Nitroalkanes determination

The work reported here is the last experimental study of the Keele Polymer Group which came to an end in 1985. The senior author believes that he has achieved one of his principal chemical objectives, to determine some credible kp values and to discover the optimum conditions. He hopes that others will adopt the use of highly polar solvents and will explore a wide temperature range. For low temperatures, the eutectic mixtures of PhN02 with one of the nitronaphthalenes or dinitrobenzenes will be needed. Another useful, highly polar, solvent is S02. The nitroalkanes should be avoided. The initiator of choice should be an aroyl salt of a stable anion, and it is clear that the ideal such salt has not yet been found, but useful guidelines for finding improved initiators (in terms of speed of reaction, shelf-life and solubility) are available [21]. 

A review appeared on the determination of nitroalkanes, polynitroalkanes, nitroalkenes, aromatic nitro and polynitro compounds, heterocyclic nitro derivatives and inactive compounds after nitration, by polarography, voltammetry and HPLC with electrochemical detection441. 

The results indicate that the kinetic acidity is markedly lower for phosphonium salts than for the corresponding nitroalkanes, but cannot be correlated with pKa values. In contrast, the measurement of kinetic acidity using double potential step chronoamperometry180 allowed the determination of pka values for a series of phosphonium salts corresponding to semi-stabilized or non-stabilized ylides ... 

An unsuccessful attempt has been made to determine the separate electronic and steric effects of alkyl groups on the acidities of hydrocarbons, acetophenone derivatives, and acetone derivatives CH3COCHR1R2 (at either site) by multivariational analyses of experimental and theoretical acidities for each set.15 A thermodynamic cycle has been used to estimate the aqueous phase p/C, = 22.7 1.0 for the methyl group of acetic acid and p/C, = 3.3 1.0 for the corresponding enol.16 Equilibrium acidities have been determined for several nitroaryl substituted nitroalkanes and cyanomethanes, 2,4,6-TNT, and 9-cyanofluorene17 in acetonitrile the influence of common cation BH+ on the electronic spectra of the anions obtained in the presence of strong guanidine bases (B) has been attributed to formation of two types of ion pair.18... 

Substitutions by the SRn 1 mechanism (substitution, radical-nucleophilic, unimolecular) are a well-studied group of reactions which involve SET steps and radical anion intermediates (see Scheme 10.4). They have been elucidated for a range of precursors which include aryl, vinyl and bridgehead halides (i.e. halides which cannot undergo SN1 or SN2 mechanisms), and substituted nitro compounds. Studies of aryl halide reactions are discussed in Chapter 2. The methods used to determine the mechanisms of these reactions include inhibition and trapping studies, ESR spectroscopy, variation of the functional group and nucleophile reactivity coupled with product analysis, and the effect of solvent. We exemplify SRN1 mechanistic studies with the reactions of o -substituted nitroalkanes (Scheme 10.29) [23,24]. 

Acidity constants and rates of reversible deprotonation of triphenylphosphonium ion (54), (55) and pyridinium ions (56), (57) by amines in water, 50 50 v/v DMSO-water, and 90 10 v/v DMSO-water have been determined.157 The intrinsic rate constants for proton transfer were relatively high for all four carbon acids and showed little solvent dependence. This is in contrast with nitroalkanes, which have much lower intrinsic rate constants and show a strong solvent dependence.158... 

Thus, the important factor in determining whether the nitroalkane will be reduced to a hydroxylamine or an amine is the temperature, since increased temperatures will speed up the rearrangement reaction (79) and favor the formation of the amine. 

Nitroalkanes are aminocyclopropylated by cyclopropanone aminals. Thus bicyclic aminals 1 were treated with excess nitroethane or nitromethane in the presence of iodomethane. The configuration of the resulting bicyclic products 2 was not determined. Dinitroethane did not react with a cyclopropanone iV,0-acetal or aminal. ... 

The direct asymmetric conjugate addition of simple aldehydes to electrophiles is crucial in organic reactions. Barbas et al. developed the first example of a highly stereoselective direct Michael reaction that involved adding unmodified aldehydes to nitro-olefins. After various p3Trolidine-diamines were screened, (S)-2-(morpholinomethyl)pyrrolidine Ic was determined to be the ideal catalyst for obtaining satisfactory stereoselectivity in the reaction. These reactions afforded various 2,3-disubstituted y-formyl nitroalkanes with satisfactory yields and moderate to good enantioselectivity (Scheme 9.12). ... 

Rate constants for the reactions of OH radicals with n-nitroalkanes, n-alkyl nitrates and n-alkyl nitrites have been determined at 298 K and 1 atmosphere total pressure using both pulse radiolysis combined with kinetic spectroscopy and a conventional relative rate method. In order to provide more mechanistic information for these reactions, rate constants for the reaction of Cl atoms with these compounds were determined using the relative rate method. The data indicate that the reaction of OH radicals with these nitrogen-containing compounds involves both an abstraction and an addition channel. These results are discussed in terms of reactivity trends and compared with the data from the literature. 

Bronsted exponents for the ionization of a series of nitroalkanes and ketones, measured mainly by Bell and his collaborators [48, 55], are shown in Table 6. Although a common set of bases was not used in all cases, the bases were confined to carboxylate anions. The values are compared with isotope effects determined for ionization of the substrates with H2O as the base [48,55], and it is apparent that kff/ko increases steadily with )8, with only ethyl acetoacetate and acetylcyclohexanone out of line, and that the correlation with p is better than that with either the reactivity or pK of the substrate. The isotope effects are rather small because water is a weak base and in most cases the transition states should be strongly asymmetric in structure. Moreover because )8 refers to the much stronger carboxylate anions the absence of an isotope maximum at a = 0.5 is not surprising [48]. As would be expected, available measurements for carboxylate anions give large values of k k, but the results are too fragmentary to permit any further conclusion. 

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