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  • 1990-1994  (375)
  • 1920-1924
  • 1990  (375)
  • Physical Chemistry  (232)
  • Genetics  (143)
  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Journal of insect behavior 3 (1990), S. 579-587 
    ISSN: 1572-8889
    Schlagwort(e): Genetics ; polymorphism ; reproductive isolation ; hovering behavior ; Tabanus nigrovittatus
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract The salt marsh horse fly, Tabanus nigrovittatusMacquart, exhibits two nonoverlapping daily periods of hovering and mating activity, which are correlated with different environmental temperatures. Allelic and genotypic frequencies of hovering males collected during the two periods were compared by electrophoresis of three polymorphic enzyme loci. Approximately 26% of early-hovering males possessed a Pgmallozyme that was absent in our sample of late-hovering males. However, based on other allozyme loci, we found no evidence for reproductive isolation between early and late hoverers. All the genetic data are consistent with the hypothesis that the Pgmpolymorphism is associated with behaviorally and physiologically distinct groups of males that, by all other criteria, form a single Mendelian population.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Pediatric surgery international 5 (1990), S. 359-360 
    ISSN: 1437-9813
    Schlagwort(e): Hirschsprung's disease ; Genetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Three male children with identical short-segment Hirschsprung's disease born to a young married couple are reported. There was no positive family history despite an extensive search. There were no associated abnormalities. Although sex-modified multifactorial inheritance, with males having a lower threshold of genes for expression of Hirschsprung's disease, is accepted, the identical expression of the disorder in the three siblings presented suggests a dominant, possibly X-linked gene with variable penetrance. Another possibility is that an identical micro-environmental factor was present prenatally resulting in all three boys having Hirschsprung's disease. This is the first report of three siblings with identical short-segment Hirschsprung's disease.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Pediatric nephrology 4 (1990), S. 533-541 
    ISSN: 1432-198X
    Schlagwort(e): Henoch-Schönlein purpura ; Pathogenesis ; Genetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Laboratory studies of the pathophysiology of Henoch-Schönlein purpura (HSP) have become more numerous in recent years with the recognition of the disease's links with the mucosal immune system in general and IgA nephropathy in particular. There are weak genetic associations with C4 null phenotypes and with HLA B35 and DR4. Studies of plasma proteins in HSP patients show an increased IgA concentration, activation of the alternative pathway of complement and consumption of factor XIII. High molecular weight (polymeric) IgA has been detected in affected individuals, which some investigators have called “immune complexes”. Many patients synthesise an IgA rheumatoid factor in the acute phase, but other autoantibodies are largely absent. In vitro studies of lymphocytes from HSP patients have demonstrated an increased number of IgA-bearing and secreting B-cells, with altered T-cell regulation of antibody synthesis. While these observations point to immune dysregulation — primarily of IgA production — as a consistent feature of acute HSP, there is as yet insufficient information available to allow a consistent theory of pathogenesis to be formulated.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Sexual plant reproduction 3 (1990), S. 31-34 
    ISSN: 1432-2145
    Schlagwort(e): Mucoraceae ; Zygomycetes ; Homothallic ; Genetics ; Nutritional complementation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary Auxotrophic strains of Mucor genevensis and Zygorhynchus exponens were crossed and the resulting zygospores germinated. The presence of a true sexual cycle in both species was demonstrated by the recovery of recombinant genotypes. Expected Mendelian ratios were not realized, however. The presence of selfed zygospores among those isolated makes this observation understandable. It was possible to demonstrate nutritional complementation when young mating mycelium was transferred to minimal medium and forced heterokaryons were recovered.
    Materialart: Digitale Medien
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  • 5
    ISSN: 1432-1076
    Schlagwort(e): Osteogenesis imperfecta ; Collagen type I ; Radiology, classification ; Genetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Abstract Congenital osteogenesis imperfecta (OI) was diagnosed by ultrasound in a 31-week-old fetus, and the diagnosis confirmed after delivery by caesarean section at week 36. The baby survived the neonatal period, but failed to thrive, had recurrent respiratory infections and ultimately died at 8 months. Cultured fibroblasts synthesized both normal type I collagen and unstable type I collagen harbouring a structural defect in the α1(I) cyanogen bromide-derived peptide number 8 (CB8) region of the molecule, indicating a heterozygous dominant mutation. A+ birth, the radiological picture was that of the “thin bone”-type of congenital OI (OI type IIB/III in the Sillence classification); at the age of 12 weeks ribs and long bones had undergone a marked expansion giving a very different picture, that of the “thick bone”-type congenital OI (OI type IIA). The mechanism responsible for this change in bone structure is not known, but fractures and callus formation are unlikely to be the only factors. Caution is needed in the interpretation of radiographs of newborns with OI for prognostic or genetic purposes.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Journal of comparative physiology 166 (1990), S. 545-552 
    ISSN: 1432-1351
    Schlagwort(e): Honeybees ; Learning ; Classical conditioning ; Selection ; Genetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Summary Four strains of the honeybee (Apis mellifera capensis), which were selected for high (N=2) or low (N=2) performance levels in classic conditioning of olfactory and mechanosensory stimuli, were examined in two instrumental visual learning tasks. Bees were trained to coloured cardboards either at the hive entrance or at the feeding station. Positive correlations were detected between olfactory/mechanosensory conditioning and visual learning. Good and poor learners from strains selected for olfactory conditioning differed significantly in their visual learning values. These strain differences reflect genetic differences in a common learning system rather than task specific differences in sensory, motor or motivational components. Parameters that were influenced by activity of the colony (duration of stay at the feeding place, time between visits) also differed among selected strains. These effects were not due to selection. Instead, they reflect a specific genetic background produced in each strain independently of selection. The results indicate that associative learning has a genetic basis which is independent of the sensory stimuli associated with reward, the learning procedure (classical conditioning or instrumental learning) or the motor patterns used to execute the learned behavior (proboscis extension, control for flight behavior, open field orientation).
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    European archives of psychiatry and clinical neuroscience 239 (1990), S. 290-292 
    ISSN: 1433-8491
    Schlagwort(e): Schizophrenia ; Linkage ; Genetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary We analysed six multiplex pedigrees of schizophrenia for linkage to two DNA probes mapping to the chromosome 5q11–q13 region where linkage to a gene for schizophrenia was recently reported. Analyses were conducted using three penetrance models and considering the affected state to be schizophrenia, the schizophrenia spectrum, and all psychiatric diagnoses. All analyses gave consistently negative lod scores. Although the region was not formally excluded, no evidence for linkage was found.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Journal of neurology 237 (1990), S. 345-351 
    ISSN: 1432-1459
    Schlagwort(e): Spinocerebellar degeneration ; Friedreich's disease ; Diagnostic criteria ; Genetics ; Natural history
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin
    Notizen: Summary The clinical and genetic features of 80 patients with Friedreich's disease from 64 families are described. Diagnostic criteria were: no evidence of dominant inheritance, onset by the age of 20 years, progressive unremitting ataxia of limbs and gait, and absence of knee and ankle jerks. Furthermore, at least one of the following accessory signs was present: dysarthria, extensor plantar response and echocardiographic evidence of hypertrophic cardiomyopathy. Two peaks of onset age were evident at 6–9 and 12–15 years. Analysis of intrafamily variation of onset age and absence of clustering of cardiomyopathy and diabetes did not suggest genetic heterogeneity. Peripheral nerve impairment was an early finding and showed slight further progression, whereas involvement of the cerebellar and corticospinal pathways appeared later and mainly accounted for the progressive worsening of the disease.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Journal of classification 7 (1990), S. 53-75 
    ISSN: 1432-1343
    Schlagwort(e): Analysis of variance ; Choropleth map ; Ecology ; Genetics ; Geography ; Permutation test ; Spatial autocorrelation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Mathematik
    Beschreibung / Inhaltsverzeichnis: Résumé Cet article présente une solution au problème de l'analyse de variance, pour certains cas où la variable à analyser est spatialement autocorr élée alors que le critère de classification représente des sous-régions connexes du territoire à l'étude. On sait que les méthodes classiques d'analyse de variance ne sont pas applicables dans ce type de situation puisque la condition d'indépendance des échantillons n'est pas respectée; l'autocorrélation positive réduit la variabilité intragroupe, si bien que la quantité relative de variabilité intergroupe s'en trouve artificiellement augmentée. Cette situation correspond en réalité à une vaste catégorie de problèmes en génétique des populations, en écologie et dans d'autres branches de la biologie, ainsi qu'en épidémiologie, en géographie, en géologie, en science économique, en science politique et en sociologie. Ce nouveau test appartient à la famille des tests par permutation. Nous calculons la somme des dispersions intragroupes et testons contre une distribution de référence obtenue en permutant les régions géographiques un grand nombre de fois sur la carte. La véritable difficulté de ce test est d'ordre algorithmique, puisqu'il n'est pas facile de permuter des régions sur une carte, de façon à ce que chaque groupe demeure connexe, et que la carte permutée occupe le même espace total que la carte d'origine. Cet article présente la théorie, les algorithmes, ainsi que des résultats obtenus par cette méthode. Un programme écrit en PASCAL est disponible.
