A simple chemical model for the electron polarization of cyclopentyl radicals produced in radiolysis

The electron polarization of cyclopentyl radicals was observed by Smaller . This paper presents an attempt to account for this observation by an initial polarization mechanism. The mechanism is based on the addition of hydrogen atoms to the product olefin to give the alkyl radicals. The electron polarization of the alkyl radicals arises from the polarized hydrogen atoms. It should be emphasized that the processes leading to polarized H atoms are not established but it is assumed that they are formed initially with the populations in αa_eα_N and α_eβ_N being greater than β_eα_N and β_eβ_N, respectively.     

Photochemische reaktionen. 108. Mitteilung. Photochemistry of N-acylazoles. VI. Photoreactivities of 1-acyl-1,2,4-triazoles and of 2-acyltetrazoles

Contrary to the findings in the photolysis of N-acylimidazoles [2] irradiation of 1-acyl-1,2,4-triazoles afforded no photo-Fries product, but instead products formed via the corresponding acyl radicals and aldehydes. Photolysis of 2-acyltetrazoles gave in part the same products as those obtained from the irradiation of the corresponding acyl-triazoles as well as 2-alkyl-1,3,4-oxadiazoles. N-Acyltetrazoles didn't give any photo-Fries product neither.     

THE U.V. PHOTOLYSIS (Λ= 185nm) OF ETHYLENE GLYCOL IN AQUEOUS SOLUTION*

Abstract— –The u.v. photolysis (Λ= 185 nm) of 2 M aqueous solutions of ethylene glycol was studied at 22°C. Products (quantum yields) are hydrogen (0.20₄) formaldehyde (0.19₄), glycolaldehyde (0.08), methanol (0.07₄), glycerol (0.06), erythritol (0.03), acetaldehyde (0.02), 3,4-dihydroxybutanal (0.01) and succinaldehyde (0.001). With increasing temperature the yields of all products remain essentially unchanged except that of acetaldehyde (φ= 0.32 at 90°C) which is formed in a chain reaction. The photolysis of (CD₂OH)₂ yields 91% HD, indicating that the most important primary process is the homolytic splitting of the O-H bond. The resulting oxy radicals fragmentate largely into formaldehyde and CH₂OH radicals. Molecular fragmentation processes yielding hydrogen and glycolaldehyde, as well as formaldehyde and methanol, are discussed in the proposed decomposition scheme.     

The chemistry of small ring compounds—XX : Cidnp effects in the oxidation of 2,2-dimethylcyclo- propanone methyl hemiacetal

Mild oxidation of 2,2-dimethylcyclopropanone methyl hemiacetal (1) with oxygen, t-butyl- hydroperoxide or di t-butylperoxalate leads to hydrogen abstraction from the OH group of 1. The cyclopropyl ring probably breaks simultaneously to give ring-opened tertiary radical 3a and primary radical 3b. In CDCl₃, CIDNP effects are observed in the saturated disproportionation product of 3a and also in products resulting from disproportionation and combination of 3a with solvent derived CCl3₃ and CDCl₂ radicals. The large difference in g-values between individual radical components in each of these latter pairs explains the observed emissions.In benzene, solvent does not interfere and CIDNP effects mainly arise from radical pairs, consisting of identical components, e.g. two radicals 3a or at least of components with practically equal g-values. Thus disproportionation leads to absorption-emission (multiplets effects) for the unsaturated esters 5 and 6 and the isovalerate 8.     

The Reaction of Peroxynitrite with Morpholine (Secondary Amines) Revisited: The Overlooked Hydroxylamine Formation

The reaction of peroxynitrite/peroxynitrous acid with morpholine as a model compound for secondary amines is reinvestigated in the absence and presence of carbon dioxide. The concentration‐ and pH‐dependent formation of N‐nitrosomorpholine and N‐nitromorpholine as reported in three previous papers ([25] [26] [14]) is basically confirmed. However, ¹³C‐NMR spectroscopic product analysis shows that, in the absence of CO₂, N‐hydroxymorpholine is, at pH ≥ 7, the major product of this reaction, even under anaerobic conditions. The formation of N‐hydroxymorpholine has been overlooked in the three cited papers. Additional (ring‐opened) oxidation products of morpholine are also detected. The data account for radical pathways for the formation of these products via intermediate morpholine‐derived aminyl and α‐aminoalkyl radicals. This is further supported by EPR‐spectrometric detection of morpholine‐derived nitroxide radicals, i.e., morpholin‐4‐yloxy radicals. N‐Nitrosomorpholine, however, is very likely formed by electrophilic attack of peroxynitrite‐derived N₂O₄. ¹⁵N‐CIDNP Experiments establish that, in the presence of CO₂, N‐nitro‐ and C‐nitromorpholine are generated by radical recombination. The present results are in full accord with a fractional (28 ± 2%) homolytic decay of peroxynitrite/peroxynitrous acid with release of free hydroxyl and nitrogen dioxide radicals.     

