Alkylation of toluene with dichloromethane in the presence of triisobutylaluminum and perfluorophenylborates

¹H NMR method showed that in systems based on triisobutylaluminum (TIBA) and triphenylcyclopropenylium [Ph₃C₃]⁺[B(C₆F₅)₄]–(CPB) or triphenylmethylium [Ph₃C]⁺[B(C₆F₅)₄]–(TB) perfluorophenylborates in a toluene–dichloromethane mixture the Friedel–Crafts process occurs with the formation of ditolylmethane (DTM) accompanied by the complete decomposition of TIBA to form isobutane. ¹⁹F NMR spectroscopy showed that the [B(C₆F₅)₄]–anion decomposes in the systems to form B(C₆F₅)₃ and HC₆F₅. The short-living [AlBu₂ ⁱ]+ cation formed in the reaction of perfluorophenylborates with TIBA is assumed to be the species initiating the process. It has been shown that CPB is less reactive than TB. The addition of a stoichiometric amount of Ph₂CCpFluHfMe₂ exerts no effect on the process with the CPB-containing system but inhibits the reaction in the case of TB.     

Chalcogenation of 1,4-dichlorobut-2-yne with organic dichalcogenides in the system hydrazine hydrate–KOH

A reaction of organic dichalcogenides R₂Y₂ (R = Ph, Bn, Pr; Y = S, Se) with 1,4-dichlorobut-2-yne in the system hydrazine hydrate–KOH leads to four principal products: 1,4-bis(organylchalcogenyl)but-2-ynes, 1-organylchalcogenylbut-1-en-3-ynes, 4-organylchalcogenylbut-1-en-3-ynes, and 3(5)-methylpyrazole. The selectivity of the formation of individual products is determined by the ratio of the substrates used and the reaction temperature. A plausible mechanism of chalcogenation considered in the work agrees with the effect of the nature of chalcogene atoms and organic substituents R on stability of intermediates and products. The stabilization of carbanions by α chalcogene-containing groups corresponds to the following order: PhS > PhSe > BnS > BnSe > PrS.     

Design and synthesis of an octavalent bolaamphiphile with terminal lactose residues

The synthesis of an octavalent bolaamphiphile with D-glucose moiety as branching unit has been designed and accomplished via 1,3-dipolar cycloaddition of bis(tetra-O-propargylglucoside) and 8 equiv of 2-azidoethyl β-D-lactoside.     

Acceleration of Acetal Hydrolysis by Remote Alkoxy Groups: Evidence for Electrostatic Effects on the Formation of Oxocarbenium Ions

In contrast to observations with carbohydrates, experiments with 4‐alkoxy‐substituted acetals indicate that an alkoxy group can accelerate acetal hydrolysis by up to 20‐fold compared to substrates without an alkoxy group. The acceleration of ionization in more flexible acetals can be up to 200‐fold when compensated for inductive effects.     

Synthesis and characterization of nano Ag end capped L-cysteine bridged diblock copolymer

The target of the present investigation is synthesis and characterization of an amphiphilic diblock copolymer with antibacterial property. Ring opening polymerization (ROP) of ε-caprolactone (CL) and tetrahydrofuran (THF) was carried out under inert atmosphere by using L-cysteine as a bridging agent in the presence of stannous octoate (SO) as a catalyst. The nano silver end capped diblock copolymer was synthesized by in situ method. Thus obtained nano silver end capped L-cysteine bridged diblock copolymer was characterized by various analytical methods like Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, circular dichroism (CD), fluorescence spectroscopy, gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and zeta potential. The antimicrobial property of the nano silver end capped diblock copolymer against e-coli was tested.     

Comparative theoretical study on the corrosion inhibition properties of benzoxazole and benzothiazole

Research on Chemical Intermediates - The electronic parameters of two azole molecules, namely benzoxazole (BOX) and benzothiazole (BTH), have been studied using DFT/B3LYP, MP2, and HF methods with...     

Selective Alkylation of C‐Rich Bulge Motifs in Nucleic Acids by Quinone Methide Derivatives

A quinone methide precursor featuring a bis‐cyclen anchoring moiety has been synthesized and its capacity to alkylate oligonucleotide targets quantified in the presence and absence of divalent metal ions (Zn²⁺, Ni²⁺ and Cd²⁺). The oligonucleotides were designed for testing the sequence and secondary structure specificity of the reaction. Gel electrophoretic analysis revealed predominant alkylation of C‐rich bulges, regardless of the presence of divalent metal ions or even the bis‐cyclen anchor. This C‐selectivity appears to be an intrinsic property of the quinone methide electrophile as reflected by its reaction with an equimolar mixture of the 2′‐deoxynucleosides. Only dA‐N1 and dC‐N3 alkylation products were detected initially and only the dC adduct persisted for detection under conditions of the gel electrophoretic analysis.     

Light‐Controlled Histone Deacetylase (HDAC) Inhibitors: Towards Photopharmacological Chemotherapy

Cancer treatment suffers from limitations that have a major impact on the patient’s quality of life and survival. In the case of chemotherapy, the systemic distribution of cytotoxic drugs reduces their efficacy and causes severe side effects due to nonselective toxicity. Photopharmacology allows a novel approach to address these problems because it employs external, local activation of chemotherapeutic agents by using light. The development of photoswitchable histone deacetylase (HDAC) inhibitors as potential antitumor agents is reported herein. Analogues of the clinically used chemotherapeutic agents vorinostat, panobinostat, and belinostat were designed with a photoswitchable azobenzene moiety incorporated into their structure. The most promising compound exhibits high inhibitory potency in the thermodynamically less stable cis form and a significantly lower activity for the trans form, both in terms of HDAC activity and proliferation of HeLa cells. This approach offers a clear prospect towards local photoactivation of HDAC inhibition to avoid severe side effects in chemotherapy.