Dielectric properties of solid hydrogen bromide.
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Bromides↗
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Iodo- and bromo-enolcyclization of 2-(2-propenyl)cyclohexanediones and 2-(2-propenyl)cyclohexenone derivatives using iodine in methanol and pyridinium hydrobromide perbromide in dichloromethane.
alpha-Allylcyclohexane-1,3-diones undergo one-pot iodine-methanol promoted iodocyclization and oxidative aromatization to afford variously substituted 2-iodomethyltetrahydrobenzofuran-4-ones (minor) and 2-iodomethyl-4-methoxydihydrobenzofuran derivatives (major). On the other hand, the alpha-allyl-1,3-cyclohexanediones react with pyridinium hydrobromide perbromide in dichloromethane to afford mixtures of 2-bromomethyltetrahydrobenzofuran-4-ones (major) and 3-bromomethyltetrahydrobenzopyran-5-ones (minor). The prepared products and their derivatives were characterized using a combination of NMR, FT-IR and mass spectroscopic techniques.
Allyl Compounds↗
Photoelectron imaging following 2 + 1 multiphoton excitation of HBr.
The photodissociation and photoionization dynamics of HBr via low-n Rydberg and ion-pair states was studied by using 2 + 1 REMPI spectroscopy and velocity map imaging of photoelectrons. Two-photon excitation at about 9.4-10 eV was used to prepare rotationally selected excited states. Following absorption of the third photon the unperturbed F (1)Delta(2) and i (3)Delta(2) states ionize directly into the ground vibrational state of the molecular ion according to the Franck-Condon principle and upon preservation of the ion core. In case of the V (1)Sigma(+)(0(+)) ion-pair state and the perturbed E (1)Sigma(+)(0(+)), g (3)Sigma(-)(0(+)), and H (1)Sigma(+)(0(+)) Rydberg states the absorption of the third photon additionally results in a long vibrational progression of HBr(+) in the X (2)Pi state as well as formation of electronically excited atomic photofragments. The vibrational excitation of the molecular ion is explained by autoionization of repulsive superexcited states into the ground state of the molecular ion. In contrast to HCl, the perturbed Rydberg states of HBr show strong participation of the direct ionization process, with ionic core preservation.
Algorithms↗
Atomic polarization in the photodissociation of diatomic molecules.
The angular momentum polarization of atomic photofragments provides a detailed insight into the dynamics of the photodissociation process. In this article, the origins of electronic angular momentum polarization are introduced and experimental and theoretical methods for the measurement or calculation of atomic orientation and alignment parameters described. Many diatomic photodissociation systems are surveyed, in order to provide an overview both of the historical development of the field and of the most state-of-the-art contemporary studies.
Chemical Phenomena↗
A comparison of alcohol ethoxylate environmental monitoring data using different analytical procedures.
Several analytical methods have been developed for analyzing alcohol ethoxylates (AE) in aqueous environmental samples. These methods differ widely in their selectivity and sensitivity for measuring the AE components; that is, they vary in their resolution of alkyl chain length homologs and ethoxymer distributions (degree of ethoxylation for each homolog). Given these differences, AE monitoring results from different studies often are inconsistent and, sometimes, are deemed to be incomparable. To address these differences, three currently available methods for determining AE concentrations in environmental matrices were compared among a common set of wastewater treatment plant samples. These methods included the detection of hydrogen bromide-derivatized homologs by gas chromatography/mass spectrometry, the detection of aqueous homologs by high-pressure liquid chromatography/electrospray mass spectrometry, and the detection of pyridinium-derivatized homologs by high-pressure liquid chromatography/electrospray mass spectrometry. Results from the present study showed that all three methods responded differently in determining the complex suite of chemical species that comprise AE in the environment. The collective information, however, allowed a consistent comparison among the methods. This comparison was then used to reevaluate results from previous AE monitoring studies. Results from this reevaluation provided a more realistic profile of both historical AE removal during wastewater treatment as well as the occurrence of AE in U.S. surface waters.
Alcohols↗
New approaches to toxicity: a seven-gas predictive model and toxicant suppressants.