    Notizen: Abstract The classical method for analysis of variance of data divided in geographic regions is impaired if the data are spatially autocorrelated within regions, because the condition of independence of the observations is not met. Positive autocorrelation reduces within-group variability, thus artificially increasing the relative amount of among-group variance. Negative autocorrelation may produce the opposite effect. This difficulty can be viewed as a loss of an unknown number of degrees of freedom. Such problems can be found in population genetics, in ecology and in other branches of biology, as well as in economics, epidemiology, geography, geology, marketing, political science, and sociology. A computer-intensive method has been developed to overcome this problem in certain cases. It is based on the computation of pooled within-group sums of squares for sampled permutations of internally connected areas on a map. The paper presents the theory, the algorithms, and results obtained using this method. A computer program, written in PASCAL, is available.
    Materialart: Digitale Medien
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  • 10
    ISSN: 1432-2242
    Schlagwort(e): Genetics ; Symbiosis ; Nitrogen fixation ; Coevolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary To determine the relationship between nodulation restriction by the Rj4 allele of soybean, rhizobitoxine-induced chlorosis, and taxonomic grouping of bradyrhizobia, 119 bradyrhizobial isolates were tested in Leonard jar culture for nodulation response and chlorosis induction. In addition to strain USDA 61, the strain originally reported as defining the Rj4 response, eight other isolates (i.e., USDA 62, 83, 94, 238, 252, 259, 260, and 340) were discovered to elicit the nodulation interdiction of the Rj4 allele. Only 16% of all the bradyrhizobial strains tested induced chlorosis, but seven of the nine strains (78%) interdicted by the Rj4 allele were chlorosis-inducing strains. Furthermore, in tests for antibiotic resistance profile, eight of the nine interdicted strains (89%) were classed in DNA homology group II. This evidence suggests that the Rj4 allele has a positive value to the host plant in shielding it from nodulation by certain chlorosis-inducing bradyrhizobia of a DNA homology group with impaired efficiency of nitrogen fixation with soybean.
    Materialart: Digitale Medien
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  • 11
    ISSN: 1432-2242
    Schlagwort(e): Beta vulgaris ; Sugar beet ; Isozymes ; Genetics ; Linkage ; Pollen fertility restorer
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Summary The NADP-specific malate dehydrogenase isozymes were controlled by multiple gene systems. Three genes coding for dimeric enzymes segregated in a dependent fashion (NADP-Mdh 1, NADP-Mdh 2, NADP-Mdh 3). A fourth gene (NADP-Mdh 4), also coded for dimers, but was not polymorphic in B. vulgaris. A fifth gene (NADP-Me 1) coded for enzymes active as monomers. Two genes were found to control the main zone of NAD-specific malate dehydrogenase: one coded for dimers (Mdh 1), while a second (Mdh 2) was not polymorphic in the assessions studied. 6-P-Gluconate dehydrogenase was not polymorphic in B. vulgaris; the two types detected on SGE1 electrophoresis were due to developmental expression of the different systems. No genetical segregations could be detected in progeny of crosses of the distinct phenotypes. A shikimate dehydrogenase gene (Skdh 1) that coded for monomers was identified. The diaphorase system was rather complex, but one gene (Dia 1) coding for monomeric enzymes could be identified. Aconitase was found to be controlled by two independent genes (Aco 1, Aco 2), both polymorphic and coding for proteins active as monomers. Tight linkage was found between the genes NADP-Mdh 1, NADP-Mdh 2 and NADP-Mdh 3. Linkage was also found between a pollen fertility restorer (Z) and the Mdh 1 gene. The identification of linkage with Aco 1 needs further investigation. R segregated independently from Mdh 1, Aco 1 and Dia 1. Independent segregations were scored for isozyme genes Pgm 2, Icd 1, Ak 1, Gpi 1, Aco 1 and Dia 1.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Biology and philosophy 5 (1990), S. 349-371 
    ISSN: 1572-8404
    Schlagwort(e): Genetics ; gene structure ; hereditary unit
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Philosophie
    Notizen: Abstract Definitions of the term ‘gene’ typically superimpose molecular genetics onto Mendelism. What emerges are persistent attempts to regard the gene as a ‘unit’ of structure and/or function, language that creates multiple meanings for the term and fails to acknowledge the diversity of gene architecture. I argue that coherence at the molecular level requires abandonment of the classical unit concept and recognition that a gene is constructed from an assemblage of domains. Hence, a domain set (1) conforms more closely to empirical evidence for genetic organization of DNA regions capable of transcription and (2) has ontological properties lacking in the traditional unit definition.
    Materialart: Digitale Medien
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  • 13
    ISSN: 1573-5133
    Schlagwort(e): Demography ; Genetics ; Geographic variation ; Stochasticity ; Fluctuating environments ; Allele frequencies ; River ecology
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Synopsis The purpose of this study was to determine the effects of unpredictable environmental fluctuations on the demographic and genetic structure of Fundulus zebrinus populations. Collections of F. zebrinus were taken from three rivers in the Arkansas River basin: the Arkansas, Chikaskia, and Ninnescah. Fish were sampled from three sites on each river on nine collection dates throughout 1984 and 1985. Totals of 2100 fish and 6000 fish were included in electrophoretic and demographic analyses, respectively. The results of the study indicate that within a limited geographic region (i.e. within rivers) spatial differences and temporal changes in both demographic and genetic population characteristics occur frequently and are primarily stochastic. However, on a larger spatial scale (i.e. across rivers), general trends emerge for demographic and especially for genetic population characteristics. These results illustrate the importance of sampling scale for conclusions of life-history evolution in fluctuating environments. In addition, it was found that regulation of Fundulus zebrinus populations includes an important density-independent component. Stochastic demographic differences across space and changes through time and spatially and temporally heterogeneous allele frequencies, are both indicative of density-independent regulation. Variation in population parameters, both demographic and genetic, was observed between populations sampled from each river. These population differences were attributed to differences between the rivers themselves.
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Journal of chemical ecology 16 (1990), S. 2935-2946 
    ISSN: 1573-1561
    Schlagwort(e): Genetics ; sex pheromone ; Lepidoptera ; Noctuidae ; Trichoplusia ni ; cabbage looper moth ; reproductive isolation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract The genetic basis of interpopulational differences in the pheromone blend emitted by the cabbage looper moth,Trichoplusia ni (Hübner), was examined by crossing individuals from a field-derived population (P1) with individuals from a long-maintained laboratory colony (P2). These colonies differed in the emission rate and relative proportions of four of the five known minor pheromone components, but not in the emission rate of the major component, (Z)-7-dodecenyl acetate (Z7-12∶Ac). These differences in pheromone blend were quantitatively small but biologically significant, because in the field, males responded preferentially to traps baited with a pheromone blend that is similar to that emitted by P1 females relative to a blend similar to that emitted by P2 females. In initial crosses, variation in the quantity and quality of pheromone blends among families of P1, P2, and F1 hybrid females was examined. In F1 females the relative proportions (quantity relative to the major component) of (Z)-5-dodecenyl acetate (Z5-12∶Ac) and (Z)-7-tetradecenyl acetate (Z7-14∶Ac) were intermediate to parental lines. In a second more extensive set of crosses, analyses included P1, P2, F1, F2, and selected backcrosses. The relative proportion of Z5-12∶Ac, Z7-14∶Ac, and Z9-14∶Ac emitted by F1 females were intermediate to parental lines. The frequency distributions of relative proportions of these components emitted by females were not consistent with those expected under a single autosomal or sex-linked gene hypothesis, suggesting that more than one gene is involved in the quantitative differences in the pheromone blend.
    Materialart: Digitale Medien
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  • 15
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 17-22 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A large number of 1,n-bis(alkylthio)alkanes, R′S(CH2)nSR″, was investigated by pulse radiolysis in aqueous solutions. The sulphur-centred radical cations, which were obtained on oxidation of the dithia compounds by ·OH radicals, are stabilized via 2σ/1σ* three-electron interaction between two sulphur atoms. Intramolecular stabilization is the only process observed for n = 2-4, whereas for longer chain compounds with n 〉 4 some intermolecular sulphur-sulphur interaction is also indicated. The stability and yields of the three-electron-bonded species also depend on the nature of the substituents R′ and R″, and for the intermolecular systems are a function of solute concentration. The results corroborate earlier investigations and demonstrate, in particular, that the optical parameters are a very sensitive measure of changes in electron density and structure of the three-electron-bonded systems.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 16
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 23-34 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The stereochemistry and mechanism of solvolysis of optically active tert-butylphenylphosphinothioic-O-trifluoromethanesulphonate (1) in solvents of different ionizing power were studied. It was found that in solvents of high ionizing power and low nucleophilicity 1 ionizes with the formation of a phosphathiacylium cation (2) as the reaction intermediate. Product resulting from the reaction of 2 with anisole was isolated and characterized.
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  • 17
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 35-37 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Studies on the stereochemistry of silver-ion-assisted solvolysis of a new optically active tert-butylphenylphosphinothioic iodidate demonstrated that the reaction proceeds with inversion of configuration at the phosphorus atom. Evidence for phosphathiacylium cation formation as a reactive intermediate is presented.
