Coupure cathodique de liaisons carbone-oxygene—I reduction electrochimique d'alcools insatures application a la reduction tetraelectronique de certaines cetones en carbures

Lund, Henning; Doupeux, Henri; Michel, Marie-Andrée; Mousset, G.; Simonet, Jacques

doi:10.1016/0013-4686(74)85019-x

Cited by 44 publications

(27 citation statements)

References 9 publications

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“…Les rtsultats de cette tlectrolyse annexe sont inttressants car, nous le verrons, ils entrent en ligne de compte dans I'interprB tation du cours de cette ttape et des suivantes. L'electrolyse 5 montre une intervention des anions -CH2CN puisqu'elle conduit a la formation des nitriles 17 et 24 selon [22] a [26]. La transformation de la fluorknone en oltfine 17 est un processus catalytique (stquence [23]- [25]) en raison de la basicitt de I'ion HO-dans l'acttonitrile (cf.…”

Section: Etape Illunclassified

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Réaction entre solvant et espèces intermédiaires apparues lors de l'électroréduction–acylation de la fluorènone et de la fluorènone-anil dans l'acétonitrile

Degrand¹,

Belot²,

Compagnon³

et al. 1983

Can. J. Chem.

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The electrogenerated anions −CH2CN induce the conversion of the various reduction–acylation products of fluorènone 1a and its anil 1b in acetonitrile into 1a and 1b; this phenomenon is controlled by the fortuitous introduction of molecular oxygen. The −CH2CN anions catalyse the transformation of 1a and 1b into fluorenylideneacetonitrile (FlC=CHCN) 17, convertible into the nitriles FlC=CHC(CN)=C(NH2)CH38, FlC=C(CN)CHFl 10, and FlC=C(CN)CH2CN 11. These observations allow us to interpret the formation of the products appearing during the electrolysis of fluorenone in acetonitrile in the presence of an equivalent of chloride or anhydride of ω-chloro acid. The products of reduction–acylation appear successively, followed by the nitriles, FlC(OH)CH2CH2CN 3a, 10, FlC(OH)CH2CN 24, and polymers. Because of its basicity the fluorenone radical anion promotes reactions with the solvent, olefin 17 being a preferred intermediate. Bis-fluorenol, fluorenol, and finally fluorene are found with 1a and the above products. [Journal translation]

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Section: Etape Illunclassified

“…[251 HO-+ CHjCN ;--+ HOH + C H~C N Compte tenu des rtsultats de cette tlectrolyse, on c o n~o i t que dans l'ttape IV, les radicaux anions 26 a nouveau apparus, livrent l'oltfine 17 selon [22] a [24]. Dans cette ttape, la formation de polymkres est induite partir de 17 selon [27] et celle du nitrile 3a s'effectue probablement selon [28] (cf.…”

Section: Etape Illunclassified

Réaction entre solvant et espèces intermédiaires apparues lors de l'électroréduction–acylation de la fluorènone et de la fluorènone-anil dans l'acétonitrile

Degrand¹,

Belot²,

Compagnon³

et al. 1983

Can. J. Chem.

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“…An example of the effect of rates on the products obtained is provided by Mairanovsky's comparison (31) of two studies (32,33) on the electrolytic reduction of carbon-oxygen bonds in unsaturated alcohols and related compounds. One paper (32) where DH represents a proton donor.…”

Section: Kinetics As a Factor In Electrode Reactionmentioning

confidence: 99%

Organic electrode processes: generalized reduction mechanisms

Elving¹

1977

Can. J. Chem.

