Über Monomethyl‐hydroperoxyd. (III. Mitteil. über Alkylperoxyde)

Rieche, Alfred; Hitz, Fritz

doi:10.1002/cber.19290620888

Cited by 68 publications

(24 citation statements)

References 11 publications

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“…In this work, it was found that pure methyl hydroperoxide could be obtained safely by fractionation a t reduced pressure and could be reliably estimated by iodine liberation and thiosulfate titration. The latter contrasts with other literature reports (11,9). Details are given in the Experimental section.…”

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confidence: 63%

The Thermal Decomposition of Methyl Hydroperoxide

Kirk¹

1965

Can. J. Chem.

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The thermal decon~position of methyl hydroperoxide has been studied in solutioll and in the gas phase. The decomposition was found to be partly heterogeneous in solution in dimethyl phthalate and no reliable rate constants were obtained. Use of the toluene carrier method for the gas phase work enabled measurement of the rate constant for the homogeneous decomposition. The first order rate constants obtained range from 0.19 s-1 a t 292 "C to 1.5 s-1 a t 378 "C, leading to log A , 11 f 2, and activation energy, 32 f 5 kcal/mole. These results are compared with the expected values of log A , 13-14, and activation energy, 42 kcal/mole. The significance of these findings is discussed.Although the mechanism of its production has not been unan~biguously established, and indeed inay not be unique, methyl hydroperoxide has now been recognized as a significant product in the low temperature ( I ) , radiolytic (2), and mercury photosensitized oxidation (3) of methane, the photooxidation of azomethane (4, 5), acetone (6), and methyl iodide (7), and the oxidation of methyl radicals (8). Although frequently not found in the products, it seeins likely to be formed in any system involving methyl radicals and oxygen below about 400 "C. The possibility that methyl hydroperoxide acts as a chainbranching agent in the low temperature oxidation of methane has been in dispute and appears to be still uncertain (9). This uncertainty exists largely because the rate of hon~ogeneous decoinposition of the hydroperoxide is not 1-~n o w n .Early ~vork (10) showed that decomposition of methyl hydroperoxide in a stream of nitrogen led to a coinplex mixture of products, almost certainly arising from simultaneous homogeneous and heterogeneous reaction. Recently, Fisher and Tipper (9) have studied the decomposition of the pure vapor in a static system and found the half-life of the peroxide to be up to 30 s a t 395 "C depending on the condition of the reaction vessel surface. The lack of inore complete data may be due to the difficulty of obtaining the h ydroperoxide pure and its fairly ready heterogeneous decomposition. In this work, it was found that pure methyl hydroperoxide could be obtained safely by fractionation a t reduced pressure and could be reliably estimated by iodine liberation and thiosulfate titration. The latter contrasts with other literature reports (11, 9). Details are given in the Experimental section.This research was undertaken to obtain evidence for the hoinogeneous decomposition of methyl hydroperoxide into radicals [I] (M +) CH3OOH -+ CHIO. + OH. (+ M) and to measure the rate constants and Arhennius parameters both in solution and in the gas phase. For the gas phase work, the toluene carrier method was adopted despite the criticisms which may be levelled against it (12). The facile heterogeneous decomposition of methyl hydroperoxide with low activation energy necessitates worlting a t high temperature and short reaction times if the homogeneous reaction is to be favored. In addition, the relative effectivene...

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confidence: 63%

The Thermal Decomposition of Methyl Hydroperoxide

Kirk¹

1965

Can. J. Chem.

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“…The actual concentration was determined spectrophotometrically before use. Methyl hydrogen peroxide was prepared according to the method of Rieche & Hitz (1929) and its concentration determined iodometrically. Notatin (glucose oxidase) was obtained from Boots Pure Drug Co. Ltd.…”

Section: Methodsmentioning

confidence: 99%

Selective inhibition by 2-heptyl-4-hydroxyquinoline N-oxide of certain oxidation-reduction reactions

Kogut¹,

Lightbown²

1962

Biochemical Journal

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“…In combination with the HR-ESI MS result, the structure of 2 a could be proven unambiguously. The geminal dihydroperoxide 2 a has the highest content of peroxide oxygen (68 %) relative to hitherto known organic peroxides and hydroperoxides.The so-called triacetone triperoxide (6; 43 % peroxidic oxygen) and methylhydroperoxide (7; [8] 66.7 %) were reported as highly explosive compounds. Despite the very high oxygen content compound 2 a is remarkably stable.…”

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confidence: 99%

Reaction of Epoxyketones with Hydrogen Peroxide—Ethane‐1,1‐dihydroperoxide as a Surprisingly Stable Product

Hamann

Bunge

Liebscher

2008

Chemistry A European J

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Oxidation of organic compounds with hydrogen peroxide has attracted attention for a long time and has been attributed to green chemistry. We used hydrogen peroxide in reactions with cyclic alcohols and observed unusual rearrangement reactions under ring enlargement giving new hydroperoxides and peroxides. [1][2][3] In this way we also obtained aliphatic primary geminal dihydroperoxides.[2] We report here on reactions of cyclic epoxyketones with hydrogen peroxide. Such epoxides are usually synthesised by the Weitz-Scheffer reaction, that is, by reaction of a,b-unsaturated ketones with H 2 O 2 under basic conditions.[4] We treated such products with 70 % H 2 O 2 in the presence of catalytic amounts of camphor sulfonic acid at room temperature.Substituted 6-ring epoxyketones 1 at the 3-position gave mixtures of products, interestingly consisting of geminal dihydroperoxides 2, dicarboxylic acids 3, carboxylic acids 4 and ketocarboxylic acids 5 (Table 1, Scheme 1).The geminal dihydroperoxides 2 show significant signals in the NMR spectra. [2,[5][6][7] Thus, the hitherto unkown ethane-1,1-dihydroperoxide (2 a) exhibits a signal at 107.9 ppm in the 13 C NMR spectrum and one typical hydroperoxide-H signal (intensity two protons) at 9.71 ppm in the 1 H NMR spectrum. In combination with the HR-ESI MS result, the structure of 2 a could be proven unambiguously. The geminal dihydroperoxide 2 a has the highest content of peroxide oxygen (68 %) relative to hitherto known organic peroxides and hydroperoxides.The so-called triacetone triperoxide (6; 43 % peroxidic oxygen) and methylhydroperoxide (7; [8] 66.7 %) were reported as highly explosive compounds. Despite the very high oxygen content compound 2 a is remarkably stable. It can be kept at room temperature for several days and at À20 8C for several weeks without decomposition. Thermogravimetric investigations (see Supporting Information) showed decomposition in the temperature range 60-130 8C with the highest decomposition rate at about 105 8C. Using differently substituted epoxyketones as reactants we were also able to isolate and characterise propane-1,1-dihydroperoxide (2 b), which is not yet described in literature, and to obtain benzylidenedihydroperoxide (2 c). The latter was previously described by using a different method from the reaction of benzaldehyde with H 2 O 2 .[ 4 [%] [b] 5 [%] [b]

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Über Monomethyl‐hydroperoxyd. (III. Mitteil. über Alkylperoxyde)

Cited by 68 publications

References 11 publications

The Thermal Decomposition of Methyl Hydroperoxide

The Thermal Decomposition of Methyl Hydroperoxide

Selective inhibition by 2-heptyl-4-hydroxyquinoline N-oxide of certain oxidation-reduction reactions

Reaction of Epoxyketones with Hydrogen Peroxide—Ethane‐1,1‐dihydroperoxide as a Surprisingly Stable Product

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