Coenzyme models. Part 36. Hydroxide-mediated disproportionation of a lipophilic acridinium salt in a micellar system

Seiji Shinkai, Takaharu Tsuno, Osamu Manabe

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

We have found that N-dodecylacridinium ion (DodAc+) is rapidly disproportionated to N-dodecylacridone (DodAcd) and N-dodecylacridan (DodAcH) via hydroxy-adduct (DodAcOH) in the presence of cationic (CTAB) or non-ionic (Brij-35) micelles. Product analyses show that two moles of DodAc+ produce one mole of DodAcd and one mole of DodAcH and the hydrogen is directly transferred from DodAcOH to DodAc+. The reaction is similar to oxidation of alcohols by NAD+ model compounds. Kinetic studies show that the reaction consists of two steps, the first an equilibrium for formation of the hydroxy-adduct and the second disproportionation to RAcd and RAcH. The first step is efficiently accelerated by CTAB and Brij-35 and the association constants (K) are enhanced by 105-106-fold. On the other hand, the second step is less susceptible to the micellar environment and is not base-catalysed. Thus the micellar effect on the first step is responsible for the overall rate enchancement. This is the first example of a micellar effect on the hydroxide ion-mediated disproportionation of heteroaromatic nuclei.

Original languageEnglish
Pages (from-to)661-665
Number of pages5
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number4
Publication statusPublished - Dec 1 1984
Externally publishedYes

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Coenzymes
Salts
Micelles
NAD
Hydrogen
Alcohols
Association reactions
Ions
Oxidation
Kinetics
Brij 35
cetrimonium
hydroxide ion

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Coenzyme models. Part 36. Hydroxide-mediated disproportionation of a lipophilic acridinium salt in a micellar system. / Shinkai, Seiji; Tsuno, Takaharu; Manabe, Osamu.

In: Journal of the Chemical Society, Perkin Transactions 2, No. 4, 01.12.1984, p. 661-665.

Research output: Contribution to journalArticle

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abstract = "We have found that N-dodecylacridinium ion (DodAc+) is rapidly disproportionated to N-dodecylacridone (DodAcd) and N-dodecylacridan (DodAcH) via hydroxy-adduct (DodAcOH) in the presence of cationic (CTAB) or non-ionic (Brij-35) micelles. Product analyses show that two moles of DodAc+ produce one mole of DodAcd and one mole of DodAcH and the hydrogen is directly transferred from DodAcOH to DodAc+. The reaction is similar to oxidation of alcohols by NAD+ model compounds. Kinetic studies show that the reaction consists of two steps, the first an equilibrium for formation of the hydroxy-adduct and the second disproportionation to RAcd and RAcH. The first step is efficiently accelerated by CTAB and Brij-35 and the association constants (K) are enhanced by 105-106-fold. On the other hand, the second step is less susceptible to the micellar environment and is not base-catalysed. Thus the micellar effect on the first step is responsible for the overall rate enchancement. This is the first example of a micellar effect on the hydroxide ion-mediated disproportionation of heteroaromatic nuclei.",
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N2 - We have found that N-dodecylacridinium ion (DodAc+) is rapidly disproportionated to N-dodecylacridone (DodAcd) and N-dodecylacridan (DodAcH) via hydroxy-adduct (DodAcOH) in the presence of cationic (CTAB) or non-ionic (Brij-35) micelles. Product analyses show that two moles of DodAc+ produce one mole of DodAcd and one mole of DodAcH and the hydrogen is directly transferred from DodAcOH to DodAc+. The reaction is similar to oxidation of alcohols by NAD+ model compounds. Kinetic studies show that the reaction consists of two steps, the first an equilibrium for formation of the hydroxy-adduct and the second disproportionation to RAcd and RAcH. The first step is efficiently accelerated by CTAB and Brij-35 and the association constants (K) are enhanced by 105-106-fold. On the other hand, the second step is less susceptible to the micellar environment and is not base-catalysed. Thus the micellar effect on the first step is responsible for the overall rate enchancement. This is the first example of a micellar effect on the hydroxide ion-mediated disproportionation of heteroaromatic nuclei.

AB - We have found that N-dodecylacridinium ion (DodAc+) is rapidly disproportionated to N-dodecylacridone (DodAcd) and N-dodecylacridan (DodAcH) via hydroxy-adduct (DodAcOH) in the presence of cationic (CTAB) or non-ionic (Brij-35) micelles. Product analyses show that two moles of DodAc+ produce one mole of DodAcd and one mole of DodAcH and the hydrogen is directly transferred from DodAcOH to DodAc+. The reaction is similar to oxidation of alcohols by NAD+ model compounds. Kinetic studies show that the reaction consists of two steps, the first an equilibrium for formation of the hydroxy-adduct and the second disproportionation to RAcd and RAcH. The first step is efficiently accelerated by CTAB and Brij-35 and the association constants (K) are enhanced by 105-106-fold. On the other hand, the second step is less susceptible to the micellar environment and is not base-catalysed. Thus the micellar effect on the first step is responsible for the overall rate enchancement. This is the first example of a micellar effect on the hydroxide ion-mediated disproportionation of heteroaromatic nuclei.

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