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• General Chemistry  (10,869)
• Atomic, Molecular and Optical Physics  (2,025)
• Physical Chemistry  (1,410)
• 1990-1994  (8,867)
• 1970-1974  (5,437)
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• 1
Electronic Resource
Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Semi-empirical (AM1) calculations on the 12 isomeric products and the corresponding transition states of ketene-1-azabutadiene [4 + 2] and [2 + 2] cycloaddition reactions as a model system for the reaction of ketenes with 4-iminobenzylfuran-2,3-diones are presented. A [4 + 2] type of reaction of the ketene C=C double bond leading to a six-membered lactam compound is found to be highly favoured both thermodynamically and kinetically. [2 + 2] Cycloadducts generally have significantly higher activation energies. Reactions involving the formation of a carbon-nitrogen bond proceed in most cases via attack of the nitrogen lone pair leading to a zwitterionic intermediate. Depending on the respective cycloadduct, both two-step and concerted, albeit asynchronous, processes were obtained. Based on the structures of the various transition states, some predictions with respect to substituent effects are made. Similarities to and differences from the analogous reaction of ketenimines with oxa-1,3-dienes are discussed.
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• 2
Electronic Resource
Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Reaction of aryliminodimagnesium [ArN(MgBr)2, IDMg] with nitrobenzene (Ar1NO2) in tetrahydrofuran (THF) gives unsymmetrical (unsym) azoxybenzene, which is deoxygenated to give unsym-azobenzene. The reaction is utilized for the independent preparation of ONN and NNO isomers of unsym-azoxy compounds. The effects of the relative value of the difference between oxidation and reduction potentials of para-substituted reactants, special effects of ortho-substituents of the substrate and also effects of structure and concentration of mono- and bis-IDMg reagents were studied previously, and ‘cooperation of their aggregate excess needed for product formation’ was proposed. This unfamiliar concept for reactions of magnesium reagents was studied further. Supporting evidence was obtained from the retarding effect of trimethylene chains of nitro [3.3] metacyclophanes and the derived azoxy [3.3] metacyclophanes and also from the effect of the length of bis-IDMg's central α,ω-polymethylenedioxy chain appropriate for azoxy deoxygenation. By comparison with deoxygenation by X3P reagents (X = EtO, Me2N), the general needs of cooperation of excess magnesium reagents were confirmed and its role in their reactions is discussed.
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• 3
Electronic Resource
Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The magnitude ρx(ρnuc) is shown to decrease with increase in the extent of bond making estimated by the kinetic isotope effect for the reactions of Y-benzoyl chlorides with anilines, XC6H4NH2, in acetonitrile at 25·0°C.
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• 4
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 364-370
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The role of orbital control in product selectivity during electrophilic aromatic alkylation catalysed by zeolites was studied both theoretically and experimentally. In order to discuss this, the alkylation of toluene and m-xylene by methanol was carried out on a series of large-pore zeolites (HY). The changes in the para to ortho ratio observed on changing the framework Si/Al ratio of the zeolites were related to ab initio molecular orbital calculations of the LUMO energy of structurally alike model clusters but containing different tetrahedral cations around the active site. The observed correlation is discussed in terms of the HSAB principle by taking into account the influence of the catalyst composition on the reactivity of the electrophilic reagent.
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• 5
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 377-384
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: N-Substituted carbonimidodithioic acid dimethyl esters, when reacted with an active methylene compound such as nitromethane, undergo carbon-carbon bond formation followed by carbon-sulphur bond cleavage in the presence of zeolite catalysts to give 1-substituted amino-1-methylthio-2-nitroethenes. This carbon-sulphur bond cleavage is facilitated by the presence of rare earth cations in the zeolite-Y framework. The shape selectivity of the zeolite also plays an important role in this cleavage reaction. Force field calculations adopted for the molecules involved in the reaction indicate the geometry and conformational flexibility of these molecules. The computer-simulated model for the zeolite-Y is correlated with the conformation and shape of the reactant and product molecules to explain the variation in yields obtained in the conversion of substituted dimethyl esters.
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• 6
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 412-419
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The effects of the concentrations of LiCl, NaCl, KCl, CsCl, Na2CO3 and BaCl2 on the rates of reactions of hydroxide ion with ionized N-hydroxyphthalimide (NHP-) at 30°C and in H2O-MeCN solvents containing 10, 50, 60, 66, 70, 76 and 80% (v/v) MeCN reveal the formation of ion-pair complexes between cations of the salts, which probably exist in solvent-separated loose ion-pair forms (Mn+⃛Xk-) and NHP-. An increase in MeCN content from 2 to 76% (v/v) causes an increase in the association constants (K) by factors of 40, 21 and 9 for LiCl, NaCl and KCl, respectively, while the respective increase in the rate constants (k′s1) for the collapse of the ion-pair complexes to product is ca two-fold. The values of k′s1 remain almost unchanged whereas the values of K increase 7·5-fold with an increase in MeCN content from 2 to 70% (v/v) for CsCl. Ion-pair complex formation was not detected in the presence of Me4NCl at 70% (v/v) MeCN. The observed pseudo-first-order rate constants are highly sensitive to the valence state of cations and almost insensitive to the valence state of the anions of the salts.
