Time-Resolved Photochemistry of Stiffened Stilbenes.

Broadband transient absorption spectroscopy is used to study the photoisomerization of stiffened stilbenes in solution, specifically E/ Z mixtures of bis(benzocyclobutylidene) (t4, c4) and ( E)-1-(2,2-dimethyltetralinylidene)-2-2-dimethyltetraline (t6). Upon excitation to S, all evolve to perpendicular molecular conformation P, followed by decay to S, while the spectra and the kinetic behavior crucially depend on the size of the stiffening ring. In 4, contrary to all previously studied stilbenes, the trans and cis absorption and excited-state spectra are nearly indistinguishable, while the corresponding isomerization times are comparable: τ = 166 ps for t4 and τ = 64 ps for c4 in n-hexane, as opposed to 114 and 45 ps in acetonitrile, respectively.

Comment on "Glycine-functionalized copper(ii) hydroxide nanoparticles with high intrinsic superoxide dismutase activity" by K. Korschelt, R. Ragg, C. S. Metzger, M. Kluenker, M. Oster, B. Barton, M. Panthöfer, D. Strand, U. Kolb, M. Mondeshki, S. Strand, J. Brieger, M. N. Tahir and W. Tremel, Nanoscale, 2017, 9, 3952.

Detoxification of cigarette smoke employing copper compounds has a potential for the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans and should not be practiced before the degree of formation has been shown to be harmless.

Enzymatic synthesis of bromo- and chlorocarbazoles and elucidation of their structures by molecular modeling.

3-Chlorocarbazole, 3,6-dichlorocarbazole, dibromocarbazole, and 1,3,6,8-tetrabromocarbazole are emerging environmental contaminants which have been detected recently in water, sediment, and soil samples. However, their sources and occurrence have not been explained. Here, we report an enzymatic synthesis of bromo- and chlorocarbazoles by chloroperoxidase from Caldariomyces fumago in water.

Verification of stereospecific dyotropic racemisation of enantiopure D and L-1,2-dibromo-1,2-diphenylethane in non-polar media.

The first example of a dyotropic rearrangement of an enantiomerically pure, conformationally unconstrained, vicinal dibromide confirms theoretical predictions: D and L-1,2-dibromo-1,2-diphenylethane racemise stereospecifically in refluxing benzene without crossover to the meso-isomer. An orbital analysis of this six-electron pericyclic process is presented.

Bis-dibenzo[a.i]fluorenylidene, does it exist as stable 1,2-diradical?

The geometries, energies, and electronic properties of the two possible configurations of bis-[dibenzo[a.i]fluorenylidene] were investigated theoretically by density functional theory DFT B3LYP at the UB3LYP/6-311 + G(2d,p) // UB3LYP/6-31 + G(d,p) level of theory. According to the performed calculations, it was found that the singlet is 3.

Reduction of benzylic alcohols and α-hydroxycarbonyl compounds by hydriodic acid in a biphasic reaction medium.

The synthetic protocol for the reduction of alcohols to hydrocarbons by using hydriodic acid, first described by Kiliani more than 140 years ago, was improved to be more applicable to organic synthesis. Instead of a strongly acidic, aqueous solution, a biphasic toluene-water reaction medium was used, which allowed the conversion of primary, secondary and tertiary benzylic alcohols, in good yields and short reaction times, into the corresponding hydrocarbons. Red phosphorous was used as the stoichiometric reducing agent.

Laboratory studies on formation and minimisation of polychlorinated dibenzodioxins and -furans (PCDD/F) in secondary aluminium process.

The objectives of this work were to study the formation mechanisms of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) in thermal aluminium recycling processes by use of laboratory experiments. The pattern of isomers of PCDD/F indicates that de novo synthesis is important in aluminium smeltery. The mechanisms of PCDD/F formation in aluminium smelting are similar to that of various incineration processes of waste material.

Degradative fate of 3-chlorocarbazole and 3,6-dichlorocarbazole in soil.

