Synthesis of furano-epothilone D

The total synthesis of furano-epothilone D by a convergent route is reported. The key fragments are available on a large scale to provide sufficient material for biological evaluation. The approach involves a palladium-catalyzed coupling that generates a highly functionalized aldehyde which is connected in a stereoselective aldol reaction to yield the framework of furano-epothilone D. Finally, a macrolactonization provides furano-epothilone D.     

Physico-chemistry of silica / Na silicate interactions during consolidation. Part 2: Effect of pH

This work aims to study the effect of the pH of a sodium silicate solution on the consolidation of silica-based aggregates at low temperature (70 °C). A diluted solution obtained by adding 50 wt% of distilled water into a concentrated commercial solution was used as starting solution. Solutions with an increasing pH values were prepared by alkalinizing the diluted solution with solid NaOH. This leads to the depolymerization of silicate species present in solution. Consolidated materials were obtained by impregnating silica sand with the solution. In order to increase the surface reactivity, the sand was also functionalized by a prior basic attack. Results reveal that the increase in the pH value or the functionalization of the sand surface leads to improve mechanical properties of materials suggesting chemical reactions between the components confirmed by FTIR experiments. Actually, the ν_asSi-O-Si broad band with a sharp peak located around 1015 cm^-1, shifts firstly to lower and then to higher wavenumber characteristic of dissolution / precipitation reactions. Moreover, the enhancement of the pH value induces intra-granular break characterized by SEM observations confirming the best consolidation. However, these samples are more soluble in water related to the excess in sodium that induces more ionic bonds.     

Novel ring enlargement of cyclobutane derivatives by oxidative radical decarboxylation

Cycloadducts obtained via [2+2] photocycloaddition between an unsaturated oxoacid and cycloalkene are readily opened by irradiation at 366nm, in the presence of catalytic amounts of acridine in toluene and under an oxygen atmosphere, leading after treatment with dimethylsulfide to the formation of polycyclic diketones or ketolactones.     

Evaluation of the fractionated crystallization of isotactic polypropylene and high density polyethylenes in their blends with Cycloolefin copolymers

Crystallization of semi-crystalline polyolefins (i-polypropylenes and HD-polyethylenes) in their blends with amorphous cycloolefin copolymers (COC) were studied. The thermal behaviour of the blends was characterized by Differential Scanning Calorimetry (DSC) whereas blend morphologies were investigated by Scanning Electronic Microscopy (SEM). In iPP/COC blends, a phenomenon of fractionated crystallization is evidenced when i-PP is finely dispersed in the COC matrix. Such a behavior is generally observed when the number of droplets is much larger than the number of heterogeneities originally present in the bulk polymer. In HDPE/COC blends, complex morphologies are observed which do not fit good correlation with DSC results. The nucleation and crystallization modes seem to be largely influenced by the characteristics of the micro-dispersed phase, largely dependent on the PE molecular weights and polydispersity indices.     

An efficient one-pot four-step domino reaction for the synthesis of C2-substituted 3-methylcyclohex-2-enones

An efficient one-pot four-step domino reaction of substituted β-ketoesters has been optimized giving rise to a large panel of C2-substituted 3-methylcyclohex-2-enones, an important scaffold for the preparation of various initiators for cationic or radical cyclizations. The developed methodology is quite general and applicable to a wide range of β-ketoester substrates, allowing the introduction of various functionalities at the C2 position of the 3-methylcyclohex-2-enones, in good to excellent yields.     

Soluble {[Rh2(μ-OOCCH3)2(dbbpy)2][BF4]}n molecular wire and [Rh2(μ-OOCCH3)2(dbbpy)2L2] complexes; dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine: Synthesis and physicochemical characterization

