V.—The action of halogens on compounds containing the carbonyl group

Lapworth, Arthur

doi:10.1039/ct9048500030

Cited by 77 publications

(32 citation statements)

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“…Since the importance of enols as reactive intermediates was recognized, there have been numerous attempts to measure or estimate the enol content of carbonyl compounds. Although these efforts quickly led to satisfactory results for β‐dicarbonyl compounds for monocarbonyl compounds, where the equilibrium enol content is much smaller, the situation was for a long time quite unsatisfactory with inconsistent results reported by various authors .…”

Section: Introductionmentioning

confidence: 99%

Equilibrium constants for enolization in solution by computation alone

Guthrie

Povar

2013

J of Physical Organic Chem

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Equilibrium free energy changes for enolization in aqueous solution can be calculated with useful accuracy (rmse = 1.3 kcal/mol for 37 reactions). These calculations involve gas phase free energy changes calculated using the G3MP2B3 method and solvation energies calculated using the IPCM method corrected by a parameterization scheme which we have reported. For chloroacetones, we find a small preference for enolization to the halogenated side and a preference for forming an enol with Cl Z to the OH. This may be partly due to weak hydrogen bonding but must be partly due to a relief of crowding; 2-butanone also shows a preference for the Z-enol. There are serious disagreements between calculated and experimental values for some of the enolization equilibria of 1,3,5-cyclohexanetrione (phloroglucinol); we argue that the problems are with the experimental values. Reasonable values are obtained for the enolization of Meldrum's acid, diethyl malonate, and 1,3-cyclohexanedione. Computational equilibrium constants in aqueous solution are now viable as supplements to and checks on experiment.

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Section: Introductionmentioning

confidence: 99%

Equilibrium constants for enolization in solution by computation alone

Guthrie

Povar

2013

J of Physical Organic Chem

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“…These observations strongly suggests the iodation of the ketone after oxidation of the ethanol, thereby forming the iodoketone and aqueous iodide, according to reaction Scheme 2 [47,48] It is important to note that in these experiments we chose a sample of "I2O5" from a particular lot of material supplied by Acrōs Organics. Reported elsewhere [8], we characterized the material as having few impurities, but note that it is completely in the first hydration state, HI3O8, and not the anhydrous form as advertised.…”

Section: Suspensions Of Iodine Oxides In Alcoholsmentioning

confidence: 99%

Physiochemical Characterization of Iodine (V) Oxide Part II: Morphology and Crystal Structure of Particulate Films

2015

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Abstract:In this study, the production of particulate films of iodine (V) oxides is investigated. The influence that sonication and solvation of suspended particles in various alcohol/ketone/ester solvents have on the physical structure of spin or drop cast films is examined in detail with electron microscopy, powder x-ray diffraction, and UV-visible absorption spectroscopy. Results indicate that sonicating iodine oxides in alcohol mixtures containing trace amounts of water decreases deposited particle sizes and produces a more uniform film morphology. UV-visible spectra of the pre-cast suspensions reveal that for some solvents, the iodine oxide oxidizes the solvent, producing I2 and lowering the pH of the suspension. Characterizing the crystals within the cast films reveal their composition to be primarily HI3O8, their orientations to exhibit a preferential orientation, and their growth to be primarily along the ac-plane of the crystal, enhanced at higher spin rates. Spin-coating at lower spin rates produces laminate-like particulate films versus higher density, one-piece films of stacked particles produced by drop casting. The particle morphology in these films consists of a combination of rods, plates, cubes, and rhombohedra structure.

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“…Jahrhunderts einen beträchtlichen Sprung nach vorne dar. In der Nachfolge der Arbeiten von vant Hoff [4] und Lapworth [16] war dies eine der ersten Anwendungen des neuen quantitativen Konzepts der Reaktionsgeschwindigkeit auf Phänomene der organischen Chemie. Seit etwa 1910 untersuchten Holleman und seine Mitarbeiter die absoluten Reaktionsgeschwindigkeiten einer Vielzahl von Substitutionen.…”

Section: Kinetisch Kontrollierte Aromatische Substitutionenunclassified

Kinetik, Thermodynamik und das Problem der Selektivität: vom Reifen einer Idee

Berson

2006

Angewandte Chemie

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Warum so langsam? Bis das Konzept der Selektivität fester Bestandteil der organischen Chemie wurde, vergingen mehrere Jahrzehnte. Fortschritte resultierten aus der Einbeziehung theoretischer Gedanken aus der physikalischen Chemie zu Reaktionsgeschwindigkeit und ‐gleichgewicht. Untersucht wird die Frage, warum die Entwicklung dieses Konzepts so lange dauerte (Bild: Energiediagramm von Woodward und Baer für die Reaktion von Pentamethylenfulven (A) und Maleinsäureanhydrid (B)).

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V.—The action of halogens on compounds containing the carbonyl group

Cited by 77 publications

References 0 publications

Equilibrium constants for enolization in solution by computation alone

Equilibrium constants for enolization in solution by computation alone

Physiochemical Characterization of Iodine (V) Oxide Part II: Morphology and Crystal Structure of Particulate Films

Kinetik, Thermodynamik und das Problem der Selektivität: vom Reifen einer Idee

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