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  • 1990-1994  (397)
  • 1991  (397)
  • Physical Chemistry  (205)
  • Genetics  (192)
  • 1
    Electronic Resource
    Electronic Resource
    Molecular heterogeneity and genetics of Vicia faba seed storage proteins (1991)
    Springer
    Theoretical and applied genetics 81 (1991), S. 50-58 
    Details
    ISSN: 1432-2242
    Keywords: Vicia faba ; Legumin ; Vicilin ; Structure ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Legumin and vicilin were purified from seeds of Vicia faba L. var. Scuro, characterized in different electrophoretic systems, and used to produce polyclonal antibodies in rabbits. Two-dimensional electrophoretic studies showed a wide range of heterogeneity in the subunits of both legumin and vicilin. Legumin was found to be composed of 29 disulphide-linked subunit pairs with different molecular weight and/or isoelectric point. Western blot analysis of legumin of several mutants revealed molecular polymorphism based on a corresponding gene family. Three different α-major legumin patterns were found, and inheritance studies showed that the 34.3-kD legumin polypeptide is the product of one locus, Lg-1α, which is the first legumin genetic locus described in Vicia faba. Vicilin was found to be composed of as many as 59 subunits distributed in a molecular weight range of 65.7 to 42.8 kD (major polypeptides) and 37.2 to 15.2 kD (minor polypeptides), with different isoelectric points. A model is proposed that explains the possible formation of the minor subunits and the major subunits of 48.2 and 46 kD molecular weight (MW) from proteolytic cleavages and/or glycosilation of precursor polypeptides. Ten different vicilin electrophoretic patterns were observed among the analyzed accessions, which showed large molecular polymorphism that proved to be under genetic control.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00226111
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  • 2
    Electronic Resource
    Electronic Resource
    Genetic analysis of rye (Secale cereale L.) Genetics of male sterility of the G-type (1991)
    Springer
    Theoretical and applied genetics 82 (1991), S. 761-764 
    Details
    ISSN: 1432-2242
    Keywords: Rye ; Male sterility ; Genetics ; Gene location ; Trisomies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The genetics and relationships between the genes in rye located in the nucleus and cytoplasm of the male sterility of the G-type were investigated. A factor inducing male sterility was found in the cytoplasms or rye cv Schlägler alt and rye cv Norddeutscher Champagner. Monogenic inheritance was observed in linkage tests. Using primary trisomies of rye cv Esto, the nuclear gene ms1 was found to be located on chromosome 4R. Modifying genes, probably masked in normal cytoplasm but expressed in male-sterility-inducing cytoplasm together with gene ms1, were located on chromosomes 3R (ms2) and 6R (ms3). Mono-, di-, and trigenic inheritance types were found in backcross progenies of trisomies.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00227322
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  • 3
    Electronic Resource
    Electronic Resource
    The effect of size at birth, maturation threshold and genetic differences on the life-history of Daphnia magna (1991)
    Springer
    Oecologia 86 (1991), S. 243-250 
    Details
    ISSN: 1432-1939
    Keywords: Daphnia ; Life-history ; Genetics ; Variation ; Maturation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Life-history traits of 101 clones from two populations of Daphnia magna were measured under controlled environmental conditions in the laboratory. Some individuals had four juvenile instars, others had five. This depended on their length at birth and on the population they came from. Females in the group with five juvenile instars were smaller at birth but larger and older at maturity than those with four juvenile instars. Within groups of females with equal numbers of preadult instars (instar groups) age and size at maturity increased with size at birth. This relationship differed significantly among instar groups for both age and size at maturity. Significant differences in age and size at maturity between two populations became non-significant when size at birth was used as a covariable in AN-COVA. Within populations, size at birth depended on the clone and on the parity of the clutch. First-clutch offspring were considerably smaller than those from later clutches. The results suggest that variability in life-history traits is common within and between clones, but that most of this variation can be accounted for by size at birth and the number of pre-adult instars.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00317537
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  • 4
    Electronic Resource
    Electronic Resource
    Association between a restriction fragment length polymorphism at the liver/islet cell (GluT 2) glucose transporter and familial Type 2 (non-insulin-dependent) diabetes mellitus (1991)
    Springer
    Diabetologia 34 (1991), S. 734-736 
    Details
    ISSN: 1432-0428
    Keywords: Genetics ; diabetes mellitus ; restriction fragment length polymorphism ; glucose-transport ; familial
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Patients with Type 2 (non-insulin-dependent) diabetes mellitus and a strong family history of the disease may represent a sub-group where genetic factors play a pree-minent role in transmission of the disease. A defect in the liver/islet cell glucose transporter (GluT 2) could explain many of the pathophysiological features of the disease. In order to test the hypothesis that genetic variation at the GluT 2 locus contributes genetic susceptibility to Type 2 diabetes, 60 unrelated Caucasian diabetic patients with at least one affected sibling were genotyped for a Taq 1 restriction fragment length polymorphism marker. Hybridisation with a cDNA GluT 2 probe identified two alleles of sizes 13 kilobase (T1) and 19 kilobase (T2). The allele frequencies in the diabetic group with a family history were significantly different from those in a racially-matched control population of 122 subjects with no personal or family history of the disease (diabetic patients T1=0.96, T2=0.04, control subjects T1=0.89, T2=0.11, p〈 0.03). However, when the study was repeated with 54 diabetic patients with indeterminate family history, statistical significance was not reached although the allele frequencies showed a similar trend. The findings of this study support the hypothesis that a genetic variant of the liver/islet cell glucose transporter may contribute to familial susceptibility in Type 2 diabetes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00401519
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  • 5
    Electronic Resource
    Electronic Resource
    Genes encoding ribulosebisphosphate carboxylase and phosphoribulokinase are duplicated in Pseudomonas carboxydovorans and conserved in carboxydotrophic bacteria (1991)
    Springer
    Archives of microbiology 157 (1991), S. 92-96 
    Details
    ISSN: 1432-072X
    Keywords: Carboxydotrophic bacteria ; Ribulosebis-phosphate carboxylase ; Phosphoribulokinase ; Hybridization ; Plasmids ; Genetics ; CO2 fixation ; Alcaligenes eutrophus ; Pseudomonas carboxydovorans ; Rhodospirillum rubrum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Heterologous gene probes derived from cfxLp and cfxPp genes of Alcaligenes eutrophus H16 revealed the presence of structural genes encoding ribulosebisphosphate carboxylase (Rubisco) and phosphoribulokinase (PRK) on the genome of carboxydotrophic bacteria. The two genes were found to be rather conserved. In Pseudomonas carboxydovorans OM5 cfx genes reside on the plasmid pHCG3 and the chromosome as well, indicating that they are duplicated. Also in all plasmidharboring carboxydotrophic bacteria cfxL and cfxP structural genes were found to be plasmid-coded. Our results extend the list of carboxydotrophy structural genes residing on the plasmid pHCG3 and strongly support the idea that the components essential for the chemolithoautotrophic utilization of CO by Pseudomonas carboxydovorans OM5 are plasmid-coded. A cfxL gene probe from Rhodospirillum rubrum did not detectably hybridize with DNA from any of the carboxydotrophic bacteria examined.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00245342
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  • 6
    Electronic Resource
    Electronic Resource
    Hemochromatosis and pyruvate kinase deficiency (1991)
    Springer
    Annals of hematology 62 (1991), S. 188-189 
    Details
    ISSN: 1432-0584
    Keywords: Hemochromatosis ; Pyruvate kinase deficiency ; Hereditary anemia ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Hemochromatosis has been reported in several patients with chronic hemolytic anemia due to pyruvate kinase deficiency. We describe here a further patient with such an association and review the literature on the subject. We hypothesize that iron overload may occur in patients with pyruvate kinase deficiency who are also carriers of the hereditary hemochromatosis gene.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01703147
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  • 7
    Electronic Resource
    Electronic Resource
    Shared genetic susceptibility of Type 1 (insulin-dependent) and Type 2 (non-insulin-dependent) diabetes mellitus: contributions of HLA and haptoglobin (1991)
    Springer
    Diabetologia 34 (1991), S. 350-355 
    Details
    ISSN: 1432-0428
    Keywords: Genetics ; Type 1 (insulin-dependent) diabetes mellitus ; Type 2 (non-insulin-dependent) diabetes mellitus ; HLA ; haptoglobin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Epidemiologic data suggest that having a parent with Type 2 (non-insulin-dependent) diabetes mellitus increases the risk for Type 1 (insulin-dependent) diabetes in siblings of a Type 1 diabetes proband. This increase in risk is consistent with a shared genetic susceptibility between Type 1 diabetes and Type 2 diabetes. We contrast genetic risk factors in three sets of families, consisting of (1) a single Type 1 diabetic child (proband) and non-diabetic parents, (2) multiple Type 1 diabetic siblings and non-diabetic parents, and (3) at least one Type 1 diabetic child and at least one Type 2 diabetic parent. Previous studies have demonstrated that HLA region genes, which elevate the risk in Type 1 diabetes, have no significant effect with respect to the risk for developing Type 2 diabetes. An earlier report cited a contribution by the haptoglobin locus to genetic susceptibility for Type 2 diabetes. We provide evidence that a high risk HLA antigen (HLA-DR3) is decreased to a greater extent in Type 1 patients with a Type 2 parent than in Type 1 patients in which the parents are not diabetic. The role of HLA-DR4 is maintained in these families, with an unexpectedly significant increased rate of transmission of the HLA-DR4 allele from Type 2 parent to Type 1 offspring. The role of haptoglobin in these families does not appear to be important, either with respect to association with diabetes or with respect to linkage with a secondary susceptibility locus. These results indicate that families with a Type 2 parent and Type 1 child, heavily determined by HLA-DR4 linked factors, may represent a homogeneous subset of diabetes susceptibility.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00405008
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  • 8
    Electronic Resource
    Electronic Resource
    Genetic architecture of growth curve parameters in chickens (1991)
    Springer
    Theoretical and applied genetics 83 (1991), S. 24-32 
    Details
    ISSN: 1432-2242
    Keywords: Genetics ; Growth curve ; Body weight ; Chickens
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Genetic improvement in growth of poultry has traditionally proceeded via selection for body weight at a fixed age. Due to increased maintenance costs and reproductive problems of adult broiler breeders, the potential for genetic manipulation of the growth curve has been receiving increased interest. Research of both male and female progeny of a three-way diallel cross was used to investigate the inheritance of growth curve parameters. The Laird form of the Gompertz equation was used to determine growth curve parameters, and was suited to the juvenile growth data frequently collected from meat-type chickens. Growth rate exhibited significant heterosis due to both autosomes and the sex chromosomes. Age at inflection point also exhibited significant average heterosis, though only among females. Growth rate was also influenced by average line effects, as was age at inflection point. Maternal effects had no influence on growth curve parameters, while additive sex linkage was observed for growth rate. Phenotypic and genetic correlations were calculated among the growth curve parameters and suggest that specific breeding programs could alter the growth trajectory of the contemporary broiler chicken. Moderate heritabilities were observed for the growth curve parameters and support the hypothesis that the growth curve could be altered via genetic manipulation of early postnatal growth, especially during the first 14 days post-hatch.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00229222
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  • 9
    Electronic Resource
    Electronic Resource
    α-Amylase structural genes in rye (1991)
    Springer
    Theoretical and applied genetics 82 (1991), S. 771-776 
    Details
    ISSN: 1432-2242
    Keywords: Secale cereale ; RFLP ; α-Amylase ; Genetics ; Isozymes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Rye α-Amy1, α-Amy2, and α-Amy3 genes were studied in the cross between inbred lines using wheat α-amylase cDNA probes. The α-Amy1 and α-Amy2 probes uncovered considerable restriction fragment length polymorphism, whereas the α-Amy3 region was much more conserved. The numbers of restriction fragments found and the F2 segregation data suggest that there are three α-Amy1 genes, two or three α-Amy2 genes, and three α-Amy3 genes in rye. These conclusions were supported by a simultaneous study of α-amylase isozyme polymorphism. The F2 data showed the three individual α-Amy1 genes to span a distance of 3cM at the locus on chromosome 6RL. The genes were mapped relative to other RFLP markers on 6RL. On chromosome 7RL two α-Amy2 genes were shown to be separated by 5 cM. Linkage data within α-Amy3 on 5RL were not obtained since RFLP could be detected at only one of the genes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00227324
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  • 10
    Electronic Resource
    Electronic Resource
    Genetic differences in the effects of competitive and non-competitive NMDA receptor antagonists on locomotor activity in mice (1991)
    Springer
    Psychopharmacology 104 (1991), S. 17-21 
    Details
    ISSN: 1432-2072
    Keywords: MK-801 ; Phencyclidine ; Ketamine ; CGP 39551 ; CGS 19755 ; NPC 12626 ; Locomotor activity ; Genetics ; NMDA/glutamate receptor complex ; Mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The effects of non-competitive (MK-801, phencyclidine, and ketamine) and competitive (CGP 39551, CGS 19755, and NPC 12626) N-methyl-d-aspartate (NMDA) receptor antagonists on locomotor activity in inbred CBA and C57, and in outbred NMRI mice were examined. Administration of the non-competitive NMDA antagonists produced a dose-dependent increase in well-coordinated locomotor activity at lower doses, followed by a bizarre behavioral syndrome (head weaving, body rolling, rotations, ataxia) after higher doses. The pharmacological profile of the competitive antagonists CGP 39551, CGS 19755, and NPC 12626 was more complex. CGP 39551 dose-dependently inhibited locomotor activity, whereas CGS 19755 and NPC 12626 displayed a biphasic action, that is low doses inhibited locomotor activity, whereas higher doses produced mild behavioral stimulation. The behavioral effects of NMDA antagonists appear to be genetically determined, since CBA animals were most sensitive to both noncompetitive and competitive antagonists, followed by NMRI and C57 animals. The differential effects of NMDA antagonists in various strains of mice suggest that the observed behavioral differences may be due to genetic differences in the NMDA/glutamate receptor channel complex.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02244548
