Charge transfer efficiency in hybrid bulk heterojunction composites

On the basis of recently published electrochemical measurements, the charge transfer efficiency within CdSe nanocrystal/conducting polymer heterojunction composites was investigated by means of luminescence interaction strength. It was found that poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] and poly-9-vinylcarbazole luminescence was not totally quenched by nanocrystals, whereas poly-3-octylthiophene and polyvinylpyrrolidone was completely quenched. In case of poly-3-hexylthiophene, the nanocrystal luminescence was quenched. The results are in complete agreement with the electrochemical findings and thus, the CdSe nanocrystal/Polyvinylpyrrolidone composite should be a promising material for electroluminescent devices.     

Enantioselective reduction of ketones with borane catalyzed by cyclic β- amino alcohols prepared from proline

New catalysts have been prepared from (S)- and (R)- proline and the asymmetric borane reduction of prochiral ketones using these catalysts has been studied. The secondary alcohols were obtained in 76–95% yield with 57– 96% enantiomeric excesses.     

Selective one-pot synthesis of substituted pyrrole-3-phosphonates from α-cyanomethyl-β-ketoesters

A one-step synthesis of 5-alkoxypyrrole-3-phosphonates is presented starting from suitable α-cyanomethyl-β-ketophosphonates. The key step in the synthesis involves a one-pot addition and heteroannulation sequence. The zinc perchlorate-catalyzed addition of alcohols to the nitrile carbon of α-cyanomethyl-β-ketophosphonates followed by annulation furnished 5-alkoxypyrrole-3-phosphonates. The addition-annulation process is carried out in the presence of water and 4,5-dihydro-5-oxo-1H-pyrrole-3-phosphonates (pyrrolinones) are obtained in good yields.     

Synthesis, spectral and thermal properties of homo- and copolymers of 2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacrylate and determination of monomer reactivity ratios

The methacrylate monomer, 2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate (IAOEMA), was synthesized by reacting 2-chloro-N-(5-methylisoxazol)acetamide dissolved in acetonitrile with sodium methacrylate in the presence of triethylbenzylammoniumchloride (TEBAC). The free-radical-initiated copolymerization of IAOEMA, with styrene (ST) and methyl methacrylate (MMA) was carried out in dimethylsulphoxide (DMSO) solution at 65 °C using 2,2^′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The monomer (IAOEMA) and copolymers were characterized by FTIR, ¹H- and ¹³C-NMR spectral studies. The copolymer composition was evaluated by nitrogen content in polymers led to the determination of reactivity ratios. The reactivity ratios of the monomers were determined by the application of Fineman-Ross and Kelen-Tüdös methods. The analysis of reactivity ratios revealed that ST and MMA are more reactive than IAOEMA, and copolymers formed are statisticalle in nature. The molecular weights (M_w and M_n) and polydispersity index of the polymers were determined using gel permeation chromagtography. Glass transition temperatures of the copolymers were found to increase with an increase in the mole fraction of IAOEMA in the copolymers. The apparent thermal decomposition activation energies (E_d) were calculated by Ozawa method using the SETARAM Labsys TGA thermobalance.     

(Liquid + liquid) equilibria of (water + propionic acid + methyl isoamyl ketone or diisobutyl ketone or ethyl isoamyl keton) at T = 298.2 K

(Liquid + liquid) equilibrium (LLE) data for (water + propionic acid + solvent) were measured at T = 298.2 K and atmospheric pressure. The solvents were methyl isoamyl ketone (5-methyl-2-hexanone), ethyl isoamyl ketone (5-methyl-3-heptanone) and diisobutyl ketone. The tie-line data were correlated by means of the NRTL and UNIQUAC equation, and compared with results predicted by the UNIFAC method. A comparison of the extracting capabilities of the solvents was made with respect to distribution coefficients, separation factors, and solvent free selectivity bases.     

Molar conductance of aqueous solutions of sodium, potassium, and nickel trifluoromethanesulfonate at 25‡C

The electrical conductivities of aqueous solutions of NaCF₃SO₃, KCF₃SO₃, and Ni(CF₃SO₃)₂ have been measured at 25‡C in the concentration range 1 to 25X 10^-3 mol-dm^-3 The data approach the Onsager limiting law at low concentrations, leading to a limiting molar ion conductivity for the CF₃SO ₃ ⁻ ion of 44.5±0.2 S-cm²-mol^-1, based on standard values for the cations. Using a simple size parameter for unsymmetrical polyatomic ions, based on the ion geometry, it is shown that the well known empirical relation between the molar conductivities of symmetrical ions and their radii can be extended to include certain polyatomic anions including CF₃SO ₃ ⁻ . The results suggest that the CF₃SO ₃ ⁻ ion is either a weak structure breaker in aqueous solution or neutral in this respect.     

