The versatility of molecular ruthenium catalyst RuCl(COD)(C5Me5)

This review reports the contribution of the catalyst precursor RuCl(COD)C₅Me₅, and of the Rennes team, for the selective transformation of alkynes to generate high value chemicals with atom economy reactions. Ruthenium activation processes are discussed. Are successively presented (i) the cross-oxidative coupling of alkyne and allyl alcohol to generate γ,δ-unsaturated aldehydes, (ii) the head-to-head dimerisation of alkynes in the presence of carboxylic acids, via a mixed Fischer-Schrock type biscarbene-ruthenium complex, to give functional dienes, and that of propargyl alcohols, via cyclobutadienyl-ruthenium intermediate, to produce cyclobutene derivatives, (iii) the addition of diazoalkanes to alkynes leading to functional dienes via double carbene addition and (iv) the reaction of diazoalkanes to enynes leading to new bicyclo[3.1.0]hexane compounds. Most of the above catalytic reactions involve carbene-ruthenium catalytic species of type Cp*(Cl)Ru(biscarbene) or Cp*(Cl)RuCHR.     

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.     

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.     

A New Sphingolipid and Furanocoumarins with Antimicrobial Activity from <i>Ficus exasperata</i>

From the methanol extract of the stem bark of Ficus exasperata, a new sphingolipid named Ficusamide, (2S,3S,4R,11E)-2-[(2',3'-dihydroxyhexacosanoylamino)]-11-octadecene-1,3,4-triol (1), along with three known furanocoumarins, (S)-(－) oxypeucedanin hydrate (2), (R)-(+) oxypeucedanin hydrate (3), bergapten (5-methoxypsoralen) and six other known compounds, were isolated. Their structures were characterized basing on spectroscopic methods and chemical evidence. Compounds (1-3) were analyzed for their antimicrobial activity. Ficusamide (1) showed wick activity (minimal inhibitory concentration (MIC)=312.5?μg/mL) against Escherichia coli, while the furanocoumarins (2) and (3) showed significant activity (MIC=9.76?μg/mL) against Bacillus cereus, Candida albicans and Microsporum audouinii.     

Synthesis and cytotoxic and antitumor activity of 1,2-dihydroxy-1,2-dihydrobenzo[b]acronycine diacid hemiesters and carbamates

A series of cis-1,2-dihydroxy-1,2-dihydrobenzo[b]acronycine diacid hemiesters and dicarbamates were prepared by acylation of cis-1,2-dihydroxy-6-methoxy-3,3,14-trimethyl-1,2,3,14-tetrahydro-7H-benzo[b]pyrano[3,2-h]acridin-7-one. The cytotoxicity of the dicarbamates depended on the steric hindrance of the esterifying groups at positions 1 and 2. Diacid hemiesters displayed significant in vitro cytotoxic activities and induced cell cycle perturbations similar to those obtained with cis-1,2-diacetoxy-1,2-dihydrobenzo[b]acronycine (S23906-1) currently under preclinical development. cis-1-Acetoxy-2-hemiglutaryloxy-1,2-dihydrobenzo[b]acronycine was the most promizing compound of the series, inducing complete inhibition of tumor growth when tested against C38 colon adenocarcinoma implanted in mice.     

On the multiplicity of parts in a random partition

Let λ be a partition of an integer n chosen uniformly at random among all such partitions. Let s(λ) be a part size chosen uniformly at random from the set of all part sizes that occur in λ. We prove that, for every fixed m≥1, the probability that s(λ) has multiplicity m in λ approaches 1/(m(m+1)) as n→∞. Thus, for example, the limiting probability that a random part size in a random partition is unrepeated is 1/2. In addition, (a) for the average number of different part sizes, we refine an asymptotic estimate given by Wilf, (b) we derive an asymptotic estimate of the average number of parts of given multiplicity m, and (c) we show that the expected multiplicity of a randomly chosen part size of a random partition of n is asymptotic to (log n)/2. The proofs of the main result and of (c) use a conditioning device of Fristedt. ©1999 John Wiley & Sons, Inc. Random Struct. Alg., 14, 185–197, 1999     

Influence of Phase Morphology on Molecular Mobility of Poly(propylene)-(ethylene-vinyl acetate) Copolymer Blends

The dynamic mechanical and dielectric behaviours of Polypropylene (PP) and (Ethylene-Vinyl Acetate) Copolymer (EVA) blends are reported as a function of the morphology. For EVA contents lower than 20%, blends show the two-phase morphology characteristic of immiscible blends, with spherical EVA droplets finely dispersed in the PP matrix. After stretching in the molten state, the morphology of EVA fibers is observed. Mechanical Relaxation Spectroscopy display three relaxation processes: the EVA and PP α-relaxations associated to the glass transitions and a β-transition corresponding to a PP crystalline phase relaxation. The PP α-relaxation shifts to higher temperatures when EVA presents a fiber morphology, corresponding to a decrease of PP chain mobility since it is hindered by the reinforcement effect of EVA fibers. Quite different results are obtained by DRS analysis. In blends containing EVA fibers, only one main relaxation associated to the EVA α-transition is observed whereas one additional relaxation can be noticed in the blends containing EVA droplets. This new relaxation might be assigned to interfacial polarization effects, phenomena that are sometimes observed in heterogeneous polymer blends when a low content of one polar component is embedded in a non conductive matrix. In this case, the occurrence of a characteristic interfacial polarization relaxation appears to be correlated to the accessible experimental frequency.