Basicities and ionization potentials of the hydrazones

Зверев, В. В.; Pylaeva, T. N.; Ermolaeva, L. V.; Filippova, N. A.; Kitaev, Yu. P.

doi:10.1007/bf00924378

Cited by 2 publications

(1 citation statement)

References 6 publications

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“…The only other report of attempts to determine the site of hydrazone protonation reached the same conclusion. [13] The observed titration of trifluoroacetylhydrazone 6 is due to the loss of its N 2 proton, which is made acidic by the proximal trifluoromethyl group.…”

Section: Pd-titration Experiments Monitored Withmentioning

confidence: 97%

Hydrolytic Stability of Hydrazones and Oximes

2008

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O toppt N, nicht aber N+: Hydrazone und Oxime sind gängige, doch leicht hydrolysierbare Verbindungen. Die Hydrolysestabilitäten isostruktureller Hydrazone und von einem Oxim wurden bei pD 5.0–9.0 untersucht. Die Geschwindigkeitskonstante der säurekatalysierten Hydrolyse war beim Oxim fast 103‐mal kleiner als bei einfachen Hydrazonen, und ein Trialkylhydrazoniumion (durch Kondensation gebildet) war noch stabiler als das Oxim.

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Section: Pd-titration Experiments Monitored Withmentioning

confidence: 97%

Hydrolytic Stability of Hydrazones and Oximes

2008

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Hydrolytic Stability of Hydrazones and Oximes

2008

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Hydrazones and oximes are common conjugates, but are labile to hydrolysis. The hydrolytic stability of isostructural hydrazones and an oxime have been determined at pD 5.0-9.0. The hydrolysis of each adduct was catalyzed by acid. Rate constants for oxime hydrolysis were nearly 10 3 -fold lower than those for simple hydrazones; a trialkylhydrazonium ion (formed after condensation) was even more stable than the oxime. The data suggest a general mechanism for conjugate hydrolysis. Keywordsconjugates; hydrazones; hydrolysis; oximes; reaction mechanisms Molecules containing carbon-nitrogen double bonds are prevalent in both chemical and biological contexts. The foundations for our current understanding of carbon-nitrogen doublebond formation and hydrolysis were laid by seminal early work on hydrazone hydrolysis and formation,[1] and by contributions from mechanistic studies on enzymes that utilize pyridoxal phosphate.[2] In particular, the meticulous kinetic analyses of Jencks resulted in the delineation of a carbinolamine intermediate in carbon-nitrogen double-bond formation and hydrolysis, and elucidation of the general mechanism of carbonyl-group addition reactions.[3,4] These principles were summarized in a landmark review. [5] Hydrazones and oximes (C 1 =N 1 −X 2 ) possess greater intrinsic hydrolytic stability than do imines. The textbook explanation for this greater stability invokes the participation of X 2 in electron delocalization (Figure 1).[6] The contribution of resonance form II in alkylhydrazones and oximes, and resonance form IV in acylhydrazones increases the negative-charge density

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Basicities and ionization potentials of the hydrazones

Cited by 2 publications

References 6 publications

Hydrolytic Stability of Hydrazones and Oximes

Hydrolytic Stability of Hydrazones and Oximes

Hydrolytic Stability of Hydrazones and Oximes

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