Reactions of thiosemicarbazones derived from beta-keto amides and beta-keto esters with Zn(II) and Cd(II) acetates: influence of metal, substitution, reagent ratio and temperature on metal-induced cyclization

Zinc(II) and cadmium(II) acetates were reacted in methanol under various experimental conditions with thiosemicarbazones derived from beta-keto amides or beta-keto esters (HTSC). Some of these reactions afforded thiosemicarbazonate complexes [M(TSC)2] with IR and NMR spectra compatible with N,S-coordination, but most gave complexes [ML2], where HL is a substituted 2,5-dihydro-5-oxo-1H-pyrazole-1-carbothioamide resulting from cyclization of the HTSC. Some of these pyrazolonates and two of the HL ligands were studied by X-ray diffractometry, and their structures are discussed. Surprisingly, the reactions of zinc(II) acetate with HTSC in 1:1 mol ratio usually gave a third, previously unreported type of complex with a dideprotonated ligand, [Zn(L-H)], which was also formed when [ZnL2] and Zn(OAc)2 interacted at room temperature in 1:1 mol ratio. These L-H complexes are highly insoluble in all common solvents, which hinders their characterization but suggests that they are polymeric in nature.     

Synthesis and photophysical properties of meso-substituted bisporphyrins: comparative study of phosphorescence quenching for dioxygen sensing

The 4,6-bis(10-mesityl-5,15-di-p-tolylporpyrinyl)dibenzothiophene (H4DPSN) free base was obtained in five steps from commercially available materials. The metalation of DPSN2- with zinc(II), copper(II), and palladium(II) led to three new homobimetallic systems, (Zn)2DPSN, (Cu)2DPSN, and (Pd)2DPSN, respectively. The cofacial structures of these molecules offer the possibility of having dioxygen molecules inside the cavity for a period of time, allowing dynamic (collisional) phosphorescence quenching to be more efficient. The bimolecular excited-state deactivation rate constant for deactivation by dioxygen (kQ: (Pd)2DPB, 2.98x10(9); (Pd)2DPSN, 3.99x10(9); (Pd)2DPX, 6.94x10(9); (Pd)TPP, 8.95x10(9); (Pd)2DPS, 8.95x10(9) M-1 s-1) of (Pd)2DPSN, which exhibits an intense phosphorescence at 699 nm, was compared to those observed for (Pd)TPP, (Pd)2DPS, (Pd)2DPX, and (Pd)2DPB (TPP2-=tetraphenylporphyrin dianion, DPS4-=4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene tetraanion, DPX4-=4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene tetraanion, and DPB4-=1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene tetraanion). These collision-induced deactivation data were interpreted by estimating a series of physical parameters such as the surface area and bisporphyrin radii, the diffusion coefficient of the bismacrocycles, and the theoretical deactivation efficiency for the five compounds addressing the role of steric hindrance of the macrocycles on each other and the aryl groups at the meso positions. For sensing purposes, (Pd)2DPX is characterized by a Stern-Volmer constant kSV of 2.91x10(6) M-1, placing the lower detection limit for [O2] in solution at 0.58 ppm, which is better than that for (Pd)TPP (kSV=2.31x10(6) M-1; lower detection limit of 0.73 ppm), the classically used monoporphyrin complex.     

Interactions between a nonionic gemini surfactant and cyclodextrins investigated by small-angle neutron scattering

The microstructure of complexes between hydroxypropyl-cyclodextrins (HPCDs) (alpha, beta, and gamma) and a novel gemini surfactant has been investigated by small-angle neutron scattering (SANS). This nonionic hetero-gemini surfactant (denoted NIHG750) contains two hydrophobic groups and two hydrophilic groups. One is a methyl-capped polyoxyethylene chain with 16 oxyethylene units and the other is a secondary hydroxyl group. Various form factor models have been considered for fitting the SANS data. Spherical aggregates (25 to 40 A) with a size slightly larger than that of NIHG750 micelles (about 23 A) appear in mixed systems. These could be micellar aggregates partly covered with a few cyclodextrin molecules. In addition, the results indicate rod formation (r approximately 8 A, L approximately 70 A) for the NIHG-HPCD complexes. This result is consistent with the threading of HPCDs onto NIHG750 to such an extent that the surfactant molecule takes an extended conformation at high levels of HPCD. Also, the results indicate that HPCDs may interact with the oxyethylene groups of the spherical micellar aggregates leading to an increase in micelle size and a gradual transformation to rod-shaped aggregates. The tendency to form rods increases in the order gamma-CD相似文献   

Calculation of cross sections for positron-Ar collisions

The three-body classical trajectory Monte-Carlo (CTMC) method is used to investigate positron-argon atom collisions. The total ionization cross sections are presented along with singly and doubly differential cross sections. The existence of the cusp-like peak in the triply differential electron and positron spectra at positron impact is predicted.     