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  • 11
    Electronic Resource
    Electronic Resource
    Evidence that genetic differences in habituation and GABAergic mechanisms may be related to sensitivity to ethanol and development of ethanol tolerance in mice (1991)
    Springer
    Psychopharmacology 105 (1991), S. 13-21 
    Details
    ISSN: 1432-2072
    Keywords: Habituation ; GABA ; Ethanol sensitivity ; Ethanol tolerance ; Genetics ; Mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Habituation to a test environment following daily exposure for 5 days was examined in three genetically different strains of mice. C57 animals showed significant habituation to the new environment already on the second day. The habituation of NMRI mice was significant on the third day, whereas CBA mice showed no habituation at all during the experimental period. There was no difference between the animal strains in learning capacity in a passive avoidance test, but CBA mice displayed a significant increase in latency in their performance. When tested for sensitivity to the convulsant actions of GABAergic antagonists, picrotoxin produced seizures at lower doses in CBA as compared to NMRI and C57 mice, whereas there was no difference between the strains in the seizure activity produced by the specific GABA receptor antagonist bicuculline. When the animals were tested for sensitivity to ethanol in a horizontal wire test, ethanol (2 g/kg, IP) produced muscle relaxation in CBA mice whereas the performance of NMRI and C57 was not affected. A large dose of ethanol (4 g/kg, IP) produced a significantly longer sleeping time in CBA mice as compared to NMRI and C57 animals. Ethanol-produced hypothermia was, however, similar in all animals. Environment-dependent development of tolerance to ethanol following daily injections of ethanol for 4 days was examined. C57 mice showed the most rapid development of tolerance towards ethanol's hypnotic actions, whereas CBA mice showed no tolerance to this effect of ethanol. No difference between the strains to the development of tolerance to ethanol's hypothermic effects was observed. The present findings indicate that sensitivity to ethanol and ethanol tolerance are complex phenomena which cannot be adequately characterized by measuring only one single functional response to ethanol. The possibility that a genetically determined perturbation in the functions of the GABA receptor-coupled chloride channel, noted as variable sensitivity to picrotoxin, may be of importance for the observed disturbance in habituation to a new environment, for the different sensitivity to ethanol, and for the different rate of development of ethanol tolerance is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02316858
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  • 12
    Electronic Resource
    Electronic Resource
    Variation between strains of the flour beetle Tribolium castaneum in relative performance on five flours (1991)
    Springer
    Entomologia experimentalis et applicata 60 (1991), S. 173-182 
    Details
    ISSN: 1570-7458
    Keywords: Genetics ; evolution ; host adaptation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract When populations are exposed to different environments, evolutionary processes can lead either to genetically differentiated strains or to the appearance of increased generalism at the individual level. For evolution to occur, genetic variability in performance in different environments is required. Here, intraspecific genetic variation across environments was estimated in the flour beetle Tribolium castaneum (Herbst) by comparing the responses of two strains of T. castaneum to different flour types. Replicated groups from each strain were allowed to develop on either the standard whole wheat medium or on one of four novel flours (wheat, rice, corn and oat). In several of the novel flours, clear differences in mean development time or population size of one or both strains were seen relative to performance in the standard medium. Moreover, the strains differed significantly in their phenotypic responses to the flours. One strain did particularly poorly on oat flour. Reduced oviposition, reduced larval survivorship and increased larval cannibalism were examined as possible causes of the low productivity on oat flour. These three factors accounted for about 70% of the reduction in population size when this strain oviposited and developed in oat flour. The difference between these two outbred strains in response to these five flours suggests that genetic variation in resource use is present within T. castaneum and may also be present within strains and natural populations in grain storage facilities. Such variation would permit an evolutionary response to selection in multiple environments (flours). This process has agricultural implications when several types of grain are stored in a single location because it could eventually lead to the evolution of highly generalized populations of T. castaneum, an important pest of stored products.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00177038
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  • 13
    Electronic Resource
    Electronic Resource
    Molecular analysis of iron transport in plant growth-promotingPseudomonas putida WCS358 (1991)
    Springer
    BioMetals 4 (1991), S. 36-40 
    Details
    ISSN: 1572-8773
    Keywords: Iron transport ; Siderophores ; Pseudomonas putida ; Genetics ; Receptors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Summary Root-colonizingPseudomonas putida WCS358 enhances growth of potato in part by producing under iron-limiting conditions a yellow-green, fluorescent siderophore designated pseudobactin 358. This siderophore efficiently complexes iron(III) in the rhizosphere, making it less available to certain endemic microorganisms, including phytopathogens, thus inhibiting their growth. At least 15 genes distributed over five gene clusters are required for the biosynthesis of pseudobactin 358. High-affinity iron(III) transport in strain WCS358 is initiated by an 86-kDa outer membrane receptor protein (PupA) which appears to be specific for ferric pseudobactin 358. PupA shares strong similarity with TonB-dependent receptor proteins ofEscherichia coli, which suggests a TonB-like protein in strain WCS358 is required for iron(III) transport. Strain WCS358 possesses a second uptake system for ferric pseudobactin 358 and structurally diverse ferric siderophores produced by other microorganisms. A second receptor gene (pupB) responsible for iron transport from pseudobactin BN7 or pseudobactin BN8 has been identified. The production of this and certain other ferric siderophore receptor proteins requires that strain WCS358 be grown in the presence of these siderophores. An apparent regulatory gene required for the expression ofpupB is located adjacent topupB. Two positive regulatory genes have been identified which can independently activate, under low-iron(III) conditions, transcription of genes coding for the biosynthesis of pseudobactin 358.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01135555
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  • 14
    Electronic Resource
    Electronic Resource
    Immunoglobulin allotypes are not associated with HLA-antigens, autoantibodies and clinical symptoms in systemic lupus erythematosus (1991)
    Springer
    Rheumatology international 11 (1991), S. 179-182 
    Details
    ISSN: 1437-160X
    Keywords: Immunoglobulin allotypes ; Systemic lupus erythematosus ; Genetics ; Gm ; Km ; HLA-antigens ; Autoantibodies ; Clinical symptoms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Immunoglobulin heavy chain (G1m, G2m, G3m, A2m) and kappa light chain (Km) allotype and phenotype frequencies of 323 central European Caucasian patients with systemic lupus erythematosus (SLE) were examined and correlated with various genetic, serologic and clinical markers of SLE. No significant associations were found between immunoglobulin allotypes or phenotypes and all 20 parameters tested (nephritis, vasculitis, arthralgias, photosensitivity, discoid lesions, central nervous system disease, Raynaud's phenomenon, sex, anti-Ro, anti-La, anti-nRNP, HLA-DR1-DR7, HLA phenotypes B8-DR3, B7-DR2). It could therefore be assumed that Gm, A2m and Km allotypes were not associated with HLA-antigens and had no influence on the serologic and clinical expression of SLE.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00332558
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  • 15
    Electronic Resource
    Electronic Resource
    Creutzfeldt-Jakob disease among libyan jews (1991)
    Springer
    European journal of epidemiology 7 (1991), S. 490-493 
    Details
    ISSN: 1573-7284
    Keywords: Creutzfeldt-Jakob diseases ; Prion disease ; Jews ; Libya ; Genetics ; Pathophysiology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract The focus of CJD among Jews of Libyan origin has been recognized for two decades, but the reasons underlying it were unknown. Prevailing views suggested transmission from sheep infected with scrapie. However, recent data show that in fact CJD in this ethnic group is a genetically determined disease due to a point mutation on the codon 200 of the prion protein gene. The clinical characteristics of CJD in this group, and particularly the less common periodic activity in the EEG, are reviewed. New findings include peripheral neuropathy of the demyelinating type in two cases, presumably due to involvement of Schwann cells. The pathophysiology of the disease includes, presumably, a focal post-translational modification of the prion protein, (predisposed by the mutation). Later, the disease progresses through cell-to-cell transmission.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00143127
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  • 16
    Electronic Resource
    Electronic Resource
    Genotype differences in catecholamine concentrations in hypothalamus, intramedial hyperstriatum ventrale, and optic tectum of newly hatched chicks (1991)
    Springer
    Neurochemical research 16 (1991), S. 105-112 
    Details
    ISSN: 1573-6903
    Keywords: Genetics ; catecholamine ; brain ; imprinting ; development
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract This study was designed to compare catecholamine concentrations among three brain areas of four pureline populations of visually isolated chicks. The purelines used were a commercial male line, a fertility selected line, an unselected fertility control line, and unselected White Jersey Giants. In general, male chicks had significantly larger brain weights than females. Six catecholamine-related compounds (norepinephrine, epinephrine,l-DOPA, dopamine, DOPAC, and MHPG) were measured via HPLC-ECD. No significant differences in neurochemical concentration were observed for any line or brain area due to sex of the chick. The hypothalamus (HT) contained the greatest concentration of catecholamines in all lines, followed by the intramedial hyperstriatum ventrale (IMHV) and optic tectum (OT). The HT exhibited consistent lateralization in all lines with the right HT containing ca. 30% more catecholamines than the left HT. While no consistent lateralization was observed among the other brain areas, the IMHV exhibited significantly different degrees of lateralization among the populations. Neuronal activity, as measured by MHPG:NE and DOPAC:DA ratio varied by line within each brain area. There were line differences for MHPG:NE in the HT, IMHV, and OT, while line differences for DOPAC:DA were observed in the HT. Since differences among purelines have been demonstrated in this study, care must be given to precisely define the genotype of chicks used in behavioral and neurochemical research.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00965696
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  • 17
    Electronic Resource
    Electronic Resource
    Inheritance of stalk rot resistance in cauliflower (Brassica oleracea var. Botrytis L.) (1991)
    Springer
    Euphytica 57 (1991), S. 93-96 
    Details
    ISSN: 1573-5060
    Keywords: Brassica oleracea ; Cauliflower ; Stalk rot ; Screening ; Genetics ; Resistance ; Sclerotinia sclerotiorum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary The inheritance of resistance in cauliflower to stalk rot (Sclerotinia sclerotiorum (Lib.) de Bary) was investigated in population from six generations of six crosses. Disease incidence was recorded on 4 parents, 6 Fs 1, 6 Fs 2 and 12 back-crosses in a screenhouse under artificially created epiphytotic conditions. Resistance to stalk rot in this set of parents was found to be polygenic and under the control of recessive genes and due primarily to additive gene action. A breeding strategy emphasizing recurrent selection should lead to improvement in resistance.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00023065
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  • 18
    Electronic Resource
    Electronic Resource
    Clinical polydiagnostic studies in a large Swedish pedigree with schizophrenia (1991)
    Springer
    European archives of psychiatry and clinical neuroscience 240 (1991), S. 188-190 
    Details
    ISSN: 1433-8491
    Keywords: Families ; Genetics ; Polydiagnostic approach ; Schizophrenia ; Swedish family complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A polydiagnostic computerized diagnostic system for psychosis was used in a Swedish family complex, and 51 patients with psychiatric symptomatology were examined with eight main diagnostic systems for schizophrenia and three systems for schizophrenic subgroups. All patients fulfilled the criteria for schizophrenia according to Taylor et al., 50 according to Carpenter, 41 according to RDC, and 31 of the 51 according to DSM-III and DSM-III-R. The hypothesis that the patients in the Swedish family complex differ from other phenotypes of schizophrenia must be refuted based on the data of the present study.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02190762
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  • 19
    Electronic Resource
    Electronic Resource
    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040101
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    Geometry of 2-benzopyrylium and pyrylium cations calculated by semi-empirical methods. Crystal and molecular structure of 1,3-dimethyl-6,7-dimethoxy-2-benzopyrylium perchlorate (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 7-12 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: X-ray data on the crystal and molecular structure of 1,3-dimethyl-6,7- dimethoxy-2-benzopyrylium perchlorate show a good correlation with the geometry of the same cation calculated by the MINDO/3 and MNDO methods with total optimization of all geometrical parameters. The geometry of substituted pyrylium cations was determined by the MNDO and AM1 methods. On the basis of the data obtained, some effects of benzo [c] annelation are displayed for the 2-benzopyrylium cation in comparison with the pyrylium cation.