Background, Aim, And Scope: 3-Chlorocarbazole and 3,6-dichlorocarbazole were isolated from Bavarian soils. The stereospecific formation of the isomers of these chlorinated carbazols can be explained by quantum mechanical calculations using the DFT method. It was shown that chlorination of carbazole and 3-chlorocarbazole respectively is preferred via the sigma-complexes 3-chlorocarbazole and 3,6-dichlorocarbazole as the most stable products.

What is the preferred structure of the Meisenheimer-Wheland complex between sym-triaminobenzene and 4,6-dinitrobenzofuroxan?

The geometries, energies, and electronic properties of possible configurations of Meisenheimer-Wheland (M-W) complexes of sym-triaminobenzenes and 4,6-dinitrobenzofuroxan (DNBF) were investigated theoretically by MP2 and a variety of DFT methods. The pi-pi complex is preferred thermodynamically by more than 15 kcal/mol over the sigma-complexes for the unsubstituted species. However, the N-substituents of the 1,3,5-triaminobenzenes influence the relative stabilities of the alternative configurations significantly.

Single-electron self-exchange between cage hydrocarbons and their radical cations in the gas phase.

We show that the radical cations of adamantane (C(10)H(16)(*+), 1H(*+)) and perdeuteroadamantane (C(10)D(16)(*+), 1D(*+)) are stable species in the gas phase. The radical cation of adamantylideneadamantane (C(20)H(28)(*+), 2H(*+)) is also stable (as in solution). By using the natural (13)C abundances of the ions, we determine the rate constants for the reversible isergonic single-electron transfer (SET) processes involving the dyads 1H(*+)/1H, 1D(*+)/1D and 2H(*+)/2H.

2-Norbornyl ion-pair leakage in electrophilic addition of HCl to nortricyclene and norbornene.

Ion pair "leakage" pathways, located computationally by means of multidimensional potential energy surface scans, rationalize the unsymmetrical D-label scrambling observed experimentally in the DCl addition products of nortricyclene and norbornene. "Classical" addition transition structures can interconvert ("leak") to symmetrical nonclassical 2-norbornyl ion pair species, either TS's or a minimum, before products form.

Correlation of PCDD/F and PCB at combustion experiments using wood and hospital waste. Influence of (NH(4))(2)SO(4) as additive on PCDD/F and PCB emissions.

The objectives of this work were to study the emissions of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) and polychlorinated biphenyl (PCB) during the combustion of wood, wood and hospital waste as well as wood, hospital waste and (NH(4))(2)SO(4) in a pilot plant and to determine the relation of the toxic emissions to the fuel properties. The presence of PVC (experiments b and c) increases PCDD/F and PCB formation compared to burning only eco-farm wood (a). However, analysis and quantification of PCDD/F and PCB showed that the amount of 5% of (NH(4))(2)SO(4) in the fuel mixture significantly impacted the dioxins emissions and suppressed it by approximately 50%.

Electrophilic bromination of alkenes: environmental, health and safety aspects of new alternative methods.

More than twenty new alternative methods for bromination of alkenes have been evaluated taking into consideration their resource demands, waste production as well as environmental, health and safety aspects. The cost of bromine and the substances designated to circumvent the application of molecular bromine have also been taken into account. As bromine is only one of several problematic substances being used, its avoidance-by applying bromine supported on solid material or by performing the in situ generation of bromine-does not significantly reduce the technological requirements.

Stable ion and electrophilic chemistry of the sterically crowded stilbene 1,1'-Bi(benzocyclobutenylidene) and its derivatives.

Generation and NMR studies of novel carbocations and carboxonium ions are reported from sterically hindered stilbene 1,1'-bi(benzocyclobutenylidene) 1, its dimethoxy derivative 5, and from their skeletally rearranged derivatives, namely, the spirocyclic ketone 6, diastereomeric alcohols 7 and isomeric diols 8. Quenching experiments on the carbocations under various conditions resulted in the formation/isolation of several novel covalent adducts. Acid-catalyzed isomerization of the diols 8 produced a remarkable dimeric molecule, whose structure was confirmed by X-ray analysis.

From dioxin to drug lead--the development of 2,3,7,8-tetrachlorophenothiazine.