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  • 18
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 38-40 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Studies on the photochemically induced hydrogen-tritium exchange in o-methyl-substituted phenyl ketones are reported. It is shown that the tritium exchange can be beneficial for probing transient photoenol formation, particularly when photochemical side-reactions are occurring.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 19
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Alkaline hydrolysis of diethyl alkylphosphonates and alkyl diethylphosphinates was studied in aqueous dimethyl sulphoxide. The behaviour of these acyclic phosphorus esters is very similar to that of some cyclic phosphorus esters. Rate constants were measured at three temperatures over a 30°C range, and the activation functions of the reaction were estimated. The basic hydrolytic process was proved to be a bimolecular AE reaction. Multiple regression analyses involving rate constants and substituent parameters gave, as a rule, poor results using steric constants derived from carbon compounds. However, the substituent steric effect on the rate of hydrolysis of phosphonates and phosphinates studied correlated very well with ΔΔE, representing the difference in steric energy calculated by molecular mechanics. It is attributed to the various degrees of susceptibility of carbon and phosphorus atoms to the steric hindrance of the substituents. Moreover, Newman's rule of six for the hydrolytic reaction of carboxylates was completely eliminated in phosphorus ester hydrolysis.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 20
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 62-68 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The free energy dependence of the kinetic deuterium isotope effect of proton-transfer reactions in solution is usually analysed in terms of the Marcus model. By means of modern computer techniques, the more general quantumstatistical mechanical model is also amenable to routine application. The differnces in the basic assumptions of the two approaches concerning the kinetic isotope effect are discussed. Reaction series for which both the Brønsted relation and the free-energy dependence of the kinetic isotope effect are available are analysed by means of the two models using one set of parameters for both free-energy relations.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 21
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 69-76 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Strong 1H and 13C nuclear polarizations are observed when aqueous solutions of synthetic water-soluble porphyrins are irradiated in the presence of tyrosine and some of its derivatives. These polarizations are strongly pH dependent. Evidence is also shown for the formation, in the dark, of a complex between the reactants. The association constants are evaluated from the NMR chemical shifts on the aromatic tyrosine protons induced by the presence of the porphyrins. The nature of the intermediate radical pair generating the CIDNP effects is discussed. An electron-transfer reaction from tyrosine to the excited triplet state of the porphyrin, or within the porphyrin-tyrosine excited complex, is expected to be the primary step in the reaction. It is followed by subsequent proton transfer within the initial ion radical pair. The spin polarizations arise principally from the back-transfer step, as the reactants are the only products which are polarized.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 22
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 95-109 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The intersecting-state model previously used to interpret proton transfers in ground and excited states and enzyme catalysis was applied to the general acid-base catalysis of carbon acids. The results are consistent with the predictions published for these systems and provide a new physical meaning for the Brønsted coefficients. It is shown that in addition to the linear free energy effect, the Brønsted coefficients are also influenced by the tightness of the transition states and by electronic effects. The model suggests that the increased reactivity of carbon acids towards proton transfer in non-hydrogen-bonding solvents is caused by an added electronic effect on the thermodynamics of the reactions. The curvatures of the Brønsted plots are interpreted in terms of an entropic contribution to the position of the transition state.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 23
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 110-118 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Gas-phase nitration of thiophene (1) and N-Methylpyrrole (2) was studied by radiolytic tecniques, supported by chemical ionization mass spectrometry. The substrate and positional selectvities of protonated alkyl nitrtes (CH3NO3H+, CF3CH2NO3H+) were deduced from competitive reactions with bezene performed under different conditions. The apparent kS/kB ratios, which are independent of the pressure and unaffected by the presence of a strong base (NEt3), depend on the nature of the electrophile, passing for 1 and 2 from 7·2 and 6·4, respectively, with CH3NO3H+ to 1·1 and 1·0, respectively, with the more reactive fluorinated caution. Predominant (88%) α-substitution takes place in 1, whereas no appreciable positional discrimination is displaced by 2. The results suggest that the electrophilic attack can also occur a the heteroatom, and point to the same mechanism postulated for gasphase nitration of aromatic substrates, the reactivity being essentially governed by electrostatic interactions within the ‘encounter pair’.
    Zusätzliches Material: 2 Ill.
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  • 24
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 485-488 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The interconversion between two equivalent enol forms of 3-hydroxyphenalenone took place predominantly through a diketo form with a free energy of activation of ca 14 kcal mol-1 in DMSO solution determined by 125·8 MHz13C NMR measurement. On the other hand, the corresponding interconversion in 2-carboxy-3-hydroxyphenalenone was not frozen on the time scale of 13C NMR spectroscopy down to -60°C. This acceleration in the interconversion rate of the latter may be interpreted by a double proton switching between the hydrogen-bonded 2-carboxyl and 3-hydroxyenone moieties.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 25
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Literature data on the change in the selectivity values, kE/kw, for several solvolysing systems in ethanol (E)-water (W) on addition of acetone were analysed. It is suggested that acetone acts as a basic cosolvent for both ethanol and water and that the change in the activity coefficients on changing the solvent composition is mainly responsible for the observed effect.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 26
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The kinetics of reactions between 2-phenylethyl benzenesulphonates (2-PEB) and benzylamines in acetonitrile at 65·0°C have been studied; the mechanism was examined on the basis of the sign and magnitude of cross-interaction constants ρij and βij. In contrast to the reactions of 2-PEB with anilines in methanol, participation of the aryl-assisted pathway was negligible, with a strong indication that the reaction proceeds largely by an intermolecular SNi mechanism with a four-centre transition state (TS). The effect of substituents on the TS variation was in accord with the predictions of the quantum mechanical model.
    Zusätzliches Material: 6 Tab.
    Materialart: Digitale Medien
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  • 27
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 534-544 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The solvent polarity of a series of organic salts in their molten state has been determined using the solvatochromic dyes: pyridinium N-phenolate betaine, the basis of the ET scale, and N,N-diethyl-4-nitroniline, one of the primary standards for the π* scale. Each of these dyes was dissolved in the following liquids: lithium acetate-sodium acetate-potassium acetate eutectic; ethylammonium chloride; dimethylammonium cloride; diethylammonium nitrate; ammonium trifluoracetate; tetraethylammonium acetate; tetrabutylphosphonium chloride; octyltributylphosphonium chloride; dodecyltributylphosphonium chloride; tetrabutylammonium bromide; tetrabutylphosphonium bromide; octyltributylphosphonium bromide; dodecyltributylphosphonium bromide; octyltributylphosphonium iodide; dodecyltributylphosphonium iodide; tetrahexylammonium benzoate; methyltrioctylphosphonium dimethylphosphate; and methyltrioctylammonium chloride. The ultraviolet and visible spectra were measured for each of these. In addition, data were collected as a function of temperature and in the presence of neutral and ionic additives. In general, these molten salts represent solvent polarities equivalent to moderately polar aprotic solvents such as acetone and acetonitrile. The salts with cations capable of being hydrogen bond donors gave considerably higher values, equivalent to or higher than water, the solvent with the highest value on the ET scale. These and the eutectic mixture are thought to involve specific dye-solvent interactions which cause these anomalously high values.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 28
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 581-586 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Pyrimidine dimers, which form by a symmetry allowed (πs2 + πs2) photocycloaddition reaction, are subject to photosensitized cycloreversion by electron donors, such as indoles. In a linked dimer-indole system, photoinitiated electron transfer occurs intramolecularly from indole to dimer to produce a charge-separated species (dimer-.-indole+.). This species undergoes cycloreversion in competition with back electron transfer. Studies of the temperature dependence and solvent dependence of this competition have allowed the relative values of the activation parameters for the competing processes to be determined. In water (5-65°C) the free energy of activation of splitting minus that of back electron transfer (ΔΔG≠ = ΔGspl≠ - ΔGbet≠) was found to be 1·3 kcal mol-1. The enthalpy of activation difference (ΔΔH≠) was found to be 1·1 kcal mol-1 and the entropy of activation difference (ΔΔS≠) was found to be -0·51 cal mol-1 K-1. In EPA (diethyl ether-isopentane-ethanol, 5:5:2; -85 to 25°C) the value of ΔΔG≠ remained the same, but the entropy and enthalpy contributions were different (ΔΔH≠ = 0·72 kcal mol-1; ΔΔS≠ = -1·8 cal mol-1 K-1). The results have been interpreted in terms of the effect of the polarity of the solvent on the transition states for the two competing processes. Enthalpy effects retard splitting more in water than in EPA, whereas entropy effects favor back electron transfer more in EPA than in water. Potential implications of these results for the mechanism of enzymatic photocycloreversion of pyrimidine dimers in DNA are considered.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 29
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 30
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 627-634 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The reactions of a series of 3-(p-substituted phenyl)-1-phenylprop-2-yn-1-ones with piperidine and morpholine in methanol were studied and their rates measured. The products were 3-piperidino- and 3-morpholino-3-(p-substituted phenyl)-1-phenylprop-2-en-1-ones. 1H NMR spectra were used to determine the configurations of the obtained products. A good Hammett correlation was obtained with ρ values of 1·15-1·10 and 1·15-0·53 for piperidine and morpholine, respectively, which suggest a carbanionic character of the transition state. A two-step mechanism is postulated for these nucleophilic additions.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 31
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The 19F NMR spectra of 30 substituted α,β,β-trifluorostyrenes (Y-TFSs, 1) covering a diverse range of substituents are reported and discussed. Values (δF1, δF2, Δδ3 - 1 and Δδ3 - 2) derived from the 19F NMR chemical shifts of the fluorine atoms of 1 are found to correlate very well with σI and σR0. The results of the correlations of the 19F chemical shifts with dual (σF and σR) and triple parameter (σF, σR and σα) treatments are compared. An unresolved substituent parameter σmb, is proposed for applications to systems in which the substitutent Y interacts with a multiple bond and is compared with σ+.
    Zusätzliches Material: 1 Ill.
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  • 32
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Direct kinetic measurements of the C-protonation rates of 1,2,5-trimethyl- and 3,4-dimethyl-pyrroles allow the first comparison of the relative kinetic proton affinities of unsubstituted and substituted positions of the pyrrole ring.
    Zusätzliches Material: 1 Tab.
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  • 33
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 697-702 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The potential energy surface for the addition of the hydride ion to hydrogen isocynide reported previously was re-examined. An improved energy surface was explored at the MP2/6-31 + + G** level while relative energies were estimated at the MP4SDTQ/6-311 + + G** level and corrected for zero-point vibrational contributions. The calculated results show the existence of transition structures for both cis and trans-additions of H- to the carbon end of HN≡C even though the corresponding barrier heights are small. These transition structures did not exist at a lower level of theory (HF/4-31G) employed previously.The cis addition is calculated to be favoured over the trans addition by 10 kcal mol-1. The overall addition is thus strongly stereoselective, if not purely stereospecific. This result confirms our previous analysis of the stereoelectronic effect in the addition-elimination process involving imidoyl anions as intermediates. Recent experimental work on the addition of OH- to ArN≡C is discussed.
    Zusätzliches Material: 2 Ill.
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  • 34
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The peak potentials of substituted α,α,α-trifluoroacetophenones were measured in acetonitrile with 0·1 M tetrabutylammonium perchlorate. The cyclic voltammograms indicated an irreversible electrochemical process for the first wave (Epc1) and a partially reversible one for the second wave (Epc2) when the scan rate was slower than 100 mV s- 1. Excellent linear correlations were observed for Epc1 with σ constants (ρ = 0·526, r = 0·999) and for Epc2 with σ- constants (ρ = 0·605, r = 0·998), respectively. Therefore, unknown σ values such as -0·36 for 3, 4-ethyleneoxy can be estimated from these correlations. The mechanism of the electrode process probably involves a single electron transfer and the formation of a pinacol.
    Zusätzliches Material: 7 Ill.
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  • 35
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 746-750 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The deprotonation reaction mechanism of methyl diethylphosphonoacetate in the presence of lithium salts and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was examined by infrared spectroscopy. It was found that the intermediate species formed by chelation of the bidentate phosphonate with a lithium cation or an ion pair of the salt deaggregated by DBU takes part in the reaction path. The role of the anion X- is to induce the elimination of a protonated DBUH+X- ion pair and that of the solvent is to compete with the bidentate phosphonate in cation solvation. A similar mechanism via a related intermediate is proposed to interpret the results obtained by other workers on the catalysis by Ba(OH)2 of the Wittig-Horner reaction.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 36
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 765-783 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The enumeration and development of conceptual tools for understanding the chemical properties of practical benzenoid hydrocarbons is stressed. Currently known isomer numbers for benzenoids having up to 60 carbons are summarized. Although there are well over 2 million isomers in this range, only approximately 500 benzenoid hydrocarbons have been characterized.
    Zusätzliches Material: 8 Ill.
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  • 37
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 789-798 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The acetylation (with acetic anhydride-pyridine in tetrahydrofuran) of the ortho, meta and para isomers of bis(hydroxymethyl)benzene (1) was studied. Third-order rate constants k1 (formation of monoacetate 2 from 1) and k2 (formation of diacetate 3 from 2) for all three isomers were determined, as were the rate constants for acetylation of benzyl alcohol and its ortho- and para-ethyl derivatives under the same conditions. The compositions of the final product mixtures (comprising 1, 2 and 3) were ascertained as a function of the initial ratio of acetic anhydride to 1. Comparisons were made with predictions based on a previously published independent functional groups model, which assumes that k2/k1 = 0·50. All three isomers gave product mixtures whose compositions were in generally good agreement with predictions based on the model. For the para and meta isomers the ratios k2/k1 were determined experimentally to be 0·548 and 0·521, respectively. The k2/k1 ratio for the ortho isomer was found to be 0·605, and its k1 and k2 values were lower than those for the para and meta isomers. Possible explanations for the anomalous behavior of the ortho isomer are discussed.
    Zusätzliches Material: 1 Ill.
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  • 38
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 812-816 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Chlorocyclohexane does not react in the dark with diphenylphosphide ions in liquid ammonia, but it reacts under irradiation to give the substitution product. Bromocyclohexane reacts slowly in the dark, but this reaction is strongly accelerated by light, and inhibited by p-dinitrobenzene. 3-Bromo-2-tetrahydropyranyl allyl ether (used as a radical probe) reacts with diphenylphosphide ions under irradiation to give both the straightforward and the cyclized substitution products. This photostimulated reaction is also inhibited by p-dinitrobenzene. It is suggested that the chlro-bromocyclohexanes and related compounds react under irradiation by the SRN1 mechanism of nucleophilic substitution.
    Zusätzliches Material: 2 Tab.
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  • 39
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 40
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 260-265 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Subtilisin BPN′ catalyzes the hydrolysis in protium and deuterium oxides of p-NO2C6H4OCOCL2NHCO2CH2C6H5(L = H, D) in the pH(D) range 5·0-8·5 (H2O) and 5·4-9·0 (D2O), according to simple Michaelis-Menten kinetics. The parameter kcat/Km exhibits pH(D) inflection points of 7·17 ± 0·05 (H2O) and 7·69 ± 0·08 (D2O), and kcat shows 6·88 ± 0·05 (H2O) and 7·50 ± 0·07 (D2O). The ‘normal’ ΔpK values of 0·5-0·6 indicate no unusual effects of D2O on enzyme properties. The solvent isotope effects (H2O/D2O) on the limiting values of the rate constants at high pH(D) are 1·13 ± 0·07 for kcat/Km and 1·29 ± 0·05 for Kcat. These small effects indicate no more than minor contributions of general acid-base catalysis for rate-limiting events for either kcat/Km or kcat. The β-deuterium secondary isotope effects (2H/2D) are roughly estimated by extrapolation as 0·95 ± 0·01 for kcat/Km, corresponding to substantial tetrahedral character in the transition state, and 1·03 ± 0·03 for kcat, consistent with no tetrahedral character. Models consistent with these results have as rate-limiting events for kcat/Km nucleophilic attack by active-site imidazole and for kcat, among other possibilities, the release of carboxylate product from the imidazolium form of the enzyme.
    Zusätzliches Material: 2 Ill.
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  • 41
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 279-284 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The gas-phase thermal decomposition of diacetyl compounds, (CH3CO)2X with X = O and S, was investigated theoretically using the semiempirical MO methods MNDO and AM1. The initial decomposition of the diacetyl compounds proceeded through a six-membered ring transition state involving the keto form with a slightly lower activation enthalpy for diacetyl sulphide (X = S); the process via an enolic form of the transition state was kinetically unfavourable. In the initial decomposition of the diacetyl compounds and in the subsequent pyrolysis of acetic and thioacetic acid, ketene formation was found to be the most preferred path, where the ease of Cα—X bond cleavage is relatively more important than nucleophilic attack on the β-hydrogen in determining the overall reactivity. In the methane formation process, the reactivity was entirely dependent on the X—H bond strength in CH3COXH where X = S, NH and O.
    Zusätzliches Material: 6 Tab.
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  • 42
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The antioxidant activity of 2-hydroxyestradiol was measured quantitatively and compared with those of other estrogens in oxidations of methyl linoleate in homogeneous solution and in aqueous dispersions, oxidations of soybean phosphatidylcholine liposomal membranes and oxidative haemolysis of rabbit erythrocytes, all induced by free radicals generated from a radical initiator. Similar antioxidant activities of estrogens were observed, irrespective of the oxidation system. 2-Hydroxyestradiol was found to be a potent radical scavenger and its antioxidant activity was close to that of α-tocopherol, the strongest natural antioxidant. Other phenolic estrogens such as estrone, estriol and β-estradiol showed a modest antioxidant activity and testosterone did not act as an antioxidant.
    Zusätzliches Material: 5 Ill.
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  • 43
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 339-345 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 2-Diazopropane, generated by photolysis of 2-methoxy-2,5,5-trimethyl-Δ3-1,3,4-oxadiazoline, was trapped in situ by cycloaddition to norbornene, endo- and exo-5-methylnorbornene, endo- and exo-5-phenylnorbornene, endo- and exo-5-methoxycarbonyl norbornene and endo- and exo-dicyclopentadiene. In all cases, only exo addition was observed. In spite of the exo approach of diazopropane to the norbornene double bond, endo substituents at C-5 and/or C-6 influenced the regiochemistry of addition whereas exo substituents did not. The results are interpreted in terms of a concerted, asynchronous mechanism in which C—C bond formation runs well ahead of N—C bond formation, as predicted from theory. The regiochemical control exercised by apparently remote endo substituents provides a new experimental criterion for asynchrony or synchrony of cycloadditions that are known to be concerted.
