Kinetics and Mechanism of the Insertion Reaction of Arylisocyanates into C‒C Bond of Phosphabetaine Obtained ont the Basis of Triisopropylphosphine and 2-Cyanoethylacrylate

Abstract

On the basis of kinetic investigation o f previously discovered [I] insertion reaction of arylisocyanates into C-C bond of nvitter-ions, obtained on the basis of trialkylphoshines and Z-cyanoacrylates, the mechanism of this unusual reaction has been suggested. According to this mechanism the nucleophilic attack of nvitter-ion anionic center on the carbon atom of isocyanate group and nucleophilic attack of nitrogen atom on carbethoxylic group, leading to breakup of C-C bond, carry out relatively synchronously within one transition state on the concerted mechanism.     

Electrochemical and photochemical approaches for the synthesis of the C28–C38 fragment of okadaic acid

Okadaic acid, a potent and selective inhibitor of Protein Phosphatases 1 and 2A (PP1 and PP2A), is widely used as a probe for various biochemical processes. We describe herein two innovative methods for the synthesis of the terminal C28–C38 fragment of the natural polyether. Suárez photochemical oxidative cyclization and electrochemical oxidation of malonates to their ketals equivalents have been successfully applied for the assembly of the key spiroketal core.     

Carbometallic derivatives of C 1v and C 5v boranes: Enumeration and identification of substitution isomers and the calculation scheme of the properties of C 5v based on pascal’s triangle numbers

Combinatorial analysis methods are employed to solve the problem of determining the number and form of X-substituted (X, XY, … are some substituents) of carbometallic derivatives of boranes (C₅H₅)Co(C₂B₉H₁₁) C _1v and (C₅H₅)Co(C₅B₆H₁₁) C _5v (over vertices) based on Polya’s theorem. formulas of Z symmetry and generating functions of the number of chiral and achiral substitution stereoisomers are determined. Family distributions of the isomers depending on the form and number of substituents and depending on the number m of possible substitution sites are found. Mono-, di-, and tri-X-substituted (X = CH₃, F, …) isomers of (C₅H₅)Co(C₅B₆H₁₁) C _5v are identified. Based on the partition of simple (n) and triangular numbers (K ₃) of Pascal’s triangle, additive schemes are obtained which take into account valence and non-valence pair interactions of atoms in the polyhedron framework and contain 2, 6, and 23 parameters for the calculation of properties of X-substituted borane (C₅H₅)Co(C₅B₆H₁₁) C _5v .     

A CAS SCF CI study of the 1Σ+g and 3IIu states of the C2 molecule and the 4Σ−g and 2IIu states of the C+2 ion

Ab initio calculations of the X ¹Σ⁺_g and a ³II_u states of C₂ and the X⁴Σ⁻_g and a²II_u states of the C⁻₂ molecular ion are performed to determine the corresponding potential curves around the potential minima and at the dissociation limits. A large Gaussian basis set augmented by three d-type polarization functions on each carbon center is used to approximate the molecular orbits. The calculations are done at the complete-active-space SCF and multi-reference configuration interactions level. Spectroscopic constants and rotation—vibration energies are derived from the ab initio calculated potentials. Good agreement between theory and experiment is obtained for the X¹Σ⁺_g and a ³II_u states of C₂. In the earlier tentative assignment of the observed electronic transition around 2490 Å to the ²Σ⁻_g ← ²II_u system in C⁺₂, the lower state is confirmed by the present calculations to be C⁺ ₂ (²II_u).     

Study on the reaction of C60 with DL-valine and cyclohexanone

Reaction of C60 with DL-valine and cyclohexanone in refluxing chlorobenzene under N2 yields three [60]fulleropyrrolidine derivatives (mono-, bis- and triadduct) which are characterized on the basis of spectroscopies and cyclic voltammetry. It is found that the ratio of the three products greatly depends on the reaction conditions.     

First principles study of the electronic and magnetic structures and bonding properties of UCoC2 ternary,characteristic of C–C units

The electronic structure of UCoC₂, a di-carbide with the C–C units is examined from ab initio with an assessment of the properties of chemical bonding. The energy–volume equation of state shows large anisotropy effects due to C–C alignment along tetragonal c-axis leading to high linear incompressibility. Relevant features of selective bonding of uranium and cobalt with carbon at two different Wyckoff sites and strong C–C interactions are remarkable. The vibrational frequencies for C⋯C stretching modes indicate closer behavior to aliphatic C–C rather than CC double bond. A ferromagnetic ground state is proposed from the calculations.     

