Reactivity of his(hydrogen periodato)cuprate (III) towards glycerophosphates in alkaline medium

1015-1017The reactivities of the isomers of glycerophosphate towards bis(hydrogen periodato)cuprate(III) in alkaline medium have been studied. The reactions are first order each in [glycerophosphate] and [Cu111).The rate is independent of [OH-] at [OH-] below 2.0 x 10-2 mol dm-3 but increases linearly at higher[OH-]. Activation parameters have been estimated and a suitable mechanism proposed

Hydroxylation and mechanistic studies of α, β-unsaturated compounds with alkaline hexacyanoferrate (III)

798-801The reactions of three α, β-unsaturated compounds of the type CH2=CHX (where X = -CN, -CONH2 and -C02 -) with alkaline hexacyanoferrate (III) have been studied. The reactions take place according to the rate expression, d[Fe(CN)63-]  / dt = k [Fe(CN)63-) (CH2=CHX] (OH-). The values of k at 318K are 7.2 x 10-4,4.45 X 10-4 and 3.2 x 10-4 (dm6mol-2s-1) in the oxidations of the respective substrates. The oxidation rates follow the order: -CN> -CONH2 > -C02  The substrates are oxidized to give diols under kinetic conditions. Tentative reaction mechanism leading to the formation of oxidation products has been suggested

Reactivities of some energy rich organic orthophosphates towards transition metal ion oxidants

332-334The orthophosphates, and -glycerophosphates, react with HCrO in HCIO4 medium to give 1:1 intermediates which subsequently decomposes to give products of the reactions. The rate is directly proportional to [H+] in each reaction. Thermodynamic parameters associated with the equilibrium step and the activation parameters associated with the slowest step has been evaluated for each substrate. An attempt has been made to correlate the results obtained earlier with other transition metal ion oxidants

Kinetics & Mechanism of Oxidation of -Glucopyranose l-Phosphate by Chromium(VI) & Vanadium(V) in Perchloric Acid Medium

23-2

Oxidative behaviours and relative reactivities of some aliphatic, heterocyclic and aromatic aldehydes towards bis(dihydrogentellurato )cuprate(III) and argentate(III) in alkaline medium

190-196The oxidative behaviours and relative reactivities of some aliphatic aldehydes, XCHO (where X = H - , Me - , MeCH2 -, Me2CH-), 2-furaldehyde and aromatic aldehydes, YC6H4CHO (where Y= -H, -NO2, -Cl and -OMe) towards bis(dihydrogentellurato)metallate(III) ion (where MIlI= CUllI or AgIII) in alkaline medium have been investigated. The reactions are first order each in [aldehyde] and [MIII(H2TeO6)2]5- - but the rate is independent of [OH-]. The values of kobs in the oxidation of some aliphatic aldehydes, 2-furaldehyde and benzaldehyde in aqueous medium follow the order: Me2CH - > MeCH2 - > Me - > H - > C4H3O - > C6H5, -. The electron withdrawing substituents facilitate the rate of oxidation of benzaldehyde whereas electron donating substituents have opposite effect and the values of kobs, follow the order: - NO2 > - H > - Cl > - OMe. The pseudofirst order rate constants decrease considerably in benzaldehyde-d1., than benzaldehyde under comparable condition of experiments. Irrespective of whether the substrate is aliphatic or aromatic, the oxidation reactions occur via free radical mechanism although the substituent and isotope effects in the oxidations of aromatic aldehydes indicate that C - H bond cleavage via proton transfer may also occur. The activation parameters of the reactions have been determined and the mechanism of the reactions is discussed