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Within the scope of phase-transfer halogenations (Br and I) of alkanes, significant H/D kinetic isotope effects (KIE = 4-5) indicate that hydrogen abstraction is rate limiting. The excellent agreement of computed and experimentally determined H/D KIE as well as trapping experiments support the involvement of trihalomethyl radicals in the activation step.
The photoinduced electron transfer reaction of halogenated 1,4-benzoquinones with 2,3-dimethyl-2-butene or 3,4-dimethyl-2-pentene gave the primary, secondary, and tertiary monoallyl ethers of hydroquinones, with the product distributions highly dependent on the steric nature of quinones and olefins.
[reaction: see text]. Room-temperature ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium bromide, and 1-butyl-3-methylimidazolium chloride, are used as "green" recyclable alternative to chlorinated solvents for the stereoselective halogenation of alkenes and alkynes.
[reaction: see text] NaIO(4) oxidizes alkali metal halides efficiently in aqueous medium to halogenate alkenes and aromatics and produce the corresponding halo derivatives in excellent regio and stereoselectivity. The system also demonstrates the asymmetric version of bromo hydroxylation using beta-cyclodextrin complexes, resulting in moderate ee.
Diiodobutadiyne (1) and diiodohexatriyne (2) form cocrystals with bispyridyl oxalamides and ureas, based on the halogen bond between the alkynyl iodine and pyridine nitrogen. In each cocrystal, the oxalamide or urea host forms one-dimensional hydrogen-bonded networks, aligning the diiodopolyyne for potential topochemical polymerization with a repeat distance matching the host repeat.
[structure: see text] Two novel tetranortriterpenoids, turrapubesins A (1) and B (2), representing the first examples of halogenated and maleimide-bearing limonoids, were isolated from the twigs and leaves of Turraea pubescens. The structures of 1 and 2 were elucidated by extensive spectroscopic analysis. Their absolute configurations were determined by X-ray crystallography of 1 and by CD analysis of a dihydrogenated derivative of 2. Turrapubesin A (1) exhibited weak cytotoxicity against the P-388 tumor cell line.
Electrophilicity as a general basis for both the mutagenicity and nucleophile inactivation of halogen-substituted 2(5H)-furanones was tested. Lowest unoccupied molecular orbital (LUMO) energy levels and stabilities of 2(5H)-furanone radical anions and C-2, C-3, and C-4 anionic hydride adducts were computed with MNDO-PM3 for each of 10 compounds. These three computed sets of values were considered electrophilicity indicators. Each individual value from a given indicator set was plotted against the logarithm of the Salmonella typhimurium (TA100) mutagenicities (log Mm) for each of the corresponding compounds. Highest occupied molecular orbital (HOMO) energy levels for the 10 compounds were also computed. Strong negative correlations were obtained from the plots of LUMO and radical anion stability against log Mm of the 10 compounds. Also, a negative correlation was observed for the plot of the stability of the C-4 anionic hydride adduct for a smaller set of six compounds possessing a 4-(chloromethyl)-2(5H)-furanone structure and having the same HOMO characteristics. HOMO energies failed to correlate with mutagenicity. Neither computed atomic charge nor 13C chemical shift values for the larger compound group of 10 correlated well with mutagenicity or with each other. Sodium borohydride and borodeuteride reductions of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone demonstrated experimentally that hydride became attached to C-4.
Fran The effects of sedation and of halogenate anesthesia on electroretinographic recordings were investigated by reviewing the hospital charts of 27 patients who were eventually diagnosed free of retinal disease. The same ERG protocol was performed in conscious (n=9), sedated (chloral hydrate or pentobarbital sodium, n=9) and anesthetized (halothane or isoflurane, in combination with N2O, n=9) young patients. Sedation decreased the a- and b-wave amplitude of the scotopic bright-flash response, without affecting implicit times. ERG recordings performed in photopic conditions showed minimal disturbances. Anesthesia spared the a-wave of the scotopic bright-flash response but decreased more severely the b-wave. In addition, anesthesia reduced the amplitude and prolonged the implicit time of the photopic responses, affecting predominantly the ionotropic glutamate dependent OFF components (peak of b-wave, 0P4 and 0P5). The normal retinal physiology is affected by sedation and anesthesia through different mechanisms that still remain to be fully elucidated. These alterations in electroretinographic recordings must be considered when evaluating ERGs obtained under similar sedation/anesthetized conditions.