    Zusätzliches Material: 5 Tab.
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  • 44
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 346-348 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Gas-phase acidities of acrolein and methyl acrylate were measured by bracketing in a flowing afterglow/SIFT apparatus. For acrolein ΔG°acid = 369 ± 4 kcal mol-1 and for methyl acrylate ΔG°acid = 373 ± 4 kcal mol-1. These acidities are substantially lower than those of the saturated analogs propionaldehyde and methyl acetate, respectively, even though hydrogens attached to sp2-hybridized carbon are intrinsically more acidic than those attached to sp3-hybridized carbon. Resonance stabilization of the neutral form by conjugation of the C=C double bond with the carbonyl group and allenic destabilization of the anionic form of the two acids can account for the relatively low acidities.
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  • 45
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 349-357 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The 4,9-dimethyltricyclo [3.3.1.02,8]nona-3,6-dien-9-yl (4,9-dimethyl-9-barbaralyl) cation (3) was generated from 4,9-dimethyl-9-barbaralol (5) at -135°C in two different superacid mixtures [FSO3H—SO2CIF—SO2F2(1:6:1) and FSO3H—SO2CIF—SO2F2—CHCl2 (2:10:10:1 by volume)]. Its 1H and 13CNMR spectra show a strong temperature dependence in the range -150 to -125°C. The changes in band shapes with temperature show that the following exchanges take place: 4-methyl with 9-methyl, C-4 with C-9, C-1 with C-3 and C-2 with C-8. C-5, C-6 and C-7 are found not to exchange rapidly either with each other or with the other carbons in 3. The mechanism of this novel rearrangement is suggested to involve the bicyclic 2,7-dimethylbicyclo [3.2.2] nona-3,6,8-trienyl cation and the secondary barbaralyl cation 4,6-dimethyltricyclo [3.3.1.02,8] nona-3,6-dien-9-yl as intermediates rather than 7,8-dimethyl bicyclo [3.2.2] nona-3,6,8-trienyl cation, which does not have a methyl group on the allyl cation moiety. Comparisons with rearrangement mechanisms for other barbaralyl cations were also made. The rate constant for the degenerate rearrangement of 3 is 160 s-1 at -140°C, which corresponds to ΔG≠s = 26 kJ mol-1 (6·3 kcal mol-1). At -125°C ion 3 rearranges non-degenerately to the 1,4-bishomotropylium cation 1,8-dimethylbicyclo [4·3·0] nona, 2,4,7-trienyl (4) with k = 3 × 10-4 s-1. A mechanism for this rearrangement and the synthesis and purification of the ion precursor 4 are also reported.
    Zusätzliches Material: 1 Ill.
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  • 46
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 390-396 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Dephosphorylation of p-nitrophenyl diphenylphosphate (pNPDPP) by OH- in aqueous cationic micelles of cetyltrimethylammonium hydroxide (CTAOH) is inhibited by tert-butyl hydroperoxide (t-BuO2H), which reduces the binding of OH-, and whose anion is a relatively ineffective nucleophile. Reaction is faster in microemulsions of CTACl, n-octane and OH-, with t-BuO2H as cosurfactant, than in otherwise similar microemulsions with t-butyl alcohol as cosurfactant. Dephosphorylation by m-chloroperoxybenzoate ion is slower in microemulsions of cetyltrimethylammonium mesylate or benzenesulfonate, with n-octane and tert-butyl alcohol, than in cationic micelles, but a wide range of concentrations can be examined. The reaction rates qualitatively follow the concentration of peroxy acid relative to surfactant, and inert anions slow the reaction. Dephosphorylation by peroxyphthalate dianion in micelles of CTACl fits a pseudophase kinetic model, except in very dilute surfactant where reaction is faster than predicted.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 47
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The four possible diastereomeric 5,7-oxido-6-hydroxyiminocholestanes and their O-acetates have been synthesized. The stereochemistry of one of the latter has been proved unequivocally by x-ray diffraction. Their 1H and 13C NMR and also their circular dichroism spectra are discussed. It is now also possible to determine unequivocally the stereochemistry of the ring-junction geometry and the oxime E or Z stereochemistry.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 48
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 509-518 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 9,10-Dicyanoanthracene (DCA) sensitized the photooxygenation of 1,4-diphenyl-1,3-butadiene(1a) and its 4,4′-dimethoxy derivative (1b) to afford the corresponding endoperoxides 2 and the other oxidized products such as aldehydes and epoxides. The mechanism of the DCA-sensitized photooxygenation of 1 was diversified by solvent polarity. In non-polar solvents the reaction involves an exciplex intermediate, which leads to formation of triplet DCA (3DCA*) with an efficiency of 0·64 in the case of 1a. The resulting 3DCA* acts as a sensitizer for the generation of singlet oxygen (1O2) and thus 1O2 reaction occurs exclusively to give 2. On the other hand, single electron-transfer quenching of 1DCA* by 1 is feasible in polar acetonitrile and a primary ion pair can be formed. Competing with fast back electron-transfer deactivation, the primary ion pair produces free ions in limited yield to furnish electron transfer oxygenation. In the case of the DCA-1a system, free ions were produced with an efficiency of ca 4%. Thus, in acetonitrile, electron-transfer oxygenation partly took place to give the other oxidized products, whereas the 1O2 pathway was still valid and responsible for the formation of 2. The effect of solvent polarity was apparently less pronounced in the case of 1b because the reactivity of 1b toward 1O2 is about five times higher than tht of 1a. For such 1O2-reactive substrates, the electron-transfer pathway would become dominant only when the substrate concentration is impractically high.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 49
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The second-order rate constants of the reactions between benzenesulphonyl chlorides and anionic nucleophiles, benzoates and cinnamates, in methanol at 30·0°C are reported. A marked increase in rate found with a p-nitro substituent in the substrate indicated the development of an electron-rich centre on the S atom in the transition state. The two types of cross-interaction constants, ρxy and λxy, suggested that bond formation in the SN2 transition state with anionic nucleophiles is greater than that for the corresponding reaction with aniline nucleophiles.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
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  • 50
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: pKa′ Values are reported for two 2H-pyrroles and their 3H-pyrrole isomers. The latter have basicities of the same order as similarly substituted pyridines, whereas the former are 2-2·5 pK units more basic, 2,2,3,5-tetramethyl-2H-pyrrole having a pKa′ of 8·40, close to that for 2-aminoimidazole. Possible reasons are given.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 51
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 599-605 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A new criterion for the reactivity of π electron systems is proposed. The method incorporates and modifies ideas of Coulson and Fukui et al. about free valence. The proposed reactivity index includes covalent and lonic components and is suitable for elctrophilic, radical and nucleophillic attack. The method is tested for a few simple π systems and differences from Coulson and Fukui et al. are discussed. Finally, it is applied to the electrophilic attack of a series of substituted benzenes and to nucleophilic attack of a series of subsituted benzoic acid esters.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 52
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 703-710 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The ionization constants of nine amphoteric 5-pyridylmethylenehydantoins were measured in 80% (w/w) dimethyl sulphoxide-water at 25 °C. The effects of structure and Z/E configuration on both pKaI and pKaII values are discussed. The especially low basicity and acidity of the Z-isomers of the N-unsubstituted and 3-methyl-substituted 5-(2-pyridylmethylene)hydantoin are attributed to the formation of intramolecular N(1)—H…N hydrogen bond in the s-cis conformation of these compounds. The existence of N(1)—CH3…N attraction is also postulated for the Z-isomer of 1-methyl-5-(2-pyridylmethylene)hydantoin.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 53
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 732-736 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A bond energy scheme has been developed and two previously existing schemes have been extended for the calculation of heats of formation of aliphatic amines using ab initio 6-31G* energies in place of experimental data. The results are in good agreement with those obtained experimentally and suggest that this method can be used to predict heats of formation of molecules of this class with an accuracy competitive with good quality experiments, and with probable errors of less than 1 kcal mol-1.
    Zusätzliches Material: 7 Tab.