    Additional Material: 2 Ill.
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    Micellar catalysis of the intramolecular aminolysis of the β-lactam antibiotic cephaclor (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 19-24 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of intramolecular degradation of cephaclor, involving the attack of the amino group at C-17 (N-18) on the β-lactam carbonyl, was increased up to 50-fold by neutral (polyoxyethylene-23 lauryl ether; Brij) and zwitterionic [3-(N-dodecyl-N, N-dimethylammonium) propane 1-sulphonate; (SDP)] micelles. The rate of OH- attack on cephaclor was increased 2-3-fold by Brij and SDP micelles. In the absence of micelles the rate of intramolecular degradation of cephaclor increased by up to 2-fold by addition of organic solvents. Distance calculations, based on the crystal structure of the antibiotic, showed that the intramolecular degration can only proceed in a conformation involving a cis-amide bond (N-14 - C-15). Micellar catalysis of the intramolecular degradation process was proposed to be due to the stabilization of the reactive conformation.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040105
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  • 22
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    Development of a model to explain the influence of the solvent on the rate and selectivity of diels-alder reactions (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 48-52 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvophobic and polarity parameters are used to explain the endo/exo selectivity of the reaction between cyclopentadiene and methyl acrylate. A good linear regression model with Sp and ETN is obtained. The existence of an intrinsic correlation between the Sp and ETN values, which makes the interpretation of the results difficult, is shown. A comparison of the results with other previously reported showed that the relative influence of Sp and ETN on selectivity depends on the nature of the reagents.
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    URL: http://dx.doi.org/10.1002/poc.610040108
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  • 23
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    Aggregation of amphiphilic molecules in water. I. α-phenylethylamine: 1H and 13C NMR study (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 58-66 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The concentration dependence of the 1H and 13C NMR chemical shifts in D2O and in CDCl3 solutions were determined for (±)-α-phenylethylamine (I). Aqueous solutions of (-)-I and (+)-I, 50% enantiomerically enriched in (-)- and (±)-2, 2, 2,-trifluoro-1-phenylethanol and the (+)- and (-)-N-formyl derivatives of I, were also studied. 1H nuclear Overhauser enhancements were used to check the conformations of the solutes at various concentrations and 1H T1 values were used to monitor the changes in molecular tumbling in solutions. The results are interpreted in terms of a spontaneous aggregation of solute molecules in water, with the possible determination of the critical micelle concentration. The time-dependent splittings in the 1H NMR spectra suggest further, more detailed, studies of the structures of the aggregates and the possibility of chiral recognition in water.
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  • 24
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    Evaluation of solvent effects on the dissociation of aliphatic carboxylic acids in aqueous N,N-dimethylformamide mixtures according to the scaled particle theory (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 87-95 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The standard Gibbs energies of transfer, ΔGt° from water to water-N,N-dimethylformamide mixtures for the dissociation process of several organic acids (formic, acetic, propionic, n-butyric, isobutyric, n-valeric, isovaleric, 2-methylbutyric and trimethylacetic acids) obtained from the pKa* values are discussed in terms of the extended Scaled Particle Theory from quantum mechanical calculations in order to estimate the cavity and electrostatic contributions. The residual energy term was correlated with the hydrogen bond acceptor density and the Kamlet-Taft β parameters. The main contribution to ΔGt° was due to dipolar and specific interactions.
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/poc.610040204
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  • 25
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    The 11C/14C kinetic isotope effect method. The 11C/14C kinetic isotope effect in the SN2 reaction of N,N-dimethyl-p-toluidine with labelled methyl iodide (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 77-86 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methodological aspects of the determination of 11C/14C kinetic isotope effects (KIEs) were investigated using the reaction of N, N-dimethyl-p-toluidine with labelled methyl iodide in methanol at 30 °C as model system. The primary 11C KIE was determined to be 1.202 ± 0.008 for this reaction. The isotope effect was determined by a one-pot technique based on liquid chromatographic fractionation of the reactant and product followed by liquid scintillation counting of the 11C and 14C radioactivity in these fractions. The KIE value obtained agrees well with the value predicted from a previously determined 12C/14C-KIE for the same reaction. Theoretical model calculations of both carbon KIEs were performed using the BEBOVIB IV program. Transition-state models ranging from reactant- to product-like were employed in the calculations, and three different reaction coordinate models with more or less pronounced Walden inversion of the methyl hydrogens were investigated.
    Additional Material: 6 Ill.
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  • 26
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    Cross-interaction constants as a measure of the transition state structure. Part 15. Kinetic isotope effects in the SN2 reactions of 2-phenylethyl derivatives with deuterated aniline nucleophiles (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 101-106 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Kinetic isotope effects (KIE) were determined for the reactions of 2-phenylethyl and 1-methyl-2-phenylethyl benzenesulphonates with deuterated aniline nucleophiles in acetonitrile at 65.0 °C. The results are in good agreement with the transition state (TS) structures proposed based on the sign and magnitude of the cross-interaction constants, pxz, between the substituents in the nucleophile (X) and the leaving group (Z). In the reactions of 2-phenylethyl derivatives, all three reaction pathways, kr, kt and kΔ, were found to be contributing competitively; the inverse secondary KIE observed with a stronger nucleophile changed into the primary KIE with a weaker nucleophile owing to the predominant contribution of the four-centre TS in the kf path. For the reactions of the 1-methyl-2-phenylethyl series, the kr path played a major role, the contribution from the front-side nucleophilic attack, kf, being negligible. In both reaction series, the aryl participation was important for the p-CH3O-substituted substrate.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/poc.610040206
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  • 27
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    Addition of hydroxylamine to cyclohexanone and bicyclic ketones. Steric, electronic and hydrogen bonding effects on the general mechanism of addition of amines to carbonyl compounds (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 107-112 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three different types of pH-rate profiles were observed for the addition of amines to carbonyl compounds, depending on the relative predominance, at weakly acidic pH, of either a concerted or a stepwise mechanism. The predominant mechanism depends on the basicity of the amine and the mutual equilibrium affinity for adduct formation between the carbonyl compound and the amine. The reaction of hydroxylamine with cyclohexanone and bicyclic ketones was studied in order to examine the roles of steric and electronic effects in this mechanism. Cyclohexanone and 3-chlorobicyclo [2.2.1] heptan-2-one exhibit the profile expected for a single change in the rate-determining step with increasing pH from uncatalysed attack of the amine on the carbonyl group to hydronium ion-catalysed dehydration of the carbinolamine. In contrast, both bicyclo [2.2.1] heptan-2-one and bicyclo [2.2.2] octan-2-one show an unexpected profile with two negative breaks and five kinetically significant regions. This profile is explained by stabilization of the zwitterionic intermediate T± by intramolecular hydrogen bonding, leading to the formation of the carbinolamine by a stepwise mechanism at weakly acidic pH.
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    URL: http://dx.doi.org/10.1002/poc.610040207
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    Crystal and molecular structure of pyrylium salts. IV. Crystal and molecular structure of 2,6-diphenyl-4-(4-carboxyphenyl)pyrylium perchlorate. Interrelations between structural parameters due to substituent effects (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 121-124 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal and molecular structure of 2,6-diphenyl-4-(4-carboxyphenyl)pyrylium perchlorate was solved by x-ray diffraction, yielding structural parameters of high precision (estimated standard deviations for bond length ≤ 0.5 pm, for bond angles ≤ 0.2°). Comparison with other 4-substituted derivatives of 2,6-diphenyl-4(4-carboxytphenylpyrylium) perchlorate shows regularities in the variations of structural parameters following classical views of substituent effects.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040209
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    Structure and dynamics of dicyandiamide: A theoretical study (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 125-134 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ab initio MO methods have been used to study the structures and energetics of dicyandiamide, [(NH2)2C=N—C≡N], its isomers, protonated species, radical anions, transition structures for internal conformational change and transition structures for isomerization. Structures were optimized at the HF/STO-3G, HF/3-21G and HF/6-31G* levels; selected barrier heights for smaller analogues were also computed at the MP4SDTQ/6-31G* level. The most stable isomer of dicyandiamide has the cyano group on the imine nitrogen [1, (NH2)2C=NC≡N]; the other isomer [2, HN=C(NH2)NH—C≡N] lies 12.8 kcal mol-1 higher. Inversion at the imino nitrogen proceeds by a linear, in plane process with a barrier of 32.5 kcal mol-1. The amino rotation barriers are 19 kcal mol-1 (single NH2) and 40 kcal mol-1 (both NH2 in a conrotaory or a disrotatory fashion; if the NH2 groups are allowed to pyramidalize the disrotatory barrier drops to 20 kcal mol)-1. Protonation occurs preferentially on the imine nitrogen (PA = 219.7 kcal mol-1 for 1); the proton affinities PA of the amino nitrogens are 25-30 kcal mol-1 lower. Isomerization between 2 and 1 would go via a 1,3-sigmatropic hydrogen shift, but the barrier is high (48.3 kcal mol-1); protonation reduces the hydrogen shift barrier by ca 15 kcal mol-1. However, the most likely mechanism for isomerization involves protonation of the imine nitrogen in 2 followed by deprotonation of the cyano-substituted nitrogen to form 1, circumventing the energetically costly 1,3-sigmatropic hydrogen shift. When an electron is transferred to dicyandiamide, a sizeable fraction of the resonance stabilization of the guanidine moiety is lost.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040302
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    The grignard reaction of α-diketones. Radical intermediates as the determinant of carbon- and oxygen-attacked products (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 158-162 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Although carbon (normal)- and oxygen (abnormal)-attacked products are usually afforded in the Grignard reaction of α-diketones, the relative ratio of the two are strongly dependent on the structure of the Grignard reagents. The product-determining factors are discussed on the basis of the intermediate radicals formed from α-diketones and Grignard reagents.
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    URL: http://dx.doi.org/10.1002/poc.610040401
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  • 32
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    Kinetics of oxidation of hydrocarbons by quinolinium dichromate (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 217-224 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quinolinium dichromate (QDC) oxidizes hydrocarbons (toluenes and phenanthrenes) smoothly in dimethylformamide in the presence of acid. The rate of the reaction was first order in each substrate, oxidant and acid. The effects of variations in solvent composition and temperature were studied. The rate data obeyed Hammett's relationship and the values of ρ were -0.20 for toluenes and -1.79 for phenanthrenes. Induced polymerization of acrylonitrile and the reduction of mercury(II) chloride were not observed. For the oxidation of toluenes, a kinetic isotope effect, kH/kD = 5.13, was observed. The initial reaction for the oxidation of toluenes involved hydrogen abstraction, forming an intermediate which was rapidly converted to the product, the corresponding aldehyde. For the oxidation of phenanthrene, the experimental data have been rationalized in terms of a hydride ion transfer in the ratedetermining step.
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    Isotope effects in acid-catalyzed aromatic hydrogen exchangePresented in part at the 68th CIC Chemical Conference, Kingston, Canada, June 1985, paper no. OR-C3-4. (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 233-241 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Deuterium- or tritium-substituted aromatics undergo isotope exchange in fairly concentrated aqueous sulfuric acid media. The rate constant for this process is complex, being composed of that for the slow electrophilic attack, and the isotope effect on the breakup of the Wheland intermediate. Using experimental rate constant data for both deuterium and tritium exchange on the same substrate, the excess acidity method and the Swain-Schaad relationship, true protonation rate constants and isotope effects have been separated out for several positions in several simple aromatic substrates. Most of the electrophilic attack rate constants are described by a Hammett-type linear free energy relationship with a ρ+ of - 6.5. The average observed deuterium isotope effect on Wheland intermediate breakup was 5.3. Using rate constants obtained at different temperatures, enthalpies and entropies of activation were also obtained for benzene, naphthalene and thiophene; the activation entropy averaged - 8 cal mol-1 K-1. Some evidence was found for general acid catalysis at the higher acidities.
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040501
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    Conversion of flavanones into chalcones in alkaline medium. Kinetic and spectroscopic studies (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 263-270 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conversion of flavanone and 7-hydroxyflavanone in alkaline water and heavy water and of the same compounds and of 4′ -nitroflavanone in alkali-methanolic media into the corresponding substituted chalcones was studied kinetically and spectroscopically. Treatment of kinetic data in this work and data for the reverse reaction determined previously allowed the estimation of the partial rate coefficients for each step and of the free-energy changes for the three systems studied. To disentangle isotope effects, the conversion of [3-D2]-flavanone was also studied. The present results confirm a previously suggested mechanism for the spontaneous reaction and afford essential information that may contribute to a more detailed understanding of the mechanism of the enzyme-catalysed reaction.
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    Kinetic modelling of the low-temperature photo-oxidation of hexafluoropropene (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 293-300 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By kinetic simulation, the significant features of the mechanism of the low-temperature photo-oxidation of hexafluoropropene were elucidated and the rate constants for the major elementary reactions of the intermediate fluorinated peroxy and alkoxy radicals were determined through a best-fit procedure. Comparison with analogue reactions in non-fluorinated systems showed a significant increase in reactivity for the self-reaction and double bond addition by peroxy radicals and β-scission by alkoxy radicals, which are discussed in terms of fluorine substituent effects.
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    URL: http://dx.doi.org/10.1002/poc.610040601
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    New ideas on phase transfer catalysts: SN2 reaction with a solid ionophoric salt (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 336-340 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new mechanism of substitution between n-hexyl bromide (RBr) and solid potassium chloride in toluene under phasetransfer catalysis conditions is suggested, involving the formation of intermediates, adsorbed on the solid phase, viz., two binary (KCl·QX and KX·QBr) and two ternary (QX·KCl·RBr and QBr·KX·RCl) complexes. According to this mechanism, the catalytic activity of onium salts (QX) in the substitution changes in the order QI 〉 QBr 〉 QCl. The nature of the catalyst cation has little or no effect on the reaction rate. A general rule is proposed according to which in this reaction the substrate is attacked by a stronger nucleophile whereas a weaker nucleophile accepts the leaving group of the substrate. These and earlier data are interpreted in term of the SN2 process occurring on the solid-phase surface. The structure of the ternary complexes and the role of the phase-transfer catalyst are discussed.
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    Origin of apparent swain-schaad deviations in criteria for tunneling (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 361-366 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Vibrational analysis calculations have been conducted in an effort to understand the origins of apparently anomalous relationships reported between kH/kT and kD/kT kinetic isotope effects. The actual isotopic substitutions used in previous work are more complex than a simple comparison between H/T and D/T isotope effects. The relationships between the actual isotope effects determined in these studies amount to tests of two standards of conventional isotope effect theory, the rule of the geometric mean (or the lack of isotope effects on isotope effects) and the Swain - Schaad rule. Model calculations illustrate the importance of violations of the rule of the geometric mean (over Swain - Schaad deviations) arising in models that incorporate both explicit reaction-coordinate coupling of two isotopic sites and reaction-coordinate tunneling. Implications for experimental studies of turneling using apparent Swain - Schaad exponents are discussed.
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    The schiff base between pyridoxal-5′-phosphate (PLP) and hexylamine. Formation of the unprotonated form of the imine by reaction of the unprotonated PLP and free amine (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 372-380 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electrochemical and spectrophotometric studies of the pyridoxal-5′ -phosphate hexylamine Schiff base (PHSB) in strongly basic media were carried out. The equilibrium constant and rate constants of the formation and hydrolysis of the unprotonated imine from the unprotonated pyridoxal-5′ -phosphate and free amine were determined by linearscan cyclic voltammetry. The acid-base dissociation constant of the imine group was obtained by spectrophotometric measurements. Absorption bands for the free imine and the conjugate acid are characterized by a log-normal distribution. These studies are for general application to the quantitative characterization of non-enzymatic model compounds.
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    URL: http://dx.doi.org/10.1002/poc.610040609
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    Factors affecting the reversibility of the electrophilic step in olefin bromination. The case of 5H-dibenzo [a, d] cycloheptene (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 387-398 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The tendency of ion-pair intermediates generated by treatment of trans-10-bromo-10, 11-dihydro-11-hydroxy-5H-dibenzo [a, d] cycloheptene (5) with HBr to release Br2 giving 5H-dibenzo [a, d,] cycloheptene (1) has been evaluated. The observed 9:1 ratio between ion-pair collapse to the trans-dibromide (7) and Br2 release to olefin 1, as compared with the 3:7 ratio found with the 5H-dibenz [b, f] azepine-5-carbonyl chloride system, has been interpreted as indicating a much lower propensity for reversibility of ion-pair formation in the bromination of 1. The structural parameters obtained by x-ray diffraction of the dibromide 7 show for this compound an angle strain at C-10 and C-11 analogous to that found in trans-10, 11-dibromo-10, 11-dihydro-5H-dibenz [b, f,] azepine-5-carbonyl chloride. Olefin 1 adds Br2 in 1,2-dichloroethane at 25°C according to a third-order rate law, with k3 = 30(3) M-2 s-1. About 10% of 5-bromo-5H,-dibenzo [a, d] cycloheptene, arising from collapse of a dibenzo [a, d] tropylium ion intermediate (9), is formed in this reaction besides the expected trans-dibromide 7. Spectral evidence for the formation of 9, arising by rearrangement of a first formed weakly bridged ionic intermediate in the reaction of 1 with Br2, is presented. the results obtained with the 5H-dibenzo [a, d,] cycloheptene system have been rationalized on the basis of the formation of very weakly bridged intermediates having a much lower tendency to revert back to olefin and Br2 with respect to the corresponding symmetrically bridged bromonium ions.
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    SRN1 Reactions of nucleophiles with radical clocks: Rate constants for some radical-nucleophile reactions (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 404-412 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Treatment of o-3-(but-3-enyloxy)benzene (1) with anions -SPh, -PPh2 and -PO(OEt)2 in ammonia, acetonitrile or dimethyl sulphoxide gives both direct substitution and cyclized products. The formation of the latter confirms the intermediacy of the o-3-(but-3-enyloxy)phenyl radical (2) and confirms that the reactions follow the SRN1 pathway. The kinetics of the coupling of the aryl radical 2 were determined by comparison with the known rate of cyclization of 2. Similar experiments with the neopentyl bromide, 6-bromo-5,5-dimethylhex-1-ene, and its 3-oxa derivative also gave cyclized and uncyclized products, thus confirming that the SRN1 mechanism applies to the reactions. Approximate rate constants for the coupling of a neopentyl radical with the nucleophiles -SPh and -PPh2 have thus been determined.
    Additional Material: 5 Tab.
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  • 43
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    Short Communications. Biphenyl-3,4′-Dinitrene (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 459-462 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photolysis of biphenyl-3,4′ -diazide in a rigid glassy matrix at 77 K yields quintet state biphenyl-3,4′ -dinitrene with zero-field splitting parameters of |D/hc- = 0.153 cm-1 and |E/hc| = 0.019 cm-1 determined by electron spin resonance spectroscopic studies. Curie plot studies are consistent with assigning the quintet to be the ground state in this species. This finding confirms qualitative connectivity-based predictions for this general connectivity type of openshell system, and is in qualitative agreement with spectral INDO-CI computational predictions for both planar and twisted geometries of the dinitrene.
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    URL: http://dx.doi.org/10.1002/poc.610040708
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  • 44
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    The α-bromocyclohexanone ring: The relationship between its conformation and the ultraviolet and infrared absorption of the keto group (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 420-438 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of diterpenoids whose C-ring was an α-bromocyclohexanone showed a discontinuity in the relationship between the Br—C—C=O torsion angle and the Br…O contact distance at about 50°, below which the Br…O distance remained effectively constant at about 3.0 Å. This effect is caused by the non-compressibility of the van der Waals radii of the Br and O atoms. Analysis of the parameters for all compounds in the Cambridge Data File containing an α-bromocyclohexanone ring confirmed this phenomenon. Once the Br…O distance approaches 3.0 Å, the Br—C—C and C—C=O angles are forced open to accommodate the Br…O compression strain as the torsion angle is further reduced. An approximate value of the Br…O distance, d in Å, can be estimated for any torsion angle, ø, by the empirical equation d2 = R - S cos φ + T cos2 φ where R = 11.73, S = 3.62 and T = 0.75. There is a linear relationship between the Br…O separation and both the infrared vibration frequency v and the ultraviolet absorption wavelength δmax of the C=O group: the greater the distance, the lower is the frequency v and longer the wavelength δmax. Thus measurement of the ultraviolet and infrared spectra of a compound containing an α-bromocyclohexanone system can yield information about the Br…O distance and hence the conformation of the six-membered ring. There are also systematic trends in the effect on the spectroscopic properties of the keto group that accompany changing the halogen from fluorine through to iodine. When the halogen is axial, its electronegativity has a maximum influence on the C=O vibration frequency by a ‘through-bond’ inductive process. When the halogen is equatorial, it exerts a steric compression on the non-bonded electrons in the 2p orbital of the oxygen atom. This enhances hybridization to the sp2 state and this simultaneously strengthens the C=O bond and enlarges the n → π* energy gap. This ‘through-space’ influence is simply a process of steric compression, dependent on the size of the halogen atom. It accounts well for all of the systematic trends in both infrared and ultraviolet frequencies of the C=O group when the halogen is equatorial and eclipses the C=O bond.
    Additional Material: 11 Ill.
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  • 45
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040801
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  • 46
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    Treatment of electrostatic effects within the molecular mechanics method. 3. Double bonds and conjugated systems (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 467-478 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The previously developed general method (IDME), which includes calculation of electrostatic and solvation effects on conformational equilibria, has been extended to molecules containing double bonds and conjugated systems. It was applied in connection with MM2 studies to the calculation of the charge distributions and dipole moments, and to the conformational energies of some β-substituted cyclohexenes, exo-methylenecyclohexanes and benzocycloheptenes. Conformational equilibria and dipole moments were well calculated. It was concluded that electrostatic interactions do not play a major role in determining conformational preferences in these compounds. On the other hand, the energies of the preferred conformations of the ten-membered ring in (E)-3β-acetoxy-5,10-seco-1(10)-cholesten-5-one are poorly calculated without the IDME procedure, and fairly well with it.
    Additional Material: 6 Ill.
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  • 47
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    Theoretical models for the reduction of arylmethyl halides by triorganotin hydridesPreliminary presentation of results at combined 45th Northwest-10th Rocky Mountain Regional Meeting of the American Chemical Society, Salt Lake City, UT, 13 June 1990. (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 485-491 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two mechanistic pathways have been proposed for halogen atom transfer from the benzylic positions of halomethylarenes to triorganotin radicals. These are direct atom abstraction, which might involve an extremely polar transition state, and single electron transfer followed by bond cleavage. AM1 semi-empirical calculations have been utilized to model the rate-determining step of these processes. A wide range of related families of compounds have been studied, including substituted halomethylbenzes, selected halomethyl-substituted polycyclic aromatic hydrocarbons and oxygen- and nitrogen-containing chloromethyl-substituted heteroaromatic systems. Although these calculations are relatively simple, the present results corroborate the view that chlorine and bromine atom transfer from the benzylic position to triorganotin radicals involves a direct atom abstraction in the rate-determining step whereas reduction of the corresponding iodides proceeds via an electron-transfer mechanism.
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  • 48
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    Ambident electrophilicity of alkyl aryl phosphates (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 516-522 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrolysis of dimethyl aryl phosphates, (MeO)2P(O)OAr where the ArO group is derived from N-methyl-8-hydroxyquinolinium or 4-hydroxy-(N,N,N-trimethylanilinium) ion, proceeds with the cleavage of the P—OAr and Me—O bonds. The effect of external factors on the relative contributions of those two reaction pathways was studied. The increase in temperature favours, owing to the difference in activation entropies, the reaction at carbon. The addition acetone to the aqueous reaction medium slows down the reaction at carbon more rapidly than the reaction at phosphorus, indicating higher hydration requirements of the dealkylation transition state. In water-triffuoracetic acid mixtures only the P—OAr bond cleavage is acid catalysed; the catalytic effect is superimposed on the general, decelerating medium effect. Specific nucleophilic catalysis was demonstrated for the Me—O bond fission by thiosulphate ion (ca 60-fold acceleration), and for the reaction at phosphorus by fluoride ion (ca 500-fold acceleration).
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/poc.610040807
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  • 49
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040901
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  • 50
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    Short communication. Structural studies of bromine adducts of 1,2- and 1,4-bis(phenylseleno)benzenes. Evidence for the (TB, MC) structure of 1,2-(PhSeBr2)2C6H4 (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 523-525 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1,2-Bis(phenylseleno)benzene reacted with equimolar amount of bromine to yield a trigonal bipyramidal (TB) adduct, in contrast to the molecular complex (MC) structure of selenanthrene with bromine. Whereas the structure of 1,4-(PhSeBr2)2C6H4 was (TB, TB) at the two selenium atoms, that of the 1,2-derivative was demonstrated to be (TB, MC), the first example of an MC structure of PhSeC6H4Y with Br2 [Y = 2-PhBr2Se(TB)]. Both electronic and steric effects of the group must play an important role in MC formation. Rapid structural exchange in this tetrabromide, (TB, MC) ⇄ (MC, TB), was also observed.
    Additional Material: 2 Tab.
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  • 51
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    Conformations of pentan-1-OL, hexan-1-OL and their thio analogues (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 536-540 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Empirical linear relationships between standard Gibbs free energy, ΔG298°, and parachor and between standard entropy, S298°, and parachor are presented for the aliphatic series H(CH2)nX with X = CH3, CH=CH2, C≡CH, Cl, OH, SH, SCH3 and SC2H5. In the series with X = OH and SH significant deviations of points for n = 4 and 5 are observed. INDO quantum-chemical analysis points to the formation of cyclic conformers of butan-1-ol, pentan-1-ol and their corresponding thio analogues. The formation energy of the cyclic conformers (higher for thiols than for alcohols) is proportional to the sum of deviations from the linearity of the points under discussion.
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    URL: http://dx.doi.org/10.1002/poc.610040903
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  • 52
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    Review commentary. Solvation, the electrophilic driving force of ionic bromination of ethylenic compounds. The addition-solvolysis analogy (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 527-535 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvation is the main driving force of electrophilic bromination since it is impossible to obtain a bromonium ion from bromine and alkene in the gas phase, whereas it is a very fast reaction in solution. The role of a protic solvent in this addition was investigated experimentally by extended Winstein-Grunwald relationships, kinetic solvent isotope effects and R, the rate ratios in two solvents of similar ionizing powers but different nucleophilicities. It is shown that electrostatic medium effects and electrophilic assistance to bromide ion departure are the main rate-determining factors of the reaction. These two contributions are roughly independent of the double bond substituents. Nucleophilic solvent assistance to positive charge development is also found; however, it provides only a small acceleration, the magnitude of which depends on alkene structure. This nucleophilic solvent involvement is annulled when crowded substituents inhibit approach of the solvent to the cationic part of the transition state or when positive charge is delocalized by conjugated electron-donating groups. These several solvent roles are identical in nature and in magnitude with those observed in heterolytic solvolysis. In halogenated solvents, the driving force of bromination arises from catalysis by a second bromine molecule which assists heterolysis of the bromine-bromine bond, leading to the bromonium-tribromide ion pair. Similar halogen catalysis occurs also in some solvolyses. Finally, return is also found in both reactions; reversible formation of bromonium ions is observed when their nucleophilic attack, the productforming last step, is made energetically difficult either by steric inhibition or by poor nucleophilicity of the trapping nucleophiles. Similarities and differences between electrophilic bromine addition and limiting solvolysis are discussed in terms of respective intermediate stabilities and heats of formation.
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  • 53
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    Photochemical transformations. 49.For Part 48, see Ref. 1. Solvent effects on singlet ionic and triplet photoreactions of some bridged polycyclic chlorides: Comparison with ground-state reactionsDedicated to Professor Kurt Schaffner on his 60th birthday. (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 541-546 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Direct irradiations of 2-chloro-6,7 : 8,9-dibenzotricyclo [3.2.2.02,4] nona-6,8-diene (5-Cl) were conducted in cyclohexane, acetic acid and wet acetonitrile. The products are 1-methylfluoranthene (8) in all three solvents, the allylic chlorides 8-chloro-7-methylene-2,3 : 5,6-dibenzobicyclo [2.2.2] octa-2,5-diene (3-Cl) and 7-chloromethyl-2,3 : 5,6-dibenzobicyclo [2.2.2] octa-2,5,7-triene (2-Cl) in acetic acid and acetonitrile and solvolysis product amides in wet acetonitrile. Compound 5-Cl had previously been shown to be the product of triplet sensitization of 2-Cl and 3-Cl, so that the singlet reaction reverses that of the triplet. The formation of 8 from 5-Cl was quenched with piperylene, whereas that of the allylic chlorides was not. Quantum yields of products and singlet lifetimes in the three solvents were measured. The solvent effects are discussed. Deuterium-labeling results on the formation of 5-Cl from 2-Cl and of 8 from 5-Cl are reported.
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  • 54
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    Methyl substituent effects on the dissociation energies of Si—X bonds (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 562-565 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Empirical expressions are obtained for bond dissociation energies (BDEs) of alkylsilanes and their derivatives. It is pointed out that the sensitivity of the BDEs of Si—X bonds to methyl substitution depends on the electronegativity of the substituent X. When X is an atom or group with low or moderate electronegativity, the Si—X BDE is insensitive to methyl substitution, but when X is a halogen atom or OH, the Si—X BDEs increase with increasing methyl substitution.
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  • 55
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    Kinetics and mechanism of the cleavage of phthalimide in buffers of tertiary and secondary amines. Evidence of intramolecular general acid-base catalysis in the reactions of phthalimide with secondary amines (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 547-561 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction rates of the cleavage of phthalimide (PTH) were studied at 30°C in buffer solutions of trimethylamine, triethylamine, triethanolamine, carbonate, piperidine, dimethylamine, morpholine, piperazine and N-methylpiperazine at different pH values. The reactivity of carbonate, triethylamine and triethanolamine toward PTH could not be detected under the experimental conditions applied. However, triethylamine revealed nucleophilic reactivity toward non-ionized PTH (SH). The steric requirements of triethylamine and triethanolamine are ascribed to the absence of nucleophilic reactivities of these amines toward SH. Secondary amines show nucleophilic reactivity toward both SH and ionized PTH (S-). The absence of nucleophilic reactivity of trimethylamine and the presence of nucleophilic reactivity of secondary amines toward S- are attributed to the occurrence of intramolecular general acid-base catalysis due to the presence of a mobile proton at the nucleophilic site of the nucleophile. Intermolecular general base catalysis was observed in the reactions of SH with all secondary amines except piperidine and such catalysis could be detected in the reactions of S- with morpholine, piperazine and N-methylpiperazine. Nucleophilic second-order rate constants for the reactions of secondary amines with SH (k1) and S- (k2) reveal the Brønsted plots of slopes of ca 0.8 and 0.3, respectively. Similarly, the general base-catalysed third-order rate constants (k4) for the reactions of secondary amines with SH yield a Brønsted plot of slope 1.2. These observations suggest the occurrence of diffusion-controlled trapping stepwise and pre-association stepwise mechanisms in the aminolysis of non-ionized and ionized phthalimide, respectively.
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  • 56
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    Multiplicities of π-ylide ground states: Computational evidence for a breakdown of aromaticity arguments (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 566-572 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: AM1 and 3-21G computations, on the lowest singlet state of selected π-ylides, support the earlier conclusion that π-ylides are highly polar with highly reactive side-chains. The computations also indicate that the corresponding triplet states are lower in energy and have substantially reduced polarity. Contrary to the expectations derived from Hückel calculations, AM1 and 3-21G calculations suggest that the best π-ylide structures have non-aromatic rings. The heats of isomerization contradict earlier conclusions reached using topological resonance energies. π-Ylides are expected to afford different product structures depending on the electronic state of the π-ylide involved in a given cycloaddition reaction.
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  • 57
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    Protein immobilization by aminolysis of cellulose xanthate esters (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 573-578 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: P-Nitrobenzyl cellulose xanthate (CelXNB) was obtained with a degree of substitution (DS) in the range 0.5-3. The first order rate constant for hydrolysis of CelXNB at 25°C, extrapolated to zero buffer concentration, is hydroxide ion catalysed, whereas the water-catalyed path is about 2000 times faster than that observed for p-nitrobenzyl ethylxanthate (EXNB), probably owing to the highly ordered cybotactic region of cellulose. Aminolysis of CelXNB produces the corresponding thioncarbamate ester; for simple alkylamines, the second-order rate constants are similar to those obtained for EXNB. The secod-order rate constants are similar to those obtained for EXNB. The second-order rate constants at pH 11 for immobilization of bacterial α-amylase and bovine serum albumin were 13.4 and 112 1 mol-1 s-1, respectively, unexpectedly high values when compared with simple alkylamines, even considering the concentration of external reactive groups of the proteins. CelXNB with low DS should release 1 mol of p-nitro-α-toluenethiol for every mole of protein that becomes immobilized. The net weight increase of the cellulose matrix allows the calculation of the absolute molecular weight of the protein. Preliminary results support this assumption.
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  • 58
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    Gas-phase thermolysis of aryl tert-butyl disulphides (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 579-585 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pyrolysis kinetics of RC6H4SS—t—C4H9 (R=H, p-NO2, p-Cl, p-F) were determined at 390-450°C and 7-15 Torr in a stirred-flow reactor using toluene as carrier gas. The reaction products were 95% isobutene, 5% isobutane and the corresponding RC6H4SSH disulphanes. The first-order rate constants, k (s-1), based on isobutene production, followed the Arrhenius equations: phenyl tert-butyl disulphide, k = 1013.49±0.31 exp (- 182 ± 4 kJ mol-1)(RT)-1; pnitrophenyl tert-butyl disulphide, k = 1013.46 ± 0.32 [exp(- 185 ± 5 kJ mol-1)(RT)-1]; p-chlorophenyl tert-butyl disulphide, k = 1014.44 ± 0.66 [exp(- 196 ± 9 kJ mol-1)(RT)-1; p-fluorophenyl tert-butyl disulphide, k = 1010.80 ± 0.16 exp(- 144.5 ± 2 kJ mol -1)(RT)-1]; The observed reactivities, within the above temperature range, follow the order p—F 〉 H 〉 p—Cl 〉 p—NO2. A four-centre, cuadrupolar cyclic transition state mechanism is proposed for the formation of the isobutene and aryldisulphane products. The optimized ground-state molecular geometries of the reactants were calculated by using the MINDO/3 procedure.
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  • 59
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610041001
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  • 60
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    Vinyl ether hydrolysis. 25. Effect of α- and β-trimethylsilyl substitution (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 587-591 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rates of hydrolysis catalyzed by dilute perchloric acid were measured for the vinyl ethers MeOC(SiMe3)=CH2, EtOC(SiMe3)=CH2, cis-EtOCH=CHSiMe3, MeOC(t-Bu)=CH2 and EtOC(t-Bu)=CH2 in wholly aqueous solution and for MeOCH=CH2, MeOC(SiMe3)=CH2 and MeOC(t-Bu)=CH2 in ethanol - water (4:1), in order to assess the effects of silyl substitution on the stability of the carbocations formed in the rate-determining step of these reactions. The results for α-substitution give the reactivity order H 〈 SiMe3 〈 t-Bu, with a greater spread (103) in wholly aqueous solution than in the mixed solvent (102). The β-trimethylsilyl substituent shows a modest 100-fold acceleration over hydrogen; the diminished magnitude of this effect relative to the 1012-fold acceleration found recently in a cyclohexyl solvolysis reaction is attributed to the imposition of a conformation in the transition state of vinyl ether hydrolysis that is far from optimum for hyperconjugative electron donation.
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    An ene reaction with a polar transition state as ascertained from solvent effects (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 605-610 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A kinetic study is reported for the ene reaction between methyl acrylate as the enophile and β-pinene, with aluminium chloride as catalyst, in a series of solvents varying in polarity. These experiments point to a transition state having pronounced zwitterionic character, in line with earlier suggestions in the literature. An unexpected and significant change of the rate constant with the initial concentrations is also found.
    Additional Material: 6 Ill.
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    Solvatochromism of dyes. Part I. Solvatochromism of merocyanines. Derivatives of the 7H-indolo [1,2-a] quinolinium system. A new model of solvatochromism (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 592-604 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new approximate model of the solvatochromism of merocyanines is presented. In solution merocyanines exist in the electronic ground state as a mixture of three different structures. Since only one longest wavelength band is observed in the UV - visible absorption spectra of such merocyanines, their lowest excited states are roughly assumed to be represented by a single structure. The molar fraction of each of the three structures of merocyanines in the ground state is a function of the solvent polarity. This (VBHB) model has been verified using merocyanines prepared from 5-(hydroxyaryl)-7,7-dimethyl-7H-indolo [1,2-a] quinolinium perchlorates. The analysis of the experimental data suggests that the three ground-state structures of merocyanines are the vinylogous amide (V) and the betaine as the free (B) or hydrogen-bonded (HB) form.
    Additional Material: 7 Ill.
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    Steric effects of alkyl groups: A ‘cone angle’ approach (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 611-617 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A ‘cone angle’, θR, is defined for an alkyl group (R), which is proposed as a measure of the steric effect exerted by the group. The θR values for some 57 groups have been calculated mathematically by constructing the corresponding Corey - Pauling - Koltun molecular models. The variation in θR with the bulk of a group is satisfactory. However not all types of alkyl groups can be accommodated in this cone angle approach. In the case of the groups for which the cone angle can be measured, correspondences between θR and the two existing steric parameters (Taft's Es scale and Dubois' E′s scale) have been established. For some 23 alkyl groups θR has been used to explain the variation in the rate constant of the base-catalysed hydrolysis of RCOOEt with the nature of R. Our studies independently substantiate the basic assumptions of the Taft - Ingold hypothesis that, while the base-catalysed ester hydrolysis is mostly controlled by the steric and electronic effects of the R group, the acid-catalysed one is controlled almost solely be the steric effect.
    Additional Material: 5 Ill.
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    Gas-phase acidity of some α-keto aldoximes: Experiment and theory (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 285-292 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental gas-phase acidities of 2-oxopropanaloximes, XCH2COCH=NOH (X = H, CH3S, CH3SO, CH3SO2; compounds 1-4), were determined by Fourier transform ion cyclotron resonance (FT-ICR) spectrometry. The values are δ Gacid° = 1401, 1381, 1360 and 1351 kJ mol-1 for 1, 2, 3, and 4, respectively. Molecular orbital calculations using the semi-empirical AM1 method provided information on the geometry and relative energy of neutrals species 1-4 and their conjugate bases, together with charge distributions and entropies of deprotonation. It is demonstrated that the proton abstraction occurs preferentially at the oxime function; the formation of an enolate as a conjugate base is unfavourable by 70-140 kJ mol-1. The large variation of the gas-phase acidities for 1-4 is explained in terms of the field/inductive empirical substituent constant σF. The variation of solution acidities appears to be comparatively strongly attenuated. This attenuation is attributed mainly to charge delocalization in the anion, which was confirmed by charge density calculations.
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    Depurination of (dien)Pt(II) complexes of purine deoxyribonucleosides. Comparison with the effects of (dien)Pd(II) ion complexing (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 301-309 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: First-order rate constants for the hydrolytic depurination of 2′-deoxyinosine and its various (dien)Pt(II) ion complexes were measured over the acidic pH range. The rate profiles obtained indicate that the uncomplexed nucleoside and its N1-(dien)Pt(II) complex are depurinated via mono- and di-protonated species, whereas the N7-(dien)Pt(II) and N1, N7-di(dien)Pt(II) complexes exhibit significant spontaneous hydrolysis, which competes with a markedly retarded acid-catalysed reaction. Rate constants for the various partial reactions were calculated and the results were employed to explain the effects that (dien)Pd(II) ion exerted on depurination rates of the same compounds. Similar measurements were carried out with the N1, N7-di(dien)Pt(II) complex of 2′-deoxyadenosine in order to further the understanding of the previously reported rate-enhancing effect of (dien)Pd(II) ion on the depurination of 2′-deoxyadenosine.
    Additional Material: 9 Ill.
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    Crystallographic studies of intra- and inter- molecular interactions. Part VI. Crystal and molecular structure of N,N′-dimethyl-N′-phenylsulphonylformamidine. Equalization of CN bond lengths in the amidine fragment as a result of substituent effects due to push-pull (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 331-335 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystal and molecular structure of N,N-dimethyl-N′-phenylsulphonylformamidine is solved by direct methods and refined to R = 0.041 for 935 reflections, Equalization of CN bond lengths in the amidine fragment is discussed in terms of a push - pull effect operating between the N,N-dimethyl and SO2Ph groups. A significant role of the substituent at the functional carbon on the degree of π-electron delocalization on the NCN fragment is interpreted by use of the HOSE model.
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    URL: http://dx.doi.org/10.1002/poc.610040602
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    Reactivity and reaction patterns of alkyl alkoxybenzene radical cations. Mechanistic pathways of the reactions between 2,5-DI-tert-Butyl-1, 4-Dimethoxybenzene and perfluorodiacyl peroxides (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 1-6 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the reactions of 2,5-di-tert-butyl-1,4-dimethoxybezene (1) with different oxidants, the radical cation 1+. is always detectable by EPR. However, the observed reactivity of 1+. depends greatly on the oxidation systems employed. In S2O82-—Cu2+—HOAc and Ce4+—HOAc systems (HOAc = acetic acid), 1+. appears to have long lifetimes and does not undergo fragmentation spontaneously. In contrast, in (RFCO2)2—CF2CICFCI2 (F113) systems, the readily formed 1+. is short-lived, and large amounts of de-tert-butylation products have been isolated. Experimental results imply that the C—C bond cleavage involved in de-tert-butylation could be a consequence of an attack by perfluoroacyloxy radical on 1+. in their original solvent cage. The fact that addition of methanol to the reaction mixture leads to the formation of a large amount of tBuOCH3 (46%) and other evidence suggest that the tert-butyl group leaves as a carbocation. On the basis of these results, we conclude that the reactions of 1 with (RFCO2)2 are initiated by electron transfer and followed by a fast coupling of various radical species, namely, 1+. with RFCO2 or with RF in the solvent cage, to form σ-complexes which collapse or react with nucleophiles to yield the final products.
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040701
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    Applicability of excess acidity functions in low-acidity media (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 413-419 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated that excess acidity functions do not correspond well to the pH scale in dilute solutions. Acidity constants, pKBH+, of seven moderately weak bases were determined; they were calculated by means of excess acidity functions, since the corresponding ionizations occur at acidity levels where the pH scale is partly used. The excess acidity method permitted extrapolation of measurements made in concentrated acids down to dilute solutions only up to about 5% (w/w) perchloric acid.
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    URL: http://dx.doi.org/10.1002/poc.610040704
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    Correlation of alkyl and polar substituents in the elimination kinetics of 2-substituted ethyl methanesulphonates in the gas phase (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 399-403 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the elimination of several polar 2-substituted ethyl methanesulphonates in the gas phase were determined in a static system, seasoned with allylbromide, and in the presence of at least equal amount of the freeradical suppressor propene and/toluene. The working temperature and pressure ranges were 290-360°C and 31°199 Torr (1 Torr = 133.3 Pa), respectively. The reactions are homogeneous, unimolecular, show a first-order rate law and take place according to the following equations: for 3-chloropropyl methanesulphonate, log k1 (s-1) = (12.01 ± 0.18) - (171.7 ± 2.1) kJ mol-1 (2.303RT)-1; for 4-chlorobutyl methanesulphonate, log k1 (S-1) = (11.78 ± 0.31) - (166.1 ± 3.5) kJ mol-1 (2.303RT)-1; for 3-methoxypropyl methanesulphonate, log k1 (s-1) = (11.50 ± 0.36) - (163.3 ± 4.0) kJ Mol-1 (2.303RT)-1; and for 2-ethoxyethyl methanesulphonate, log k1 (s-1) = (11.52 ± 0.37) - (167.3 ± 4.1) kJ mol-1 (2.303RT)-1. The present data together with those reported in the literature show that alkyl 2-substituted ethyl methanesulphonates give an approximate straight line when log k/ko vs σ* values (ρ* = -0.82 ± 0.088, intercept = 0.0084 ± 0.0209 and correlation coefficient r = 0.967 at 320°C) are plotted. However, polar substituents at the 2-position of ethyl methanesulphonates give rise to an inflection point at σ*(CH3) = 0.00 into another very good straight line (σ* = -0.29 ± 0.013, intercept = -0.0065 ± 0.0213 and r = 0.994 at 320°C). The mechanism of these reactions is considered to be heterolytic in nature, proceeding in terms of an intimate ion-pair intermediate.
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    Correlations between empirical lewis acid-base solvent parameters and the thermodynamic parameters of ion solvation. Part II. Acidity parameters of cations and basicity parameters of anions (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 439-448 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The parameters α, β and γ of the equation WΔsGf(MX) = αBKT + βET + γ were calculated and analysed for different salts (MX) in pure solvents and in non-aqueous solvent-water mixtures (S). Among 109 different equations, only 64 were taken for the final analysis since in the case of 38 equations the parameters BKT and ET were highly correlated. After a statistical analysis and normalization, on the basis of the coefficients α and β obtained, it was found that the ions analysed may be divided into three classes characterized by the different dependences of α on β: class I, H+, Li+, Na+, Rb +, Cs+, Me4N+, Cl-, Br- and I-, where αN = 1.074βN + 1.639; class II, Ag+, Cl-, Br-, I-, OAc-, SCN- and N3- where αN = 2.057βN + 2.147; and class III, Ph4As+, BPh4-, Ph4C and Ph4Ge, where αN is variable and βN is almost constant. Two main conclusions can be drawn out from the results obtained: the behaviour of ions considered as Lewis acids and bases reflects different hard-soft properties of the ions, and the behaviour of the Ph4As+ ion is different from that of BPh4-.
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    AM1 studies on the intramolecular cyclization of ω-haloenolate anionsDetermination of reactivity by MO Theory, Part 72. For Part 71, see Ref. 1. (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 449-458 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intramolecular cyclizations of ω-haloenolate anions, -CαH2—C(=O)—(CH2)n-3—CωH2—X with X = F, Cl and Br and n = 3-7, were investigated by the AM1 method. In most cases, cycloketone formation proceeds more favourably than cycloether formation, as predicted by the HSAB principle. The reactivity increases in the order X = F 〈 Br 〈 Cl for both processes, and for cycloether formation it is in the order n = 3 〈 4 〈 7 〈 6 〈 5 for all X but the relative order for n = 5 and 6 reverses in favour of n = 6 for cycloketone formation with X = Cl and Br. The softness of the acid centre, Cω, decreases for a harder X( = F) whereas it increases for a softer X( = Br). Thus the reactivity order with respect to X suggests that the softness of the base centres O and Cα belongs to the borderline class. The transition state (TS) structures indicate that the BEP principle is obeyed in all cases, and a less reactive process has a more product-like TS.
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    Short communication. Solvolysis of some benzylic and non-benzylic tertiary p-nitrobenzoates. A new YBnOPNB scale (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 463-466 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new Y scale for the correlation of solvolytic reactivities for benzylic ρ-nitrobenzoates was established based on rate data for 2-phenyl-2-adamantyl ρ-nitrobenzoate, and from which the solvent assistance in the solvolysis of tert-cumyl ρ-nitrobenzoate is suggested.
    Additional Material: 3 Ill.
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    Experimental and theoretical studies of the effects of hydration on proton exchange equilibria (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 479-484 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Theoretical calculations with the ab initio molecular orbital STO-3G basis set on the effect of trihydration on the relative acidities of 3- and 4-substituted phenols, 4-substituted quinuclidinium ions and 4-substituted bicyclo [2.2.2]octylammonium ions are reported. These results are contrasted with calculations on non-hydrated species and compared with results in aqueous solution and in the gas phase. Unlike results for smaller molecules such as substituted acetic acids and methylammonium ions, the solvation effects of three molecules of water are far short of that observed in going from the gas phase to aqueous solution. Reasons for this are discussed in the context of solvent attenuation factors for various molecules.
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    Preparation, characterization and rearrangement pathways of 10-alkyl-9-decalyl carbocations (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 492-500 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation and characterization of 10-methyl- and 10-ethyl-9-decalyl cations is described. Both cations undergo a rapid, degenerate 10, 9-alkyl shift, but the ethyl group migration is about 700 times slower at -120°C than that of the methyl group. This preference is opposite to that usually found for alkyl migration rates and, on the basis of MO calculations, it is suggested that a conformational interchange may be the rate-determining step. Both cations irreversibly rearrange at about -100°C, giving in the methyl case the rearrangement cascade 10-methyl-9-decalyl → cis-1-methyldecalyl → trans-1-methyldecalyl → trans-2-methyldecalyl. Each of these rearrangement ions was independently prepared and characterized by NMR spectroscopy. One can rationalize the initial formation of the less stable cis ring junction on the basis of suprafacial hydride and methyl shifts. Attempts to add molecular hydrogen to the 10-methyl-9-decalyl cation were unsuccessful.
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    Product-determining factors in the grignard reactions of benzophenones. The role of the structure of alkyl groups in grignard reagents (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 501-515 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of the Grignard reactions of substituted benzophenones with two kinds of alkyl Grignard reagent, n-C3H7MgBr, and i-C3H7MgBr, was investigated. In these reactions, both addition and reduction products were also generated. Based on the results of product analysis and stopped-flow, ESR and association measurements, it was confirmed that the product distribution was governed by several factors: the oxidizing ability of benzophenones, the association ability of Grignard reagents and the structure of alkyl groups of Grignard reagents. In particular, the strength of C—Mg and β-C—H bonds of Grignard reagents could strongly affect the product distribution.
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    The effect of pressure on swern-moffatt oxidations (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 639-642 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rates of oxidation of cyclohexanol by dimethyl sulphoxide in conjunction both with acetic anhydride and with dicyclohexylcarbodiimide have been measured with variation of both temperature and pressure. Activation volumes were found to be -25 and -34 cm3 mol-1, respectively, and the absence of an α—d PKIE was noted. The reaction mechanism is discussed in the context of these values.
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    Estimation of thermodynamic stability and charge distribution for unknown molecules: Nitro derivatives of cubane (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 714-720 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three useful procedures for estimating the thermodynamic stability and charge distribution of moderately complex unknown species are illustrated by the successive nitration of cubane. (1) Five different, but interrelated, energy criteria are employed, which leads to mutually supportive conclusions that overcome deficiencies in any one of the single measures. (2) Mulliken charge and overlap populations can lead to correct bond strength trends if appropriate averaging over bond types is carried out. (3) Lewis - Langmuir atomic charges, an interpolation between the formal charges of Lewis dot structures and oxidation numbers which does not require use of computers, provides atomic charges similar to those from ab initio, wavefunctions. The simplicity of this scheme aids in identifying the chemical and topological origin of molecular charge distributions. Ab initio, calculations for the strain energies and heats of reaction for four different reaction sequences are reported, together with Mulliken atomic charges and overlap populations for the nitrocubanes. Trends in these measures suggest that hexa- and octa-nitrocubane are thermodynamically stable species.
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    URL: http://dx.doi.org/10.1002/poc.610041203
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    Effect of hexadecyltrimethylammonium bromide micelles on the hydrolysis of substituted benzoate esters (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 13-18 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis of nine para-substituted phenyl esters of para-substituted benzoates was studied in the presence and absence of hexadecyltrimethylammonium bromide (CTAB) micelles. The second-order rate constant for alkaline hydrolysis in CTAB micelles (K2m) was calculated using a pseudo-phase ion-exchange model. the substituent effect on the second-order rate constant in the aqueous phase (k2w) and on k2m was analysed using Hammett's σ ρ plots. The calculated ρ values in micelles were 0.8 unit. larger than those in water. The effective low dielectric constant in the micellar surface may be responsible for the general effect of increasing the sensitivity of reactions to the electronic effect of substituents in micelles.
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    URL: http://dx.doi.org/10.1002/poc.610040104
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    1,5-Sigmatropic shifts of bromine over a cyclopentadiene ring (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 31-47 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The intrinsic mechanism of circumambulatory rearrangements of 5-bromo-5-methyl-1,2,3,4-tetramethoxycarbonylcyclopentadiene, 5-bromo-1,2,3,4 5-pentamethoxycarbonylcyclopentadien and 5-bromo- 1,2,3,4,5-pentaphenylcyclopentadiene due to sigmatropic shifts of bromine over the cyclopentadiene ring was proved, using the dynamic 13C and 1H NMR technique, to be governed by successive intramolecular 1,5-sigmatropic shifts. Semi-empirical AM1 and MINDO/3 calculations of reactions paths performed for fluoro-, chloro- and bromocyclopentadienes are in accord with the conclusion of a preference for a 1,5- over a 1,3-shift reaction path of halogen migration over a cyclopentadiene system. Intramolecular 1,5-sigmatropic shifts of chlorine in 5-chloro-5-methyl-1,2,3,4-tetramethoxycarbonylcyclopentadiene with the free energy barrier of ΔG298+ = 26.1 kcal mol-1 were studied using 1H NMR spectroscopy.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040107
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    Taft's substituent constants, σ* and σI, and Huheey's group electronegativity (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 96-100 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For 34 groups, Taft's substituent constants σ* and σI are found to correlate well (r = 0.962 and 0.948) with Huheey's group electronegativity (χH) when Taft's steric parameter Es for a group is mixed with σ* and σI: From these equations, it follows that for a particular chemical group G, σ*(G) ≍ 8σI(G). Since the σ* scale is essentially based on the σI scale, the small inherent steric component in σI is amplified in the case of the σ* by a factor of ca 8. An analysis shows that χH represents the electronegativity of a group when the group is considered to be a mere collection of non-bonded, charged and suitably hybridized atoms. Thus σ* and σI are found to represent the electronegativity of a group in the spirit of the χH. It is concluded that a chemical group can be viewed as a collection of non-interacting atoms. Although there is evidence that a molecule can sometimes be treated similarly, for a group such a situation is novel.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040205
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  • 82
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    Masthead (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040301
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  • 83
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    Theoretical study of simple push-pull ethylenes in solution (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 141-148 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of solvation on the Z - E isomerization process of three representative molecules of simple push-pull ethylenes [H2N(H)C1=C2(H)R = NO2, COH and CN] derived from aminoethylene was investigated by means of RHF-SCF ab initio calculations at the 3-21 + G level. Solute-solvent interactions were modelled by a cavity model. The shape of the cavity is based on electronic isodensity surfaces. By using an ellipsoidal cavity very close to the isodensity surface, the perturbation due to the solvent takes an analytical form which is incorporated into the Hartree-Fock equations and leads to efficient quantum chemical computations. The polarization of the solutes under the influence of the solvent is noticeable and was analysed in detail. Similarly, the barriers to internal rotations are substantially modified by the solvent: the barrier around the C=C double bond is appreciably decreased in the thermal mechanism whereas its lowering is less important in the anionic mechanism; in contrast, the barrier around the C-1—N bond is slightly increased. The variation of the barriers with the nature of the acceptor group is fairly well reproduced by the computations. The electronic structure of the push-pull ethylene molecules and the modifications of this structure under the influence of the solvent are analysed in detail.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040304
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  • 84
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    Aromaticity as a multi-dimensional phenomenon (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 163-169 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The classification of aromaticity criteria is studied. New aromaticity criteria are developed and discussed. A statistical analysis of such criteria is presented and compared with a similar analysis of the recent literature. It is shown that aromaticity is at least a two-dimensional phenomenon. The classification of the compounds depends on the type of criteria included in the analysis.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040307
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  • 85
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    AB initio MO study of the halogen cation basicities of some organic bases (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 177-191 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hartree - Fock calculations were performed to investigate the structure and relative stabilities of complexes between halogen cations and first- and second-row bases. It is shown by means of both a qualitative perturbation molecular orbital treatment and a topological analysis of the electronic charge density that second-row bases present enhanced halogen cation basicities compared with first-row bases. In this respect the results predict that although the fluorine cation basicity of water is smaller than its proton affinity, the fluorine cation basicities of SH2, thioether, phosphine and trimethylphosphine are considerably higher than their proton basicities. Similarly, phosphine and trimethylphosphine should have chlorine cation basicities greater than their proton affinities, in contrast with ammonia and trimethylamine. The results also show that fluorine and chlorine cation basicities are more sensitive to methyl substitution than proton affinities.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040309
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  • 86
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    Micellar effects on the alkaline hydrolysis of N-alkyl-4-cyanopyridinium ions. An example of micelle-induced regiochemical selectivity (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 207-216 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rates of the reaction of N-alkyl-4-cyanopyridinium (RCP) ions [alkyl = CH3 (MCP), n-C4H9 (BCP), n-C8H17 (OCP), n-C12H25 (DCP)] with OH- ion in water are independent of chain length and RCP concentration up to 0.001 M. The ratios of the concentrations of the reaction products, N-alkyl-4-pyridone (P) and N-alkyl-4-carboxamidopyridinium (A), P/A, are similar for all substrates. In water the P/A ratios increase with pH, reaching a plateau value of ca 2 at pH ≥ 13. Added salts slightly decrease the reaction rate and do not affect the P/A ratios. In aqueous solutions, addition of dioxane increases both rates and P/A ratios. Micelles of hexadecyltrimethylammonium bromide (cetyltrimethylammonium bromide; CTAB) and 3-(N,N-dimethyl dodecyl ammonium)propane-1-sulphonate (SDP) catalyse the alkaline hydrolysis of OCP and DCP and increase the yield of pyridone with BCP, OCP and DCP. In micellar CTAB and SDP the attack of OH- on RCP occurs almost exclusively at the 4-position of the pyridinium ring. Sodium dodecyl sulphate micelles inhibit the reaction and produce small changes in the P/A ratio. The regiochemical selectivity produced by micelles, leading to a preference for the attack of OH- at the pyridinium ring, was rationalized in terms of the low effective dielectric constant at the micelle-water interface.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040403
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  • 87
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    Structure, topological electron density analysis and aromaticity of 4-heterosubstituted methylenecyclopropenes: X= X=CH2, NH, O, SiH2, PH and S (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 242-250 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structures of a series of heterosubstituted methylenecyclopropenes and methylenecyclopropanes were optimized at the HF/6-31G* level. All methylenecyclopropenes are planar except for the silicon analogue, which is bent at both C-3 and Si. The planar silicon structure is a transition state. The relative aromaticity of these compounds were evaluated using the C-1—C-3 bond length, the integrated charge on C-3 and the heteroatom, and delocalization energy. Second-row systems have slightly larger delocalization energies than their first-row counterparts, owing to their larger polarizability. Using these criteria, methylenecyclopropene and the silicon analogue are not aromatic and the N, O, P and S analogues are moderately aromatic. The planar silicon analogue is antiaromatic and bends from planarity to reduce this antiaromaticity.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040407
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  • 88
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    Kinetics and mechanism of the alcoholyses of ethyl fluorosulphate (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 251-259 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alcoholyses of ethyl fluorosulphate in methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and n-pentyl alcohols in the initial concentrations and temperature ranges of (1-10) 10-3 M and - 15.00 to 22.00 °C, respectively, were studied. The reactions follow pseudo-first-order kinetic laws up to at least ca 75 per cent ester conversions. At 10°C the experimental rate constant for ethanolysis is similar to that of ethyl triflate but much smaller than for its hydrolysis. The reactivity of the ester is ca 104-105 times higher than that of alkyl halides and benzenesulphonates. In alcohol-benzene and alcohol-acetone mixtures the ΔH≠ and ΔS≠ activation parameters are only slightly affected by the media composition. The effect of the ‘lyate ion’ on the kinetics of these reactions were investigated and the effects of changes in the dielectric constant of the media were evaluated. It is concluded that the alcoholyses of the ester fulfil the requirements for predominant SN2-type mechanism, where the reaction ground states are more polar than the corresponding transition states.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040408
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  • 89
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    NMR study of polycrystalline azoles (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 271-276 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polycrystalline pyrazole, imidazole and benzotriazole were investigated by 1H and 2H NMR spectroscopy. In addition to the usual broad line of the 1H NMR signal due to the dipole-dipole interaction, a significantly narrowed component (δν = 1-2 kHz) of a complex triplet structure was detected in all three compounds. To interpret this observation, a mechanism with virtually complete averaging of the dipole-dipole interaction for a small part of the sample protons is suggested. The mechanism is based on proton interaction with the unpaired electron of a short-lived radical of the type Az· or (H-Az·-H).
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040503
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  • 90
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    Controlling factors determining addition and reduction products in the grignard reaction of substituted benzophenones, acetophenone and fluorenone with ‘EtMgBr’ (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 381-386 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Addition (Add.) vs reduction (Red.) products in the reactions of substituted benzophenones, acetophenone and fluorenone with ‘EtMgBr’ were compared in diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran. Plots of log (Add./Red.) vs σ-values or the oxidation potentials of ketones showed characteristic upward curves depending on the polarity of the solvents. The results are discussed on the basis of both the combined effects of the stability of the monomeric radical ion pair and the dimeric radical ion pair derived from ketone and ‘EtMgBr’, and the well known Schlenk equilibrium of ‘EtMgBr’ in solutions.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040610
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  • 91
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    Acid hydrolysis of 2-substituted 3-methyl-tetrahydro-1,3-oxazines: Simple models for tertiary glycosylamines (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 53-57 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydrolytic decomposition of 2-phenyl- and 2-isopropyl-3-methyltetrahydro-1,3-oxazines to 3-methylaminopropan-1-ol and appropriate aldehydes was studied by 1H NMR and UV spectroscopy in acidic solutions. The time-dependent spectra confirmed that the formation of the final products was preceded by an equilibration of three components, the two Schiff base intermediates and the starting material, of which the former produced a carbinolamine which in turn underwent heterolysis to the final products.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040109
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  • 92
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    Internal rotation of CH3 groups and entropy difference between diastereoisomers: A 13C NMR study via relaxation time measurements (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 113-120 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Overall and internal rotation can be studied by means of relaxation time measurements on carbon-13. Diffusion constants associated with overall rotation and internal rotation can be used to quantify the intermolecular and intramolecular motional constraints. During the course of the study, a very careful examination of monomethyl and dimethylnorbornanes was performed and the results were compared with data obtained by neutron inelastic scattering. This study led to a clear conclusion concerning the real usefulness of relaxation time measurements as a very good alternative method for the determination of entropy contributions, which are usually calculated on the basis of vibrational studies.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040208
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  • 93
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    Reactivity in radical abstraction reactions: Application of the curve crossing model (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 135-140 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The curve crossing model was applied to a series of hydrogen abstraction reactions from a family of alkanes, RH (R = methyl, ethyl, isopropyl, tert-butyl) by alkyl, hydrogen and chlorine radicals. The analysis was based on quantitative data obtained from an ab initio MO study. Schematic reaction profiles for the reaction of RH with alkyl and hydrogen radicals are built up from just two configurations: reactant, DA, and product D3* A. For the Cl atom reaction, however, a significant contribution of D+ A-, a charge-transfer configuration, is also shown to be present. A simple explanation for differences in the intrinsic barrier for the identity radical abstraction reaction based on the initial gap size between DA and D3* A configurations is provided. The influence of the D+ A- configuration on the nature of the transition state of the Cl atom reaction and its intrinsic barrier is described. It is the D+ A- configuration that is responsible for the polar character often observed in radical abstraction and addition reactions.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040303
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  • 94
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    Formation of adsorption complexes in phase-transfer nucleophilic substitution. Kinetic analysis of solid-phase system (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 149-157 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the nucleophilic substitution between n-hexyl bromide and solid potassium chloride (KCl) in toluene were studied in the presence of catalytic amounts of tetra-n-butylammonium bromide at 84°C. This reaction is characterized by an induction period that disappears on activation of the solid salt. The substitution with the activated salt constitutes a reversible pseudo-first-order reaction with variable orders in the substrate and the catalyst equal to 0 ≤ n ≤ 1. A quantitative increase in the solid KCl at first accelerates the substitution reaction, but when the level reaches KCl/RBr ≥ 7 the rate constant is no longer influenced by the amount of salt. Comparing data obtained with kinetic equations for several possible substitution schemes, the mechanism of the reaction can be derived, including the formation of a ternary adsorption complex (TC) from the substrate, catalyst and solid salt. The data obtained allow the evaluation of the equilibrium constant of TC formation (KΣ= 20.48 l2 mol-2) and the rate constant of its disintegration into substitution products (k+ = 0.75 × 10-2 s-1). Through kinetic analysis the adsorption sequence on the surface of the solid salt was determined, including primary formation of the binary complex KCl.QX and subsequent TC formation. The concentration of active KCl molecules, estimated on the basis of the primary kinetic data is 10-2 M and is commensurate with the catalyst concentration. This concentration of active KCl molecules is achieved owing to the formation of subcolloidal-sized particles in the process of the solid salt activation.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610040305
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  • 95
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    Intermolecular and intramolecular hydrogen bonding in 5-pyridylmethylenehydantoins: IR and NMR study (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 170-176 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The patterns of the NH stretching vibrations in the solid-state IR spectra of a series of 5-pyridylmethylenehydantoins revealed the presence of various modes of hydrogen bonding: intermolecular NH&4nldr; &4nldr;OC and intermolecular or intramolecular NH&4nldr; ‥‥N(py). These variations are related to the orientation of the pyridyl nitrogen and to stereochemistry. A distinction between intramolecularly and intermolecularly hydrogen-bonded compounds was also provided by comparison of the 1H NMR spectra in (CD3)2SO and in CDCl3.
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    URL: http://dx.doi.org/10.1002/poc.610040308
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  • 96
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    Substituent effects in the photohydration of styrenes and phenylacetylenes. An attempt to establish a σhν scale for excited-state reactions (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 193-206 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The acid-catalysed rate constants (kH+) for the photohydration of 18 meta- and para-substituted styrenes and phenylacetylenes were determined in H2SO4 solutions by means of fluorescence quenching measurements and the standard Stern-Volmer approach. Singlet lifetimes of the substrates were determined in the reference solution (water at pH 7) by single photon counting. The log kH+ values obtained did not correlate well with any previously reported σ scales, and were used to try to establish a σhν scale (for H-, p-F, m-F, p-Me, m-Me, p-Et, m-Et, p-OMe and m-OMe substituents) for possible use in other photochemical reactions. Correlation of all available literature data versus the new σhv scale gave reasonable correlations (r = 0.957-0.966). The problems associated with establishing linear free energy relationships for photoreactions are discussed.
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    URL: http://dx.doi.org/10.1002/poc.610040402
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  • 97
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    Long-range deuterium isotope effects in tautomeric β-thioxoketones. A 1H and 13C NMR study (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 225-232 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Equilibrium displacements within the enol-enthiolic tautomeric systems of β-thioxoketones caused by long-range isotope effects were monitored by 1H and 13C NMR spectroscopy. Thioacetylacetone and 1,3-diphenyl-3-thioxopropanone deuteriated at various positions were investigated. Both compounds are in fast (Z)-enol-(Z)-enethiol equilibrium on the NMR time scale. The investigations showed that CD3 and C6D5 groups changes the equilibrium so that the tautomer having a C = X bond next to the CD3 or C6D5 groups decreases. Deuteriation at the methine position pushes the equilibrium towards the (Z)-enol form. The study further showed that deuteriation at the phenyl ring next to the C = O group causes the largest effect if the deuterium is at the ortho position and the smallest if it is at the para position. Long-range effects on equilibrium are discussed in general in order to establish a common pattern. Deuterium scrambling is observed both during the coupling reaction of ethyl thionoacetate with hexadeuterioacetone and during preparation of specifically labelled acetophenone. The latter compounds are synthesized by acetylation of specifically labelled benzenes. The scrambling reaction is suggested to be a transdeuteriation of the deuteriated benzenes rather than involving the acetophenones.
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    URL: http://dx.doi.org/10.1002/poc.610040405
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  • 98
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    Kinetic and equilibrium study of the interaction of N-(1-Ethylpropyl)-3, 4-Dimethyl-2, 6-Dinitroaniline with hydroxide ion (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 277-284 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reversible interaction of N-(1-ethylpropyl)-3, 4-dimethyl-2, 6-dinitroaniline (1) with HO- is characterized by several kinetic processes. The relaxation times of two of them were measured. It is suggested that the faster one is related to the protonation-deprotonation of the 3-methyl group and the value of the protonation rate is 0.19 s-1. The slowest process leads to the dianionic species with maximum absorption at 340 nm where one HO- group adds to the unsubstituted ring position of an anion derived from 1 by deprotonation of either the NH or the 3-methyl group. The rate and equilibrium constants for the formation of this species are reported.
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    URL: http://dx.doi.org/10.1002/poc.610040504
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  • 99
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    Two reintroduced solvatochromic indicators for hydrogen bond donation and acceptance (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 310-314 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The behaviour of cis-dicyanodi-1-10-phenanthrolinoiron(II) and acetylacetonato-N, N,N′,N′-tetramethylethylene-diaminocopper(II) perchlorate as solvatochromic indicators for the ability of solvents to donate a hydrogen atom or a pair of electrons, respectively, towards the formation of a hydrogen bond is examined by multivariable linear regressions and principal component analysis.
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    URL: http://dx.doi.org/10.1002/poc.610040508
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  • 100
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    Theoretical studies on the gas-phase smiles rearrangementDetermination of Reactivity by MO Theory, Part 71. For Part 70, see Ref. 1. (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 315-329 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas-phase Smiles rearrangements and SNi processes of ions C6H5X(CH2)nY- (X, Y = 0 or S, and n = 2-4) have been studied by the AM1 MO method. The Smiles rearrangement to an ortho position of the phenyl ring is diffcult owing to involvement of a high-energy barrier process involving a 1,2-hydrogen shift. The reactivity of the Smiles rearrangement to the ipso position increases in the order X — O and Y — S 〈 X — S and Y — O 〈 X — Y — 0 as a result of steric and electronic effects in the transition state (TS). The reactivity order with respect to the side-chain length, n = 3 〈 4 〈 2, is mainly determined by ring strain in the TS. For the SNi process, in which Y attacks the β-carbon (β to phenyl), the enthalpy (δH≠) factor becomes more favourable but the entropy (δS≠) factor becomes unfavourable with an increase in the side-chain length, in agreement with a general trend for cyclization processes. The product ratio in the Smiles rearrangement and the SNi process is largely controlled by the thermodynamic stabilities of the products, as observed in gas-phase experiments.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040509
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