Binuclear Rh(II) compounds [Rh₂(μ-OOCCH₃)₂(dbbpy)₂(H₂O)₂](CH₃COO)₂ (1) (dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine), [Rh₂(μ-OOCCH₃)₂(dbbpy)₂(H₂O)₂](BF₄)₂·H₂O·CH₃CN (2), [Rh₂(CH₃COO)₂(C₁₈H₂₄N₂)₂(CH₃CN)₂](BF₄)₂·4CH₃CN (3) and {[Rh₂(μ-OOCCH₃)₂(dbbpy)₂][BF₄]}_n (4) have been synthesized and characterized with spectroscopic methods. Structure of complex 3 has been determined using X-ray crystallography. Rhodium atoms in compound 3 have distorted octahedral coordination with O and N atoms in equatorial positions and Rh atom and CH₃CN molecule in axial coordination sites. Reduction of rhodium(II) compounds with aqueous 2-propanol leads to the formation of polymetallic compound {[Rh₂(μ-OOCCH₃)₂(dbbpy)₂][BF₄]}_n (4) containing [Rh₂]³⁺ core. Compound 4 shows strong antiferromagnetic properties, μ = 0.18–1.73 M.B. in the range 1.8–300 K, J = −597 cm⁻¹. Electrochemistry of compounds 3 and 4 in CH₃CN has been investigated. Compound 4 exhibits a poorly reversible oxidation system at E_1/2 = −0.92 V (ΔE_p = 0.19 V) and in solution in DMF is slowly oxidized to 3 even in total absence of oxygen. Complex 3 is irreversibly oxidized to Rh(III) compound at E_pa = 1.48 V and irreversibly reduced at E_pc = −1.02 V to lead to the unstable polynuclear complex 4 in CH₃CN.     

Regioselective N-alkylation of imidazo[4,5-b]pyridine-4-oxide derivatives: an experimental and DFT study

Regioselectivities were determined for N-alkylations of imidazo[4,5-b]pyridine-4-oxide and 2-methyl-imidazo[4,5-b]pyridine-4-oxide with benzyl bromide or benzyl iodide at RT using K₂CO₃ in DMF as a base. Experimental attempts have shown that N-1/N-3 ratios slightly varied according to the substitution on C-2 position. This was confirmed by DFT calculations in solvent phase. This computational study has shown first that this N-benzylation reaction passed through a S_N2 mechanism. Moreover, regioselectivity of N-benzylation has appeared essentially governed by ‘steric approach control’. It explained that opposite N-1/N-3 ratios were obtained with imidazo[4,5-b]pyridine-4-oxide and its 2-methyl-substituted analog. Finally, regioselectivities slightly varied with the nature of benzyl halide.     

Persistent Organochlorine Insecticide Residues in Some Paddy,Upland and Urban Soils of India

Abstract

A wide variety of agricultural soils from different regions of India such as paddy, wheat, mustard, potato, cotton, tea, tomato, sugarcane, grape and urban soils were surveyed for the residual levels of persistent organochlorine insecticide residues in 1988 and 1989. DDT and HCH concentrations were found to be higher in upland soils and lower in paddy field soils. These results indicate the large application of HCH and DDT compounds for agricultural purposes in India. In urban soil DDT levels were higher than HCHs reflecting the use of the former insecticide in relatively large amounts for vector control. Among DDT compounds, p,p′-DDE showed higher percentage in paddy and upland soils. On the other hand, p,p′-DDT contributed to higher levels in urban soils. The β-HCH was detected as the dominant isomer in both agricultural and non agricultural soils. The levels and percentage compositions of DDTs and HCHs revealed the extent of environmental contamination caused by the continuous usage of persistent organochlorine insecticides in large quantities in tropical areas like India.     

Built-in axial base binding on phenanthroline-strapped zinc(II) and iron(III) porphyrins

In addition to the need for functional models of cytochrome c oxidase, structural models are still required for a better understanding of the small reorganizations occurring during the catalytic cycle. An efficient synthetic approach has been designed to prepare several phenanthroline-strapped porphyrins, two of them bearing two pendant imidazoles. These built-in bases are both potentially able to act as axial bases for the metalloporphyrin and as complementary ligands for copper if necessary. Diamagnetic zinc(II) was used to demonstrate that the distal/proximal selectivity demonstrated by exogenic bases binding studies can be extended to the coordination of iron(III). Combination of EPR and paramagnetic 1H NMR shows that the imidazole binding on the zinc species can be further extended to the iron(III) species in dilute conditions.