate compounds, (R2C2S2)P(S)(SR'), which are readily isolated and purified. The compounds that have been prepared and identified spectroscopically are those with R = p-anisyl, R' = Me (1); R = p-anisyl, R' = Bz (2); R = Ph, R' = Me (4); R = Et, R' = Bz (5). Compounds 1, 2, and 4 were structurally characterized by X-ray crystallography and found to possess a tetrahedral coordination geometry about the phosphorus atom, with overall Cs symmetry. In each case, the mirror plane bisects the dithiolene S-P-S chelate and contains the thiophosphoryl bond, which ranges in length from 1.9241(8) to 1.9361(7) A. The use of 2-(bromomethyl)naphthalene as organic electrophile in the P4S10/acyloin reaction produced bis(2-methylnaphthalenyl) disulfide as the only identifiable product. The substitution of Lawesson's reagent for P4S10 in reactions with acyloins produced deoxy acyloin rather than products resulting from chalcogen exchange. Compounds 1-2 and 4-5 are Group 5 analogues of 1,3-dithiol-2-ones, (R2C2S2)C=O, and undergo a similar hydrolysis in aqueous base to liberate ene-1,2-dithiolate dianions from which corresponding metal dithiolene complexes may be prepared. Deprotection of 1 in MeO-/MeOH, followed by the addition of NiCl2.6H2O and then I2, produces square planar [Ni(S2C2(C6H4-p-OCH3)2)2] (8) in 93% yield. A high-resolution structure of 8 (P) reveals dithiolene C-C and C-S bond lengths that are clearly indicative of the thionyl radical monoanionic nature of the ligand. The use of isolated (R2C2S2)P(S)(SR') compounds as a dithiolene ligand source for the preparation of metal dithiolene complexes offers the advantages of clean reactivity and high yield.     

Synthesis, spectroscopic, redox, catalytic and antimicrobial properties of some ruthenium(II) Schiff base complexes

A new series of mixed ligand semicarbazone or thiosemicarbazone complexes of Ru(II) having the general formula [RuCO(EPh₃)(B)L] (where E = P or As; B = PPh₃, AsPh₃ or Pyridine; L = dibasic tridentate ligand derived by the condensation of ethylacetoacetate/methylacetoacetate and thiosemicarbazide/semicarbazide) have been synthesized and characterized by physico-chemical, spectroscopic and electrochemical studies. A comparative study on the catalysis of oxidation of benzyl alcohol, cyclohexanol, cinnamyl alcohol, n-butanol, n-propanol and iso-butyl alcohol has been done with N-methylmorpholine-N-oxide and molecular oxygen as co-oxidants. Catalytic activity studies of the complexes in coupling reactions have been carried out. The antibacterial properties of the complexes have also been examined.     

Reactivity of the -C(Cl)C-CN- moiety towards AlCl3-induced C-C bond forming reactions: a new synthesis of 7-(hetero)aryl-substituted pyrazolo[1,5-a]pyrimidines

The reactivity of the -C(Cl)C-CN- moiety towards an AlCl₃-induced C-C bond forming reaction was investigated through the reaction of 7-chloro-5-phenyl-pyrazolo[1,5-a]pyrimidine with arenes and heteroarenes. This study furnished a novel and highly selective methodology for the preparation of 7-(hetero)aryl substituted-pyrazolopyrimidines in good to excellent yields under mild reaction conditions.     

A concise enantioselective synthesis of (+)-decarestrictine L via proline-catalyzed sequential α-aminooxylation and Horner–Wadsworth–Emmons olefination

A short enantioselective synthesis of (+)-decarestrictine L, a cholesterol biosynthesis inhibitor metabolite, is described using a d-proline catalyzed sequential α-aminooxylation and a Horner–Wadsworth–Emmons olefination.     

Alkali ion exchanged Nafion as a confining medium for photochemical reactions

Methanol-swollen Nafion beads were used as microreactors to control the photochemical reaction pathways. Product selectivity in three unimolecular reactions, namely, the photo-Fries rearrangement of naphthyl esters, Norrish Type I reaction of 1-phenyl-3-p-tolyl-propan-2-one and Norrish Type I and Type II reactions of benzoin alkyl ethers were examined. The influence of cations over the photodimerization of acenaphthylene and cross-photodimerization between acenaphthylene and N-benzyl maleimide included within Nafion were also examined. The photochemical behaviors of the above substrates were significantly altered within Nafion compared with their solution photochemistry. Of particular interest, the product distributions were found to depend on the counter cations of Nafion.     