    Materialart: Digitale Medien
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  • 54
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 737-745 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The ab initio SCF-MO method was employed to examine the possibility of a reaction pathway without a carbocation intermediate in the pinacol rearrangement. The molecular geometries of the transition states were obtained for the 1,2-hydride shift together with H2O elimination, starting from the various methyl-substituted protonated 1,2-diols. It was found that the activation energies depend strongly on the substitutents. A comparison of the relative energies between β-hydroxycarbonium ions and the transition states of the concerted mechanism suggests that the stepwise mechanism is less favourable than the concerted path in each case.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 55
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Kinetic studies on the reactions of methyl (MBS) and ethyl benzenesulphonates (EBS) with N,N-dimethylanilines (DMA) in methanol and acetonitrile are reported. The cross interaction constants ρXZ and βXZ, between the substituents in the nucleophile (X) and the leaving group (Z) indicated that the transition states (TS) are looser than those for the reactions with anilines, but the relative tightness between the two substrates was the same; the TS was tighter for EBS despite the increase in steric effect leading to looser TSs for MBS and EBS alike. The TS variation between two different reaction series expected from the simple Hammett and Brønsted coefficients, ρX, ρZ, βX and βZ, was incompatible with that predicted by the cross interaction constants, demonstrating again the unreliability of the simple parameters.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 56
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 757-759 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The kinetics of conformation-dependent charge delocalization in radical cations generated from a series of α,ω-diaminoalkanes, (CH3)2N(CH2)nN(CH3)2, (n = 1-3) in a 3-methylpentane glassy solution at 90 K are discussed in terms of dispersive kinetics with the use of the time-dependent rate constant in the form k(t) = Btα - 1. It was found that the activation energy distribution function became broader as the number of methylene groups separating the two nitrogen atoms increased, and that this process was accompanied by a substantial increase in the mean value of the activation energy.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 57
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 784-788 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Absolute hardness calculated by the MNDO method has been shown to be a good measure of aromaticity for 14 benzenoid hydrocarbons. Comparisons among hardnesses at different levels of approximation are given. The parallelism of the aromaticity and hardness concepts in benzenoids is elaborated.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 58
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The bromine atom is a major chain carrier in the photobromination of toluenes by N-bromosuccinimide. Only an uncomplexed bromine atom can abstract hydrogen atoms from toluenes. The nature of the polar transition state is entirely different from that of solvolytic reactions and the solvent polarity therefore cannot infuence the rates of the bromination.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 59
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 807-811 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The kinetics of the acylation of 2,3-dihydrobenzoxazol-2-one with dodecanoic acid in polyphosphoric acid were investigated. Two competitive reactions occurred at the 3- and 6-positions. The acylation reactions in polyphosphoric acid of 2,3-dihydrobenzoxazol-2-one and 2H-1,4-benzoxazin-3(4H)-one give 6- and 7-acyl derivatives. 4-Acetyl-2H-1,4-benzoxazin-3(4H)-one rearranged in polyphosphoric acid exclusively to the 7-acetyl derivative. Two mechanisms are proposed to explain the different reaction sites for the acylation of 2H-1,4-benzoxazin-3(4H)-one.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 60
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 1-8 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The effect of substituents on the rate of a reaction and the effect of the same substituents on the equilibrium can often be related by a linear free energy relation (LFER): log k- = α log K= + constant, where k+ and K= are the rate constant and the equilibrium constant, respectively. This review, concentrating on group transfers, adds to many studies describing the use of α to describe the transition state. Although the use of α to describe transition states is general, group transfers constitute a simple class allowing a fairly complete description yet illustrating two often neglected contributions. Group transfers can be described by the Marcus equation relating rate to an average identity rate and the equilibrium constant; a major contributor to the slope, α, of the rate-equilibrium LFER is the variation of identity rates with substituent, rather than reflecting product-like character. Substituent effect LFERs are predominantly attributable to interaction of charges with the substituent. However, α is not an exact measure of the charge on the substituent-containing group, because in a transition state, but often not in a reaction product, there are more remote centers of charge which exert a smaller attenuated effect. A simple treatment of this attenuation for group transfers is proposed. The possibility of application of these ideas to proton transfer reactions and the interpretation of the Brønsted α (or β) is proposed.
    Zusätzliches Material: 1 Ill.
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  • 61
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 77-80 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The gas-phase elimination kinetics of (2-bromoethyl)benzene and 1-bromo-3-phenylpropane were studied in a static system and seasoned vessels over the temperature range 390-450 °C and the pressure range 32-104 Torr. The reactions, under maximum inhibition of 4-fold pressure of the free-radical suppressor cyclohexene and/or propene, are homogeneous, unimolecular and obey a first-order rate law. The rate coefficients are given by the following Arrhenius equations: for (2-bromoethyl)benzene, log k1 (s-1) = (13·04 ± 0·10) - (210·8 ± 1·3) kJ mol-1 (2·303RT)-1, and for 1-bromo-3-phenylpropane, log k1 (s-1) = (14·09 ± 0·27) - (227·7 ± 3·6) kJ mol-1 (2·303RT)-1. The phenyl group of (2-bromoethyl)benzene appears to provide anchimeric assistance in the HBr elimination of this compound. However, neighbouring C6H5 participation at the 3-position in 1-bromo-3-phenylpropane for a C-4 conformation is apparently absent. The mechanisms of these reactions are discussed.
    Zusätzliches Material: 8 Tab.
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  • 62
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 89-94 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The hydration of 2,2-dichloro-1-arylethanones was studied in water and tetrahydrofuran (THF)-water mixtures and the equilibrium constants in water were estimated for four ethanones. The process is subject to specific acid and to general base catalysis. The proton inventory technique was applied to the study of the reaction in L2O and THF-L2O solutions (L = H or D). In pure water and water-rich mixtures, a very large number of protons participate in the open transition state, this number decreasing gradually with increasing water content in the mixture, until the minimum value of 2 is reached, corresponding to a cyclic, closed transition-state structure.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 63
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 126-134 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The additivity of experimental bond separation energies is demonstrated. This thermodynamic function can be reproduced by summation of group equivalents with a correction for the ‘stabilization’ energy. For this purpose, several group equivalents have been developed for alkanes and alkenes. The correlation between the computed and the experimental bond separation energies is good. These equivalents are then used in evaluating the stabilization (destabilization) energies for aromatic hydrocarbons and polyenes. The results obtained are in good agreement with values reported in the literature.
    Zusätzliches Material: 7 Tab.
    Materialart: Digitale Medien
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  • 64
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 135-138 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 2-Naphthylphenylcarbene (2-NPC) was studied by low-temperature EPR spectroscopy and by solution-phase laser flash photolysis. 2-NPC was found to have a triplet ground state with two distinct rotomeric forms. The triplet carbene was found to react with methanol, 1,1-diphenylethylene, styrene, carbon tetrachloride, isoprene, toluene and 2-methyltetrhydrofuran.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 65
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The quantitative description of ring puckering suggested by the authors is compared with that of Cremer and Pople. The applicability of both methods is discussed for the case of six-membered rings with the use of model calculations simulating various ring distortions and with the analysis and comparison of puckering parameters computed on the basis of x-ray data for 40 six-membered rings in different cyclic structures. The 2N times reduction of the field of variation of puckering parameters for the N-membered ring is suggested and the algorithm for the renumbering of the ring atoms for this purpose is described for six-membered rings.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 66
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 181-189 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The determination of uniform scaling factors for force constants calculated at the STO-3G and 4-31G levels of ab initio SCF MO theory is described; scaled 4-31G force constants provide reasonable estimates of reduced partition function ratios for deuteriated/protiated molecules. Gas-phase deuterium fractionation factors relative to methane calculated using scaled 4-31G force constants are, however, consistently too high, whereas those obtained by the MP2/6-31G* and scaled STO-3G methods are inconsistent. Scaled 4-31G deuterium fractionation factors relative to water for a range of structural moieties correlate linearly with experimental aqueous-phase values, but are also consistently overestimated. Substitution at a hydrogen-bearing carbon atom affects the deuterium fractionation factor through the combined effect of changes in reduced mass and changes in force constants other than for CH stretching.
    Zusätzliches Material: 8 Tab.
    Materialart: Digitale Medien
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  • 67
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 195-199 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The decay of 2-phenyl-1,3-dioxolane-2-ylium salts in 1,2-dichloroethane solution has been studied by means of 1H NMR and UV spectroscopy and conductimetry. The influence of the nature of the anion (SbCl6-, SbCl5Br-, AsF6-) and of the methyl substituents on the rate constants of decay is discussed.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 68
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 69
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 219-229 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Following the observation that allyl radicals trapped in an argon matrix can be photolytically converted into cyclopropyl radicals (λ = 410 nm, 18 K), the IR spectrum of the cyclopropyl radical was recorded for the first time and interpreted. Bicyclopropane and cyclopropane are formed when the photolysed argon matrix is warmed from 18 to 35 K. The identification of these new species unequivocally proves the presence of cyclopropyl radicals in the photolysed matrix. This radical is shown to be a σ-type (Cs symmetry) and not a π-type (C2v symmetry) radical; of the 18 normal frequencies of the Cs cyclopropyl radical, all active in the IR, 16 were observed and were assigned to their corresponding normal modes. For this assignment advantage was taken of ab initio frequency computations reported in the literature and performed by the authors.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 70
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 248-254 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Ionization constants of N-phosphonomethylglycine (glyphosate) and three structurally related plant-growth regulators were determined by potentiometric titration. The effect of pD on the chemical shifts of the 1H and 13C nuclei of the methylene groups and of the 31P nucleus in these substrates was measured by NMR spectroscopy. The results allowed an assignment to be made of a specific site (carboxylic, phosphonic, ammonium) in the molecule to each of the determined pKa values.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 71
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 273-278 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A deuterium isotope effect on the arene-alkene meta photocycloaddition, reported earlier for toluene/toluene-d8 photoaddition to cyclopentene, was found to depend on the concentration of both arene and alkene. This phenomenon is explained in terms of an unbalanced dissociation of ‘mixed’ excimers, which play a role in the intermolecular competition experiments.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 72
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 285-288 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Reactions between acrylic esters, nitriles and similar compounds on the one hand and aldehydes and ketones on the other, catalysed by tertiary amines, lead to α-(hydroxyalkyl)acrylic compounds. Evidence on the basis of kinetics, volumes of activation and of reaction, and kinetic isotope effects is presented to deduce a mechanism in which amine first undergoes Michael addition, the resulting enolate ion adds to the carbonyl compound in a rate-determining step and finally base is eliminated. An analysis of the solvent effect on rates is also presented.
