The Structure of Cobalt(II) Acetate and Cobalt(III) Acetate in Acetic Acid Solution

Hendriks, Ch.F.; Beek, H. C. A. van; Heertjes, P.M.

doi:10.1021/i360069a009

Cited by 29 publications

(20 citation statements)

References 7 publications

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“…It has been shown that cobalt(M) decomposes the acetic acid yielding methyl radical and carbon dioxide (Hendriks, 1979). The methyl radical formation in the p-xylene oxidation process is evidenced by the presence of CH4 in the off-gases and of methanol and methyl acetate in the mother liquor.…”

Section: B*[fex3br]mentioning

confidence: 99%

Byproduct identification in the terephthalic acid production process and possible mechanisms of their formation

Roffia¹,

Calini²,

Motta³

et al. 1984

Ind. Eng. Chem. Prod. Res. Dev.

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Ind. Eng. Chem. Prod. Res. Dev. 1984, 23, 629-634 629 cyclo[2.2.2]octane, 1449-91-8; trans-2-chloro-5-(chloromethyl)-5methyl-2-oxo-l,3,2-dioxaphosphorinane, 21071-81-8; cis-2-methoxy-5-(chloromethyl)-5-methyl-2-oxo-l,3,2-dioxaphosphorinane, 28097-12-3; trans-2-methoxy-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-27-3; cis-2-hydroxy-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-29-5; cis-2-phenoxy-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-30-8; trans-2-phenoxy-5-(chloromethyl)-5methyl-2-oxo-1,3,2-dioxaphosphorinane, 36895-18-8; cis-2-(4methoxyphenoxy)-5-(chloromethyl)-5-methyl-2-oxo-l,3,2-dioxaphosphorinane, 36912-31-9; trans-2-(4-methoxyphenoxy)-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-32-0; cis-2-(4-methylphenoxy)-5-(chloromethyl)-5methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-33-1; trans-2-(4methylphenoxy)-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-34-2; cis-2-(4-bromophenoxy)-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosporinane, 36912-35-3; trans-2-(4-bromophenoxy)-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-36-4; cis-2-(4-nitrophenoxy)-5-(chloromethyl)-5-methyl-2-oxo-l,3,2-dioxaphosphorinane, 36912-37-5; trans-2-(4-nitrophenoxy)-5-(chloromethyl)-5methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-38-6; cis-2-(2,4dinitrophenoxy)-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-39-7; trans-2-(2,4-dinitrophenoxy)-5-(chloromethyl)-5-methyl-2-oxo-l,3,2-dioxaphosphorinane, 36912-40-0; cis-2-benzoyloxy-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphosphorinane, 36912-41-1; trans-2-benzoyloxy-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-42-2; cis-2-thiophenoxy-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 36912-43-3; trans-2-thiophenoxy-5-(chloromethyl)-5-methyl-2-oxo-l,3,2-dioxaphosphorinane, 36912-44-4; cis-2-(pentylamino)-5-(chloromethyl)-5-methyl-2oxo-1,3,2-dioxaphosphorinane, 92366-30-8; trans-2-(pentylamino)-5-(chloromethyl)-5-methyl-2-oxo-1,3,2-dioxaphosphorinane, 92366-31-9; trans-2-(4-acetylphenoxy)-5-(chloromethyl)-5methyl-2-oxo-1,3,2-dioxaphosphorinane, 92366-32-0. Literature Cited Bauman, M.; Wadsworth, W. S., Jr. J . Am. Chem. SOC. 1978, 100, 6380. Gillespie, P.; Ramirez, F.; Ugi, 1.; Marquarding, D. Angew. Chem., Int. Ed. Engl. 1973, 12, 91. Rajan, S.; Kang, S.; Gutowsky, H.; Oidfield, E. J . 8/01,

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Section: B*[fex3br]mentioning

confidence: 99%

Byproduct identification in the terephthalic acid production process and possible mechanisms of their formation

Roffia¹,

Calini²,

Motta³

et al. 1984

Ind. Eng. Chem. Prod. Res. Dev.

