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.     

Epoxides,cyclic sulfites,and sulfate from natural pentacyclic triterpenoids: theoretical calculations and chemical transformations

Several triterpenic derivatives, with the A-ring functionalized, were semisynthesized from oleanolic and maslinic acids. The reactivities of sulfites, sulfate, and epoxides in these triterpene compounds were investigated under different reaction conditions. Moreover, contracted A-ring triterpenes (five-membered rings) were obtained, by different treatments of the sulfate 7. From the epoxide 8, deoxygenated and halohydrin derivatives were semisynthesized with several nucleophiles. Ozonolysis and Beckmann reactions were used to yield 4-aza compounds, from five-membered ring olanediene triterpenes. The X-ray structure of sulfate 7 is given and compared with density functional theory geometries. Theoretical (13)C and (1)H chemical shifts (gauge-invariant atomic orbital method at the B3LYP/6-31G*//B3LYP/6-31G* level) and (3)J(H,H) coupling constants were calculated for compounds 5-9 and 34-36, identifying the (R)- or (S)-sulfur and alpha- or beta-epoxide configurations together with 4-aza or 3-aza structures.     

Laser spectroscopy of Si3C

The C 1B1<--X 1A1 band system of the potential interstellar species Si3C has been recorded in a silane/acetylene discharge by resonant two-color two-photon ionization spectroscopy. The origin band is located near 24,925 cm-1 (3.09 eV). Several other features in the spectrum are assigned to progressions in the Si-Si stretching modes as well as to sequence and hot band transitions. The assignment was facilitated by ab initio calculations, which also indicate that this is the strongest electronic transition of Si3C in the visible region of the spectrum. Features in the spectrum are broadened considerably (ca. 10 cm-1), and suggest an excited state lifetime of a few picoseconds. Possible reasons for the short-lived nature of the excited state are discussed.     

Infrared Study of Solid Dispersions of β-Cyclodextrin with Naphthalene Derivitaves

The inclusion complexes of β-cyclodextrin (β-CD) with naphthalene and some of its derivatives in the solid state have been studied by infrared spectroscopy. Digital subtraction, deconvolution and curve fitting have been used to investigate the interactions between the naphthalene derivatives andβ-CD. Several preparation methods for the solid dispersions have been tested, using FTIR as an effective tool to evaluate the interactions at the molecular level. The effects of temperature and humidity on the spectra have been also analyzed. A carbonyl moiety in the guest molecule can increase the stability of the complex by establishing specific interactions with the hydroxyl groups of the CD cavity rims. The stability of the complexes is higher for 2-naphthylacetate than that for 1-naphthyl acetate, andso is the degree of association of its carbonyl groups. On the other hand, 2-acetylnaphthaleneforms very stable inclusioncomplexes although its carbonyl groups appear to be significantly less associated.     

Recherches sur la structure électronique de composés soufrés (méthode L.C.A.O. améliorée)

Improved L.C.A.O. method primitively built for conjugated molecules holding only atoms of second row in the periodic classification is extended to molecules holding atoms of the third row. The application is done for thiophen, thioketones, SO₂ and SO₃. d orbitals are not introduced in this study. Discussion about results shows that d orbitals must be introduced when the sulphur atom is strongly positively charged like in sulphur oxides.     

High-performance liquid chromatographic determination of tocopherols in infant formulas

A method for the simultaneous determination of alpha-tocopherol acetate and alpha-, delta-, and gamma-tocopherols by normal-phase high-performance liquid chromatography (HPLC) with a fluorescent detector in infant formula is proposed. The values obtained in the determination of the analytical parameters: linearity, precision, limit of detection and accuracy (analysis of a standard reference material, SRM 1846), confirm the quality of the method. The proposed method is useful for the determination of alpha-, delta-, and gamma-tocopherols and alpha-tocopherol acetate in infant formulas at a low cost and in a total time of 2 h.     

