10.1016/j.tet.2008.04.042
The research investigates the inhibitory effect of iodide anions on phase-transfer catalyzed reactions of carbanions, which are generated in liquid-liquid two-phase systems using aqueous NaOH. The study suggests that iodide anions preferentially locate in the interfacial region between the organic and aqueous phases, reducing the basic activity of NaOH and disfavoring the deprotonation equilibrium of carbanion precursors. The experiments involved the use of various substituted phenylacetonitriles as carbanion precursors, tetrabutylammonium (TBA) halides as catalysts, and n-propyl halides as alkylating agents. The reactions were carried out in a chlorobenzene/50% aqueous NaOH two-phase system, and the equilibrium contents of carbanions and halides in the organic phase were determined by titration and potentiometric analysis. Gas-liquid chromatography (GLC), nuclear magnetic resonance (NMR), and mass spectrometry (MS) were employed for product analysis and confirmation. The results indicated that the concentration of carbanions in the organic phase and the subsequent reaction rates were influenced by the acidity of the carbanion precursors and the nature of the halide anions, with iodide anions exhibiting the most significant inhibitory effect.
10.1021/jo01225a006
The study investigates the preparation, alkylation, and acylation of salts derived from phenylnitroacetonitrile, a secondary nitro compound. The researchers used various chemicals, including potassium ethoxide, d- and I-2-octyl nitrate, and benzyl cyanide, to synthesize the salts. They explored the optical properties of these salts and found that they were optically inactive, suggesting a conjugated aci-structure. In the alkylation process, the silver salt of phenylnitroacetonitrile reacted with methyl iodide to produce a nitronic ester, which was confirmed through catalytic reduction to phenylethylenediamine. The acylation process involved treating the salts with benzoyl chloride, resulting in a benzoyl derivative whose structure was established as an oxygen acylated compound through reduction to benzoic acid and phenylethylenediamine. The study provides insights into the structural preferences and reactivity of these nitro compound salts.
10.1039/c3cc41703d
The research aims to investigate the coordination preferences of lithium (Li), magnesium (Mg), and copper (Cu) cations with nitriles, focusing on whether these metals preferentially coordinate to the nitrogen (N-metalation) or carbon (C-metalation) atoms in nitriles. The study used a series of metalated arylacetonitriles and cyclohexanecarbonitriles to analyze the influence of the carbon scaffold and the nature of the metal on the preference for N- or C-metalation through 13C NMR analyses. The chemicals used in the process include phenylacetonitrile, cyclohexanecarbonitrile, and various metalating agents such as BuLi, i-PrMgCl, CuI, and Me2CuLi. The research concluded that lithium and magnesium preferentially coordinate to the nitrile nitrogen in arylacetonitriles, while copper favors C-metalation. The study also found that the carbon scaffold can significantly influence the coordination preferences, with magnesiated nitriles showing a preference for N-metalation with arylacetonitriles and C-metalation with cyclohexanecarbonitrile. These findings underscore the complex nature of metalated nitriles and their structural identity, which is intimately tied to the metal cation and the nature of the substituents on the nucleophilic carbon.
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