Two new research approaches in combustion toxicology are: 1. the prediction of smoke toxicity from mathematical equations, which are empirically derived from, experiments on the toxicological interactions of complex fire gas mixtures and 2. the use of toxicant suppressants in materials or products to prevent the formation of toxic combustion products. The predictive approach consists of burning materials using a bench-scale method that simulates realistic fire conditions, measuring the concentrations of the primary fire gases--CO, CO2, low O2, HCN, HCl, HBr, and NO2--and predicting the toxicity of the smoke using either the 6- or 7-gas N-Gas Model. These models are based on the results of toxicological studies of these primary gases as individual gases and as complex mixtures. The predicted toxic potency is checked with a small number of animal (Fischer 344 male rats) tests to assure that an unanticipated toxic gas is not generated or an unexpected synergistic or antagonistic effect has not occurred. The results indicate if the smoke from a material or product is extremely toxic (based on mass consumed at the predicted toxic level) or unusually toxic (based on the gases deemed responsible). The predictions based on bench-scale laboratory tests have been validated with full-scale room burns of a limited number of materials of widely differing characteristics chosen to challenge the system. The advantages of this new approach are 1. the number of test animals is minimized by predicting the toxic potency from the chemical analysis of the smoke, 2. smoke may be produced under conditions that simulate the fire scenario of concern, 3. fewer tests are needed, thereby reducing the overall cost of the testing and 4, information is obtained on both the toxic potency of the smoke and the responsible gases. The N-Gas Models have been developed into the N-Gas Method (described in this paper) and these results have been used in computations of fire hazard. The 6-Gas Model is now part of the international standard ISO 13344 approved by 16 member countries of the International Standards Organization (ISO) and is also included in the U.S. national standard ASTM E1678 approved by the American Society for Testing and Materials (ASTM). In addition, the 6-Gas Model is used in the American National Standard--NFPA 269--approved by the National Fire Protection Association (Quincy, MA). The second new research approach, toxicant suppressants, examines the potential of chemical compounds, which when added to a material, to inhibit or reduce the concentration of a specific toxic gas normally generated during the material's thermal decomposition. The effectiveness of this approach was demonstrated at the National Institute of Standards and Technology (NIST) when HCN generation was reduced by 90% and the resultant toxicity of the combustion products was lowered by 50% when a flexible polyurethane foam (FPU) was treated with 0.1% (by weight) cuprous oxide (Cu2O). Copper and cupric oxide (CuO) also reduced the HCN generation but were not as efficient as Cu2O. Although melamine-treated FPU foams are being promoted as more fire safe than standard foams, a melamine-treated foam generated 10 times more HCN than a foam without melamine. The addition of Cu2O to this melamine foam also reduced the HCN generation by 90%.
Animal Testing Alternatives↗
Reporting degree of deacetylation values of chitosan: the influence of analytical methods.
PURPOSE: To investigate and compare the effect of three analytical methods, hydrogen bromide titrimetry (HBr titrimetry), infrared spectroscopy (IR spectroscopy), and first derivative UV-spectrophotometry (FDUV-spectrophotometry) in the determination of degree of deacetylation (DD) of chitosan. METHODS: Three different chitosan samples were selected for the DD quantification employing HBR titrimetry, IR spectroscopy with samples in the forms of KBr disc (at ratios of 1:2 and 1:3) and thin film (concentrations of 0.5 percent and 1 percent), and FDUV- spectrophotometry. RESULTS: The mean DD values of chitosan samples obtained by HBr titrimetry was significantly lower (p < 0.05) compared to IR spectroscopy using film (concentrations of 0.5 and 1 percent) as well as FDUV-spectrophotometry (purified and unpurified samples), but were significantly higher (p< 0.005) than those obtained using IR spectroscopy using KBr disk except for Chit-S2 computed using baseline (a), which were closely comparable (p > 0.05). In the IR spectroscopic method, the DD values differed when computed using different baseline. It can be observed that the values calculated using baseline (b) was generally higher than those calculated using baseline (a). On the other hand, chitosan samples prepared in the form of film might not be significantly affected by the different baseline as no consistent trend was observed. For FDUV-spectrophotometry, the DD values of purified Chit-S2 samples dried using oven and freeze dryer were comparable and not significantly different (p > 0.05). Similarly, no significant difference was observed for unpurified chitosan samples when dried using freeze dryer and oven (p > 0.05). Furthermore, the DD values of the purified and unpurified chitosan samples dried using freeze dryer were not significantly different except for Chit-S2. CONCLUSION: The DD values of chitosan were highly affected by the analytical methods employed. Hence, we proposed that the quantification method for DD should also be stated when reporting the DD value of chitosan sample.
Acetylation↗
Disinfective action of methyl bromide, methanol, and hydrogen bromide on anthrax spores.
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Anthrax↗
[Determination of hydrogen chloride in the air of the workplace in the presence of hydrogen bromide].
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Air Pollutants, Occupational↗
The synthesis of methyl 3 alpha, 7 alpha-diacetoxy-11-oxo-5 beta-cholan-24-oate.
Reaction of methyl-3 alpha-7 alpha-diacetoxy-11 alpha-bromo-12-oxo-5 beta-cholan-24-oate with sodium borohydride in pyridine solution containing sodium acetate gave the corresponding 11 beta, 12 beta-epoxide in 65% yield. The epoxy-ring was opened with hydrobromic or hydroiodic acid to give the corresponding 12 alpha-halo-11 beta-alcohols, which were converted to the halo-ketones and finally to methyl 3 alpha,7 alpha-diacetoxy-11-oxo-5 beta-cholan-24-oate.
Borohydrides↗
Functionalized nanodiamonds part 3: thiolation of tertiary/bridgehead alcohols.
[reaction: see text] Treatment of acyclic as well as polycyclic tertiary mono- and dihydroxy hydrocarbon derivatives with thiourea in the presence of hydrobromic and acetic acid represents a convenient one-step route to the respective tertiary thiols and dithiols. This procedure was used for the preparation of diamondoid thiols of diamantane, triamantane, [121]tetramantane, and others that are prospective nanoelectronic materials.
Journal Article↗