Zirconium(IV) catalysis in perborate oxidation of iodide

Karunakaran, C.; Muthukumaran, B.

doi:10.1007/bf02475703

Cited by 16 publications

(10 citation statements)

References 3 publications

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“…In aqueous and partly aqueous solution it affords hydrogen peroxide which acts as the oxidizing agent (1)(2)(3)(4)(5)(6). It oxidizes morpholine and N -methylmorpholine to the corresponding hydroxylamine and N -oxide, respectively (6).…”

Section: Introductionmentioning

confidence: 99%

FORMATION OF PERACETIC ACID ON AGING OF PERBORATE SOLUTIONS IN ACETIC ACID: KINETICS OF THE OXIDATION OF MORPHOLINE ANDN-METHYLMORPHOLINE

Karunakaran

Kamalam

2001

Synthesis and Reactivity in Inorganic and Metal-Organic Chemist

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Perborate solutions in glacial acetic acid generate peracetic acid on aging and the peracetic acid oxidation of morpholine and N -methylmorpholine is fast. But perborate dissolved in ethylene glycol or propylene glycol does not show the aging effect and the oxidation is smooth. The smooth oxidation exhibits Michalis-Menten dependence on [morpholines] and is of apparent zero order in the oxidizing agent but the rate increases linearly with [perborate] 0 . The mechanism of oxidation is discussed and the rate law derived.

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Section: Introductionmentioning

confidence: 99%

FORMATION OF PERACETIC ACID ON AGING OF PERBORATE SOLUTIONS IN ACETIC ACID: KINETICS OF THE OXIDATION OF MORPHOLINE ANDN-METHYLMORPHOLINE

Karunakaran

Kamalam

2001

Synthesis and Reactivity in Inorganic and Metal-Organic Chemist

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“…In aqueous and partly aqueous media perborate yields H 2 O 2 . [1][2][3][4][5][6] The specific rate of oxidation of diphenyl sulfide by H 2 O 2 in partly aqueous medium, under identical condition, is the same as that of perborate (1.1 × 10 -3 dm 3 /mol/s, HOAc:ethylene glycol:H 2 O::2:1:1 v/v, 50°C). Perborate in glacial acetic acid generates peracetic acid.…”

Section: Resultsmentioning

confidence: 99%

“…In aqueous and partly aqueous solutions it yields H 2 O 2 which acts as the oxidising agent. [2][3][4][5][6] Perborate in glacial acetic acid is an effective oxidising agent in organic synthesis and oxidises sulfides to sulfoxides in good yield. 7,8 Here we report the kinetics of the oxidations under anhydrous conditions.…”

Section: Introductionmentioning

confidence: 99%

Generation of peracetic acid on aging of perborate solution in acetic acid: Kinetics of oxidation of organic sulfides

Karunakaran

Sheerin

Palanisamy

2001

Journal of Chemical Research

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“…This shows that the catalystaniline complex is likely to be the electrophile and free aniline may be the nucleophile. The influence of the substituents on the reactivity of the nucleophile is approximately compensated by the influence of the same substituent on the reactivity of the electrophile 12 . In some of the substituted aniline exact compensation is doubtful and the resultant effect is experienced on the oxidation rate.…”

Section: Substituents Effectmentioning

confidence: 99%

meso-Tetraphenylporphyriniron(III) Chloride Catalyzed Oxidation of Aniline and Its Substituents by Sodium Perborate: Degradation Kinetics

Raja¹,

Karunakaran²

2013

Asian J. Chem.

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Chemists have a great deal of attention towards modeling of cytochrome P450 monooxygenase using synthetic metalloporphyrins as they have a strapping resemblance to heme in both structures and catalytic property. The potential of the heme group is to combine with tiny ligands (including molecular oxygen) in enzymatic oxidations. In order to learn, the core of the heme group, the porphyrin ring with the central metal iron atom, has been selected. These complexes can catalyze the oxidation of aniline in simulating the function of cytochrome P450. Literature study 1-9 has revealed that halogenated metalloporphyrin complexes are excellent catalysts for difficult oxidations with high selectivity. Iron complexes of tetraphenylporphyrins, which has an intermediate structure sandwiched between common natural iron porphyrins with cytochrome P450. To complement the studies in the field of the catalytic oxidation of aniline, the oxidation of aniline by sodium perborate catalyzed by first generation catalyst mesotetraphenylporphyriniron(III) chloride (5,10,15,20-tetraphenyl-21h,23h-porphineiron(III) chloride) was taken for the study. Kinetics of oxidation of anilines by variety of oxidants has been reported 10-14 and only few of them authenticate Hammet equation. EXPERIMENTALThe catalyst meso-tetraphenylporphyriniron(III) chloride (Sigma Aldrich) was used as received. All chemicals and Heme-enzymes such as cytochromes P450 have ability to perform extremely difficult oxidations with high selectivity. The kinetic study of oxidation of aniline by sodium perborate with respect to the meso-tetraphenylporphyriniron(III) chloride reveals that there is a slow degradation of the catalyst in this oxidation reaction. The thermodynamic parameters for the oxidation have been determined and discussed. The increase in concentration of H + ions retards the rate of the reaction revealed that the protonated aniline is less reactive in this oxidation reaction. The sodium perborate oxidation with 12 meta-and para-substituted anilines complies with isokinetic relationship and Exner relationship but not to any of the linear free energy relationships. The solvent interaction plays a major role in governing the reactivity. A suitable mechanism and rate law was proposed for this reaction.

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Zirconium(IV) catalysis in perborate oxidation of iodide

Cited by 16 publications

References 3 publications

FORMATION OF PERACETIC ACID ON AGING OF PERBORATE SOLUTIONS IN ACETIC ACID: KINETICS OF THE OXIDATION OF MORPHOLINE ANDN-METHYLMORPHOLINE

FORMATION OF PERACETIC ACID ON AGING OF PERBORATE SOLUTIONS IN ACETIC ACID: KINETICS OF THE OXIDATION OF MORPHOLINE ANDN-METHYLMORPHOLINE

Generation of peracetic acid on aging of perborate solution in acetic acid: Kinetics of oxidation of organic sulfides

meso-Tetraphenylporphyriniron(III) Chloride Catalyzed Oxidation of Aniline and Its Substituents by Sodium Perborate: Degradation Kinetics

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