Strahlungschemie von Kohlenwasserstoffen. 16. Mitteilung. Benzol-Brombenzol

The decrease of the concentration of bromobenzene and the formation of biphenyl and bromobiphenyl have been studied in the system benzene-bromobenzene under the influence of γ-rays. Bromobenzene is in competition with its own products for the reactive state of benzene or it can transfer its energy to its products. The rate of this transfer to decomposition is 74 l/Mol. With the help of additives it has been shown that they can act in two ways: firstly they compete with bromobenzene for an activated state of benzene in a reaction that does not depend on temperature. The nature of this activated state has not been determined. Secondly they scavenge phenyl radicals that have been formed in about 70% of the decomposed bromobenzene molecules. This yield depends slightly on temperature. The relative reactivities compared to bromobenzene for the first case and to benzene in the second have been determined as follows: naphthalene (0.6; 23); anthracene (5.8; 800); benzophenone (0.5; 17); cyclohexene (-; 20); N₂O (0.018; -); NO (1.7; 250); O₂ (-; 3400). Naphthacene in benzene is strongly decomposed in the presence of bromobenzene, but it also enhances the decomposition of the latter.     

Photodissociation of bromobenzene, dibromobenzene, and 1,3,5-tribromobenzene

Quantum chemical calculations have been performed on the ground state and several low-lying excited states of bromobenzene, ortho-, meta-, and para-dibromobenzene, and 1,3,5-tribromobenzene using high-level ab initio and hybrid density-functional methods. Experimental observations of ultrafast predissociation in these molecules are clarified from extensive theoretical information about all low-energy potential-energy curves together with symmetry arguments. The intriguing observation that o- and m-dibromobenzene have two ultrafast predissociation channels while bromobenzene, p-dibromobenzene, and 1,3,5-tribromobenzene only have one such channel is explained from the calculated potential-energy curves. These show that the lowering of point-group symmetry from C2v to Cs along the main photodissociation reaction coordinate, which only occurs in o- and m-dibromobenzene, opens up a new predissociation channel. Dynamical quantum simulations based on the calculated potential-energy curves are used to estimate the coupling strength at the intersystem crossing point in bromobenzene.     

Synthesis of chiral ADMET polymers containing repeating d-chiro-inositol units derived from a biocatalytically prepared diene diol

Several chiral hydroxylated polymers have been prepared, via ADMET techniques, from the diene diol derived from bromobenzene, obtained by means of whole-cell fermentation with Escherichia coli (JM109 pDTG601).     

Synthesis of penicillin analogs, (--)-methyl 6-epi-6-bromobisnorpenicillanate and (+/-)-methyl 6-epi-bromopenicillanate.

The [(4-methoxycarbonylthiazolidino)carbonyl-dihalomethyl]phenylmercury compounds 2a,b and 5a,b have been synthesized. When heated in refluxing bromobenzene they form halogenated penicillin analogs. (--)-Methyl 6-epi-6-bromobisnorpenicillinate (3a) and methyl 6-epi-6-bromopenicillinates (6a,b) have been prepared and isolated.     

Photopromoted carbonylation of bromobenzene under ambient conditions

The photopromoted carbonylation of bromobenzene with carbon monoxide catalyzed by inexpensive commercially available cobalt salts[Co(OAc)_2,CoCl_2]was carried out under ambient conditions.The results revealed that methyl benzoate was produced in the presence of basic additives(CH_3ONa,NaOAc or(n-C_4H_9)_3N).The catalytic activity of Co(OAc)_2was higher than that of CoCl_2.Furthermore,the activity of the carbonylation was greatly improved by addition of acetophenone,e.g.both the yield and selectivity of t...     

Chemoenzymatic formal synthesis of (−)-balanol. Provision of optical data for an often-reported intermediate

Formal total synthesis of (−)-balanol was accomplished from bromobenzene in 13 steps via the bis-benzyl derivative 3, whose optical rotation data have been provided.     

Role of angular momentum conservation in unimolecular translational energy release: validity of the orbiting transition state theory

The translational kinetic energy release distribution (KERD) for the halogen loss reaction of the bromobenzene and iodobenzene cations has been reinvestigated on the microsecond time scale. Two necessary conditions of validity of the orbiting transition state theory (OTST) for the calculation of kinetic energy release distributions (KERDs) have been formulated. One of them examines the central ion-induced dipole potential approximation. As a second criterion, an adiabatic parameter is derived. The lower the released translational energy and the total angular momentum, the larger the reduced mass, the rotational constant of the molecular fragment, and the polarizability of the released atom, the more valid is the OTST. Only the low-energy dissociation of the iodobenzene ion (E approximately 0.45 eV, where E is the internal energy above the reaction threshold) is found to fulfill the criteria of validity of the OTST. The constraints that act on the dissociation dynamics have been studied by the maximum entropy method. Calculations of entropy deficiencies (which measure the deviation from a microcanonical distribution) show that the pair of fragments does not sample the whole of the phase space that is compatible with the mere specification of the internal energy. The major constraint that results from conservation of angular momentum is related to a reduction of the dimensionality of the dynamics of the translational motion to a two-dimensional space. A second and minor constraint that affects the KERD leads to a suppression of small translational releases, i.e., accounts for threshold behavior. At high internal energies, the effects of curvature of the reaction path and of angular momentum conservation are intricately intermeddled and it is not possible to specify the share of each effect.     