Polychlorinated dibenzo-p-dioxins are persistent environmental pollutants. The most potent congener, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), causes a wasting syndrome and is a potent carcinogen and immunosuppressant in the rat at high doses. However, low doses cause opposite effects to some of those observed at higher doses, resulting in chemoprevention, stimulation of the immune system, and longevity in experimental animals.

The first intermediates in the bromination of bicyclo[3.3.1]nonylidenebicyclo[3.3.1]nonane, combination of experiments and theoretical results.

Bicyclo[3.3.1]nonylidenebicyclo[3.

Primary measures for reduction of PCDD/F in Co-combustion of lignite coal and waste: effect of various inhibitors.

Co-combustion of coal and waste in power plants poses both environmental and economic challenges, especially because of the high polychlorinated dibenzo-p-dioxin and furan (PCDD/F) emissions from solid waste. In this study, we performed a series of experiments focusing on the prevention of PCDD/F formation by the use of various inhibitors added to the fuel before combustion. A mixture of lignite coal, solid waste, and poly(vinyl chloride) (PVC) was thermally treated in a laboratory-scale furnace at 400 degrees C.

Selective adsorption of polychlorinated dibenzo-p-dioxins and dibenzofurans by the zeosils UTD-1, SSZ-24, and ITQ-4.

Zeosils are microporous solids with a pure silica framework. Due to their hydrophobic properties, zeosils are ideal host materials for the adsorption of hydrophobic guest molecules. We tested zeosils with different pore diameters (UTD-1, SSZ-24 and ITQ-4 as well as CIT-5) for the selective adsorption of the polychlorinated dibenzo-p-dioxins and dibenzofurans.

The bioaccumulation and fate of a branched 14C-p-nonylphenol isomer in Lymnaea stagnalis L.

A single branched isomer of p-nonylphenol, 4(3',6'-dimethyl-3'-heptyl)-phenol, previously identified by gas chromatography-mass spectrometry as one of the major constituent isomers in p-nonylphenol (constituting approximately 10% of all its isomers), was synthesized and used in studies of its bioaccumulation and excretion in the hermophroditic pond snail Lymnaea stagnalis L. Branched isomers of nonylphenol are perceived to have more estrogenlike toxicity than the straight-chain isomers in addition to being more resistant to biodegradation in the environment. With an average static exposure concentration of 104 microg/L (range: 92-116 microg/L) in water at 19 degrees C for 8 d, the uptake of the compound was found to be fairly rapid, reaching a peak concentration of 23,548 microg/kg of whole tissue wet weight after 5 d and a peak bioaccumulation factor (BAFw) of 242 (5,562, based on lipid weight) after 3 d.

Sustainable chemistry: starting points and prospects.

We review here the concept of sustainable chemistry (SC), which is still in its early development. One important element of SC is commonly defined as chemical research aiming at the optimization of chemical processes and products with respect to energy and material consumption, inherent safety, toxicity, environmental degradability, and so on. An increasing number of assessment systems containing quantitative indicators for these aspects are currently being developed.

Polarizability effects and dispersion interactions in alkene-Br2 pi-complexes.

Weakly bound molecular complexes play an important role in chemistry, physics, and biodisciplines. The preequilibrium pi-complexes of various alkenes with bromine have been examined quantitatively, and a direct relationship between association constants (KF) of these pi-complexes and polarizability of the olefins was found. The stability of the Br2-olefin pi complexes is affected by both the donor ionization potential and the polarizability of the olefin, and an equation able to take into account both effects is proposed.

What is the nature of the first-formed intermediates in the electrophilic halogenation of alkenes, alkynes, and allenes?

The pi complexes first formed as essential intermediates from alkenes, alkynes, and allenes with bromine have been investigated in different solvents by UV-spectroscopy in combination with stopped-flow techniques allowing the determination of the equilibrium constants, K(f). Using alkenes with sterically protected double bonds, such as di-tert-butylstilbene and tetraneopentylethylene, the reaction stops at the stage of the 1:1 and 1:2 pi complex of the alkene with bromine as persistent species in 1,2-dichlorethane as solvent. Calculations by state-of-art ab initio and DFT methods reproduces the experimentally determined thermodynamic values quite well, and reveal the preferred structures and nature of both complexes for ethene, ethyne, and allene.