Visible Light-Mediated Polychlorination of Alkenes via Dichloromethyl Radical Generated by Chloroform and Chlorides

We report a novel visible light-mediated protocol for polychlorination of alkenes by employing the commercially available bulk chemicals chloroform and chlorides. This methodology enables the installation of multiple chlorine atoms...

Extraction of Chlorobenzenes and PCBs from Water by ZnO Nanoparticles

Metal oxide nanoparticles have great potential for selective adsorption and catalytic degradation of contaminants from aqueous solutions. In this study, we employ mass spectrometry and molecular dynamics simulations to better understand the chemical and physical mechanisms determining the affinity of chlorobenzenes and polychlorinated biphenyls (PCBs) for zinc oxide nanoparticles (ZnO NPs). The experiments and simulations both demonstrate that the adsorption coefficients for chlorobenzenes increase steadily with the number of chlorine atoms, while, for PCBs, the relation is more complex. The simulations link this complexity to chlorine atoms at ortho positions hindering coplanar conformations. For a given number of chlorine atoms, the simulations predict decreasing adsorption affinity with increasing numbers of ortho substitutions. Consequently, the simulations predict that some of the highest adsorption affinities for ZnO NPs are exhibited by dioxin-like PCBs, suggesting the possibility of selective sequestration of these most acutely toxic PCBs. Remarkably, the experiments show that the PCB adsorption coefficients of ZnO NPs with diameters ≤80 nm exceed those of a soil sample by 5–7 orders of magnitude, meaning that a single gram of ZnO NPs could sequester low levels of PCB contamination from as much as a ton of soil.

Synthesis of a new phorbazole and its derivatives

Phorbazoles are chlorinated marine alkaloids isolated from sea sponges and nudibranchs. In this work, a convenience synthetic method leading to a new phorbazole and its derivatives was developed. This synthesis of the novel phorbazole G and its derivatives has been Phorbazoles are chlorinated marine alkaloids containing pyrrole, oxazole, phenol ring units and differ in the number and positions of chlorine atoms. They are isolated from sea sponges and nudibranchs. In this work, a convenient synthetic method leading to a new phorbazole and its derivatives was developed. This synthesis of the synthetic phorbazole G and its derivatives has been achieved in seven steps in good overall yields of 26-52 %. It involved formation of the pyrrole oxazole skeleton followed by chlorination. The pyrrole oxazole skeleton was synthesized from pyrrole and substituted acetophenones, and the key step was cyclodehydration of the amides to give protected oxazoles, followed by hydrolysis. achieved in seven steps in good overall yields of 26.3 - 52.5 %. It involved formation of the pyrrole oxazole skeleton followed by chlorination. The pyrrole oxazole skeleton was synthesized from pyrrole and substituted acetophenones, and the key step was cyclodehydration of the amides to give protected oxazoles, followed by hydrolysis

STRUCTURE OF BIS(LIDOCAINE) TETRACHLORIDOCUPRATE(II)

The present paper reports on the synthesis and structure of bis(2-(diethylamino)-N-(2,6-dimethylphenyl)acetamide) or bis(lidocaine) tetrachloridocuprate(II). The complex with the formula (C14H23ON2)2CuCl4 (or (LidH)2[CuCl4]), crystallizes in the monoclinic space group P21/c with a = 15.7831(2), b = 24.2992(2), c = 17.8748(2) Å, β = 104.874(1)°,V = 6625.58(13) Å3, Z = 8, and Dc = 1.355 Mg/m3. The coordination of the Cu2+ ions with chlorine atoms generates two differently distorted tetrahedral anions [CuCl4]2–, while four protonated cations LidH+ remain in an outer coordination sphere. Anions and cations are associated by hydrogen bonds of the N–H···Cl type to form the 2((LidH)2[CuCl4]) dimer, in which the distance between two copper atoms is 8.95 Å. With the help of hydrogen bonds of the type N–H···O and N–H···Cl, each dimer is connected with four neighboring dimers, resulting in a three-dimensional structure in which dimers lie at an angle of 28.39° to the a crystallographic axis in the ab planes located at a distance of 10.67 Å from each other.

Chlorine Modulation Fluorescent Performance of Seaweed-Derived Graphene Quantum Dots for Long-Wavelength Excitation Cell-Imaging Application

Biological imaging is an essential means of disease diagnosis. However, semiconductor quantum dots that are used in bioimaging applications comprise toxic metal elements that are nonbiodegradable, causing serious environmental problems. Herein, we developed a novel ecofriendly solvothermal method that uses ethanol as a solvent and doping with chlorine atoms to prepare highly fluorescent graphene quantum dots (GQDs) from seaweed. The GQDs doped with chlorine atoms exhibit high-intensity white fluorescence. Thus, their preliminary application in bioimaging has been confirmed. In addition, clear cell imaging could be performed at an excitation wavelength of 633 nm.

Synthesis and Structure of the Bis- and Tris-Polyhedral Hybrid Carboranoclathrochelates with Functionalizing Biorelevant Substituents—The Derivatives of Propargylamine Iron(II) Clathrochelates with Terminal Triple C≡C Bond(s)

A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate precursor with amine N-nucleophiles of different natures in various solvents was performed. One of its two chlorine atoms with morpholine or diethylamine in dichloromethane gave reactive monohalogenoclathrochelate complexes functionalized with abiorelevant substituents. Further nucleophilic substitution of their remaining chlorine atoms with propargylamine in DMF led to morpholine- and diethylamine-functionalized monopropargylamine cage complexes, the molecules of which contain the single terminal C≡C bond. Their “click” 1,3-cycloaddition reactions in toluene with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate gave spacer-containing di- and tritopic iron(II) carboranoclatrochelates formed by a covalent linking between their different polyhedral(cage) fragments. The obtained complexes were characterized using elemental analysis, MALDI-TOF mass, UV-Vis, 1H, 1H{11B}, 11B, 11B{1H}, 19F{1H} and 13C{1H}-NMR spectra, and by a single crystal synchrotron X-ray diffraction experiment for the diethylamine-functionalized iron(II) carboranoclathrochelate. Its encapsulated iron(II) ion is situated almost in the center of the FeN6-coordination polyhedron possessing a geometry intermediate between a trigonal prism and a trigonal antiprism with a distortion angle φ of approximately 28º. Conformation of this hybrid molecule is strongly affected by its intramolecular dihydrogen bonding: a flexibility of the carborane-terminated ribbed substituent allowed the formation of numerous C–H…H–B intramolecular interactions. The H(C) atom of this carborane core also forms the intermolecular C–H…F–B interaction with an adjacent carboranoclathrochelate molecule. The N–H…N intermolecular interaction between the diethylamine group of one hybrid molecule and the heterocyclic five-membered 1Н-[1,2,3]-triazolyl fragment of the second molecule of this type caused formation of H-bonded carboranoclathrochelate dimers in the X-rayed crystal.