Catalytic decomposition of azomethane and reactions of adsorbed methyl radicals on the molybdenum surface

The methods of temperature-programmed reaction/desorption (TPR/TPD) are used to study azomethane (CH³N=NCH³) decomposition and the reactions of the products of its pyrolysis (CH ₃ ^* radicals and N₂) on the polycrystalline molybdenum surface. A TPR spectrum of adsorbed azomethane decomposition shows mainly N₂, H₂, and unreacted azomethane. Upon preliminary adsorption of azomethane pyrolysis products on a catalyst sample, a TPR spectrum shows N₂, H₂, and CH₄ in comparable amounts. The difference in the composition of desorption products found for these two types of experiments shows that, in the decomposition of adsorbed azomethane, surface methyl moieties are not formed. The rate constants were calculated for the dissociation of adsorbed CH₃, CH₂, and CH, recombination of hydrogen atoms with each other and with CH₃ and CH₂, and the recombinative desorption of nitrogen atoms. Deceased.     

Disproportionation reactions between alkyl and fluoroalkyl radicals. V. Perfluoro-n-propyl and ethyl radicals revisited

A redetermination of the disproportionation/combination ratio for n–C₃F₇ and C₂H₅ radicals gives a value of Δ(n–C₃F₇, C₂H₅) = 0.13 ± 0.01, independent of the temperature. The radicals were produced by the photolysis of n–C₃F₇COC₂H₅. The previous determinations of this ratio are discussed and are found to be largely incorrect. The values for Δ(CF₃, C₂H₅) and Δ(C₂F₅, C₂H₅) are also re-evaluated, and the recommended values are 0.10 ± 0.02 and 0.12 ± 0.02, respectively. Systems involving perfluoroalkyl and ethyl radicals are complicated due to rapid perfluororadical addition to the ethylene formed in the disproportionation process. The extent of this reaction, and its consequences, are discussed and evaluated. The role of the propionyl (C₂H₅CO) radical in the room temperature photolysis is also assessed. However, it is found that the Δ values determined by the intercept method used in this work are not affected by the secondary reactions that occur. It is concluded that high cross-combination ratios are general to perfluoroalkyl-alkyl radical interactions. For C₃F₇ and C₂H₅ radicals the ratio is 2.7–2.8. Above 100°C ratios exceed 3 due to secondary reactions.     

Bimodal Polyethylenes Obtained with a Dual‐Site Metallocene Catalyst System. Effect of Trimethylaluminium Addition

Bimodal polyethylenes were obtained with the dual site Cp*₂ZrCl₂( 1 )/Et(IndH4)₂ZrCl₂( 2 ) metallocene catalyst system with a mixture of methylaluminoxane (MAO) and trimethylaluminium (TMA) as the cocatalyst. Polymer properties can be controlled by the amount of TMA added, monomer pressure, polymerization temperature and the addition of hexene or hydrogen. TMA is suggested to be partly coordinated to the active sites, thereby enhancing termination ( 1 ), increasing comonomer incorporation ( 2 ), but also partially blocking coordination and chain transfer to hydrogen. For the ansa catalyst, hydrogen probably relieves dormant (β‐agostic) sites.     

High pressure photochemistry of alkenes. 6. the caee of 1-methylcyclopentene at 184.9 and 147.0 nm

The degradaiion of the 184.9 nm photoexcited 1-methyl-1-cyclopentene molecule shows the involvement of various excited isomers. The most important fragmentation products are 1- and 2-methyl-1,3-cyclopentadiene. These products are probably the result of a one-step elimination process of a hydrogen molecule. This process has also been observed in the case of the 184.9 nm photochemistry of cyclopenten. On the other hand, the involvement of isomers, although possible, is not so obvious at 147.0 nm. Moreover, in this case, the 1- and 2-methyl-1,3-cyclopentadiene formation is the result of hydrogen atom elimination in a two-step process. Cyclopentadiene, ethylene, and various C₃ and C₄ compounds are formed as well as methyl radicals and hydrogen atoms. These products are probably formed in successive elimination reactions as this is also observed in acyclic alkenes.     

tert‐Butyl N‐{2‐[N‐(N,N′‐dicyclohexyl­ureido­carbonyl­ethyl)­carbamoyl]prop‐2‐yl}carbamate

The title compound, C₂₅H₄₄N₄O₅, exhibits a turn with the main chain reversing direction, held together by an intramol­ecular N—H?O hydrogen bond. In the urea fragment, a notable amide C—N bond between the carboxyl C and the tertiary N atom shows marked single‐bond character [1.437 (2) Å]. The dihedral angle of the β‐alanyl residue, centrally located in the turn, is gauche [69.2 (2)°]. The packing is mediated by two intermolecular hydrogen bonds and van der Waals contacts involving the methyl moieties and the cyclo­hexyl rings.     