NaIO4-mediated selective oxidation of alkylarenes and benzylic bromides/alcohols to carbonyl derivatives using water as solvent

A new transition-metal-free, sodium metaperiodate (NaIO4)-mediated direct oxidation of methylarenes and benzylic bromides to the corresponding aromatic carboxylic acids is described. Under the same reaction conditions, benzylic alcohols are selectively oxidized to afford the corresponding aldehydes in good yields without undergoing overoxidation. Unprecedentedly, oxidation of benzyl bromide, toluene, or benzyl alcohol with NaIO4 underwent nuclear bromination followed by oxidation to give 4-bromobenzoic acid in 60-79% yields.     

Redox magnetohydrodynamic enhancement of stripping voltammetry: toward portable analysis using disposable electrodes, permanent magnets, and small volumes

The use of redox magnetohydrodynamics (MHD) to enhance the anodic stripping voltammetry (ASV) response of heavy metals has been investigated, with respect to achieving portability: disposable electrodes consisting of screen-printed carbon (SPC) on a low temperature co-fired ceramic (LTCC) substrate, small volumes, and permanent magnets. The analytes tested (Cd(2+), Cu(2+), and Pb(2+)) were codeposited on SPC with Hg(2+) to form a Hg thin film electrode. High concentrations of Fe(3+) were used to produce a high cathodic current which generates a significant Lorentz force in the presence of a magnetic field. This Lorentz force induces solution convection during the deposition step, enhancing the mass transport of analytes to the electrode and increasing their preconcentrated quantity in the mercury thin film. Therefore, larger ASV peaks and improved sensitivities are obtained, compared to analyses performed without a magnet. The effects on ASV signal of varying Hg(2+) concentration (0.10 and 1.0 mM), deposition time (10-600 s), and electrode surface roughness were investigated. In addition, analyses were performed using a real lake water matrix. By using the disposable LTCC-SPC working electrodes in small volumes (150 microL) and with small permanent magnets (0.78 T), peak areas were increased by 75% when compared to the signal obtained in the absence of a magnetic field. A limit of detection of 25 nM for Cd(2+) was observed with only a 1 min preconcentration time.     

Acute and sub-acute toxicity study of hydroalcoholic fruit extract of Pithecellobium dulce

This study was carried out to evaluate the acute and sub-acute toxicity profile of the hydroalcoholic fruit extract (HAEPD) of Pithecellobium dulce (Leguminosae). Albino rats were treated orally with 100, 200 and 500?mg?kg(-1) bodyweight (BW) of HAEPD for 90 days to assess its sub-acute toxicity. HAEPD at single doses of 100, 500, 1000, 2000 and 4000?mg?kg(-1) BW was also administered to rats to assess its acute toxicity. The rats were observed for physical discomfort, BW change and feeding habits. Pithecellobium dulce did not cause any abnormal changes in haematological or biochemical parameters. Pathologically, no gross abnormality in the tissue architecture was observed. The LD(50) was found to be 3916?mg?kg(-1) BW and potential effective doses for efficacy studies are 100 and 300?mg?kg(-1) BW as the minimum and maximum doses, respectively. It is concluded that HAEPD can be used safely for experimental and clinical trials.     

Polyprotic acid catholyte for high capacity dual-electrolyte Li-air batteries

The polyprotic acid H(3)PO(4) in a Li(2)SO(4) supporting electrolyte has been effectively utilized as a catholyte donating three protons in dual-electrolyte Li-air cells. The cell offers a high capacity of 740 mA h g(-1) at an average cell voltage of 3.3 V with good rechargeability and stability.     

Synthesis of the anti-influenza agent (-)-oseltamivir free base and (-)-methyl 3-epi-shikimate

A new enantioselective synthesis of the anti-influenza agent (-)-oseltamivir free base (7.1% overall yield; 98% ee) and (-)-methyl 3-epi-shikimate (16% overall yield; 98% ee) has been described from readily available raw materials. Sharpless asymmetric epoxidation and diastereoselective Barbier allylation of an aldehyde are the key reactions employed in the incorporation of chirality, while the cyclohexene carboxylic ester core was constructed through a ring closing metathesis reaction.