Ultraviolet Spectra of Anions of Mononitro Compounds<sup>1</sup>

Williams, Francis T.; Flanagan, P. W.; Taylor, William J.; Shechter, Harold

doi:10.1021/jo01019a040

Cited by 23 publications

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“…(Spectra of anions of nitroalkanes in water have been reported. 13 Reactant spectra and extinction coefficients of NM, NE and 2-NP are shown in Fig. S4, electronic supplementary information (ESI)).…”

Section: Resultsmentioning

confidence: 99%

Reactions of the simple nitroalkanes with hydroxide ion in water. Evidence for a complex mechanism

Li¹,

Cheng²,

Parker³

2011

Org. Biomol. Chem.

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Conventional kinetic analysis of the reactions of nitromethane (NM), nitroethane (NE) and 2-nitropropane (2-NP) with hydroxide ion in water revealed that the reactions are complex and involve kinetically significant intermediates. Kinetic experiments at the isosbestic points where changes in reactant and product absorbance cancel indicate the evolution and decay of absorbance characteristic of the formation of reactive intermediates. The deviations from 1st-order kinetics were observed to increase with increasing extent of reaction and in the reactant order: NM < NE < 2-NP. The apparent deuterium kinetic isotope effects for proton/deuteron transfer approach unity near zero time and increased with time toward plateau values as the reaction kinetics reach steady state. It is proposed that the initially formed preassociation complexes are transformed to more intimate reactant complexes which can give products by two possible pathways.

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Section: Resultsmentioning

confidence: 99%

Reactions of the simple nitroalkanes with hydroxide ion in water. Evidence for a complex mechanism

Li¹,

Cheng²,

Parker³

2011

Org. Biomol. Chem.

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“…ZThe absorption maximum of sodium methanenitronate in water is at 232 nm (8), and the maxima of the sodium salts of other primary and secondary nitroalkanes and nitrocycloalkanes fall in the region 226-244 nm (9). *Molar absorbance = absorbance of a solution 10-4 M in nitro compound, multiplied by 10 000.…”

Section: Lists Molar Absorbances (A) Ofmentioning

confidence: 99%

A Study of Steric Effects on Nitromethylene Acidity and the Mechanism of Epimerization in Partially Blocked Nitro Hexoses

Baer¹,

Rank²

1971

Can. J. Chem.

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The extent of nitronate formation in seven methyl 4,6-O-benzylidene-3-deoxy-3-nitrohexopyranosides and four methyl 4,6-O-benzylidene-2,3-dideoxy-3-nitrohexopyranosides in dilute potassium hydroxide solution was compared by means of u.v. spectroscopy. Considerable differences were found to exist in the nitromethylene acidities, and these were correlated with stereochemical features of the molecules. A facile manno → gluco epimerization occurring in this series was investigated. It was shown that, in alkaline alcoholic solution, the epimerization proceeds by an elimination–addition via an intermediate nitroalkene if the hydroxyl group at C-2 is acetylated. However, if the hydroxyl is free, the nitroalkene is not an intermediate and, in accord with the low nitromethylene acidity in this particular case, the mechanism is suggested to involve a reverse Henry reaction.

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“…which appears at 226-239 nm, is thought to be due to a tt 7 * transition having the character of an intramolecular charge transfer from the oxygens of the anion to the carbon. 20 This transition shifts appreciably to longer wavelength on conjugation (e.g., salts of phenylnitromethane absorb at 293 nm21) and is probably also responsible for the 360-nm absorption of salts 1, 2, and 4. The transfer of charge from the oxygens to the hydrocarbon portion of these salts in the excited state should result in lesser stabilization of the excited state by hydrogen bonding, and accordingly the transition should occur at higher energy (shorter wavelength) in hydrogen-bonding solvents than in aprotic solvents.…”

Section: Appendixmentioning

confidence: 99%

Effect of solvents on anion structure

Kerber¹,

Porter²

1969

J. Am. Chem. Soc.

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Ultraviolet Spectra of Anions of Mononitro Compounds¹

Cited by 23 publications

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Reactions of the simple nitroalkanes with hydroxide ion in water. Evidence for a complex mechanism

Reactions of the simple nitroalkanes with hydroxide ion in water. Evidence for a complex mechanism

A Study of Steric Effects on Nitromethylene Acidity and the Mechanism of Epimerization in Partially Blocked Nitro Hexoses

Effect of solvents on anion structure

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Ultraviolet Spectra of Anions of Mononitro Compounds1

Cited by 23 publications

References 0 publications

Reactions of the simple nitroalkanes with hydroxide ion in water. Evidence for a complex mechanism

Reactions of the simple nitroalkanes with hydroxide ion in water. Evidence for a complex mechanism

A Study of Steric Effects on Nitromethylene Acidity and the Mechanism of Epimerization in Partially Blocked Nitro Hexoses

Effect of solvents on anion structure

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Product

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Ultraviolet Spectra of Anions of Mononitro Compounds¹