Addition of hot hydrogen atoms to 1-butene in the gas phase and dissociation of excited butyl radicals

The reaction of hot hydrogen atoms originating from 253.7- and 228.8-nm photolyses of hydrogen sulfide with 1-butene was investigated. Of the hydrogen atoms undergoing addition a substantial part undergoes it in a first collision (37 and 48% at 253.7 and 228.8 nm, respectively) yielding highly excited butyl radicals. The ratio of nonterminal to terminal addition is 0.5 and practically does not depend on the energy of the hydrogen atoms over the range of 15–33 kcal/mol. Comparing the results of 229- and 254-nm photolyses of hydrogen sulfide with those of 313- and 334-nm photolyses of hydrogen iodide with the use of the decomposition rate constants of n-butyl radicals calculated by the RRKM methods, the conclusion is reached that the hydrogen atom from H₂S photodissociation has 90–95% of the available energy.     

Ethylene-hexene-1 copolymers through modified phillips catalysis

Copolymerization of ethylene and hexene has been carried out using Phillips' catalysts (chromium oxide deposited on silica) modified with small amounts of triethylaluminium [Al(C₂H₅)₃], without solvent other than hexene itself and under constant ethylene pressure. The copolymers are highly disperse, not only in molecular weight but also in composition; the amount of hexene incorporated in the solid fraction is always less than 4%. Most of the hexene units are in a waxy fraction, which may account for a very high proportion of the copolymer produced. The behaviour of the catalyst is strongly dependent upon the amount of Al(C₂H₅)₃ used.     

New Insight on Carbon Dioxide-Mediated Hydrogen Production**

A new approach to hydrogen production from water is described. This simple method is based on carbon dioxide-mediated water decomposition under UV radiation. The water contained dissolved sodium hydroxide, and the solution was saturated with gaseous carbon dioxide. During saturation, the pH decreased from about 11.5 to 7–8. The formed bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals, preventing the recombination of hydroxyl and hydrogen radicals and prioritizing hydrogen gas formation. In the presented method, not yet reported in the literature, hydrogen production is combined with carbon dioxide. For the best system with alkaline water (0.2 m NaOH) saturated with CO₂ under UV-C, the hydrogen production amounted to 0.6 μmol h⁻¹ during 24 h of radiation.     

Ion and radical reactions in the silane glow discharge deposition of a-Si:H films

A mass spectrometric analysis of the positive ions and neutral products in a silane glow discharge has been performed. The active species, created by dissociation, disproportionation, and ion-molecule reactions are mainly SiH₂, SiH₃, and H. A calculation of the distribution of the SiH _n ⁺ ions shows that the silane concentration monitors the abundance of SiH ₃ ⁺ . The diffusional transport of radicals toward the discharge-tube walls can explain the observed deposition rates. The study of SiH₄-SiD₄ and SiH₄-D₂ plasmas emphasizes several reactions which modify the free-radical populations depending on the discharge conditions: disproportionation, termination, recombination, and abstraction. Heterogeneous reactions have also been observed: etching of the film by H atoms and direct incorporation of hydrogen in the growing film. A general scheme for the plasma deposition mechanism is proposed.     

Thermochemical Aspects of the Conversion of the Gaseous System CO2-N2-H2O into a Solid Mixture of Amino Acids

Conversion of the gaseous mixture CO₂(g)+N₂(g)+H₂O(g) to a solid amino acid condensate in an electric discharge plasma has high efficiency of the energy transfer from the different plasma components into chemical processes. The basic activation process is activation of the N₂ metastable electronic state, followed by formation of NCO* and ON-NCO free-radicals and generation of many reactive radicals. These radicals help to overcome the high activation energy of thermal dissociation of N₂ to N (950 kJ=9.846 eV). The major product is a statistical polycondensate containing the amino acids: arginine, lysine, histidine, methionine, glycine, alanine, serine and aspartic acid. This information was obtained by comparing the IR spectra of the products with reference IR absorption spectra of pure components. Identification of the individual amino acids in the solid product was performed by HPLC, when samples were dissolved using 6 M HCl applied at 100°C for 24 h. Properties of the condensate were estimated using thermogravimetric analysis. Small amounts of oxamidato complexes and oligo pyrrole structures are formed on the electrode surface giving the surface catalytic properties. The gas cleaning process has practical applicability (production of useful fertilizers, reduction of the CO₂ concentration in the atmosphere) and may also contribute to explanation of the origin of life on Earth. This revised version was published online in August 2006 with corrections to the Cover Date.     

