Über das Auftreten freier Radikale bei chemischen Reaktionen. VI. Die thermische Spaltung der Diacyl‐peroxyde

Wieland, Heinrich; Rasuwajew, G.

doi:10.1002/jlac.19304800110

Cited by 36 publications

(7 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Furthermore, the alkoyloxy moiety of an unsymmetrical peroxide in general loses its carbon dioxide more readily than does the aroyloxy part (73,74). The benzoxy half of an unsymmetrical peroxide in turn loses its carbon dioxide more readily than does a substituted benzoxy moiety; this is true whatever the substituent (73).…”

Section: Peroxide Decomposition a Diacyl Peroxidesmentioning

confidence: 99%

“…Such behavior is incompatible with an ionic mechanism but does not clash with the view that free radicals are involved. The substituents tested (73) were phenyl, chloro, methoxy, and nitro, all in the para position. If the mechanism were cationic, it would be reasonable to expect the methoxy group to increase and the nitro group to decrease decarboxylation.…”

Section: Peroxide Decomposition a Diacyl Peroxidesmentioning

confidence: 99%

See 1 more Smart Citation

Cleavages and Rearrangements Involving Oxygen Radicals and Cations.

Leffler¹

1949

Chem. Rev.

View full text Add to dashboard Cite

Section: Peroxide Decomposition a Diacyl Peroxidesmentioning

confidence: 99%

Section: Peroxide Decomposition a Diacyl Peroxidesmentioning

confidence: 99%

Cleavages and Rearrangements Involving Oxygen Radicals and Cations.

Leffler¹

1949

Chem. Rev.

View full text Add to dashboard Cite

“…The same scheme has been advocated subsequently by other workers (Wieland and Razuvaev, 1930;Wieland, Schapiro and Metzger, 1934;Erlenmeyer and Schoenauer, 1936;Bowen and Rohatgi, 1953). Recently, Huisgen and Horeld (1949) and Huisgen and Sorge (1950) have advanced the so-called "kryptoradical" theory, in which the radicals are never actually free, but in which the dissociation of the radical-source and the attack on the aromatic compound take place synchronously.…”

Section: (B) Mechanism Of the Substitution Stepmentioning

confidence: 77%

Quantitative Investigation of Homolytic Arylation

Williams¹

1960

Homolytic Aromatic Substitution

View full text Add to dashboard Cite

“…Why are the rates for the loss of BP groups from photoperoxidized VBZ and PCOCO the same? Some insights come from the product distributions observed during thermolyses of benzene solutions of BP s with a para −OCH 3 , −C 6 H 5 , −Cl or −NO 2 substituent on one of the phenyl rings, under an inert atmosphere and in the absence [ 83 ] or presence [ 84 ] of BF 3 as a Lewis acid catalyst. The thermolysis of the nitro-substituted BP yielded more product attached to the solvent than the other substituted BP s. Of the molecules investigated, the methoxy-substituted BP reacted fastest at one temperature.…”

Section: Polymers Bearing Covalently Attached 12-dicarbonyl Groupsmentioning

confidence: 99%

Benzil Photoperoxidations in Polymer Films and Crosslinking by the Resultant Benzoyl Peroxides in Polystyrene and Other Polymers

et al. 2021

View full text Add to dashboard Cite

Benzil (BZ) can be converted almost quantitatively to benzoyl peroxide (BP) in aerated polymer films upon irradiation at >400 nm (i.e., the long-wavelength edge of the n→π* absorption band of BZ, where BP does not absorb). Here, we summarize results for the photoperoxidation of BZ structures with molecular oxygen, principally in glassy polymer matrices. Some of the polymers are doped directly with BZ or its derivatives, and others, contain covalently attached BZ pendant groups from which BP groups are derived. While the decomposition of low-molecular-weight BP doped into polymer films (such as those of polystyrene (PS)) results in a net decrease in polymer molecular weight, thermal decomposition of pendant BP groups is an efficient method for chain crosslinking. Crosslinking of PS films doped with a molecule containing two covalently linked BZ or BP groups proceeds in a similar fashion. Free radicals from the covalently attached BP allow grafting of new monomers, as well. Additionally, the use of radiation filtered through masks has been used to create patterns of polymers on solid surfaces. Crosslinking of photodegradable poly(phenyl vinyl ketone) with BP structures obtained by photoperoxidation of BZ structures for the preparation of photodegradable polymer networks is described as well. In sum, the use of BZ and BP and their derivatives offers simple and convenient routes for modifying polymer chains and, especially, for crosslinking them. Specific applications of each use and process are provided. Although applications with PS are featured here, the methodologies described are amenable to a wide variety of other polymers.

show abstract

Über das Auftreten freier Radikale bei chemischen Reaktionen. VI. Die thermische Spaltung der Diacyl‐peroxyde

Cited by 36 publications

References 4 publications

Cleavages and Rearrangements Involving Oxygen Radicals and Cations.

Cleavages and Rearrangements Involving Oxygen Radicals and Cations.

Quantitative Investigation of Homolytic Arylation

Benzil Photoperoxidations in Polymer Films and Crosslinking by the Resultant Benzoyl Peroxides in Polystyrene and Other Polymers

Contact Info

Product

Resources

About