Salting-in of alcohols in aqueous solutions by tetraalkylammonium bromides at the freezing temperature

The freezing-point depression of the ternary systems tetraalkylammonium bromides-t-butanol-water for the first five homologs of R₄NBr was measured. In the case of Bu₄NBr, the effect of size of the alcohol (methahol ton-butanol) was also investigated. From the corresponding freezing-point data for the binary systems the apparent salting constants were calculated. The true salting constantsk _s were obtained by extrapolation to infinite dilution. These are all very close to zero at the freezing temperature. From the corresponding thermochemical data the temperature dependence ofk _s was calculated, and above 5°C all the R₄NBr salts int-butanol; the salting-in increases with temperature and with the size of the hydrophobic cations. The scaled-particle theory is at present the only one which can account semiquantitatively for the temperature dependence of the salting-in effect. On leave of absence from Chemistry Department, The University, Sheffield S3 7HF, England To whom correspondence should be addressed.     

Thermolyse des β-énaminodiesters cycliques: Accès à divers β-énaminoesters, β-énaminothioesters et β-enaminoamides.

A new synthesis of β-enaminoesters, β-enaminothioesters et β-enaminoamides by thermic decomposition of β-enaminodiesters is described.     

Derivative spectrophotometric resolution of mixtures of the food colourants Tartrazine, Amaranth and Curcumin in a micellar medium

A study of the absorption spectra of the food colourants Tartrazine (E-102), Amaranth (E-123) and Curcumin (E-100) in various organic solvents and pH media, have been carried out. In addition, the spectral behaviour in aqueous micellar systems of anionic, cationic and non-ionic surfactants, as well as beta-cyclodextrin, was investigated. Analytical methods are proposed for the determination of the three dyes in mixtures without any prior separation step, by the application of the derivative technique to the normal absorption spectra, based on the use of cetyltrimethylammonium bromide (CTAB) in 0.1 M NaOH, over the concentration range 2-50 mug ml(-1). The methods are applied for determining the three dyes in commercial food products.     

Thermodynamic properties of alkali halides. IV. Apparent molal volumes,expansibilities, compressibilities,and heat capacities in urea-water mixtures

The apparent molal volume φ_v, expansibility φ_E, compressibility φ_K, and heat capacity φ_c of NaCl were measured in urea-water mixtures, as a function of salt (<1.5m) and urea (<13m) concentrations at 25°C. At a fixed urea concentration, the transfer functions from H₂O to 3m urea are linear functions of the NaCl aquamolality. At a fixed salt aquamolality, (0.1m), the sign of the transfer functions is in the direction of a decrease in the structure-breaking effect, and the absolute values of the transfer functions tend to level off at high urea concentrations (13m). The functions φ_v, φ_E, φ_K, φ_c, and (?φ_v/?T)_p were measured for the sodium halides and alkali, bromides (chlorides in the case of φ_K) at a fixed salt aquamolality of 0.1m and fixed urea molality of 3m. The corresponding transfer functions from H₂O to 3m urea are opposite those from H₂O to D₂O and similarly are relatively independent of ionic size. This suggests that urea, shows no specific interaction affinity for ions and that the overall number of water molecules influenced by the ions is relatively constant for all alkali halides. The lithium halides are an exception in that Li⁺ seems to have hardly any structure-breaking effect.     

Synthesis and acid-base properties of (1H-benzimidazol-2-yl-methyl)phosphonate (Bimp2-). Evidence for intramolecular hydrogen-bond formation in aqueous solution between (N-1)H and the phosphonate group

The synthesis of (1H-benzimidazol-2-yl-methyl)phosphonic acid, H2(Bimp)+/-, is described: 2-chloromethylbenzimidazole was reacted with ethylchloroformate to give 1-carboethoxy-2-chloromethylbenzimidazole which was treated with trimethyl phosphite and after hydrolysis with aqueous HBr H2(Bimp)+/- was obtained. In H2(Bimp)+/- one proton is at the N-3 site and the other at the phosphonate group; both acidity constants were determined in aqueous solution by potentiometric pH titrations (25 degrees C; I = 0.1 M, NaNO3) and this furnished the pKa values of 5.37 +/- 0.02 and 7.41 +/- 0.02, respectively. The acidity constant for the release of the primary proton from the P(O)(OH)2 group of H3(Bimp)+ was estimated: pKa = 1.5 +/- 0.2. Moreover, Bimp2- can be further deprotonated at its neutral (N-1/N-3)H site to give the benzimidazolate residue, but this reaction occurs only in strongly alkaline solution (KOH); application of the H_ scale developed by G. Yagil (J. Phys. Chem., 1967, 71, 1034) together with UV spectrophotometric measurements gave pKa = 14.65 +/- 0.12. Comparisons with acidity constants taken from the literature show that this latter pKa value is far too large and this allows the conclusion that an intramolecular hydrogen bond is formed between the (N-1/N-3)H site and the phosphonate group of Bimp2-; the formation degree of this hydrogen-bonded isomer is estimated to be 98 +/- 2%. The general relevance of this and the other results are shortly discussed and the species distribution for the Bimp system in dependence on pH is provided.