Cyclotriphosphazatriene Derivatives. XXIX. Reaction of Cyclophosphazatriene Dichloride With Sodium Hydrosulfide

The chlorine substitution reaction of trimeric dichlorocyclophosphazene with sodium hydrosulfide has been examined. The reaction proceeded easily in dioxane and THF solutions. The reaction product, which had the chemical composition P₃N₃S₆H₆, was examined by ³¹P-NMR and IR spectroscopy. Further, it is suggested that the product was polymerized by heating with hydrogen sulfide, and the polymer (PNS) was formed.     

6‐Amino‐5,5,7‐tri­cyano‐3,3a,4,5‐tetra­hydro‐2H‐indene‐4‐spiro­cyclo­pentane

The positions of the C=C double bonds in the title compound, C₁₆H₁₆N₄, the subject of some dispute in the literature, have been clearly identified. The cyclo­hexene ring has a distorted half‐chair conformation and the cyclo­pentene and cyclo­pentane rings adopt envelope conformations. The dihedral angles between planar fragments of the cyclo­hexene and cyclo­pentene rings and of the cyclo­hexene and cyclo­pentane rings are 7.5 (1) and 86.98 (9)°, respectively. In the crystal, intermolecular N—H?N hydrogen bonds link the mol­ecules into infinite chains running in the [10] direction.     

Combination and disproportionation reactions of allylic radicals with ethyl,propyl, and t-Butyl Radicals

1-Methylallyl, 1,1-dimethylallyl, 1,2-dimethylallyl, 1,3-dimethylallyl, 1,1,2-trimethylallyl, and 1-ethylallyl radicals have been generated in the gas phase at 20 ± 1°C by addition of H atoms, formed by Hg(6³P₁) photosensitization of H₂, to appropriate dienes. Their combination reactions with ethyl radicals have been studied and the relative reactivities of the reaction centers in each allylic radical determined. Similar measurements have been made for some combination reactions of n-propyl, i-propyl, and t-butyl with 1-methylallyl and 1,1,2-trimethylallyl radicals. The more substituted reaction centers are found to be the less reactive. In addition the self-combination and disproportionation of 1-methylallyl radicals has been investigated, as has cross disproportionation of each allylic radical with ethyl. The results establish a general pattern of reactivity for these radicals, which is interpreted primarily in terms of the effects of steric interaction during reaction.     

Disproportionation reactions between alkyl and fluoroalkyl radicals. IV. Pentafluoroethyl and ethyl radicals

A new determination of the disproportionation/combination ratio for C₂F₅ and C₂H₅ radicals gives a value of Δ(C₂F₅, C₂H₅) = 0.24 ± 0.02, independent of temperature. The cross-combination ratio for the two radicals was found to increase with temperature and the significance of this is discussed in evaluating Δ.     

512—Energetics of the chemical coupling between ATP production and oxygen reduction: Comparison with electrochemical data

The chemiosmotic coupling hypothesis of the mechanism of mitochondrial oxidative phosphorylations implies that molecular oxygen is reversibly reduced by four electrons at a time directly to water at potentials near equilibrium values for this redox couple.Since many experimental data show that this is certainly not the case, at least one and probably two ATP per exchanged pair electron must be derived from another kind of coupling mechanism.If one assumes that all intermolecular electron transfers involving more than two electrons at a time and/or any kind of change of covalent topology of relatively heavy atoms are kinetically forbidden, it appears that in fact oxygen must be primarily reduced by the electron-transfer chain to hydrogen peroxide near equilibrium potentials of the O₂(g)|H₂O₂ redox couple. This production of hydrogen peroxide is followed more slowly by its disproportionation.An energetic analysis of the mechanism of this disproportionation, taking into account the proposed kinetic forbidding rule, leads to the conclusion that the production of one or two ATP must be coupled by this catalytic process. Possible coupling enzymes and artificial coupling disproportionation catalysts can be a priori defined by a few functional characteristics.