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PHILIP J. ELVING. Can. J. Chem. 55,3392 (1977). Prototype formulations are considered for the reaction pathways commonly encountered for the electrolytic reduction of organic compounds in aqueous and nonaqueous media on the basis that the essential feature is severance of a chemical bond which requires transfer into the reaction site of one or two electrons; multiple electron processes result from instability at the applied potential of initially produced species or their chemically altered products. To obtain electrical neutrality, uptake of electrons may have to be accompanied by that of a cation, generally a proton. Pertinent factors in the path followed in the overall electrode process may include a sequence of free radical or radical anion going to dimeric or carbanion species (depending on the relative rates of chemical and charge-transfer steps), possible interaction of intermediate products with their progenitors, proton donor activities, medium properties (e.g in respect to rates of chemical reactions accompanying charge-transfer and control of the chemical states of reactants and intermediates), stereochemical factors inherent in reactant and intermediate species, and chemical interaction with the electrode material. Application of the general mechanistic considerations are illustrated by various types of electrolytic reductions: aromatic hydrocarbon, nitrogen heterocycle, carbon-halogen bond, ketone carbonyl group, and beta halogenated and/or unsaturated acids. PHILIP J. ELVING. Can. J. Chem. 55,3392 (1977). Des formules modkles sont considerees pour des chemins rkactionnels souvent rencontres dans la reduction tlectrolytique de composks organiques en milieu aqueux et non aqueux. On se base sur le fait que la rupture du lien chimique exige le transfert d'un ou deux Blectrons au site rtactionnel. Les processus multi-electroniques resultent de I'instabilite au potentiel appliquk des espkces initialement produites ou de leurs produits transformks. Afin d'obtenir une neutralitk Blectrique, le transfert d'un Blectron doit &tre accompagne par celui d'un cation, gknkralement un proton. Les facteurs appropriks dans ce chemin rkactionnel suivi, tout au long du processus prenant place aux klectrodes, peut impliquer : (a) la sequence d'un radical libre ou d'un radical anionique donnant des dim&res ou carbanions (dkpendant des vitesses relatives des Btapes chimiques et celles de transfert de charge) ; (b) I'interaction possible des intermkdiaires avec les produits initiaux, (c) des activitks proton-donneur; (d) des propriktes de milieu (i.e. par rapport aux reactions chimiques accompagnant le transfert de charge ainsi que du contrBle des Btats chimiques des rkactifs et intermkdiaires); (e) des facteurs stkrtochimiques propres aux rtactifs et intermkdiaires; (f) l'interaction chimique avec I'klectrode. L'application des considkrations mkcanistiques generales est illustrte par diffkrents types de reduction tlectrolytique, un hydrocarbure aromatique, un hkterocycle contenant un atome d'azote, un lien carbone-haloghe...

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“…2,3,4 This is difficult to achieve by direct reduction of alcohols because very negative potentials are required 5 and in any event the hydroxyl anion is a poor leaving group. Derivatives such as tosylates 6 , methanesulfonates 7 , diethylphosphates 8 , and acetates 9 are more easily cleaved by cathodic reduction but only at very negative potentials.…”

Section: Introductionmentioning

confidence: 99%

Electroorganic reactions. Part 58. Revisiting the cleavage of oxalate ester radical-anions

Utley¹,

Ramesh²

2003

Arkivoc

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Electrochemically-generated radical-anions of oxalate esters undergo cleavage. For those of ethyl 4-substituted benzyl oxalates the rates of cleavage have been measured by cyclic voltammetry combined with digital simulation. Consideration of substituent effects and earlier product studies presents compelling evidence for an EC mechanism with the cleavage resulting in oxalate anions and benzyl radicals.

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Coupure cathodique de liaisons carbone-oxygene—I reduction electrochimique d'alcools insatures application a la reduction tetraelectronique de certaines cetones en carbures

Cited by 44 publications

References 9 publications

Réaction entre solvant et espèces intermédiaires apparues lors de l'électroréduction–acylation de la fluorènone et de la fluorènone-anil dans l'acétonitrile

Réaction entre solvant et espèces intermédiaires apparues lors de l'électroréduction–acylation de la fluorènone et de la fluorènone-anil dans l'acétonitrile

Organic electrode processes: generalized reduction mechanisms

Electroorganic reactions. Part 58. Revisiting the cleavage of oxalate ester radical-anions

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