    Zusätzliches Material: 1 Ill.
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  • 73
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 295-300 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The molecular structure of [4]paracyclophane was optimized at the semiempirical MNDO and the ab initio STO-3G level. A comparison of the results showed that the benzene ring is much less bent at the STO-3G level. Although some bond alternation is predicted at both levels of theory, the aromatic carbon-carbon bond lengths are still in the range typical of highly delocalized compounds. The calculated strain energy [SE(tot.)] of [4]paracyclophane is larger for the STO-3G structure. Nevertheless, the distributions of SE(tot.) over the bent benzene ring [SE(bb.)] and the oligomethylene bridge [SE(br.)] are the same for the MNDO and STO-3G structures.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 74
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The dipole moments of the Z and E isomers of O-methylbenzohydroximoyl cyanides [ArC(CN)=NOCH3, Ar = C6H5 and 4-NO2C6H4], the Z isomers of benzohydroximoyl cyanides [ArC(CN)=NOH, AR = C6H5 and 4-NO2C6H4] and the Z isomers of O-benzoylbenzohydroximoyl cyanides [ArC(CN) = NOCOC6H5, Ar = C6H5 and 4-NO2C6H4] were measured. An analysis of these dipole moments indicates that anti delocalization from the OCH3 (OH) group has a small but significant effect on the overall direction and magnitude of the dipole moment. Semi-empirical molecular orbital calculations at the MNDO level support this proposal. The x-ray crystal structure of (Z)-O-methyl-p-nitrobenzohydroximoyl cyanide was carried out to confirm the configuration of the compound.
    Zusätzliches Material: 5 Ill.
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  • 75
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 76
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 375-378 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The reactions of a series of methyl para-substituted phenylpropiolates with thiophenoxide ion in methanol were studied and their rates measured. Methyl β-thiophenyl esters were obtained as mixtures of Z and E isomers and their configurations were established by 1H NMR spectroscopy. Good Hammett correlations with ρ values of 1·57-1·97 were obtained, which suggest a carbanionic character of the transition state. A stepwise mechanism proceeding via an intermediate carbanion is postulated for this non-sterospecific addition reaction.
    Zusätzliches Material: 1 Ill.
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  • 77
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 1H, 13C, 77Se and 125Te NMR spectra were measured for several sulphides, selenides, tellurides and their halogen adducts to establish the criteria for distinguishing trigonal bipyramidal (TB) adducts from molecular complexes (MCs). TB formation caused large downfield shifts for methyl protons and methyl, ipso and para carbons of methyl and phenyl selenides and tellurides. Large downfield shifts (〉 100 ppm) were also observed for selenium and tellurium by the formation of TB from the parent selenides or tellurides. The plots of the 125Te vs 77Se chemical shifts for a set of corresponding compounds gave a straight line with a slope of 1·74, showing that the linear relationship holds well for tellurides and selenides and their TB adducts examined in this work. Upfield shifts of the ipso carbons were characteristic of MC formation. The para carbon signals of MC appeared downfield relative to those of the parent selenides, although the shift values were not so large. The 77Se signals for MC shifted slightly downfield (≤ 10 ppm). The dissociation constants for iodine adducts of dimethyl selenide and selenoanisole were determined. The MC structure of bromine adducts of sulphides is well demonstrated on the basis of the criteria set out. 1H and 13C NMR spectra of ethylbenzene and ethers were also recorded in the presence of iodine or bromine. However, their chemical shifts were the same as those in the absence of iodine or bromine, within experimental errors.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 78
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Reaction of diphenyl diketones (benzils) with aryliminodimagnesium [ArN(MgBr)2, IDMg], a magnesium reagent having condensation ability, was investigated. By comparison of the relative amounts of heat evolved in the reactions of IDMg (mildly electron donating) and ArMgBr (strongly electron donating) with some carbonyl and nitro compounds, results were obtained supporting the reported correlation of the relative yields of normal and abnormal (radical) products with single electron transfer (SET) efficiency estimated by the oxidation and reduction potentials of reactants. A sole exceptional result, i.e. the great heat evolution caused by the combination of benzil and IDMg, was attributed to the generation of tightly chelated radicals via SET. The involvement of stepwise SET was confirmed by ESR. On the basis of these results, substituent effects of benzil and mono-condensation products on their reduction potentials and on the relative yields of normal (mono- and di-condensation) and abnormal (dimerization) products were examined. All the results were consistently explained in terms of the relative efficiency of chelation (or σ-complexation) and SET in two main processes. The role of the initial stages involved in the processes governing the final product distribution is discussed.
    Zusätzliches Material: 4 Ill.
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  • 79
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 414-418 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The rate and endo/exo selectivity of the Diels-Alder reaction between cyclopentadiene and methyl (E)-α-cyanocinnamate at 25°C, in several acetone-water and 1,4-dioxane-water mixtures, were measured. The linear correlations of log k and log(endo/exo) vs solvophobicity are reported. Correlations for selectivity are considerably improved when the results obtained in acetone-water and 1,4-dioxane-water are taken as separate series.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 80
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 449-455 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The substituent effect on the rates of solvolysis of substituted benzyl tosylates in acetic acid was analysed based on the Yukawa-Tsuno LArSR equation. Neither the LArSR nor simple σ+ treatment was capable of providing any linear correlation plot for the full range of substituents. The σ+ plot was not simply bilinear but widely scattered, giving a split pattern of parallel curves with significant gaps. Since any mechanistic transition with substituents should bring about a single continuous curve when plotted against an appropriate substituent constant scale, the split σ+ plot is not in line with an interpretation in terms of a mechanistic transition. On the other hand, the LArSR plots with r = 1·3 coalesced into a single smooth curye including the meta correlation curve. A different resonance demand as high as r = 1·3 is required in order to give a smooth single-curve correlation for the entire substituent range without splitting. For the reactive substituents down to p-halogens, a sufficiently linear plot can be obtained against a set of substituent constants with r = 1·3 which can be referred to the substituent effect correlation for the kc mechanism of this system. An identical r value was likewise assigned for the kc mechanism of the hydrolysis for a more severely restricted range of activating substituents down to the 4-MeS-3-CN group.
    Zusätzliches Material: 3 Ill.
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  • 81
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 459-469 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: N-[2,3-Bis(dimethylamino)cyclopropenylio]- and N-(tetramethylamidinio)pyridinium salts (trifluoromethanesulphonates and tetrafluoroborates) form 1:1 and 1:2 charge-transfer complexes with the pentakis(methoxycarbonyl)cyclopentadienide anion. The x-ray crystal structures of 1-[2,3-bis(dimethylamino)cyclopropenylio] pyridinium pentakis(methoxycarbonyl)cyclopentadienide tetrafluoroborate hydrate and of 1-[2,3-bis(dimethylamino)cyclopropenylio] pyridinium bis[pentakis(methoxycarbonyl)cyclopentadienide] were determined. In constrast, the tetra-cyano-p-quinodimethane (TCNQ) radical anion reacts with the first-mentioned salts by C—C bond formation to give novel dicationic salts. Thereby, the radical anion attacks the pyridinium γ-position of the N-(tetramethylamidinio)-pyridinium dication, but the three-membered ring of the N-[2,3-bis(dimethylamino)cyclopropenylio] pyridinium system.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 82
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 2-Nitrobenzoyl chlorde was reacted with superoxide in acetonitrile to form 1 2-nitrobenzoylperoxy radical intermediate which showed a stronger oxidizing ability than that from superoxide, as confirmed by ESR spin trapping studies.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 83
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 489-492 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Rate constants and activation parameters have been measured for the acid hydrolysis of six 2-carboethoxypyridine N-oxides. The correlations of log kobs. vs Hammett's constants and chemical shifts of intramolecular hydrogen-bonded protons in parent acids are analysed. Evidence was found for the participation of intramolecular hydrogen bonding in the hydrolysis of the esters.
    Zusätzliches Material: 2 Ill.
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  • 84
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 519-533 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The geometries of the reactants, the reactant π-complex, the transition state and the product for exo and endo addition of BH3 to norbornene were optimized at the HF/3-21G level, and their energies were calculated at the MP2/6-31G level. The analysis of activation energy and model calculations singled out the endo deformability, a major portion of the norbornene deformation energy, as the origin of exo selectivity; norbornene, with the olefinic hydrogens already bent toward endo in the equilibrium geometry, requires less deformation to reach the exo than the endo transition state. The reason why olefinic hydrogens are bent in norbornene has been elucidated. An analysis indicates that the difference between norbornene exo side and bicyclo [2.2.1] hex-2-ene is also dictated by the endo deformability.
    Zusätzliches Material: 10 Ill.
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  • 85
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 86
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 575-580 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The 1H NMR spectra of eleven substituted 2-benzopyrylium salts are interpreted with the aid of the CNDO/2 method for standard geometry. Some effects of the substituents are considered for the charge distribution in the 2-benzopyrylium cation.
    Zusätzliches Material: 2 Tab.
