2011
DOI: 10.5155/eurjchem.2.2.130-135.405
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Detailed analysis for the solvolysis of isopropenyl chloroformate

Abstract: The specific rates of solvolysis (including those obtained from the literature) of isopropenyl chloroformate (1) are analyzed using the extended Grunwald-Winstein equation, involving the NT scale of solvent nucleophilicity (S-methyldibenzothiophenium ion) combined with a YCl scale based on 1-adamantyl chloride solvolysis. A similarity model approach, using phenyl chloroformate solvolyses for comparison, indicated a dominant bimolecular carbonyl-addition mechanism for the solvolyses of 1 in all solvents except … Show more

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Cited by 9 publications
(19 citation statements)
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“…The ethanolyses rate of isopropenyl chloroformate (2) at 25.0 °C was reported to be (110 ± 6) × 10 −5 [57]. A comparison of this pure EtOH data point together with the other values listed in Table 1 show, k 4 > k 2 >> k 1 > k 5 ≈ k 3 .…”
Section: Resultsmentioning
confidence: 70%
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“…The ethanolyses rate of isopropenyl chloroformate (2) at 25.0 °C was reported to be (110 ± 6) × 10 −5 [57]. A comparison of this pure EtOH data point together with the other values listed in Table 1 show, k 4 > k 2 >> k 1 > k 5 ≈ k 3 .…”
Section: Resultsmentioning
confidence: 70%
“…On the other hand for the alkenyl containing isopropenyl chloroformate ( 2 ), it was proposed [57] that a superimposed unimolecular (S N 1) type ionization process was making a significant contribution in 97%–70% HFIP, and 97% TFE due to the formation of a resonance stabilized intermediate carbocation.…”
Section: Resultsmentioning
confidence: 99%
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“…The extended Grunwald-Winstein equation [3-6], which has been found to be very useful in its application to the specific rates of solvolysis of a wide variety of substrates, such as phosphorus compounds [34], silicon compounds [35], acid chlorides [36], chloroformate esters [37], chlorothioformate esters [38], and heterocyclic compounds [39], is here applied to the solvolyses of tertiary alpha-substituted ketones, some of which have, contrary to earlier opinions summarized elsewhere [12], been found to be capable of forming carbocations with the charge formally adjacent to the carbonyl group under solvolytic conditions [10-12]. …”
Section: Discussionmentioning
confidence: 99%