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• 7
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 455-464
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The rates and products of solvolyses of 4-methylene-2ax- and -2eq-adamantyl p-toluenesulphonates (tosylates) (4a-OTs and 4e-OTs, respectively) were studied. Compound 4a-OTs solvolysed more slowly than 2-adamantyl tosylate (1) in methanol and 2,2,2-trifluoroethanol (TFE) by factors of 2·3 and 2·5, respectively, at 25°C. However, by taking the inductive decelerating effect of a β-methylene substituent into account, the rates were revealed to be enhanced by α-participation by a factor of 50. The products of solvolyses of 4a-OTs in methanol, 80% acetone and TFE at 100°C were 2ax- and 2eq-alkoxy(or hydroxy)-4-methyleneadamantanes (4a-OR and 4e-OR, respectively), exo-4-alkoxy(or hydroxy)-5-methyleneprotoadamantane (exo-5-OR) and 5-[alkoxy(or hydroxy)methyl]-4-protoadamantene (6-OR) with adamantyl to protoadamantyl product ratio of 39:61 (in methanol), 56:44 (in 80% acetone) and 71:29 (in TFE). Despite the nearly symmetric nature of the intermediate cation, the 4a-OR: 4e-OR product ratio was essentially constant with 83:17 (in methanol), 85:15 (in 80% acetone) and 82:18 (in TFE). The formation of considerable amounts of 4e-OR was interpreted as showing the intermediacy of a pair of rapidly equilibrating classical ions. The rates of 4e-OTs were 2300-4300 times faster than those expected from inductive electron-withdrawing effect of a β-methylene substituent. The major product (84·5% in methanolysis and 98·7% in trifluoroethanolysis) was 4e-OR accompanied by small amounts of 2-alkoxy-2,4-methanoadamantane (9-OR) and 2-(alkoxymethyl)-2,4-didehydroadamantane (10-OR), no formation of 4a-OR having been observed. These results suggested that 4e-OTs solvolyses via a π-bridged intermediate cation.
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• 8
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
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• 9
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 551-554
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Molecular mechanics (MM3) calculations were carried out on the title compounds. Comparison between the MM3 results and those of semi-empirical and ab initio calculations and experiment indicates that the MM3 results are at least as good as results of much more expensive calculations. The MM3 calculations predict that unlike corannulene and cyclopentacorannulene, the transition state of the bowl-to-bowl inversion of the related C30H10 is non-planar, and the activation barrier is too high for this motion to occur.
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• 10
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 567-577
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Reactions of benzo-, naphtho- and anthraquinone derivatives (unsubstituted and substituted) with aryliminodimagnesium [ArN(MgBr)2] and aryloxymagnesium of a weak electron-donating ability were studied. In addition to the reduction products (quinhydrones and hydroquinones), nuclear substitution and condensation products were formed. The efficiency of single electron transfer (SET) from ArN(MgBr)2, evaluated by the relative values of the difference between the oxidation and reduction potentials of the reactants (ΔE = Eox - Ered), varies with the electron-accepting power of quinones. ΔE governs the modes of semiquinone appearance (ESR signals) and the relative amounts of the heat of reactions, reflecting the types and yields of the products. It is concluded that condensation products of both components are produced in the reactions of quinones with the lower SET efficiency by the presence of a fused benzene ring or MeO substituent. The structure-reactivity relationship proposed previously for reactions of various magnesium reagents is extended in the reactions with a variety of quinones even in cases of higher SET efficiency.
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• 11
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The low temperature 1H NMR spectra of 2,2-bis(3,5-dibromomesityl)ethenol in CS2-CD2Cl2 (3:7) display new signals which indicate the presence of four enol species whose OH is hydrogen bonded. Oligomerization to intermolecularly hydrogen-bonded enol dimers or tetramers is suggested.
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• 12
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
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• 13
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Measurements of absorption and emission spectra, fluorescence quantum yields (Φf) and lifetimes (τf) of ω-(1-pyrenyl)alkyl para-substituted benzoates PnX (X = H, Cl, CF3, CN, NO2, with n = 1-4) were carried out in solvents of various polarity. Intramolecular interaction in the ground state is not observed in any of these compounds. PnCN (n = 2-4) shows an intramolecular exciplex emission in solvents of low to high polarity. The broad, structureless emission at longer wavelength observed in ethyl acetate solution of P1CN is ascribed to an ‘exciplex-type’ emission which does not require actual overlapping of the two chromophores. P2CF3 also shows an exciplex emission in solvents of medium to high polarity. The solvent dependence of both Φf and τf increases as the electron-withdrawing ability of the para-sustituents increases. The relationship between fluorescence quenching by electron transfer and para-substituent of PnX is discussed by means of the free energy for electron transfer, ΔGET, obtained from the oxidation and reduction potentials of pyrene and methyl para-substituted benzoates in acetonitrile, respectively. PnH, with positive ΔGET, does not show a solvent dependence of Φf, except for P1H, in which ca 40% of the fluorescence is quenched in acetonitrile. PnCl, with slightly negative ΔGET, shows more efficient quenching, but does not show exciplex emission. PnCN, PnCF3 and PnNO2 have ΔGET values between -0·36 and -0·65 eV, and their fluorescence is fairly efficiently quenched. The fluorescence of PnCN is concluded to be strongly quenched by intersystem crossing from the singlet exciplex to the locally excited pyrene, and by electron transfer from the pyrene part to the benzoate part. That the formation of a singlet exciplex is necessary for intersystem crossing in bichromophoric compounds containing pyrene is thus clearly illustrated.
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• 14
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The evidence for the mechanisms proposed for aromatic nucleophilic substitution reactions by primary and secondary amines in aprotic solvents of low relative permittivity is reviewed.
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• 15
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: A rigorous procedure was developed for measuring the relative rates of addition of bromine atoms to eleven substituted α-methylstyrenes (1-Y, with Y = CF3, NO2, F, CN, Cl, Br, CO2Me, Me, COMe, OMe and SMe). The reaction was run in tetrahydrofuran in the presence of HBr, O2 and dibutyl peroxyoxalate at 30°C. All products were derived from the YC6H4CMeCH2Br adduct radicals, which were immediately intercepted by O2. Correlation analysis of all the data confirmed the proposition that in the absence of measurable steric effects, the relative rates for radical additions can be correlated only by a dual-parameter equation and not by a single-parameter equation. Among various combinations of σ* and σx, the (σJJ* + σmb) combination yields the best correlation.
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• 16
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 105-115
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Protonation of tetrafluoro-2,11-dithia [3·3]paracyclophane and tetrafluoro-2,11-dithia [3·3]metaparacyclophane in high-acidity super acid media, namely FSO3H.SbF5 (1:1) ‘magic acid’-SO2CIF, gave their corresponding acidic disulfonium ions. Additional ring protonation to give a disulfonium-monoarenium trication was not observed. With the non-fluorinated 2,11-dithia [3·3] cyclophanes, the disulfonium ions can be ring protonated in equilibrium to give a dynamic disulfonium-monoarenium trication. Tetrafluoro [2·2]-metaparacyclophane is monoprotonated at the meta ring and gives a complex mixture of conformational isomers. Multinuclear magnetic resonance data on the cyclophane precursors and their derived cations are compared and analysed. The energies, conformations and charge distributions of the isometric fluorinated and non-fluorinated [2·2] - and dithia [3·3] cyclophanes were calculated by the AM1 and PM3 methods, respectively. In all but one case the cyclophane arenium ions predicted by theory to be energetically most favoured are those observed in solution under stable ion conditions. In agreement with experiment, the instabilities of S,S,C-cyclophane trications are also theoretically predicted.
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• 17
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 122-141
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Ionization constants for 214 dye molecules were calculated from molecular structures using the chemical reactivity models developed in SPARC (SPARC Performs Automated Reasoning in Chemistry). These models used fundamental chemical structure theory to predict chemical reactivities for a wide range of organic molecules from molecular structure. The energy differences between the protonated state and the unprotonated state for a molecule of interest are factored into mechanistic components including the electrostatic and resonance contributions and any additional contributions to these energy differences. The RMS deviation was found to be less than 0·62 pKa units, which is similar to the experimental error.
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• 18
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 169-169
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
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• 19
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 162-168
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Solvent effects on the absorption spectra of N-(p-nitrophenyl)dimethylenediamine (Ia), N-(p-nitrophenyl)trimethylenediamine (Ib), N-(p-nitrophenyl)tetramethylenediamine (Ic). N-methyl-N-(p-nitrophenyl)tetramethylenediamine (II), N-butyl-p-nitroaniline (III) and N-(o-nitrophenyl)trimethylenediamine (IV) were studied at different temperatures. Whereas II, III and IV do not show any variation in their spectra characteristics with changes in temperature, I shows a hypsochromic shift with a hypochromic effect when the temperature is increased. The Kamlet and Taft solvatochromic comparison method was applied. A strong effect of the β parameter on I and III was interpreted as being due to the hydrogen bond donor ability of the H atom in the aromatic amino groups. In I, the β influence increases with increase in temperature. These facts are explained by proposing the formation of intramolecular hydrogen bonds between amine groups in all compounds I, besides the intermolecular interactions between compounds I and the solvent. On the other hand, the values of vo, s and b for Ib are smaller than the corresponding values for Ia and Ic. Since in Ib a six-membered ring may be formed, a more stable bond is expected. Comparative 1H NMR of the aniline hydrogen for I and IV (in non-hydrogen bond acceptor solvents) shows a particular downfield chemical shift for I which suggests hydrogen bond formation. Since this effect is independent of concentration, the hydrogen bond is assumed to be intramolecular, in agreement with solvatochromic and thermochromic studies. These conclusions were corroborated by IR spectroscopy in the solid state and in chloroform solutions.
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• 20
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
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• 21
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 192-195
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The secondary α-deuterium isotpe effect on the equiliburium constant (KD/KH) for the hydration of p-nitrobenzaldehyde is 1·39 ± 0·05. The Kinetic secondary α-deuterium isotope effect (KD/KH) for the addition of water to p-nitrobenzaldehyde is 1·18 ± 0·07. This result demonstrates that there is extensive carbon-oxygen bond formation in the transition state for addition of water to the carbonyl group of p-nitrobezaldehyde.
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• 22
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 545-550
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The rate of the reaction of 2-chloroquinoxaline with piperidine in dimethyl sulphoxide was measured over a wide range of amine concentrations and at several temperatures. It was found that the order with respect to the nucleophile is close to 1 between 300 and 320 K, but is definitely less at lower and higher temperature. It is suggested that below 300 K an unreactive charge-transfer complex is formed between the reactants which dissociates at higher temperatures, whereas at temperatures higher than 320 K an unproductive σ complex is formed, the concentration of which increases with increase in temperature.
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• 23
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 561-566
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The enthalpic contribution to the anomeric effect in r-2-carboethoxy-trans-4,trans-6- and r-2-carboethoxy-cis-4,cis-6-dimethyl-1,3-dithianes was determined by reaction-solution calorimetry. The enthalpy of solution of both isomers in pure p-dioxane and the enthalpy of solution and isomerization in the same solvent and in the presence of trifluoroacetic acid were experimentally measured. From these results the corresponding enthalpies of isomerization in solution were calculated, and were found to be ΔHax→eq = -0·16 ± 0·04 kcal mol-1 (-0·67 ± 0·18 kJ mol-1) and ΔSax→eq = -2·68 ± 0·1 cal K-1 mol-1 (-11·2 ± 0·4 J K-1 mol-1). The slightly negative ΔH term nevertheless reflects a substantial anomeric effect owing to the countervailing steric effects in the axial isomer. The significant entropy loss in the equatorial isomer was explained in terms of intramolecular electrostatic effects. The results are in agreement with those obtained from NMR studies of the conformational behaviour of 2-carboethoxy-5-methyl-5-aza-1,3-dithiacyclohexane.
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• 24
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 591-609
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The MM3 molecular mechanics program calculates a fair representation of hydrogen bonding interactions, but to improve the MM3 hydrogen bond potential, a directional term has been added to the hydrogen bonding function. The resulting total function was reoptimized. Comparisons of the hydrogen bonding potential functions from ab initio, the original MM3, the current MM3(92) force field and the reoptimized MM3 force field MM3(94) for a variety of C,N,O systems are described.
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• 25
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Journal of Physical Organic Chemistry 7 (1994), S. 585-590
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The title sulphenamides were pyrolysed in a stirred-flow reactor at temperatures of 310-410°C, pressures of 8-15 Torr and residence times of 0·4-2 s using toluene as the carrier gas. N-(tert-Butylthio)allylamine formed 73 ± 4% isobutene, 23 ± 3% propene and N-allylthiohydroxylamine. The first-order rate coefficients for the formation of isobutene and propene, respectively, followed the Arrhenius equations kC4(s-1) = 1012·52 ± 0·36 exp(-163 ± 5 kJ mol-1 RT) and kC3(s-1) = 1010·99 ± 0·29 exp(-151 ± 4 kJ mol-1 RT) N-(tert-Butylthio)diethylamine gave 97 ± 1% isobutene, 1·9 ± 0·4% isobutane and N,N-diethylthiohydroxylamine. The first-order rate coefficients for isobutene elimination followed the Arrhenius equation k(s-1) = 1013·45 ± 0·24 exp(-164 ± 3 kJ mol-1 RT). The formation of the products is interpreted in terms of an elimination reaction with a unimolecular, four-centered, cyclic transition state. The reactivity of these sulphenamides was found to be much higher than that of previously studied alkyl or aryl tert-butyl sulphides and disulphides.
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• 26
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Journal of Physical Organic Chemistry 7 (1994), S. 296-302
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The aromatic odd-alternant phenalenyl anion and a number of its derivatives were prepared in order to study the perturbation of this conjugated anion by methyl and methoxy groups. The conjugated anions were studied by means of 1H and 13C NMR spectrometry, alkylation experiments and semi-empirical calculations. It was found that a substituent at a charged carbon atom perturbs the entire conjugated system, whereas substituents at inactive (uncharged) carbon atoms have a large effect on the positions ortho to the substituent.
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• 27
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Journal of Physical Organic Chemistry 7 (1994), S. 287-295
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The spontaneous hydrolysis of p-nitrobenzyl cellulose xanthate (CelXNB) with a degree of substitution (DS) in the range 2-9 was studied in 10% aqueous ethanol at pH 10, and was followed spectrophotometrically by the appearance of p-nitro-α-toluenethiol, in a continuous-flow system where the reactor was shaken. CelXNB was characterized by solid-state 13C NMR spectra. The reaction occurs through two parallel processes due to two xanthate ester groups with different reactivities. The fast hydrolysis was ascribed to the reaction of the C-2 + C-3 isomers, whereas the slow hydrolysis was due to the C-6 isomer. The percentage of the latter is much higher than C-2 + C-3. The solvent isotope effect of the fast hydrolysis (k′H2O/)k′H2D 11 was 2·22 ± 0·16 and the proton inventory indicated that there is only one proton transfer involved in the transition state, where a second water (or a neighbouring OH group) acts as a general base. The entropy of activation of the fast hydrolysis was only 3·3 ± 0·8 e.u., suggesting that the water molecules involved are highly oriented with respect to the coordinates required to reach the transition state. It is proposed that they form part of the three-dimensional hydrogen-bonded ice-like structure that involves the cellulose matrix.
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• 28
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Chichester : Wiley-Blackwell
Journal of Physical Organic Chemistry 7 (1994), S. 316-322
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Rates of hydrolysis of the vinyl ether functional groups of (Z)- and (E)-β-methoxyacrylic acid and (Z)-and (E)-β-methoxymethacrylic acid and their methyl esters were measured in aqueous perchloric acid solution. Additional rate measurements were also made for one substrate, (Z)-β-methoxymethacrylic acid, in buffer solutions down to pH 7, and a rate profile was constructed. The results show that the β-carboxy and β-carbomethoxy substituents produce strong rate retardations, ranging from 2000- to 25 000-fold, for both Z- and E-isomers in both the acrylic and methacrylic acid series. The rate profile for (Z)-β-methoxymethacrylic acid indicates that ionization of this substrate to the carboxylate ion form rises the rate of hydrolysis by a factor of 240. It is argued that this difference in reactivity of ionized and non-ionized forms of the substrate is due to conjugative and inductive effects of the substituents, rather than β-lactone formation as suggested in an earlier observation of the same phenomenon in a different system.
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• 29
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Journal of Physical Organic Chemistry 7 (1994), S. 352-358
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The stereochemistry and kinetics of the methoxide ion substitution reactions (Z)- and (E)-methylbenzohydroximoyl cyanidc [PhC(CN)=NOCH3] were investigated. The reaction of the (Z)-hydroximoyl cyanide with sodium methoxide in DMSO-methanol (9:1) solution at 44·8°C gives a mixture of methyl (Z)-O-methylbenzohydroximate [PhC(OCH3)=NOCH3] and the O-methyloxime of α-ketophenylacetamide PhC(CONH2)=NOCH3. The (E)-hydroximoyl cyanide undergoes methoxide ion-catalyzed isomerization to the E-isomer faster than it undergoes nucleophilic substitution. These observations were interpreted in terms of an addition-elimination mechanism in which the rate-limiting step is elimination of the nucleofuge (AN + DN#).
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• 30
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Journal of Physical Organic Chemistry 7 (1994), S. 394-394
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
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• 31
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Journal of Physical Organic Chemistry 7 (1994), S. 399-402
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The reaction of nitrosobenzene with aniline, to give azobenzene, in basic conditions was studied. It was shown that the reaction exhibits general base catalysis by different buffers giving a Brønsted coefficient β = 0·318. As in previous studies, a two-step process with a first step of attack of aniline on nitrosobenzene to give an addition intermediate and a second step of dehydration of this intermediate is proposed to interpret the mechanism of the reaction. The analysis of the Brønsted relationship and of the intermediate of the reaction led to the suggestion that hydoxide ion catalyses the reaction by a mechanism of general base catalysis in the dehydration step.
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• 32
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Journal of Physical Organic Chemistry 7 (1994), S. 431-436
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Imidazole (Imz)-catalysed hydrolysis of benzoate esters proceeds via the intermediate formation of N-benzoylimidazoles. This paper considers the second step of this reaction, viz., Imz-catalysed hydrolysis of N-(4-X-benzoyl)imidazoles, X = CH3, H, Cl, CN and NO2, and N-(disubstituted benzoyl)imidazoles, 2-chloro-4-nitro, 2, 4-dinitro and 3,5-dinitro, in water-acetonitrile mixtures (10% or 14%, v/v, in organic solvent). On the basis of catalytic rate constants and the kinetic solvent isotope effect, it is shown that catalysis by Imz is of the general-base type. Unexpectedly, the hydrolysis of N-(2,4-dinitrobenzoyl)imidazole was found to be slower than that of N-(4-nitrobenzoyl)imidazole. It is shown that this reactivity order is due to a combination of a steric effect and stabilization of the reactant state due to a donor-acceptor interaction between the Imz moiety and the 2,4-dinitrophenyl ring.
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• 33
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Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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• 34
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Journal of Physical Organic Chemistry 7 (1994), S. 485-494
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: The rates of the solvolysis of 3-R-4-homoadamantyl methanesulphonates (mesylates) (3) were determined in 80% aqueous ethanol. The relative first-order rate constants at 25 °C were 1·0 (R = H), 2·29 (R = Ph), 3·26 (R = p-anisyl), 73·6 (R = Me) and 209 (R = Et). The methanolysis of 3 gave rearranged methyl ethers and rearranged olefins as major products together with small amounts (0·9-3·4%) of unrearranged products. The order of the accelerating effect suggests that the transition states involve significant σ-participation, despite the fact that 3 (R = H) solvolyses via a classical ion intermediate. The logarithms of the solvolysis rate constants of 3 showed linear correlations with those of 1-R-2-adamantyl tosylates (1) and 1-R-exo-2-norbornyl tosylates (2), indicating that the linear free-energy relationship between the β-substituent effects on the solvolysis rate is not a definite measure to distinguish between classical and non-classical intermediates.
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• 35
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Journal of Physical Organic Chemistry 7 (1994), S. 518-524
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: The kinetics of the nucleophilic cleavage of phthalimide (PTH) in buffer solutions of ammonia and pyrrolidine were determined. The reaction rates for ammonolysis of PTH revealed a buffer-catalysed second-order term in the rate law, but the reaction rates for pyrrolidinolysis of PTH showed buffer-catalysed second- and third-order terms in the rate law. Both ammonia and pyrrolidine revealed nucleophilic reactivity towards ionized PTH (S-) only within the pH range of the present study. This is attributed to the occurrence of intramolecular general base-acid catalysis. General base catalysis is detected in the reactions of pyrrolidine with both non-ionized PTH (SH) and S-. The general base-catalysed third-order rate constant for pyrrolidinolysis of SH is nearly 28 times larger than that of S-.
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• 36
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Journal of Physical Organic Chemistry 7 (1994), S. 534-544
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: The bisporphyria N,N′-bis[4″-(meso-triphenylporphyrinyl)benzyl]-4,13-diaza-18-crown-6 and its mono- and dizinc derivatives were synthesized in 66%, 46% and 53% yields, respectively, from 5-(4′-bromomethylphenyl)-10,15,20-triphenylporphyrin or its zinc derivative and 4,13-diaza-18-crown-6. The zinc-containing bisporphyrins form dimers in solution at low temperature or at high concentration. The unsymmetrical bisporphyrin; monozinc N,N′-bis[4″-(meso-triphenylporphyrinyl)benzyl]-4,13-diaza-18-crown-6 shows singlet-singlet energy transfer from the zinc porphyrin moiety to the free base moiety in both the monomeric and the dimeric form. The energy transfer rates were determined using time-resolved fluorescence spectroscopy and were found to be 1·26 × 109 and 2·29 × 109 s-1 for the monomeric and dimeric form, respectively. The difference in energy transfer rates between the two forms can be rationalized by the difference in overlap between the donor fluorescence spectrum and acceptor absorption spectrum, donor-acceptor distance and donor-acceptor orientation.
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• 37
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Journal of Physical Organic Chemistry 7 (1994), S. 221-226
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: In constrast with recent molecular orbital calculations on the decarboxylation of O-protonated 2-oxetanone, this experimental work indicates that no decarboxylation of this cation occurs in sulphuric acid solution up to 150°C, but instead a clean isomerization to protonated acrylic acid takes place. Parallel theoretical work shows that the gas-phase model is too crude to account successfully for the experimental facts obtained in acidic media. However, the latter are well reproduced when the effect of the solvent is taken into account. The present findings do not necessarily invalidate the reaction mechanism currently accepted to explain the rate enhancement and change of stereochemistry accompanying the decarboxylation of 3,4-disubstituted 2-oxetanones under acid catalysis.
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• 38
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Journal of Physical Organic Chemistry 7 (1994), S. 280-286
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: The 15N chemical shifts of various m- and p-substituted anilides and related derivatives, ZNHC6H4Y [Z = C6H5CO, CH3CO, CF3CO, CH3SO2, (C6H5O)2PO and H], were correlated with σ- constants. With all series of anilides investigated, the plotted points for the m- and p-substituted derivatives tend to be separated from each other and to lie on two different regression lines. Reinvestigation from this point of view revealed that similar separations occur generally with substituted aniline derivatives. The anomalous polar substituent effect was ascribed to the very large contribution of a resonance effect. In addition, the local π-polarization effect causes a negative slope for the m-substituted series in the case of carboxylic anilides.
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• 39
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Journal of Physical Organic Chemistry 7 (1994), S. 303-308
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: Cubane diester crown ethers were tested as ion-selective electrodes in poly(vinyl chloride) (PVC) membranes. The four ionophores studied proved to be good K+ neutral carriers, showing Nernstian and near-Nernstian responses to this ion, in the range 10-4-10-1 M. The fixed interferences method was used to determine relative selectivity coefficients for all the electrodes. The highest selectivity for potassium relative to sodium, lithium, calcium and magnesium ions using potassium tetrakis(p-chlorophenyl)borate (KTpClPB) as a resistance modifier and NPOE as a plasticizer was obtained with the 1,4-cubyl diester-25-crown-7 ether ionophore. The effects of KTpCIPB on membrane selectivity were assessed; its removal was found to increase the selectivity of the four ionophores for potassium relative to cesium, sodium, calcium and magnesium ions with minimal effects on lithium and ammonium ions. The compounds tested exhibited a fast Nernstian response to changes in K+ concentration which was stable to within 〈100 μV h-1.
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• 40
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• 41
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Journal of Physical Organic Chemistry 7 (1994), S. 244-250
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: Calculations were carried out to study the validity of σ-scales for hydrogen abstraction from substituted toluenes by tert-butyl, tert-butoxyl and tert-butylperoxyl radicals. Rate constants were compiled and evaluated from the literature for meta- and/or para-substituted toluenes. The substituents were characterized by factored ionic sigmas (σI, σR, σR+), ionic scales (σ, σ+) and various radical sigmas (σσ). The dependence of log k values on these substituent descriptors was investigated using ‘stepwise linear regression’ and ‘all possible regression’ methods. The following predictive equations can be recommended: for tert-butyl radicals, at 321 K: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {\log \,k_1 \, = \,1.024\, + \,0.776\,\sigma _1 \, + \,0.653\,\sigma _{\mathop C\limits^. }} \quad {(R\, = \,0.8137)} \end{array}$$\end{document} for tert-butoxyl radicals, at 313 K: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {\log k_2 = 5.529 - 0.623\sigma ^ +} \quad {(R = 0.9376)} \end{array}$$\end{document} and for tert-butylperoxyl radicals, at 303 K: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {\log k_3 = - 1.410 - 0.810\sigma + 0.337\sigma _{\mathop C\limits^. } } \quad {(R = 0.9628)}\end{array}$$\end{document} The results suggest that there is no unversal radical scale for hydrogen abstraction reactions, that the rate is primarily influenced by polar factors (inductive, resonance) and that only two radical scales (σĊ and σα·) are appropriate, showing a small, yet significant, role of radical stabilization.
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• 42
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Journal of Physical Organic Chemistry 7 (1994), S. 273-279
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: Nucleophilic substitution reactions of benzoic anhydrides, in which one of the rings is substituted, with anilines were investigated in methanol. The product-formation step coincides with the rate-limiting step so that the two rate constants, kXZ and kXZ, for the competitive reaction pathways can be dissected. The two cross-interaction constants, ρXY and ρXY, especially an unusually large magnitude of the latter, indicate that the reaction proceeds by a frontside SN2 attack on either one of the caronyl carbon with a strong interaction between the nucleophile (X) and the leaving group (Z). The mechanism is also supposed by the trends in the activation parameters.
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• 43
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Journal of Physical Organic Chemistry 7 (1994), S. 323-323
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Keywords: Organic Chemistry ; Physical Chemistry
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• 44
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• 45
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Journal of Physical Organic Chemistry 7 (1994), S. 359-363
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: Nucleophilic substitution reactions of 1-(trimethylsilyl)ethyl arenesulphonates with anilines and benzylamines in acetonitrile and methanol at 65·0°C were studied. The cross-interaction constants, ρXZ, between substituents in the nucleophile (X) and leaving group (Z) are relatively small (0·10 for XC6H4NH2 in MeCN) but similar to those for other SN2 processes at a secondary carbon atom. This provides further evidence for an approximately constant, loose SN2 transition state at a secondary carbon regardless of the size of the Cα substituent. The transition-state variations with substituents X and Z are in accord with that expected from the positive ρXZ value observed: a stronger nucleophile and/or nucleofuge leads to an earlier transition state, i.e. a lower degree of bond making and breaking.
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• 46
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Journal of Physical Organic Chemistry 7 (1994), S. 385-393
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: Substrate and positional selectivity in the nitration reactions of benzene and its derivatives (halobenzenes, toluene and o-xylene) by nitric acid and acyl nitrates supported on zeolites H-Y and H-ZSM-11 were studied. The reaction mechanism and effects governing selectivity of the process are discussed.
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• 47
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Journal of Physical Organic Chemistry 7 (1994), S. 395-398
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Keywords: Organic Chemistry ; Physical Chemistry
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Notes: The reaction which forms hydroxymethylbenzodioxane from epibromohydrin and catecholate anion was examined by ultraviolet spectroscopy for the kinetics and by proton nuclear magnetic resonance spectroscopy to follow the fate of CD2 from reactant to product. Over the practical temperature range it was found that both CH2 positions in the epihalohydrin are attacked by catecholate anion to give product. Therefore, the difference in energy for the two pathways was small. The individual rate constants were obtained from the total rate constants. Further, the individual ΔH
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• 48
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Journal of Physical Organic Chemistry 7 (1994), S. 437-441
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
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Notes: The critical micelle concentration of solutions of cetyltrimethylammonium bromide and of tetradecyltrimethylammonium bromides were determined by a kinetic method. This involved the determination of the rates of the hydroxydehalogenation of some activated aromatic substrates over a wide range of detergent concentrations. Measurements were made in solutions containing significant quantities of added hydroxyl ion and substrates which were themselves amphiphilic. Conventional methods cannot be applied with confidence to such systems. The effects of changing hydroxyl ion concentrations, added sodium bromide, changing the nature of the aromatic substrate (whether neutral or charged), the identity of the micellar counterion and the temperature were investigated. It was wound that added bromide or hydroxyl ions resulted in a lower CMC whereas increased temperature led to an increase in the CMC. The nature of the micellar counterion (Br, F, OH, SO4) had little effect on the CMC. The presence of a charged aromatic substrate led to a considerable lowering of the CMC, whereas the neutral aromatic substrate used showed very little effect.
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• 49
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Journal of Physical Organic Chemistry 7 (1994), S. 442-447
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: The reaction of several nitro activated aromatic halides with hydroxide ions was studied in the presence of hydroxy functionalized micelles containing bulky head groups, e.g. C16H33N+R2CH2CH2OH Br-, where R = Me, Et, Bu. In a biphasic reaction, the aryl halide is first converted into an aryl mincellar ether which subsequently reacts with hydroxide ions to form the phenolic product. Despite the increased nucleophilicity of hydroxide ions as water is squeezed away from the micelle surface by the bulky head groups, no direct reaction of the aromatic substrate with hydroxide ion is detectable. In the second phase of reaction, the breakdown of the aryl micellar ether to form the phenolic product, the order of reactivity in the different micelles is dependent on the steric interactions between substituents ortho to the reaction centre and the head group of the micelle. For compounds having one substituent ortho to the reaction centre, the order of reactivity is Bu 〉 Me 〉 Et, whereas for 2-chloro-1,3-dinitrobenzene, which has two substituents ortho to the reaction centre, the order is Me 〉 Et 〉 Bu.
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• 50
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Journal of Physical Organic Chemistry 7 (1994), S. 465-478
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: The utility of desorption/ionization mass spectrometric (DI/MS) techniques in dealing with physical organic problems involving fragile onium salts and carbocation salts has been explored. The efficacy of these methods, especially when coupled to tandem mass spectrometry, goes much beyond the analytical aspects dealing with identity/purity determinations. For example, insight can be gained regarding the role of the counterion in subsequent cation decomposition pathways. Guest-host chemistry of onium ions and various hosts (crowns, calixarenes) can be probed. The decomposition chemistry of the resulting ion-molecule clusters can be studied. Examples of onium salts and carbocation salts that have been studied are few, probably because research in this area has been mainly a domain for analytical chemists. This paper calls attention to the possibilities for dealing with topical physical organic problems.
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• 51
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Journal of Physical Organic Chemistry 7 (1994), S. 503-510
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Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: The mechanism of the photochemical decomposition of 1,4-oxazin-2-one to azacyclobutadiene and carbon dioxide was investigated by the semi-empirical MO method SINDO1. The relevant singlet and low-lying triplet potential energy hypersurfaces were studied and intermediates and transition structures were optimized with limited configuration interaction. The first step transforms 1,4-oxazin-2-one into a bicyclic lactone via internal cyclization. Then a stepwise bond breaking mechanism on the first excited triplet state yields azacyclobutadiene and CO2, whereas a reaction on the first excited singlet state is not common. It is shown that a simultaneous bond-breaking mechanism on the first excited singlet or on the first excited triplet is possible.
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• 53
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Journal of Physical Organic Chemistry 7 (1994), S. 615-624
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
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Notes: Substitutent effects of acceptor groups were measured for the gas-phase basicities of some substituted benzonitriles, methyl benzoates and acetophenones, and for gas-phase acidities of some substituted benzoic acids. Substitutents considered were NO2, CN, SO2CH3, SO2F, CF3, CH2Cl, COCH3 and COOCH3, always in the meta and para positions. By combination with the literature data, a general conclusion is drawn that the substituent effects are proportional in the two positions and almost equal (the para:meta ratio is 1·06). No sign of any resonance effect was detected within the accuracy of the approach. The substituent effects in solution were recalculated statistically and the result was similar with a higher ratio, 1·09-1·19. It follows that the conjugation of acceptor groups, particularly of NO2 as a typical example, has been overestimated by current theories when compared with the much stronger conjugation of typical donors. Moreover, the inductive effect is propagated more effectively from the para than from the meta position. Many correlations in the literature, neglecting this situation, have been in fact controlled by the more complex, and more striking, behaviour of donors, which has obscured the simpler and more monotonous effect of acceptors, usually less represented in the sample.
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Journal of Physical Organic Chemistry 7 (1994), S. 641-645
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Keywords: Organic Chemistry ; Physical Chemistry
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Notes: Transition states for the hetero-Diels-Alder addition of formaldehyde, formaldimine, diazene and nitrosyl hydride to cyclopentadiene were located with ab initio molecular orbital calculations. Asynchronous transition structures were located for the asymmetric hetero-dienophiles, whereas the symmetrical hetero-dienophile, cis-diazene, produced a synchronous transition structure. The relative reactivities are in good agreement with the LUMO energies of the hetero-dienophiles, and the transition states with the exo oxygen or nitrogen lone pairs have lower energies than the corresponding endo lone electron pair transition states. Endo/exo energy differences are much higher than in the addition of ethylene derivatives to cyclopentadiene.
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• 56
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Journal of Physical Organic Chemistry 7 (1994), S. 117-121
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Keywords: Organic Chemistry ; Physical Chemistry
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Notes: The kinetics of oxidation of metol (N-methyl-p-aminophenol) by thallium(III) have been studied in a perchloric acid medium. This organic compound is employed extensively in photographic work. The stoichiometry of the reaction is represented by: C6H4(OH)NHCH3 + TIIII → C6H4(O)NCH3 + TII + 2H+The kinetics indicate the rate law: \documentclass{article}\pagestyle{empty}\begin{document}$$k' = \frac{{Kk\left[{metal} \right]}}{{1 + K\left[{metal} \right]}}$$\end{document} where k′ is the pseudo-first-order rate constant. The rate constants and thermodynamic parameters for the rate-limiting step have been evaluated.
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Journal of Physical Organic Chemistry 7 (1994), S. 169-169
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Journal of Physical Organic Chemistry 7 (1994), S. 178-180
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Notes: The volumes of activation and of reaction were measured for the reaction between sulphur dioxide and 2,3-dimethylbuta-1,3-diene to form 3,4-dimethylsulpholene. Values of ΔV and ΔV* are -33 and -35 cm3 mol-1, respectively in accordance with a concerted reaction having a very product-like transition state.
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• 59
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Journal of Physical Organic Chemistry 7 (1994), S. 196-206
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Notes: Structural effects on the melting points of substituted alkanes, both branched and unbranched, ranging in length from 1 to 19 carbon atoms, were successfully correlated with a variant of the intermolecular force equation which included a variable capable of accounting for the packing energy contribution of the alkyl group. The final data set had 366 data points. The regression equation obtained accounted for 91·85% of the variance of the data with a standard error of 17·9 K. Twenty-nine data points could not be included in the correlation; nine of these are carboxamides. The contributions of the polar variables are slightly larger than those of the nonpolar variables while the contribution of structural variation in the substituent is greater than that in the alkyl group. It will be necessary to determine appropriate values of the packing parameter if compounds with chains longer than 20 carbon atoms are to be included in the model.
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Journal of Physical Organic Chemistry 7 (1994), S. 207-217
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Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
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Notes: A semi-empirical configuration interaction (CI) algorithm is presented for predicting the ground-state spin multiplicity of open-shell systems. The computed energy gaps ΔE(LS—HS) of model systems, Y-phenyl-X-phenyl-Y, where Y is a nitrene or nitroxide radical and X is an exchange coupling unit, are critically compared with the available experimental data. The current method has attenuated the deficiencies of the earlier algorithm proposed by Lahti and Ichimura and the predictions are qualitatively clearer, facilitating the classification of high- and low-spin topologies for isomeric species. The relative effectiveness of different exchange couplers can be discerned semi-quantitatively, and several new exchange couplers are described. The reasons for the qualitative failure of the earlier algorithm are discussed.
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Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: The relative basicities of six monosubstituted dipolar trimethylamines (XCH2NMe2) were determined in nine different solvents from potentiometric titration. Solvation effects on basicity variations were analyzed by the solvatochromic parameters (π*, α and β). Non-specific solvation of the substituted dimethylammonium ions is not reflected adequately by the solvent's dipolarity-polarizability constant, π*. A better representation of non-specific interaction between solvents and the monosubstituted dipolar trimethylammonium ions is gained from the product of π* and the solvent dipole moment (μ). For these ions where the dipolar substituents are separated from the reaction center by one methylene unit, there is an interaction between the charge of the ammonium ion and the dipolar substituent. As a result, solvent molecules must not only solvate the dipolar substituents, but must also gain access between the lines of force of the dipolar substituent and the charge. Bulky solvents, such as nitrobenzene, cannot access adequately the region between the dipolar substituents and the reaction center to accomplish similar solvation as less bulky solvents.
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Measured pseudo-first-order rate constants for intramolecular formation of tetrahedral intermediates from N-2-hydroxyethylphthalimide, N-2-aminoethylphthalimide and N-2-thioethylphthalimide at pH 〉 6 are reported. The reaction is specific and general base catalysed, with β(Brønsted) values 0·44, 0·52 and 0·52 respectively. From a plot of log kb (general base rate constants) vs γ′ [the affinities of EtXH (X = O, NH, S) toward the carbonylic carbon], β′nuc values of 0·01 (with OH- as specific base), 0·25 (with imdidazole as general base) and 0·27 (with HPO42- as general base were obtained). The observed relationships pxy = ϑβ′/ - ϑpKa = -ϑ(Brønsted)/ϑγ′ = 0·03 is supported by the predictions of an energy contour diagram, which, on extrapolation to a non-stable tetrahedral intermediate, predicts a late and slightly protonated transition state for the cleavage process. At pH 〈 3, these intermediates cleave to yield only the corresponding diacylimides. These reactions are general base and acid catalysed with β 〉 0·3 and α 〈 0·1. A fast equilibrium between the intermediate and its N-protonated (amide) form is reached. The general base rupture of the latter is faster than that of the corresponding non-protonated intermediate by a factor of ca 109 - 1010-fold.
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• 63
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: Transfer of the cobalt-bound methyl in MeCo(III)Pc to thiophenoxide ion was studied (H2Pc is the planar macrocyclic phthalocyanine; the cobalt is held in the center in this plane). In dimethylacetamide solution, the reaction is rapid, requiring stopped flow for the kinetics, and yielding MeSPh and Co(I)Pc- in good yield. The kinetics are not simple second order, but instead approach a constant rate at high [PhS-], attributed to the reversible formation of an inert complex with PhS- occupying the vacant octahedral site in MeCo(III)Pc, on the other side of the phthalocyanine plane from the methyl group. The kinetics allow the estimation of the equilibrium constant, K, and the SN2 rate constant, k, which at 25°C have values of ca. 9·4 × 103 l mol-1 and 1·8 × 104 l mol-1, respectively. Although these values are rough, the ratio k/K is firm at 1·91 ± 0·02 s-1; this is the limit of the rate at high [PhS-]. An alternative mechanism, which is entirely consistent with the kinetics, involves a rate-determining homolysis of the Co—S bond of the same complex. The mechanism is not favored because the product yields are high for a radical combination process and alternative chain processes are kinetically unacceptable. Further, the rate constant is about what would be expected from the reactivity of other nucleophiles in SN2 reactions. Further arguments in favor of the SN2 mechanism are presented. This transfer of the methyl group from Co to S is part of the possible analogy to the vitamin B12-promoted methionine synthesis in nature. The other step in the biological, enzymatic process is the transfer of methyl from the nitrogen of N-methyltetrahydrofolate to cobalt. An attempt to model this with the very reactive N-methyl-2,6-dichloropyridinium ion was unsuccessful; the reaction took an entirely different course, presumably initiated by electron transfer, but leading to substantial loss of Cl- from the pyridine. No more than 0.5% methyl transfer took place. This system does mimic well the complete natural enzymatic process.
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• 64
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Chichester : Wiley-Blackwell
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
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Journal of Physical Organic Chemistry 7 (1994), S. 142-146
ISSN: 0894-3230
Keywords: Organic Chemistry ; Physical Chemistry
Source: Wiley InterScience Backfile Collection 1832-2000
Topics: Chemistry and Pharmacology , Physics
Notes: An empirical formula relating directly H⃛O interatomic distance to H⃛O interaction energy is used to estimate this energy in intramolecular O—H⃛O hydrogen bonds calculated for systems of known precise geometry. The values obtained were correlated with spectroscopic characteristics of the H-bond (Δv for OH bands in IR spectra and NMR chemical shifts, δ, for protons) and CNDO and INDO estimations of H-bond energy. The regressions obtained had good or very good correlation coefficients.