BACKGROUND: Halogenated volatile anesthetics (HVAs) are considered to be inhibitors of nitric oxide synthase (NOS). On other hand, NO mediates the vasodilation produced by HVAs. Thus, both increase and decrease of NO concentration in brain tissues are possible during anesthesia. Previously, we have observed an increase of NO content in rat brain cortex under halothane anesthesia. The goal of this study was to determine whether the observed phenomenon was general for this anesthetic group, if it was specific for brain cortex, and if the NO increase was due changes in NOS activity. METHODS: NO scavengers were injected to adult rats 30 min prior to anesthesia. Rats were anesthetized by inhalation of an O2 mixture with volatile anesthetics (1.5% for halothane; 1% for isoflurane, 2% for sevoflurane). After 30 min of anesthesia, rats were decapitated and brain cortex, cerebellum, liver, heart, kidneys and testes were dissected, frozen in liquid nitrogen and subjected to EPR spectroscopy. Nitric oxide content was determined quantitatively based on the intensity of the NO-Fe-DETC complex spectrum and its comparison with the calibration curve. RESULTS: In rats anesthetized with HVAs, we observed a greater than twofold increase of NO content in brain cortex as compared to the nonanesthetized animals. No significant changes were detected in other organs. The NOS inhibitor N(omega)-nitro-L-arginine abolished the increase of NO content in brain produced by volatile anesthetics. CONCLUSION: The action of volatile anesthetics is coupled with an increase of NO content in the cortex dependent on NOS activity.
Bromide ion is rapidly converted to HOBr via BrCl by reaction with HOCl. The subsequent slow reactions of (HOCl, OCl-)/(HOBr, OBr-) mixtures are monitored directly by multiwavelength UV-vis absorbance methods and simultaneously by ion chromatographic measurement of ClO2-, ClO3-, and BrO3- (p[H+] 5.6-7.6). A first-order loss of HOCl is observed which is catalyzed by trace concentrations of Br- and BrCl. Chlorite ion forms first and is subsequently oxidized to ClO3-. The loss of HOBr is slower and is second-order in HOBr, so that BrO3- formation takes longer than ClO3- formation. Under the conditions of this work, the relative yield of BrO3- increases with increase in pH. The decomposition of HOCI by bromide proceeds primarily by a series of halogen(I) cation-transfer reactions with subsequent halide release. The presence of HOCI increases the BrO3- yield three-fold from HOBr decay alone.
A halogen-free inorganic photochromic soda-lime silicate glass containing silver ions has been developed; reversible change between colorless and yellow color in this glass is achieved through combined 193 nm excimer laser irradiation and heat treatment.
Two novel tweezer-like 25,27-dihydroxy-26,28-bis(phenylthiaethoxy)calix[4]arenes 6 and 7 were synthesized by the reaction of 25,27-dihydroxy-26,28-bis(bromoethoxy)calix[4]arenes 3 and 4 for the evaluation of their ion-selectivity in ion-selective electrodes (ISEs). X-ray structural analysis indicated that calix[4]arene 7 is in an interesting infinite linear aggregate via self-inclusion. For investigation of the influences of substitutes on the behavior of the ISEs, the halogen substituted aryl analogues of 25,27-dihydroxy-26,28-bis(arylthiaethoxy)calix[4]arenes 8-12 were also synthesized and their ISE performances were evaluated under the same conditions. ISEs based on 6-12 as neutral ionophores were prepared, and their selectivity coefficients for Ag+ (log KAg,M(pot)) were investigated against other alkali metal, alkaline-earth metal, lead, ammonium ions and some transition metal ions using the fixed interference method (FIM). These ISEs showed excellent Ag+ selectivity over most of the interfering cations examined, except for Hg2+ having relative smaller interference (log KAg,Hg(pot) < or = 2.1). The 19F NMR spectra of 9 and 9.AgClO4 were recorded for investigation the fluorine environments in the complex. The 19F NMR spectra strongly suggested that the fluorine atoms on ionophore 9 participated in ligation with silver cation.
Selectivity promotion in the Ag-catalysed heterogeneous epoxidation of ethene correlates with halogen electron affinity showing that it is an electronic phenomenon rather than a steric or geometrical effect.
The preparation of 1,4,8,11-tetrabromo-5b[small alpha],6,12b[small alpha],13-tetrahydropentaleno[1,2-b:4,5-b[prime or minute]]diquinoline is described. This is a further member of the tetrahalo aryl host family, and forms crystalline lattice inclusion compounds with many guests. The X-ray structures of the allyl cyanide, 1,2,3-trichloropropane, chlorobenzene, toluene, benzene-water, methyl chloroform and carbon tetrachloride inclusion compounds are described, and compared with that of the solvent-free apohost. Although several different structural types are produced, the recently reported pi-halogen dimer (PHD) interaction plays an important role in all of these, except for that of pure (where the packing energy is the least favourable of the series).
The halogen bonding driven self-assembly of 1,4-dicyanobutane and 1,6-dicyanohexane with a range of perfluorinated telechelic diiodoalkanes yields layered 1D, infinite chain co-crystals. The structure and metrics of these co-crystals are remarkably predictable.
Whether or not tri(isopropoxo)aluminium catalyses halogen exchange for an ATRP catalyst depends on the number of valence electrons.
The halogen bonding driven self-assembly of 1,8-diiodoperfluorooctane and N,N,N',N'-tetramethyl-p-phenylenediamine induces the formation of a chiral and enantiopure co-crystal wherein the fluorinated chains adopt an unusual gauche arrangement.
Here we report a new high capacity battery system referred to as RAH batteries, which is based upon a high energy cathode-halogen (such as Br2 or Cl2) and metal hydride anode.