Valence-shell charge concentrations and electron delocalization in alkyllithium complexes: negative hyperconjugation and agostic bonding

In this paper we present the results of density functional theory (DFT) calculations on the ethyl ligand and some related organic moieties; we then proceed to consider a range of alkyllithium complexes studied by DFT calculations and high-resolution X-ray and neutron diffraction. Topological analysis of the charge density is used to follow changes in the electronic structure of the organic fragment. The charge concentrations (CCs) in the valence shell at the alpha and beta atoms reveal faithfully the delocalization of the lone pair at the Calpha atom or of the Li-C bonding electrons. Negative hyperconjugation is thus shown to arise from delocalization of the lone pair or the Li-C bonding electrons over the alkyl fragment, with depletion of the metal-directed charge concentration at Calpha, and characteristic ellipticity profiles for the bonds involved in hyperconjugative delocalization. In the case of so-called lithium agostic complexes, we show that close Li.H contacts are a consequence of this delocalization and further secondary interactions, with Li.H-C agostic interactions, playing only a minor role. The ellipticity profiles and the magnitude of the CCs at Calpha provide a quantitative measure of the extent of delocalization, and show excellent agreement between experiment and theory.     

Vibrational spectra of mono-, di- and trichloroacetamide and mono- and trifluoroacetamide

The Raman and infrared spectra of five α-halogenoacetamides; mono-, di- and trichloroacetamide (MCA, DCA and TCA) and mono- and trifluoroacetamide (MFA and TFA), in solid phase (KBr pellets and Nujol dispersion) and in solution in several solvents (ClCH₃, Cl₂CH₂, Br₂CH₂, CH₃CN and benzene), have been recorded in order to assign the fundamental bands. The vibrational assignments, the intermolecular hydrogen bonds and the equilibrium mixture of cis and trans isomers have been discussed.     

The Soret effect of mono-, di- and tri-glycols in ethanol

We employed thermal diffusion forced Rayleigh scattering (TDFRS) to investigate the chain length dependence of the thermal diffusion behavior of short glycols in ethanol. We studied three glycols, monoethylenglycol (MEG), diethylenglycol (DEG) and triethylenglycol (TEG), in an ethanol solution. In contrast to the polymer polyethylenglycol, the shorter glycols used within the framework of this study are completely soluble in ethanol, at least for low molar fractions. In order to guarantee a good solubility of the glycols, the measurements were limited to molar fractions of 10% and 20%. As the different glycols only differ by their chain length it will be possible to deduce its influence on the thermal diffusion properties. Due to the fairly short persistence length of the glycols, D(T) reaches already for the dimer a plateau value. This finding agrees with simulation results. Furthermore, the thermal expansion and the kinematic viscosity are measured to investigate if empirical correlations seen for other systems could be confirmed.     

Facile synthesis of mono-, di-, and trisubstituted alpha-unbranched hydrazines

Methods for the alkylation of di-tert-butyl hydrazine-1,2-dicarboxylate were investigated. It was found that under mild conditions mono- or di-substituted hydrazine derivatives were obtained in good to excellent yield. Furthermore, it was shown that one of the two Boc-groups of the disubstituted derivatives was selectively removed by heating, leading to precursors for trisubstituted hydrazines.     

Thermal analysis of ammonium,mono-, di- and triethanolammonium alginates

Thermal behaviour of ammonium (NH₄alg), mono- (MEAalg), di- (DEAalg) and triethanolammonium (TEAalg) salts of alginic acid (Halg) was investigated by thermogravimetry (TG) and differential scanning calorimetry (DSC). Salts were prepared by the direct reaction of alginic acid with the ammonium hydroxide and with the respective ethanolamines. After preparation the compounds were lyophilized during 24 h and characterized by FTIR spectroscopy and elemental analysis (C, H and N). Under air the compounds exhibited three successive thermal decomposition steps: dehydration, decomposition of the polymeric matrix and finally, burning of carbonaceous residue. Under nitrogen two steps (dehydration and decomposition) were observed. The stability order of this series of compounds was: TEAalg this series of compounds was: TEAalg<DEAalg<NH₄alg<Halg≈MEAalg. DSC curves between –50 and 150°C did not show any thermal events suggesting that after lyophilization probably non-freezing type water is present in the system.     

Synthesis of mono-, di- and trisulfated Lewis x trisaccharides

3′-Sulfated and 3′,6′-disulfated Lewis x trisaccharides have been prepared through selective sulfation of methyl 2-acetamido-6-O-benzyl-2-deoxy-4-O-β-D-galactopyranosyl-3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-glucopyranoside, followed by catalytic hydrogenolysis. In a similar manner, 3′,6-disulfated and 3′,6,6′-trisulfated Lewis x trisaccharides have been selectively obtained from methyl 2-acetamido-2-deoxy-4-O-β-D-galactopyranosyl-3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-glucopyranoside.     

Synthesis of new chiral mono-, di-, tri-, and tetraalkylglycolurils

Two general procedures were developed for the synthesis of chiral N-mono-, N, N′-di-, N, N′ N″-tri-, and N, N′, N″, N′″-tetraalkylglycolurils based on the reactions of 4,5-dihydroxy-imidazolidin-2-ones or glyoxal with one or two moles of alkylureas, respectively, by acid catalysis. The reactions of N-monoalkyl- and N, N′-dialkylureas with glyoxal proceed regioselectively. The mechanism of these reactions was suggested and partly confirmed by quantum-chemical calculations and experimental data. The enantiomeric separation of some chiral glycolurils by chiral-phase HPLC was carried out for the first time.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 680–692, March, 2005.     

Complexation of zinc octaalkylporphyrin with mono-, di-, and triethylenediamines in toluene

The complexation of zinc octaalkylporphyrin with mono-, di-, and triethylenediamines in toluene was studied by spectrophotometry using the molar ratio method and by ¹H NMR. The effect of the structure of the two-center organic base on the formation of 1 : 1 or 2 : 1 metal porphyrin-ligand complex was established. The stability constants of the resulting complexes were calculated and the concentration ranges of their existence were determined.     

Partition chromatography of mono-, di- and trisaccharides on ion-exchange resins

Summary Complicated mixtures of mono-, di- and trisaccharides were separated on ion-exchange resins by partition chromatography using a mixture of water and ethanol as eluant. Among the resins studied, a cation exchanger in the lithium form gave the best separations of most common disaccharides. Mixtures containing several monosaccharides and some higher saccharides are better resolved when an anion exchanger in the sulfate form is employed. With some complex mixtures of mono-, di- and trisaccharides some overlapping occurred with both types of resin. A complete resolution of such mixtures can be achieved if fractions containing overlapping compounds are rechromatographed on the other resin form.

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Zusammenfassung Mischungen von Mono-, Di- und Trisacchariden wurden durch. Verteilungs-Chromatographie an Ionenaustauscherharzen getrennt, wobei eine Wasser-Äthanolmischung als Eluierungsmittel diente. Die besten Ergebnisse bei der Trennung der gebräuchlichsten Disaccharide wurden mit einem Kationenaustauscher in der Li-Form erhalten. Für Mischungen, die mehrere Monosaccharide sowie höhere Saccharide enthielten, war ein Anionenaustauscher in der Sulfatform vorteilhafter. Bei einigen Mischungen von Mono-, Di- und Trisacchariden traten bei beiden Austauscherarten Überlappungen auf. Eine vollständige Trennung solcher Gemische konnte durch nochmalige Chromatographie der entsprechenden Fraktionen mit Hilfe des jeweils anderen Harzes erreicht werden.

     

Surface characterizations of mono-, di-, and tri-aminosilane treated glass substrates

The surface properties and structure of mono-, di-, and tri-aminosilane treated glass surfaces were investigated using surface analytical techniques including X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, atomic force microscopy (AFM), and streaming potential. An optimized dip-coating process was demonstrated to produce roughly silane monolayer coverage on the glass surface. The surface charge measurements indicated that aminosilanization converts the glass surface from negative to positive potentials at neutral pH values. Higher positive streaming potential was observed for tri-compared with mono- and di-aminosilane treated glass surfaces. For all aminosilane treated glass samples, the high-resolution N 1s XPS spectra indicated a preferential orientation of the protonated amino-groups towards the glass surface whereas the free amino groups were protruding outward. This study aimed to obtain uniform, reproducibly thin, strongly adhering, internally cross-linked, and high positively charged aminosilane-coated glass surfaces for the attachment of DNA fragments used in microarraying experiments.     