Simulation of the random scission of C–C bonds in the initial stage of the thermal degradation of polyethylene

We performed molecular dynamics simulations to analyze the initial stage of the thermal degradation of polyethylene, which is dominated by the random scission reaction. The simulations were initiated from structures that were taken from previously equilibrated snapshots of the amorphous polymer and of a free-standing thin film. Isolated chains were also used for comparison. Our systems were coupled to a thermal heat bath, and the effect of different coupling constants was studied. Rate of random scission increases as the strength of the temperature coupling increases. Rates of reaction are almost similar in thin films and the bulk, whereas the rates are much faster in isolated chains. Expansion of the free-standing thin film accompanies degradation, producing fragments of various sizes. Chains of higher molecular weights than the initial chains can be produced due to recombination of fragments during the expansion of thin films. The polydispersity index of the resulting fragments is higher in thin films compared to the bulk. The bonds at the low density portion of the thin films have a higher probability of being broken.     

Studies of the dissociation and the protonation of TB-chlorosulphophenol

The dissociation constant of each step for TB-chlorosulphophenol has been determined by potentiometric method, and the thermodynamic constants, △G°, △H° and △S°, of the dissociation process have been calculated. The protonation constants were measured by the spectrophotometric method. The pH values of various forms of anions of the chromogenic reagent at their concentrations were also calculated.     

Influence of aluminium on the oxidation of titanium between 550 and 750 °C

In order to study the influence of aluminium on the oxidation resistance of titanium at high temperature, a range of binary alloys containing 1.65, 3, 5 and 10 wt.% of aluminium was prepared. Their oxidation kinetics were studied at temperatures between 500 and 750 °C using either continuous thermogravimetry or daily weighing for periods of up to several thousand hours. The results obtained for oxidation in air confirm the beneficial role of aluminium which has been observed previously for oxidation in oxygen. With regard to morphology and structure, aluminium modifies the internal structure of the oxide layers and their growth laws. A general dispersion of aluminium in rutile is observed, although a concentration of this phase is noted near the external interface; there is also a reduction in the amount of oxygen dissolved in the metal substrate which is related to the aluminium content in the alloy. Moreover, the presence of aluminium also modifies the adhesion of the oxide layers to the substrate.     

ESR spectra and electronic structure of the C120 ·+ radical cation and the paramagnetic C120O2+ dication and C120O2− dianion

Electronic structure of the C₁₂₀ ^·+ radical cation and the paramagnetic C₁₂₀O²⁺ dication and C₁₂₀O²⁻ dianion in the triplet state was calculated by the MNDO/PM3 method in the valence approximation. The density distributions of the unpaired electrons in these systems were found and the ESR spectra of the above species were interpreted. Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 7, pp. 1257–1260, July, 1999.     

Intensity of the η(C≡C) Bands in the IR Spectra of Acetylene Derivatives and σR 0 Constants of Organosilicon,Organogermanium, and Organotin Substituents

The integral absorptivities of shape-characteristic (CC) bands in the IR spectra of 66 acetylene derivatives RCCX (R = H, Me₃M; X are inorganic and organic substituents) are related by a common linear equation to the _R ⁰ constants of the R and X substituents. The _R R⁰ constants of 10 Alk₃M substituents were calculated. The _R ⁰, _R , and _R ⁺ constants of Me₃M substituents were analyzed. The positive _R ⁰ values (0.12, 0.06, and 0.04 for R = Si, Ge, and Sn, respectively) suggest that in the ground electronic state of Me₃MCCX molecules the resonance acceptor effect of the Me₃M substituents (d, conjugation) prevails over donor (, conjugation). The first effect attenuates and the second enhances as the atomic number of M increases.     

Studies of the Total Synthesis of Epothilone B and D:A Facile Synthesis of C7-C14 and C15-C21 Fragments

A mild and highly efficient synthesis of C7-C14 and C15-C21 fragments of epothilone B and D is described in which racemic C7-C14 fragment is prepared from nerol through four steps and C15-C21 fragment is obtained from 1,3-dichloroacctone.thioacetamide and propionaldehyde.     