Study of collisional relaxation of ions by two-photon photodissociation

Collisional relaxation of bromobenzene molecular ion by several neutral molecules has been measured by a two-photon photodissociation method. This new technique allows a quantitative estimation of energy loss in the relaxation process. Collisional relaxation rates have been found to be much slower than expected from orbiting collision rates.     

Fluorescence labeling method for aryl halides with 4-(4,5-diphenyl-1H-imidazol-2-yl)phenylboronic acid based on Suzuki coupling reaction

For the first time, fluorescence labeling methods for aryl halides with a fluorescent arylboronic acid was developed on the basis of a Suzuki coupling reaction. 4-(4,5-diphenyl-lH-imidazol-2-yl)phenylboronic acid (DPA) was used as a fluorescence labeling reagent. In order to explore its analytical performance, the reaction conditions were optimized using simple bromobenzene derivatives. The reactivity was then investigated with chloro- and iodobenzene derivatives, and also bromobenzene derivatives with different position of substituents. The order of reactivity with DPA: iodobenzene > bromobenzene more more than chlorobenzene derivatives, and p- > m- > o-substituted bromobenzenes. The detection limits of bromobenzene, 4-bromotoluene, and 4-bromoanisole ranged from 0.2 to 1.4 pmol/injection at a signal-to-noise ratio, (S/N) of 3. The applicability of the method to biological samples was also evaluated using clofibrate as the analyte. The reaction was found not only to proceed well but also to be selective for clofibrate even in the presence of plasma components. The method allowed the sensitive detection of clofibrate in human plasma with the detection limit of 170 pmol/mL (260 fmol/injection) at a S/N = 3. The proposed method is highly selective and sensitive and thus would be useful for labeling of aryl halides that do not have other functional groups that could be labeled by currently available fluorescent labeling reagents.     

Palladium catalyzed oxidations of secondary alcohols

Palladium catalyzed oxidations of secondary alcohols making use of bromobenzene as an oxidant have been described, where 6 kinds of alcohols have been oxidized to the corresponding ketones in excellent yields.     

Viscosities of Binary Liquid Mixtures of Tetrachloroethylene with Some Aliphatic,Alicyclic and Substituted Aromatic Hydrocarbons

Abstract

Viscosities of binary mixtures of tetrachloroethylene with hexane, heptane, cyclohexane, methylcyclohexane, toluene, chlorobenzene, bromobenzene and nitrobenzene were measured at 303.15 K. The values of η^E are negative in all the systems except in tetrachloroethylene + bromobenzene system. An inversion in sign from positive to negative is observed in the system, tetrachloroethylene + bromobenzene. The viscosity data were analysed in terms of absolute reaction rate and free volume theories of liquid viscosity. Further, Grunberg and Nissan Parameter has also been evaluated.     

Chemoenzymatic preparation of (6R)-5,6-dihydro-2H-pyran-2-one: a ubiquitous structural motif of biologically active lactones

A chemoenzymatic synthesis of an enantiopure 6-substituted 5,6-dihydro-2H-pyran-2-one using bromobenzene as a starting material is presented. This important structural motif is found in a large number of chiral lactones that present a wide range of biological activities. The key features of the preparation include enzymatic dioxygenation of bromobenzene using Escherichia coli JM109 (pDTG601), microwave-assisted acyloin cleavage, and tin mediated lactonization. The stereochemical assignment for the alcohol was confirmed by NMR analysis of Moshe?s derivatives.     

Theoretical analysis of the performance of a model supercapacitor consisting of metal oxide nano-particles

The factors influencing the electrochemical behaviour of a supercapacitor have been partly examined in this work. The effects of so-called intrinsic parameters, i.e. exchange current density, unit cell length and double layer (DL) capacitance; as well as the so-called application parameters, i.e. cell current, on the cell potential discharge time have been considered. The contributions of each type of capacitors, DL capacitor and faradaic supercapacitor under various states of operation and material have been analyzed, and the competing (compensating) effects of the two types of capacitors as regards to the discharge and power characteristics manifested by current–potential and energy–power (Ragone plots) are elucidated.     

