Synthesis of novel steroids bearing a spirochromene side chain by BF3·Et2O catalyzed aldol condensation of spirostane sapogenins and salicylaldehyde

Treatment of a CH₂Cl₂ solution of sarsasapogenin acetate with salicylaldehyde and BF₃·Et₂O afforded a mixture of two C-22 epimeric steroids bearing a spirochromene moiety in the side chain. The elucidation of the structures of the new compounds were carried out employing a combination of 1D and 2D NMR techniques that includes ¹H, ¹³C, HSQC, HMBC, COSY and NOESY.     

Copper nanoparticles grown under hydrogen: Study of the surface oxide

Copper nanoparticles with sizes between 10 nm and 50 nm were grown by condensation in hydrogen at pressures from 10 Pa to 1200 Pa. The crystallite size ranged from 10 nm to 25 nm using the Scherrer method. X-ray diffraction showed the reflections of metallic copper occasionally mixed with an oxidized phase (CuO or Cu₂O). As shown by TEM examination, the smaller particles that did not exceed 25 nm exhibited faceted morphologies whereas the bigger ones had ovaled-spherical forms sometimes containing twins. X-ray photoelectron spectroscopy revealed that the nanoparticles consist of a copper core, completely surrounded by a Cu₂O shell, which is oxidized to CuO at the surface layer.     

Simple and Convenient One‐Pot Synthesis of Benzimidazoles and Benzoxazoles using N,N‐Dimethylchlorosulfitemethaniminium Chloride as Condensing Agent

N,N‐Dimethylchlorosulfitemethaniminium chloride (SOCl₂‐DMF) has been found to be an efficient reagent for the one‐pot synthesis of benzimidazoles and benzoxazoles in excellent yield by condensation of carboxylic acids with o‐phenylenediamine/2‐amino‐phenol.     

Syntheses of New Pyrimidine Derivatives Starting from 1,1-Diamino-2,2-dicyanoethylene

A ready one-pot preparation for 6-amino-4-chloro-5-cyano-2-dimethylaminopyrimidine (3), 4-chloro-5-cyano-2-dimethylamino-6-(dimethylamino-chloro)azomethinopyrimidine (4) and their derivatives from 1,1-diamino-2,2-dicyanoethylene and dichloromethylenedimethyliminium chloride (phosgeneiminium chloride) is reported.

     

Ionic Liquid–Mediated Synthesis of Coumarin-3-carboxylic Acids via Knoevenagel Condensation of Meldrum's Acid with ortho-Hydroxyaryl Aldehydes

A simple, efficient, and green protocol for synthesis of coumarin-3-carboxylic acids is described via Knoevenagel condensation of Meldrum's acid with ortho-hydroxyaryl aldehydes in [Hmim]Tfa ionic liquid, which was found to give better results than other ionic liquids. Furthermore, ionic liquid is easily reused without any appreciable loss in activity.     

1H-Pyrazolo[3,4-b]quinolines: Synthesis and Properties over 100 Years of Research

This paper summarises a little over 100 years of research on the synthesis and the photophysical and biological properties of 1H-pyrazolo[3,4-b]quinolines that was published in the years 1911–2021. The main methods of synthesis are described, which include Friedländer condensation, synthesis from anthranilic acid derivatives, multicomponent synthesis and others. The use of this class of compounds as potential fluorescent sensors and biologically active compounds is shown. This review intends to summarize the abovementioned aspects of 1H-pyrazolo[3,4-b]quinoline chemistry. Some of the results that are presented in this publication come from the laboratories of the authors of this review.     

Symmetry-breaking vortex-lattice of a binary superfluid in a rotating bucket

We study spontaneous-symmetry-broken phase-separated vortex lattice in a weakly interacting uniform rapidly rotating binary Bose superfluid contained in a quasi-two-dimensional circular or square bucket. For the inter-species repulsion above a critical value, the two superfluid components separate and form a demixed phase with practically no overlap in the vortex lattices of the two components, which will permit an efficient experimental observation of such vortices and study their properties. In case of a circular bucket with equal intra-species energies of the two components, the two components separate into two non-overlapping semicircular domains for all frequencies of rotation Ω generating distinct demixed vortex lattices. In case of a binary Bose superfluid in both circular and square buckets, (a) the number of vortices increases linearly with Ω in agreement with a suggestion by Feynman, and (b) the rotational energy in the rotating frame decreases quadratically with Ω in agreement with a suggestion by Fetter.     

方解石纳米孔隙内二氧化碳毛细凝聚的分子模拟

在二氧化碳地质封存、增产非常规油气以及孔隙材料表征测量方面,纳米孔隙中二氧化碳相态的准确预测具有重要意义.然而,由于纳米尺度下毛细力、分离压等作用力占据主导因素,流体在孔隙中的相行为与体相流体存在根本不同.已有实验和模拟表明,Kelvin毛细凝聚理论无法预测特征尺度10 nm下的,孔隙内流体凝聚压力与体相饱和蒸气压的偏...     

Molecular simulation of the adsorption and structure of benzene confined in mesoporous silicas

Grand Canonical Monte Carlo simulations are used to study the adsorption of benzene at 298 K in an atomistic cylindrical silica nanopore of a diameter 3.6 nm. The adsorption involves a transition from a partially filled pore (a two layers thick film at the pore surface) to a completely filled pore configuration. Strong layering of the benzene molecules at the pore surface is observed. It is found that the layering decays as the distance to the pore surface increases. The position of the peaks for the density of the C, H atoms and the center of mass of the molecules shows that benzene molecules prefer an orientation in which their ring is perpendicular to the pore surface. This result is corroborated by calculating orientational order parameters and examining the distribution of the distances between the H and C atoms of the benzene molecules and the H and O atoms of the silica substrate.     

Hydrolysis and Condensation Processes of Titanium iso-Propoxide Modified with Catechol: An NMR Study

The hydrolysis and condensation processes of titanium iso-propoxide modified with catechol (C₆H₄(OH)₂; H₂cat) have been investigated by ¹H, ¹³C and ¹⁷O nuclear magnetic resonance spectroscopy. The hydrolysis reactions of the modified titanium iso-propoxide in the system with Ti:tetrahydrofuran (THF):H₂O = 1:20:x (x = 1, 2 and 5 in a molar ratio) are essentially completed in the initial stage (<1 h), and the condensation reactions also proceed significantly during this stage. Upon hydrolysis with H₂O/Ti = 1, the iso-propoxy groups are selectively hydrolyzed and the catecholate groups remain bound to titanium. With H₂O/Ti = 2 and 5, both the iso-propoxy and catecholate groups are hydrolyzed, and the hydrolysis of the iso-propoxy groups is relatively preferential. Approximately half the catecholate groups are stably bound to titanium, even after hydrolysis with H₂O/Ti = 5.