1, 1'-联二萘酚的拆分研究进展

概括了近年来1,1'-联二萘酚类化合物等具有C~2轴不对称联芳香族化合物的拆分研究进展。     

Synthesis,characterization and DFT calculations of a Re(V)-thiazolidine-2,4-dione complex

This article presents a combined experimental and computational study of a new oxorhenium(V) complex of thiazolidine-2,4-dione (HTDO). The complex has been synthesized by direct reaction of NH₄ReO₄ with thiazolidine-2,4-dione in the presence of Na₂S₂O₆ as a reducing agent. The complex [ReO(TDO)(H₂O)₃](S₂O₈) has been characterized by spectroscopy (FT-IR, NMR, UV-vis, mass), thermogravimetry, microanalysis, and HPL chromatography. The complex was geometrically optimized by DFT with B3LYP level of theory and satisfactory theoretical–experimental agreement was achieved for analysis of IR and NMR data of the complex. Additional information about binding between rhenium and oxo ligand in the complex has been obtained by NBO analysis. The antibacterial activity of the investigated complex has been tested and evaluated.     

Density functional theory of freezing of a system of conjugated oligomers parameterised via Gay–Berne potential

Density functional theory (DFT) of freezing is used to study the isotropic–nematic, isotropic–smectic A and nematic–smectic A phase transitions in a system of large, semi-flexible conjugated oligomers parameterised within Gay–Berne (GB) potential. The pair correlation functions of the isotropic fluid, used as structural inputs in the DFT, are calculated by solving the Percus–Yevick integral equation theory. Large number of spherical harmonic coefficients of each orientation-dependent functions has been considered to ensure the numerical accuracy at different densities and temperatures for the system of these model GB ellipsoids having large aspect ratio (length-to-breadth ratio). We found that the system of GB ellipsoids parameterised for conjugated oligomers shows stable isotropic, nematic and smectic A phases. At low temperatures, on increasing the density, isotropic fluid makes a direct transition to smectic A phase. Nematic phase get stabilised in between the isotropic and smectic A phases on increasing the temperature. Using the transition parameter obtained through the DFT, we have plotted the temperature–density and pressure–temperature phase diagrams which are found to be qualitatively similar to the one obtained in simulations for the systems with low aspect ratio GB particles.     

Facile Assembly of Benzo[b]naphtho[2,3‐d]azocin‐6(5 H)‐ones by a Palladium‐Catalyzed Double Carbometalation

The palladium‐catalyzed reaction of 2‐alkynylanilines with 2‐(2‐bromobenzylidene)cyclobutanone as an efficient route to 7,8‐dihydrobenzo[b]naphtho[2,3‐d]azocin‐6(5 H)‐ones was developed. The fused eight‐membered ring was constructed conveniently. During the reaction process, double carbometalation was involved, which resulted in excellent selectivity with the formation of three new bonds. This transformation is highly efficient and leads to fused polycycles in good to excellent yields with good functional group tolerance.     

Stereoselective Synthesis of Functionalized Pyrrolidines by the Diverted N−H Insertion Reaction of Metallocarbenes with β‐Aminoketone Derivatives

A highly stereoselective route to functionalized pyrrolidines by the metal‐catalyzed diverted N?H insertion of a range of diazocarbonyl compounds with β‐aminoketone derivatives is described. A number of catalysts (rhodium(II) carboxylate dimers, copper(I) triflate, and an iron(III) porphyrin) are shown to promote the process under mild conditions to give a wide range of highly substituted proline derivatives. The reaction starts as a metallocarbene N?H insertion but is diverted by an intermolecular aldol reaction.     

Mechanistic insights on DBU catalyzed β‐amination of nbs to chalcone driving by water: Multiple roles of water

DFT calculations were conducted to pursue deeper understandings on the mechanism and the explicit role of trace water in the DBU‐catalyzed β‐amination of NBS to chalcone. Being different from previously proposed by Liang et al., a cooperative participation of both DBU and water is noticed in the preferred mechanism. The preferential mechanistic scenario assisted by water undergoes three major steps: the formation of succinimide and HBrO, concerted nucleophilic addition and H‐shift, and keto‐enol tautomerization. Moreover, we found that DBU‐HBrO is unnecessary in the third step and three‐water‐cluster assisted keto‐enol tautomerization is the most advantageous case. It is further noted that the catalytic position of the third water molecule and the proton shift orientation to some extent affect step 3 via O···H O and O H···π interactions, which is confirmed by AIM analysis. The computational results suggest that water molecules play pivotal roles as reactant, catalyst, and stabilizer to promote the reaction of chalcone and NBS. The origin of the more stable transition state structure in the rate‐determining step of DBU‐water catalyzed mechanism is ascribed to noncovalent interactions, halogen bond, and electrostatic interactions than DBU only ones. © 2017 Wiley Periodicals, Inc.     

A simple method for evaluation of the self-consistency of the radial distribution functions and the orientation of water molecules in the first coordination sphere from the results of molecular dynamics calculations

A simple method for determination of the angular orientation of water molecules in the first coordination sphere from the radial distribution functions is proposed. A comparative analysis of the ability of the model potentials of pair interaction to take into account the effects of manybody interactions (MBI) was performed. The responses of the model pair potentials to the MBI effects in the first and second coordination spheres were found to be poorly correlated with each other. It was concluded that it is necessary to derive a new analytical type of potential functions of pair interaction. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 11, pp. 1842–1846. November. 2000.     

Kinetic Equations for Thermal Dissociation Processes. Part I. KEKAM equation

Relationships have been established between the average conversion degree and the dissociation time for polydisperse granular material, taking its grain size distribution into account. It has been checked in which cases the kinetic curves obtained by a numerical solution can be described in terms of KEKAM equation. This revised version was published online in August 2006 with corrections to the Cover Date.     

The Use of Thermogravimetry in the Study of Rubber Devulcanization

Thermogravimetry was employed to study the changes occurring in rubber vulcanizates during devulcanization carried out by microwave treatment, a new promising method of recycling rubber waste. The thermogravimetric parameters T _i , T ₅ and T _p and the compositions of devulcanizates in comparison with vulcanizates were determined. The results obtained allowed estimation of the degree of destruction of the polymer chains in response to microwave treatment and permitted establishment of the most advantageous conditions of devulcanization in order to obtain the best properties of rubber devulcanizates for reuse in rubber processing. The results demonstrated that thermogravimetry is a very useful method for investigation and control of the microwave devulcanization process. This revised version was published online in August 2006 with corrections to the Cover Date.     

Naphthoindoles. 9. Synthesis of N-derivatives of 4,11-Dimethoxynaphtho-[2,3-f]indole-5,10-dione

N-Acetylation and several N-alkylation reactions have been carried out for the previously synthesized 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione.