Search results for "Proton"
showing 10 items of 5886 documents
Competition between decarboxylation and isomerization in the C3H5O 2+ energy surface. Justification of the experimental results by molecular orbital …
1994
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 ac…
Proton Acid-induced Rearrangements of α-Alkynylestradiol Methyl Ethers
1993
When subjected to proton catalysis, the α-alkynylestradiol methyl ethers 1a and 1b furnish the Rupe or Meyer-Schuster rearrangement products 2, 4, and 5a. In the presence of sulfuric acid, α-ethynylestradiol 3-methyl ether (1a) is converted into the D-homosteroid 3a. The use of deuterated acids gives rise to the formation of the corresponding deuterated steroids 2b, 2c, 3b, and 5b. Some mechanistic implications of these results are also discussed.
ChemInform Abstract: Trienediolates of Hexadienoic Acids in Synthesis. Synthesis of Retinoic and nor-Retinoic Acids.
2010
Abstract Double deprotonation of either (E,E)-3-methyl-2,4-hexadienoic acid 2, or 4,6-dimethyldihydro-2-pyrone 3 generates apparently the same lithium trienediolate, which affords ω-hydroxy acids 9 on reaction with ketones 7. Hydroxy acids 9 are easily dehydrated to octatrienoic acids 5, which are structurally related to retinoic acid. Similarly, sorbic acid 1 leads to nor-retinoic acid analogs 6.
Binding of acrylic and sulphonic polyanions by open-chain polyammonium cations
2000
Abstract The interactions between some acrylic and sulphonic polyanions and some protonated amines (diamines NH 2 -(CH 2 ) x -NH 2 , x =2,…,10; linear tri-, tetra-, penta- and hexa-amines) were studied potentiometrically in aqueous solution, at 25°C. For both types of polyanions AL 2 H i (L − , monomer of polyanion, A, amine) species are formed, with i =1,…, n ( n =number of amino groups in the amine). The stability of these species is strictly dependent on the polyammonium cation charge, and fairly independent of the type of amine (in diamine species maximum stability is observed for x =4, 5). Acrylic and sulphonic polyanion complexes are considerably stronger than analogous species formed…
ChemInform Abstract: Proton Coordination by Polyamine Compounds in Aqueous Solution
2010
Abstract The present article is concerned with proton transfer reactions in aqueous solution of open-chain, macrocyclic and macropolycyclic or cage compounds having nitrogen atoms as protonation sites in the molecular framework, although several compounds with additional different donors will be considered. The main purpose of this review is to collect some significant examples of proton transfer processes in order to show how the electronic properties and molecular topology of polyamines affect the thermodynamic parameters of their protonation equilibria.
Studien zum Vorgang der Wasserstoffübertragung, 52. Zur Kenntnis der elektroreduktiven Spaltung der N - N-Bindung
1978
Am Beispiel von 35 Hydrazinderivaten wird die elektroreduktive Spaltung polarographisch und praparativ untersucht. Es wurde gefunden: 1) Beim mono-, tri- und tetrabenzoylierten Hydrazin 9, 11 bzw. 12 verschiebt sich das Potential proportional der Anzahl der Benzoylgruppen nach positiveren Werten. Beim symmetrischen 1,2-Dibenzoylhydrazin (10) wird das Halbstufenpotential E1/2 — bedingt durch H-Verbruckung und mesomere Stabilisierung — stark nach negativen Werten verschoben. — 2) Bei den cyclischen Hydrazinderivaten 14–16 werden die E1/2-Werte sowohl in Abhangigkeit von der Ringspaltung als auch durch cis-Fixierung der Benzoylgruppen noch zusatzlich nach positiveren Werten verlagert. — 3) Ube…
Conformational study of methyl esters of some aliphaticerythro- andthreo-dichlorocarboxylic acids
1984
The average conformations of methyl esters of some aliphatic erythro- and threo-dichlorocarboxylic acids in dilute carbon tetrachloride solutions have been determined from the vicinal proton–proton coupling constants and 1H NMR shifts. The 13C shift differences between the erythro and threo forms are compared and discussed with regard to the differences in the average conformations.
Ground and excited state properties of polyamine chains bearing two terminal naphthalene units
2002
A series of compounds bearing two naphthalene units linked through methylene groups to both ends of different open-chain polyamines has been investigated. The fluorescence emission studies show the presence of an excimer species whose formation depends on the protonation state and length of the polyamine chains and implies the existence of a bending movement in the excited state allowing the two naphthalene units to approach and interact. This interpretation was clearly proven by time-resolved fluorescence with the appearance of double exponential decays with a rise time observed at the excimer emission wavelength. For comparison purposes one bis-chromophoric compound containing a rigid cha…
Stufenweise darstellung eines cycloheptamers aus p-kresol, 4-tert-butylphenol und formaldehyd. Vergleich mit einem phenolischen, heptanuklearen kette…
1980
A phenolic cycloheptamer (11) and an analogous chain oligomer (10) with nearly the same structure were gained by stepwise syntheses. The cycloheptamer has a higher melting point and a better solubility in chloroform. In contrast to the chain oligomer his infrared spectrum indicates a stronger association of the hydroxyl groups which is not influenced by the solvent. The mass spectra announce a preferred statistical cleavage along the chain of compound 10 and a great stability of the ring of 11 which preferentially loses his substituents. The 1H NMR spectra confirm the constitutions of the chain (10) and ring compound (11). The cycloheptamer is distinguished by a ring inversion or a pseudoro…
Steady-state fluorescence emission studies on polyazacyclophane macrocyclic receptors and on their adducts with hexacyanocobaltate(III)
1995
The steady-state fluorescence emission spectra of the azacyclophanes 2,5,8,11-tetraaza[12] paracyclophane (L1), 2,6,9,13-tetraaza[14]paracyclophane (L2), 14,15,17,18-tetramethyl-2,5,8,11-tetraaza[12]paracyclophane (L3) and 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane (L4) as a function of pH have been measured. The fully protonated species of each cyclophane gives the highest fluorescence-emission quantum yield. The shapes of the titration curves have been explained by the existence of an electron-transfer quenching effect from a non-protonated amine to the benzene chromophore. This effect is greater for macrocycles in which the first deprotonated amine group is closer to the…