Kinetic thermal analytical study of saturated mono-, di- and tri-glycerides

A thermal degradation study using TG–DTG thermogravimetry was performed on three saturated fatty acids esterified with glycerol (i.e. glyceryl-tristearate (C₁₈), -tripalmitate (C₁₆) and -trimyristate (C₁₄)) at different heating rates. In addition, thermogravimetry (TG) and derivative thermogravimetry (DTG) of glyceryl di-stearate and glyceryl mono-stearate were also carried out at different heating rates. A deconvolution procedure applied to the first process and overlapping at least two steps between about 200 and 350 °C, enabled the activation energy of decomposition to be determined both by the Kissinger and the Ozawa–Flynn–Wall isoconversional methods for the deconvoluted steps of the above-mentioned fatty acids.     

Halogen bonding in mono- and dihydrated halobenzene

Density functional theory calculations were performed on halogen-bonded and hydrogen-bonded systems consisting of a halobenzene (XPh; X = F, Cl, Br, I, and At) and one or two water molecules, using the M06-2X density functional with the 6-31+G(d) (for C, H, F, Cl, and Br) and aug-cc-pVDZ-PP (for I, At) basis sets. The counterpoise procedure was performed to counteract the effect of basis set superposition error. The results show halogen bonds form in the XPh-H₂O system when X > Cl. There is a trend toward stronger halogen bonding as the halogen group is descended, as assessed by interaction energy and X•••O_w internuclear separation (where O_w is the water oxygen). For all XPh-H₂O systems hydrogen-bonded systems exist, containing a combination of CH•••O_w and O_wH_w•••X hydrogen bonds. For all systems except X = At the X•••H_w hydrogen-bonding interaction is stronger than the X•••O_w halogen bond. In the XPh-(H₂O)₂ system halogen bonds form only for X > Br. The two water molecules prefer to form a water dimer, either located around the C H bond (for X = Br, At, and I) or located above the benzene ring (for all halogens). Thus, even in the absence of competing strong interactions, halogen bonds may not form for the lighter halogens due to (1) competition from cooperative weak interactions such as C H•••O and OH•••X hydrogen bonds, or (2) if the formation of the halogen bond would preclude the formation of a water dimer. © 2018 Wiley Periodicals, Inc.     

Analysis of mono-, di-, and triglycerides by capillary supercritical fluid chromatography

The separation of mixed mono-, di-, and triglycerides by capillary supercritical fluid chromatography is described. The separations were performed at low operating temperatures, using a carbon dioxide mobile phase, a conventional flame ionization detector, and two different stationary phases, DB-5 (95% dimethyl-(5%)-diphenylpolysiloxane) and DB-225 (50% cyanopropyl-methyl-(50%)-methylphenylpolysiloxane). Because the separations were performed at low operating temperatures, no thermal degradation of the glycerides was observed. Even under these mild operating conditions, trinervonin, a triglyceride having a molecular weight over 1100 amu, was readily eluted. When rapid pressure programming of the carbon dioxide mobile phase was employed, trinervonin was eluted in less than two minutes. On DB-5, the mono-, di-, and triglycerides eluted in order of increasing molecular weight. A graph of t′_r (on DB-5) versus molecular weight is linear. When DB-225 was used as the stationary phase, triglycerides eluted in the order of increasing unsaturation. Thus, the order of elution on DB-225 was tristearin, triolein, trilinolein, and trilinolenin.     

Hydrogen bonding with mono- and di-carbonyls

The electronic absorption and i.r. spectroscopic studies are reported for the hydrogen bonding systems involving alcohol and various ketones. It is shown that the hydrogen bonding abilities of ketones are determined by the extent of delocalization of the lone pair electrons in their non-bonding molecular orbitals. Evidence for the formation of very weak intermolecular hydrogen bonds between alcohol and the π-electron part of the dicarbonyls has also been presented from the i.r. studies in the 3400–3700 cm⁻¹ region.     

Synthesis,crystal structure and negative hyperconjugation study of quinoxaline derivatives containing piperazine

The negative hyperconjugation (NHC) of sp² and sp³ hybrid nitrogen atoms were studied based on the calculation of quinoxaline derivatives containing piperazine moiety. The energy level, electronic density and spatial position of acceptor orbital are all important factors of NHC. NHC of nitrogen atom does not limit in the case that the σ*-acceptor orbital is in the anti-staggered positon of donor orbital, but it will switch off when nitrogen atom loses its lone pair electron. These results are proved by the crystal structure and the calculation of vibration frequencies. At last, two quinoxaline derivatives synthesized in this work show good anticancer activities against leukemia cell lines.