Solvent assistance in the solvolysis of secondary substrates. Use of added azide ion as a mechanistic probe

Harris, J. Milton; Raber, Douglas J.; Hall, Robert E.; Schleyer, Paul von Ragué

doi:10.1021/ja00722a033

Cited by 15 publications

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“…A strong nucleophilic reagent, e.g., sodium azide, might be used as a trap-to-trap carbonium ion . The IR spectra of AA in acidic aqueous solutions containing sodium azide (Figure ) can be explained by means of reaction scheme 2…”

Section: Resultsmentioning

confidence: 99%

Mechanism of Electroreduction of Allyl Alcohol at Platinized Platinum Electrode in Acidic Aqueous Solution

et al. 2001

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The electroreduction of allyl alcohol to form propene at the platinized platinum electrode in acidic aqueous solution has been studied using CV plots, IR, ESR, and MS spectra, and a semiempricial MO method (MOPAC7/AM1, PM3). From the determinations of charge-transfer coefficients, reaction orders and apparent activation energy for the given reaction, the detection of the intermediates such as C(3)H(5)(+), C(3)H(5)(*), and C(3)H(5)(-) species, and PM3 calculations of charge distribution and frontier orbital energies of the reaction species C(3)H(5)OH and C(3)H(5)(+), the authors suggest that in acidic aqueous solution the production of propene via reductive splitting of the C-OH bond situated in the allyl position of allyl alcohol obeys a carbonium ion-carbanion mechanism.

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Section: Resultsmentioning

confidence: 99%

Mechanism of Electroreduction of Allyl Alcohol at Platinized Platinum Electrode in Acidic Aqueous Solution

et al. 2001

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“…Experiments with added sodium azide, similar to those outlined earlier for 2-propyl tosylate, were performed [22]. Behaviour of this kind is found in the solvolysis of 2-adamantyl tosylate in aqueous ethanol.…”

Section: Plots Of [Q]/[p ] Against [T ] or Of The Inverse Mole Fractmentioning

confidence: 94%

“…Behaviour of this kind occurs, for example, in the solvolysis of 2-propyl tosylate in aqueous ethanol [22]. Behaviour of this kind occurs, for example, in the solvolysis of 2-propyl tosylate in aqueous ethanol [22].…”

Section: The Detection and Characterisation Of Intermediates In Chemimentioning

confidence: 99%

The Detection and Characterisation of Intermediates in Chemical Reactions

Watt¹

2006

The Investigation of Organic Reactions and Their Mechanisms

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“…Only two of these will be presented in this paper, one here and one in a later section. When 2-AdOTs was solvolyzed in ethanol-water (80:20 v/v) with added azide anion (N 3 -), a superior nucleophile, the observed rate constant was essentially independent of azide anion concentration (Milton Harris et al 1970). In other words, 2-AdOTs only reacted by the S N 1 mechanism, a so-called k c process, even when superior nucleophiles such as azide were present in solution.…”

Section: Adamantanementioning

confidence: 99%

Do the solvolysis reactions of secondary substrates occur by the SN1 or SN2 mechanism: or something else?

Pagni

2011

Found Chem

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Primary and methyl aliphatic halides and tosylates undergo substitution reactions with nucleophiles in one step by the classic S N 2 mechanism, which is characterized by second-order kinetics and inversion of configuration at the reaction center. Tertiary aliphatic halides and tosylates undergo substitution reactions with nucleophiles in two (or more) steps by the classic S N 1 mechanism, which is characterized by first-order kinetics and incomplete inversion of configuration at the reaction center due to the presence of ion pairs. When the nucleophile is also the solvent, the substitution reaction is called a solvolysis, and both the S N 2 and S N 1 reactions now obey first-order kinetics. Schleyer and Bentley have provided solid, but not conclusive, evidence that secondary substrates undergo solvolysis by a merged mechanism, one that blends characteristics of both the S N 2 and S N 1 mechanisms. The following paper presents the history of their sustained pursuit of a merged mechanism and subsequent rebuttals to this claim. Several issues related to the philosophy and sociology of science are also discussed.

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Solvent assistance in the solvolysis of secondary substrates. Use of added azide ion as a mechanistic probe

Cited by 15 publications

References 0 publications

Mechanism of Electroreduction of Allyl Alcohol at Platinized Platinum Electrode in Acidic Aqueous Solution

Mechanism of Electroreduction of Allyl Alcohol at Platinized Platinum Electrode in Acidic Aqueous Solution

The Detection and Characterisation of Intermediates in Chemical Reactions

Do the solvolysis reactions of secondary substrates occur by the SN1 or SN2 mechanism: or something else?

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