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  • 87
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 567-574 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Unimolecular decomposition of 0·1 Torr of diethyl carbonate, diethyl-d5 carbonate and diethyl-d10 carbonate induced by irradiation with a CO2 TEA laser was investigated. In all cases only ethylene, ethanol and CO2 were obtained. In the case of diethyl-d5 carbonate, both ethylene-d4 and ethylene-d0 were observed together with the corresponding isotopic variants of ethanol. The chemical branching ratio was determined as a function of irradiation frequency and laser fluence by analysis of the ethylene-d0/ethylene-d4 ratio. RRKM theory applied to the branching ratio data requires very different average energies for two sets of fluence and frequency conditions that give identical total yields.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 88
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 559-566 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Nine 5-pyridylmethylenehydantoins were prepared. Each of the 1-methyl-substitute compounds was obtained in two stereoisomeric forms. Only one form of each of the 3-methyl-substituted and N-unsubstituted compounds was obtained directly from synthesis but could be partially converted into the other stereoisomer photochemically. The Z/E configurations and the conformational relationship between the pyridine and hydantoin rings were studied by 1H and 13C NMR spectroscopy, including variable-temperature 1H NMR. The existence of N—H…N or C—H…N interactions and the possibility of tautomerism are suggested for some of the compounds. The Z-isomers of compounds with 2- or 3-pyridyl rings prefer an s-cis conformation whereas the E-isomers prefer an s-trans conformation.
    Zusätzliches Material: 1 Ill.
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  • 89
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 594-598 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The reductions of propiophenone and octanophenone to 1-phenylpropan-1-ol and 1-phenyloctan-1-ol, respectively, with sodium borohydride and tetrabutylammonium borohydride were performed on a reverse-phase highperformance liquid chromatographic (HPLC) column of macroporous 10-μm poly(styrene-divinylbenzene) undr HLPC conditions. In these reactions a lower concentration of tetrabutylammonium borohydride than of sodium borohydride was needed to effect the same extent of reduction, and modest substrate selectivity was obtained.
    Zusätzliches Material: 1 Ill.
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  • 90
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 606-610 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Electronic absorption spectra of radical cations generated by steady-state and pulse radiolysis from a series of α,ω-diaminoalkanes (R2N(CH2)nNR2; n = 1-6, R = CH3 or C2H5), 1,4-dimethylpiperazine and 1,4-diazabicyclo [2.2.2] octane (DABCO) were measured. In some cases spectral evidence was obtained for an interaction between the nitrogen atoms leading to charge delocalization in the radical cation. A delayed formation of radical cations was associated with a conformational change necessary for achieving the most stable structure having a favourable conformation for charge delocalization.
    Zusätzliches Material: 5 Ill.
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  • 91
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 620-626 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Nitrone formation from furfural and 5-nitrofurfural with phenylhydroxylamine was studied in water at 25°C and ionic strength 1·0 (KCl). The reaction exhibits general acid catalysis (α = 0·52), specific base catalysis and a pH-independent process. The results are consistent with a mechanism where dehydration of an N,N′-dihydroxy addition intermediate, formed by a rapid pre-equilibrium, is the only rate-determining step over the pH range studied (1-11). In contrast, nitrone formation from p-chlorobenzaldehyde and N-methylhydroxylamine exhibits a clear change of rate-determining step, from dehydration of the addition intermediate to attack of the nucleophile on the aldehyde, with increase in pH. The profile of log k2 (k2 = second-order rate constant) vs pH indicates, by comparison with the corresponding profile for similar reaction, that phenylhydroxylamine exhibits unexpected nucleophilic behaviour in this reaction. The pH-indpendent dehydration process, which has a higher rate constant than that predicted from the Brønsted line for the water catalysis, appears to involve intramolecular catalysis rather than bifunctional catalysis by water.
    Zusätzliches Material: 3 Ill.
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  • 92
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 639-642 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The second ionization of the 4-chloro-3-methylbutanoyl ion forms a primary alkyl acyl dication, as a tight ion pair. Methyl and hydrogen shifts occur to comparable extents indicating that the relative stability of the product (sec- or tert-carbocation) does not influence the energy barrier for the shift. The product of methyl shift (1,3-sec-alkyl acyl dication) loses the proton closest to the counterion in the tight ion pair and forms the pent-3-enoyl cation. Protonation-deprotonation of the latter, followed by internal acylation, gives the protonated cyclopent-2-enone. The dication resulting from hydrogen shift loses a proton from C-2 and gives the 3-methylbut-2-enoyl cation.
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  • 93
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Microelectrodes can be used to measure redox half-wave potentials in aprotic solvents containing no purposely added supporting electrolyte. By employing an electrode of sufficiently small size, the accessible potential range in solution is considerably extended. The electrochemical oxidation of vinyl (enol) triflates, which are oxidized at high electrode potentials, can therefore be studied using an ultramicroelectrode. Oxidation and ionization potentials, determined by ultramicroelectrode voltammetry and He I photoelectron spectroscopy, respectively, of 2-methylprop-1-enyl, cyclohexenyl, cyclopentenyl, 1,1-diphenylethenyl and prop-2-enyl triflate are reported. The results from electrochemical measurements and photoelectron spectra were compared.
    Zusätzliches Material: 3 Ill.
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  • 94
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The catalytic effects of micelles of cetyltrimethylammonium bromide (CTAB) and fluoride (CTAF) on several SNAr and BAC2 reactions were studied. Rate versus detergent concentration curves predicted by the pseudophase models PPIE (ion exchange) for CTAB studies and PPMA (mass action) for the CTAF studies were fitted to the experimental results to determine the best values of the substrate binding constant (Ks), the second-order rate constant for reaction in the micelles (K2M) and the exchange constant KOH/X (PPIE) or binding constant (PPMA) for the counterions. Better catalysis by micelles of CTAF is shown to be due to the combined effects of a more favourable exchange constant in CTAF than in CTAB, slightly different rates of reaction within the two micelles and different values of β, the fraction of micellar head groups neutralized in CTAF and in CTAB.In both micelles the magnitude of catalysis depends on the charge produced in the intermediate complex and the presence of electron-withdrawing groups to stabilize that charge. Strongest catalysis was found for a reaction leading to a monoanionic intermediate complex in which the charge was stabilized by two nitro groups, and the weakest catalysis was found for a reaction leading to a dianionic intermediate in which no electron-withdrawing groups were present.
    Zusätzliches Material: 1 Ill.
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  • 95
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 96
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 711-722 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A comparative study on the use of the MINDO/3, MNDO and AM1 semi-empirical methods for the description of formamide and aliphatic amide systems is reported. For formamide, ab initio Hartree-Fock calculations are also reported using both the STO-3G and 3-21G basis sets, as well as a basis set obtained by a minimal relaxation of the STO-3G contraction scheme. It is shown that both the MNDO and the STO-3G methods cannot properly reproduce the experimental results. In both cases this appears to be due to inadequacies of the basis sets used. Again in both cases only small improvements in the basis set necessary to allow for the diffuse character of the pπ orbitals lead to dramatic improvements in the calculated results. In the case of the STO-3G basis set this is demonstrated by the fact that a small relaxation in the contraction leads to results even superior to those with the 3-21G set. The conclusions reached for amide systems can be extended to other systems where planarity around or inversion with respect to nitrogen is an issue. This is demonstrated for ammonia.
    Zusätzliches Material: 3 Ill.
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  • 97
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 760-763 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Additions of phenylchlorocarbene and phenylfluorocarbene to representative alkynes are rapid (106-107 l mol-1 s-1). The variation of the rate constants with alkyne structure parallels that observed with analogous alkene substrates. The addition of phenylchlorocarbene to 3-hexyne is characterized by a very low activation energy (∼ 2 kcal mol-1) and a large, negative entropy of activation (∼ -20 e.u.).
    Zusätzliches Material: 1 Ill.
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  • 98
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990) 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 99
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 799-802 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The kinetics of the oxidation of α-amino acids (glutamic acid and aspartic acid) by alkaline hexacyanoferrate(III) were studied at constant ionic strength and over the temperature range 323-348 K. The rate was dependent on the first power of the concentrations of substrate and oxidant, but was independent of the concentration of alkali in the range studied. The value of kH/kD was in the range 8·1-8·3 for the slow step, indicating the loss of a hydrogen atom from the C—H bond, giving a radical species which was characterized by ESR spectroscopy. The reaction proceeds by way of the α-imino acid, formed in a fast step, which undergoes hydrolysis to give the corresponding α-keto acid.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 100
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 3 (1990), S. 9-12 
    ISSN: 0894-3230
    Schlagwort(e): Organic Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Polarization of the π-electron systems of indenyllithium (In -Li+) and indenylpotassium (In -K+), which is generally indicative of the degree and tightness of contact ion pairing, was investigated by 13C NMR spectroscopy. The effect of changing solvent is about two thirds as great for In -K+ as for In -Li+. The indenyl anion is more strongly polarized with Li+/dimethyl sulfoxide than with Li+/ammonia, whereas the reverse is observed for In -K+. Complexation of In -K+ in tetrahydrofuran (THF) by cryptand(2,2,2) results in a π-electron distribution identical with that of In -Li+ in hexamethylphosphoramide, indicative of solvent- or agent-separated ion pairs or free ions. Small but significant cation-anion interactions are observed for In -K+ in hexamethylphosphoramide and for In -N+Me4 in THF.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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