Kinetics of the Hydrogenation of α-Pinene to cis- and trans-Pinanes on Pd/C

The liquid-phase hydrogenation of -pinene on a Pd/C catalyst at 0–100° and hydrogen pressures of 1–11 atm was studied. It was found that the order of reaction with respect to pinene increased with hydrogen pressure and did not depend on temperature, whereas the selectivity of cis-pinane formation decreased with temperature and increased with hydrogen pressure. A mechanism was proposed for the hydrogenation of -pinene. According to this mechanism, the selectivity of cis-pinane formation depends on the following two factors: (a) a temperature-dependent equilibrium between adsorbed -pinene species, which are cis- and trans-pinane precursors, and (b) competition between the hydrogenation and -H-elimination of surface -pinanyl complexes. The ratio between the rates of these reactions depends on the concentration of surface hydride species, and this concentration depends on the pressure of hydrogen.     

Applied Aspects of the γ-Radiolysis of C1–C4 Alcohols and Binary Mixtures on Their Basis

Generalized data on the -radiolysis of aliphatic C₁–C₄ alcohols are summarized. These data can be used for solving practical problems in the related areas of research. In particular, a rate equation that relates the radiation-chemical yield of an 1 : 1 adduct formed from saturated and unsaturated components upon the -radiolysis of a binary system to the concentrations of these components was derived. An equation was obtained for estimating the reaction rate constants of decay of identical hydroxyalkyl radicals in collisions with each other from the reciprocal viscosity (fluidity) of corresponding alcohols. An empirical equation for calculating the concentration of the free (desolvated) form of formaldehyde in alcohol–formaldehyde systems at various temperatures and total formaldehyde concentrations and an equation for evaluating solvent concentrations in these systems were derived.     

NR transfer reactivity of azo-compound I of P450. How does the nitrogen substituent tune the reactivity of the species toward C-H and C=C activation?

We studied electronic structures and reactivity patterns of azo-compound I species (RN-Cpd I) by comparison to O-Cpd I of, e.g., cytochrome P450. The study shows that the RN-Cpd I species are capable of C=C aziridination and C-H amidation, in a two-state mechanism similar to that of O-Cpd I. However, unlike O-Cpd I, here the nitrogen substituent (R) exerts a major impact on structure and reactivity. Thus, it is demonstrated that Fe=NR bonds of RN-Cpd I will generally be substantially longer than Fe=O bonds; electron-withdrawing R groups will generate a very long Fe=N bond, whereas electron-releasing R groups should have the opposite effect and hence a shorter Fe=N bond. The R substituent controls also the reactivity of RN-Cpd I toward C=C and C-H bonds by exerting steric and electronic effects. Our analysis shows that an electron-releasing substituent will lower the barriers for both bond activation reactions, since the electronic factor makes the reactions highly exothermic, while an electron-withdrawing one should raise both barriers. The steric bulk of the substituent is predicted to inhibit more strongly the aziridination reactions. It is predicted that electron-releasing substituents with small bulk will create powerful aziridination reagents, whereas electron-withdrawing substituents like MeSO(2) will prefer C-H bond activation with preference that increases with steric bulk. Finally, the study predicts (i) that the reactions of RN-Cpd I will be less stereospecific than those of O-Cpd I and (ii) that aziridination will be more stereoselective than amidation.     

AM1 Study on Structure and Electronic Properties of the Derivatives of C60-S-TTF

The chemistry of [60]fullerene has been attracted much attention owing to its special structure and unusual property.In recent years, scientists have produced a number of C60-based molecules as well as many materials. Gu et al.[1] have investigated nonlinear optical properties of the derivatives of [60]fullerene, and gained many significant results. The above efforts make photoinduced intra- or inter-molecular electron transfer become currently highly active areas for fundamental study of materials science.     

Stereoselective synthesis of the middle (C10–C17) and right (C18–C30) segments and their coupling to complete a formal synthesis of the polyether antibiotic salinomycin

The middle (C10–C17) and right (C18–C30) segments of the polyether antibiotic salinomycin were stereoselectively synthesized from D-glucose, D-mannitol and ethyl L-lactate. Coupling of the two segments followed by construction of the bisketal ring system gave the C10–C30 segment, which was already converted to salinomycin by Kishi.