Eta6-mesityl,eta1-imidazolinylidene-carbene-ruthenium(II) complexes: catalytic activity of their allenylidene derivatives in alkene metathesis and cycloisomerisation reactions

The reaction of electron-rich carbene-precursor olefins containing two imidazolinylidene moieties [(2,4,6-Me(3)C(6)H(2)CH(2))NCH(2)CH(2)N(R)Cdbond;](2) (2a: R=CH(2)CH(2)OMe, 2 b R=CH(2)Mes), bearing at least one 2,4,6-trimethylbenzyl (R=CH(2)Mes) group on the nitrogen atom, with [RuCl(2)(arene)](2) (arene=p-cymene, hexamethylbenzene) selectively leads to two types of complexes. The cleavage of the chloride bridges occurs first to yield the expected (carbene) (arene)ruthenium(II) complex 3. Then a further arene displacement reaction takes place to give the chelated eta(6)-mesityl,eta(1)-carbene-ruthenium complexes 4 and 5. An analogous eta(6)-arene,eta(1)-carbene complex with a benzimidazole frame 6 was isolated from an in situ reaction between [RuCl(2)(p-cymene)](2), the corresponding benzimidazolium salt and cesium carbonate. On heating, the RuCl(2)(imidazolinylidene) (p-cymene) complex 8, with p-methoxybenzyl pendent groups attached to the N atoms, leads to intramolecular p-cymene displacement and to the chelated eta(6)-arene,eta(1)-carbene complex 9. On reaction with AgOTf and the propargylic alcohol HCtbond;CCPh(2)OH, compounds 4-6 were transformed into the corresponding ruthenium allenylidene intermediates (4-->10, 5-->11, 6-->12). The in situ generated intermediates 10-12 were found to be active and selective catalysts for ring-closing metathesis (RCM) or cycloisomerisation reactions depending on the nature of the 1,6-dienes. Two complexes [RuCl(2)[eta(1)-CN(CH(2)C(6)H(2)Me(3)-2,4,6)CH(2)CH(2)N- (CH(2)CH(2)OMe)](C(6)Me(6))] 3 with a monodentate carbene ligand and [RuCl(2)[eta(1)-CN[CH(2)(eta(6)-C(6)H(2)Me(3)-2,4,6)]CH(2)CH(2)N-(CH(2)C(6)H(2)Me(3)-2,4,6)]] 5 with a chelating carbene-arene ligand were characterised by X-ray crystallography.     

A new and efficient chemoenzymatic route to both enantiomers of 4-hydroxycyclohex-2-en-1-one

[reaction: see text] A chemoenzymatic synthesis of both enantiomers of the pharmacologically interesting 4-hydroxycyclohex-2-en-1-one in three steps starting from 3-methoxycyclohex-2-en-1-one is described. Manganese(III) acetate-mediated acetoxylation followed by enzyme-mediated hydrolysis of alpha-acetoxy enone affords acetoxy enone 3 and hydroxy enone 4 with high enantiomeric excesses and in good yields. The reduction of the acetoxy and hydroxy enones furnished both enantiomers of 4-hydroxycyclohex-2-en-1-one in high enantiomeric excess.     

Synthesis of a bipyridine-derived achiral thiourea trifluoromethanesulfonic acid salt and its application as an additive in organocatalytic asymmetric reactions

The host–guest complex of a proline–thiourea bipyridine trifluoromethanesulfonic acid salt can catalyze organocatalytic asymmetric reactions such as aldol, Michael, and Mannich in polar protic medium with high stereoselectivities. The privileged bipyridine backbone and the thiourea motif are essential to the activity and enantioselectivity through hydrogen bonding interactions.     

Study of asymmetric aldol and Mannich reactions catalyzed by proline–thiourea host–guest complexes in nonpolar solvents

A proline–thiourea host–guest complex has been described as a good catalyst for asymmetric reactions such as aldol and Mannich reactions. High stereoselectivities were obtained under optimal conditions. Thiourea was observed to have an important effect on the reactivity and selectivity, even in an unconventional nonpolar reaction medium and without the need to utilize low temperatures. This proline–thiourea host–guest system has the ability to participate in a hydrogen bonding network.