Tungsten(VI)-gluconic acid complexes: Polarimetric and13C-N.m.r. Studies in an excess of tungsten(VI)

Summary A polarimetric study of the tungsten (VI)-gluconic acid system in an excess of metal reveals the formation of four stable complexes: two monomers with 1 : 2 and 2: 1 stoichiometries and two dimers of 2:2 composition. The pH ranges of these species, the amount of acid equivalents their formation requires, and their conditional stability constants have also been calculated.The probable coordination of the organic ligand to the metallic centre in solutions containing different metal : ligand ratios has been investigated by¹³C-n.m.r. spectroscopy. The results confirm the formation of different complexes depending on the reagent which is in excess. The behaviour of the system when the metal is in excess is related to that of other polyhydroxylic ligands such as mannitol and sorbitol.     

Liquid chromatographic determination of diminazene diaceturate (Berenil) in raw bovine milk

A simple liquid chromatographic (LC) method is presented for the determination of diminazene (DZ) in raw bovine milk. DZ is extracted from raw milk by chilled aqueous centrifugation and is isolated from milk components on a cyano solid-phase extraction column. DZ is eluted by using a methanol-ion pairing reagent. A Phenomenex LUNA CN column and an acetonitrile-buffered mobile phase with a counter ion are used for gradient LC. The LC effluent is monitored at a detection wavelength of 372 nm by using a deuterium lamp. Under the parameters described, the retention time of DZ is 8-10 min with a peak area response of 6.5 mAU/ng. The method demonstrated excellent precision over all levels tested (25-400 ppb) with an overall average recovery of 90.4 +/- 14.5%. The method is applicable to the monitoring of milk for DZ residues at the 25 ppb level with a limit of quantitation of 10 ppb.     

Effect of absolute laser phase on reaction paths in laser-induced chemical reactions

Potential surfaces, dipole moments, and polarizabilities are calculated by ab initio methods [unrestricted MP2(full)/6-311++G(2d,2p)] along the reaction paths of the F+CH4 and Cl+CH4 reaction systems. It is found that in general dipole moments and polarizabilities exhibit peaks near the transition state. In the case of X=F these peaks are on the products side and in the case of X=Cl they are on the reactants side indicating an early transition state in the case of fluorine and a late transition state in the case of chlorine. An analysis of the geometric changes along the reaction paths reveals a one-to-one correspondence between the peaks in the electric properties and peaks in the rate of change of certain internal geometric coordinates along the reaction path. Interaction with short infrared intense laser fields pulses leads to the possibility of interferences between the dipole and polarizability laser-molecule interactions as a function of laser phase. The larger dipole moment in the Cl+CH4 reaction can lead to the creation of deep wells (instead of energy barriers) and new strongly bound states in the transition state region. This suggests possible coherent control of the reaction path as a function of the absolute phase of the incident field, by significant modification of the potential surfaces along the reaction path and, in particular, in the transition state region.     

Comprehensive study of the methyl effect on the solvolysis rates of bridgehead derivatives

The effect of a bridgehead methyl group on the hydride ion affinity in the gas phase of bicyclo[1.1.1]pent-1-yl (1+), 1-norbornyl (3+), cubyl (5+), 1-adamantyl (7+), bicyclo[2.2.2]oct-1-yl (9+),and bicyclo[3.1.1]hept-1-yl (11+) cations has been studied using density functional theory and ab initio methods. It is concluded that the methyl group always increases the stability of the substituted cations. The effect of the solvent on the stability of methyl-substituted cations in relation to the unsubstituted cations has been studied using the polarizable continuum model of the self-consistent reaction field theory. In the case of rearranging cations, the nucleophilic assistance of the solvent is determined by means of the interaction energy of the corresponding water complexes. It is concluded that the solvent causes the relative stabilization of the parent cations. As a consequence, most of the methyl-substituted bridgehead derivatives show a lower solvolysis rate than the corresponding unsubstituted compounds. A nonqualitative explanation of the methyl effect on the relative stability of bridgehead cations in both gas phase and solution is given for the first time. The ratios of solvolysis products in the case of rearranging bridgehead cations have also been computed from the relative stability of the intermediate water complexes.