Kinetics and mechanism of oxidation of phenylhydrazine and P-bromophenylhydrazine by hexacyanoferrate(III) in acidic medium

Kietics of oxidation of phenylhydrazine and p-bromophenylhydrazine by hexacyanoferrate(III) in acidic medium have been studied. The reactions follow similar kinetics, being first order with respect to both hydrazine and exacyanoferrate(III) and inverse first order with respect to the hydrogen ion. Addition of hexacyanoferrate(II) has no retarding effect on the rate of oxidation. The effects of varying ionic strength, dielectric constant, and temperature on the reaction rates have been investigated. A plausible mechanism has been proposed to account for the experimental results. Benzene and bromobenzene have been identified as the oxidation products.     

A source of screw dislocation in polyoxymethylene crystals

Polyoxymethylene crystallizes as hexagonal lamellar crystals accompanied by spiral growth from dilute bromobenzene solution. Spirals of this polymer are formed by several mechanisms. There is discussion of various origins of screw dislocation due to interlocking of two independently growing crystals with crevices. After entanglement, various growth stages of crystals have been observed.     

Ship-in-a-bottle synthesis of triphenylamine inside faujasite supercages and generation of the triphenylamminium radical ion

The ship-in-a-bottle synthesis of triphenylamine encapsulated within basic X zeolite has been accomplished by reacting sodium diphenylamide with bromobenzene in the presence of a bifunctional palladium (Hartwig-Buchwald conditions). The presence of incarcerated triphenylamine was demonstrated by dissolving the zeolite with concentrated HF and analyzing the organic material in the dichloromethane extract. Laser flash photolysis (266 nm) gives rise to the generation of triphenylamminium radical cation detected as a transient species decaying in hundreds of microseconds. Upon repetitive cyclic voltammograms, zeolite encapsulated triphenylamine shows a reversible oxidation-reduction process. In contrast, in solution triphenylamine undergoes irreversible oxidation with the formation of coupling dimers.     

二苯并[b,f][1,5]二氮杂芳辛四烯衍生物的合成及拆分

以邻氨基二苯甲酮为原料,经自身缩合环化合成了3种二苯并[1,5]二氮杂芳辛四烯衍生物(1a~1c);以邻苯二甲酸酐和溴苯为原料经傅-克反应制得中间体2-(4-溴苯甲酰溴)苯甲酸(M1);M1经叠氮化后自缩合制得6,12-二(4-溴苯基)二苯并[b,f][1,5]二氮杂环辛四烯(1d);以邻氨基苯甲酸甲酯为原料,经自身缩合环化制得中间体二苯并[b,f][1,5]二氮杂环辛四烯-6,12(5H,11H)-二酮(M2);M2经氯化合成6,12-二氯二苯并[b,f][1,5]二氮杂环辛四烯(1e),化合物1a~1e的结构经~1H NMR,~(13)C NMR和ESI-MS表征,其中化合物1c为新化合物。利用超临界色谱(SFC)技术对化合物1a~1e实现了手性拆分,获得5对具有高旋光度的光学活性异构体(ee99%)。     

Sensor materials for the future: Intelligent materials

Recently, there has been a renewed interest in the development of sensor materials. Four major trends can be discerned in this new research, i.e., (1) single crystal to poly crystal to amorphous material; (2) static material to dynamic material; (3) simple material to composite material; (4) atomic (molecular) synthesis of sensor material. These trends are an approach to obtaining ‘intelligent materials’.Up to now, sensor devices have been made using materials with given characteristics. In future, however, sensor materials should be designed to give the desired characteristics of sensor devices. These trends towards intelligent materials will be discussed here.     

High efficiency voltage stabilizers for XLPE cable insulation

A set of new voltage stabilizers has been synthesized, tested and has shown to suppress a degradation mechanism, i.e. electrical treeing, present in cross-linked polyethylene used for high-voltage cables. Electrical treeing is seen at very high and divergent electrical fields and has a rapid lapse from initiation to total breakdown of the insulation material. The new voltage stabilizers presented in this paper have increased the electrical tree inception field with up to 50% at such low additions as 0.4%-wt. Furthermore, the best-performing materials have also proven to increase the threshold level for tree inception, i.e. before this level no deterioration of the material is seen, up to 50%.     

Volumetric behaviour of binary liquid mixtures of dimethylsulphoxide with substituted benzenes at 303.15 k

Excess molar volumes (V ^E ) for binary mixtures of dimethyl sulphoxide (DMSO) with substituted benzenes have been measured at 303.15?K. The substituted benzenes include toluene, ethylbenzene, chlorobenzene, bromobenzene and nitrobenzene. The measured V ^E data is positive for the mixtures of DMSO with nitrobenzene and is completely negative over the entire composition range in the mixtures of toluene, ethylbenzene and chlorobenzene and an inversion in sign is observed in the bromobenzene system. The experimental results are analysed in terms of intermolecular interactions and effect of substitutents on benzene ring between unlike molecules.