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“…In addition to functioning as an autoxidation initiator, Co(III) species can oxidize peracids to generate peroxy radicals (i.e., oxidation of D to generate C), and Co(II) species are readily oxidized to Co(III) by peracids (i.e., D). 82 One might also envision direct oxidation of PhI by Co(III). 82,83 The following lines of experimental evidence suggest that Co-based additives are not intimately involved in the oxidation of PhI.…”

Section: Co(oac)mentioning

confidence: 99%

“…82 One might also envision direct oxidation of PhI by Co(III). 82,83 The following lines of experimental evidence suggest that Co-based additives are not intimately involved in the oxidation of PhI. (1) Co-based promoters are not necessary for aldehyde-promoted aerobic oxidation of aryl iodide.…”

Section: Co(oac)mentioning

confidence: 99%

“…Removal of these additives from aerobic oxidation reactions results in variable initiation time, but a high yield of PhI(OAc) 2 can still be obtained. 58 (2) Exposure of PhI to an AcOH solution of Co(OAc) 3 , 82 which is the product of aerobic oxidation of Co(II) in AcOH, did not result in the observation of any PhI(OAc) 2 (Figure S11). (3) Comparison of the concentration-versus-time plots for aerobic oxidation with and without Co(II) (1 mol % CoCl 2 $6H 2 O; Figure S12) revealed that although the length of time that is required for initiation depends intimately on the presence of Co(II), once oxidation commences, the presence of Co initiators does not affect the kinetics of oxidation.…”

Section: Co(oac)mentioning

confidence: 99%

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The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry

Hyun

Yuan

Maity

et al. 2019

Chem

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Aerobic hypervalent iodine chemistry provides a strategy for coupling the oneelectron chemistry of O 2 with two-electron processes typical of organic synthesis. We show that in contrast to the canonical two-electron oxidation of aryl iodides, aerobic synthesis proceeds by a radical chain process initiated by the addition of aerobically generated acetoxy radicals to aryliodides to generate iodanyl radicals. Robustness analysis reveals that the developed aerobic oxidation chemistry displays substrate tolerance similar to that observed in peracid-based methods and thus holds promise as a sustainable synthetic method.

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“…The latter is oxidized to methyl acetate according to the following equation, which summarizes both stages (Hendriks et al, 1979): formation of methyl acetate, and their kinetics can be modified by varying the reaction conditions, the methyl acetate formation was also expected to depend on given specific parameters of the oxidation process. In fact, during our investigation of the p-xylene oxidation reaction, we could verify that the methyl acetate formation is namely affected by variations in the following parameters: water concentration in the reaction medium, oxidation temperature, p-xylene oxidation rate, and catalytic system composition.…”

Section: Methyl Acetate Formationmentioning

confidence: 99%

Methyl acetate: by-product in the terephthalic acid production process. Mechanisms and rates of formation and decomposition in oxidation

Roffia¹,

Calini²,

Tonti³

1988

Ind. Eng. Chem. Res.

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Methyl acetate is one of the main byproducts in the terephthalic acid process. This investigation has been aimed to shed more light on particular aspects concerning this byproduct: the relationship between the ester production and the process variables, methyl acetate behavior in the oxidation vessel, and recycle of the ester to the oxidation. The effect of some parameter variations on the ester formation is reported. Ester formation rate and the decomposition rate constant have been also calculated for operating conditions adopted in our oxidation. The ester decomposition preferably occurs through a hydrolysis reaction. The recycle of the ester to the oxidation appears then to be a valid solution to recover selectively acetic acid from this byproduct and to reduce solvent makeup, while CH3OH decomposes to COx.The air oxidation process of p-xylene in acetic solution and in the presence of a Co-Mn-Br catalytic system is practically the only process applied on an industrial scale all over the world to terephthalic acid production (Hizicata, 1977;Roffia et al., 1980;Pohlmann et al., 1983).This process however has a drawback: part of the acetic acid used as solvent is decomposed to CO, C02, and other byproducts (Nippon Chemical Consultants, Inc., 1980;Dermietzel et al., 1983).

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The Structure of Cobalt(II) Acetate and Cobalt(III) Acetate in Acetic Acid Solution

Abstract: Optical and ion migration experiments were carried out with acetic acid solutions of Co" and Co"' acetate. The results indicate a mononuclear structure with six ligands. The largest amount of these complexes is uncharged.

Cited by 29 publications

References 7 publications

Byproduct identification in the terephthalic acid production process and possible mechanisms of their formation

Byproduct identification in the terephthalic acid production process and possible mechanisms of their formation

The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry

Methyl acetate: by-product in the terephthalic acid production process. Mechanisms and rates of formation and decomposition in oxidation

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