Effect of ultrasound on the kinetics of oxidation of octan-2-ol and other secondary alcohols with sodium bromate, mediated by ruthenium tetraoxide in a biphasic system

Mills, Andrew; Holland, Carolyn

doi:10.1016/1350-4177(94)00009-h

Cited by 21 publications

(8 citation statements)

References 7 publications

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“…Their subsequent oxidation at the OH level would yield the piperazinediones 3 and 11, as well as the benzoyl derivative 12, respectively. It is well-known that alcohols are easily converted by RuO 4 into the corresponding carbonyl derivatives [15][16][17][18][19]. At the same Scheme 3 Oxidation by RuO 4 of piperazinone 7 ([ox] means oxidation).…”

Section: Resultsmentioning

confidence: 99%

RuO4-mediated oxidation of N-benzylated tertiary amines. 3. Behavior of 1,4-dibenzylpiperazine and its oxygenated derivatives

Petride¹,

Drăghici²,

Florea³

et al. 2006

Open Chemistry

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1,4-Dibenzylpiperazine (1), -2-piperazinone (7), -2,6-piperazinedione (9), and 1-benzoyl-4-benzylpiperazine (30) were oxidized by RuO 4 (generated in situ) by attack at their endocyclic and exocyclic (i.e., benzylic) aminic N -α-C-H bonds to afford various oxygenated derivatives, including acyclic diformamides, benzaldehyde, and benzoic acid. The reaction outcome was complicated by (i) the hydrolysis of diformamides, occurred during the work-up, and (ii) the reaction of benzaldehyde with the hydrolysis-derived amines giving imidazolidines and/or Schiff bases. Benzoic acid resulted from benzaldehyde only. Compounds 7, 30, and 1-benzylpiperazine, but not 9, were transiently formed during the oxidation of 1. In the same reaction conditions, 1,4-dibenzyl-2,3-(or 2,5)-piperazinedione, 1,4-dibenzyl-2,3,6-piperazinetrione, 4-benzoyl-1-benzyl-2-piperazinone, and 1,4-dibenzoylpiperazine were inert. The proposed oxidation mechanism involves the formation of endocyclic and exocyclic iminium cations, as well as of cyclic enamines. The latter intermediates probably result by base-induced deprotonation of the iminium cations, provided an N + −β-proton is available. In the case of 1, the cations were trapped with NaCN as the corresponding α-aminonitriles. The statistically corrected regioselectivity (endocyclic/exocyclic) of the RuO 4 -induced oxidation reaction of 1, 7, and 30 was 1.2-1.3.

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Section: Resultsmentioning

confidence: 99%

RuO4-mediated oxidation of N-benzylated tertiary amines. 3. Behavior of 1,4-dibenzylpiperazine and its oxygenated derivatives

Petride¹,

Drăghici²,

Florea³

et al. 2006

Open Chemistry

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“…The ability of ultrasound to create fine emulsions is very beneficial to biphasic systems. For example, it was used successfully to enhance the oxidation of secondary alcohols with sodium bromate in an aqueous-CCl 4 biphasic system mediated by ruthenium tetraoxide (Mills and Holland, 1995). For each of the four alcohols investigated, the reaction time was decreased from several hours to several minutes, and the yield of ketone in each case was 100% when ultrasound was used in conjunction with supplementary stirring.…”

Section: Ultrasound In Conjunction With Other Enhancement Techniquesmentioning

confidence: 99%

Sonochemistry: Science and Engineering

Thompson

Doraiswamy

1999

Ind. Eng. Chem. Res.

1,089

613

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Sonochemistry is the use of ultrasound to enhance or alter chemical reactions. Sonochemistry in the true sense of the term occurs when ultrasound induces “true” chemical effects on the reaction system, such as forming free radicals which accelerate the reaction. However, ultrasound may have other mechanical effects on the reaction, such as increasing the surface area between the reactants, accelerating dissolution, and/or renewing the surface of a solid reactant or catalyst. This comprehensive review summarizes several topics of study in the sonochemical literature, including bubble dynamics, factors affecting cavitation, the effects of ultrasound on a variety of chemical systems, modeling of kinetic and mass-transfer effects, the methods used to produce ultrasound, proposed cavitation reactors, and the problems of scaleup. The objective of this paper is to present a critical review of information available in the literature so as to facilitate and inspire future research in the field of sonochemistry.

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“…Na(BrO 3 )/CCl 4 was studied with respect to mixing speeds and sonication. The latter is an effective technique for increasing yields of products [141,142]. Oxidation of desethermuscarine with RuCl 3 /aq.…”

Section: Specific Examplesmentioning

confidence: 99%

Oxidation of Alcohols, Carbohydrates and Diols

Griffith

2009

Catalysis by Metal Complexes

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This is one of the most important classes of oxidation effected by Ru complexes, particularly by RuO 4 , [RuO 4 ] − , [RuO 4 ] 2− and RuCl 2 (PPh 3 ) 3 , though in fact most Ru oxidants effect these transformations. The chapter covers oxidation of primary alcohols to aldehydes (section 2.1), and to carboxylic acids (2.2), and of secondary alcohols to ketones (2.3). Oxidation of primary and secondary alcohol functionalities in carbohydrates (sugars) is dealt with in section 2.4, then oxidation of diols and polyols to lactones and acids (2.5). Finally there is a short section on miscellaneous alcohol oxidations in section 2.6.In this chapter the first of the two most important categories of oxidations catalysed by Ru complexes (the other being alkene and alkyne oxidations in Chapter 3) are considered. The approach in this and subsequent chapters differs from that of Chapter 1, concentrating here on the substrate rather than on the oxidant. The text is divided into the categories of alcohols and their oxidations. There are summaries in section 2.3.6 of systems of limited applicability which are mentioned only in Chapter 1, and in section 2.3.7 of large-scale (>1 g) oxidations.The first oxidations of alcohols by stoicheiometric RuO 4 /H 2 O were reported in 1958, of primary alcohols to aldehydes or carboxylic acids and secondary alcohols to ketones [1]. The first Ru-catalysed oxidation of an alcohol was reported in 1965 when Parikh and Jones used RuO 2 /aq. Na(IO 4 )/CCl 4 1 ( Table 2.3) [2] to oxidise secondary alcohol groups in carbohydrates.Oxidation of alcohols is the most frequently reviewed topic for Ru-catalysed oxidations [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Mechanisms of alcohol oxidation by Ru complexes have been reviewed [21].

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Effect of ultrasound on the kinetics of oxidation of octan-2-ol and other secondary alcohols with sodium bromate, mediated by ruthenium tetraoxide in a biphasic system

Cited by 21 publications

References 7 publications

RuO4-mediated oxidation of N-benzylated tertiary amines. 3. Behavior of 1,4-dibenzylpiperazine and its oxygenated derivatives

RuO4-mediated oxidation of N-benzylated tertiary amines. 3. Behavior of 1,4-dibenzylpiperazine and its oxygenated derivatives

Sonochemistry: Science and Engineering

Oxidation of Alcohols, Carbohydrates and Diols

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