Rate Law for the Oxidation of Methanol and Ethanol by Peroxydisulfate Ion

Edwards, John O.; Gallopo, Andrew R.; McIsaac, John E.

doi:10.1021/ja00968a059

Cited by 12 publications

(8 citation statements)

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“…(+)-(R)-Neopentylamine-1-d (I) of 93.5 Z6 optical purity was treated with n-butyl nitrite in acetic acid to give a mixture of (-)-(R)-2-methyl-l-butene-3-d (11), 2-methyl-2-butene-3-d of 58 isotopic purity, (-)-(R)-l,l-dimethyl-l-propyl-3-d acetate (111), and a trace of neopentyl aceqe-he optical rotation observed for I1 was c r a~ -0.64 f 0.05". Pyrolysis of I11 at 500" gave I1 with a a~ -0.56 f 0.03" and a * *~ -0.52 f 0.03O.…”

Section: Resultsmentioning

confidence: 99%

“…+ CHsOH + ArH + .CH20H (10) termination reactions (11) Reaction 7 is an acid-base reaction; l D the species' anion or ketyl anion.20 The pK, of diphenylhydroxymethyl radical, (CsH&COH, has been estimated as 9.2 by Porter and Wilkinson.21 This radical is several pK units more acidic than its "parentyYy benzhydrol, from which it can be derived by removal of a hydrogen atom. It is probable that a-hydroxyalkyl radicals in general are stronger acids than the parent alcohols.…”

Section: Cl'mentioning

confidence: 99%

“…Abstract: (+)-(R)-Neopentylamine-1-d (I) underwent deamination in acetic acid to give (-)-(R)-2-methyl-lbutene-3-d (11) and the corresponding deuterated t-amyl acetate which was converted to I1 of the same optical purity by pyrolysis. The mechanistic implications of the high degree of stereospecificity observed are discussed.…”

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confidence: 99%

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Radical-induced deiodination of aryl iodides in alkaline methanol

Bunnett¹,

Wamser²

1967

J. Am. Chem. Soc.

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m-Chloroiodobenzene is cleaved to chlorobenzene and iodide ion when exposed to the combination of a source of reactive radicals and a high concentration of sodium methoxide in methanol. Effective radical sources include 1-phenyl-2-benzenesulfonhydrazide (3) (with atmospheric oxygen), peroxydisulfate ion, benzenediazonium ion, phenylazotriphenylmethane, and azobisisobutyronitrile. The chlorobenzene formed in CHsOD solution is substantially free of deuterium and m-chlorobiphenyl is formed in a benzene-rich solvent; the intermediacy of rn-chlorophenyl radicals is indicated. Nitrobenzene, even in small amount, largely inhibits deiodination. The cyclic mechanism of eq 6-11 is proposed. Its unique features are formation of aCH20-from -CHzOH in an acid-base reaction and electron transfer from .CHzO-to the aryl iodide, with concomitant or subsequent ejection of iodide ion and formation of aryl radical.he reaction of 1-(2-iodo-4-chlorophenyl)-2-ben-T zenesulfonhydrazide (1) with sodium methoxide in methanol was found to produce chlorobenzene, an ~~--@H--KH-SO,C,H, ' I 1 unexpected product, in addition to m-chloroiodobenzene and other products which were anti~ipated.~ Happer, who performed that experiment, obtained evidence that the chlorobenzene resulted from deiodination of the m-chloroiodobenzene under the conditions of the reaction. Moreover, his experiments suggested that for deiodination to occur, it was necessary to provide both a high concentration of sodium methoxide and a 1-aryl-2-benzenesulfonhydrazide.Thus, m-chloroiodobenzene underwent deiodination on treatment with l-(o-chlorophenyl)-2-p-toluenesulfonhydrazide in 2 M methanolic sodium methoxide, but not in the alcoholic base alone or with benzenesulfonamide in alcoholic base.Hydrazide-Induced Deiodinations. Our investigation of the deiodination reaction therefore began with the system m-chloroiodobenzene (2)-phenyl-2-benzenesulfonhydrazide (3)-sodium methoxide-methanol. A series of experiments was performed to reveal the 2 3 effects of several variables. In these experiments, 240 mg (0.001 mole) of m-chloroiodobenzene was treated

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Section: Resultsmentioning

confidence: 99%

Section: Cl'mentioning

confidence: 99%

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Radical-induced deiodination of aryl iodides in alkaline methanol

Bunnett¹,

Wamser²

1967

J. Am. Chem. Soc.

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“…There is evidence in the literature of acetone hydrolysis in UV light. The authors [20,2 1 ] propose the overall reaction (CH3)zCO + H20 + CHI + CH3COOH…”

Section: E Efect Of Acetonementioning

confidence: 99%

“…Our study of related reactions involving peroxodiphosphate has been confined to the oxidation of water, ethanol, and 2-propanol: (2) P2OS4-+ (CH3)2CHOH * 2 HP04*-+ (CH3)2C0…”

Section: Introductionmentioning

confidence: 99%

A comparison of the thermal and photochemical oxidation of 2‐propanol by two peroxoanions

Bida¹,

Curci²,

Edwards³

1973

Int J of Chemical Kinetics

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The chain length (i.e., relative quantum yield) for the oxidation of 2-propanol by peroxodisulfate ion at 25°C has been studied. A number of initial experiments were carried out in order to clarify the influence of dissolved oxygen, light intensity, cupric ion, and acetone absorption. After these problems were understood, conditions satisfactory for evaluation of chain length were chosen. The chain length was found to be 500 (to within &loo). The difference between this value and the thermal oxidation chain length of I800 at 60" is, in both direction and magnitude, as expected for a common mechanism and a low activation energy for the propagation steps. A remarkable difference is seen for comparable reactions of peroxodisulfate and peroxodiphosphate anions.

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Persulfate and perphosphate oxidation of 2‐propanol: A relative rate study

Levey

Bida

Edwards

1981

Int J of Chemical Kinetics

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A competitive reaction study for two isoelectronic peroxides (peroxodisulfate SzOi-and peroxodiphosphate P20:-) interacting with the free radical .C(CH&OH is described. The radical formation is initiated by photolysis, the amounts of peroxide remaining analyzed volumetrically. It is found that persulfate reacts with the organic radical over 100 times more rapidly than does perphosphate. Mechanistic consequences in relation to previous work are briefly discussed.

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Rate Law for the Oxidation of Methanol and Ethanol by Peroxydisulfate Ion

Cited by 12 publications

References 0 publications

Radical-induced deiodination of aryl iodides in alkaline methanol

Radical-induced deiodination of aryl iodides in alkaline methanol

A comparison of the thermal and photochemical oxidation of 2‐propanol by two peroxoanions

Persulfate and perphosphate oxidation of 2‐propanol: A relative rate study

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