A Series of Tertiary Butyl Peresters Showing Concerted Decomposition

Bartlett, Paul D.; Hiatt, R.

doi:10.1021/ja01539a031

Cited by 214 publications

(86 citation statements)

References 2 publications

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“…A comparison of the relative rates of these bridgehead perester decompositions with those reported for peracetate and trimethylperacetate (15) esters is given in Table 11. Bartlett and Greene (6), and Sager (16) concluded from a kinetic study of diapocamphoyl peroxide that a 1-bicyclo[2.2. llheptyl (i.e., 1-norbornyl) structure largely eliminates from tertiary radicals the considerable degree of stabilization that they otherwise normally have over primary methyl radicals.…”

Section: Discussionmentioning

confidence: 99%

Bridgehead free radical stability. The decomposition of t-butylperoxyesters of the 1-adamantyl, 1-bicyclo[2•2•2]octyl, and 1-norbornyl systems

Humphrey¹,

Hodgson²,

Pincock³

1968

Can. J. Chem.

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The I-butylperoxyesters of 1-adamantyl, 1-bicyclo[2-2.2]octyl, and 1-norbornyl carboxylic acids thermally undergo first order, free radical decomposition in cumene with relative rate constants at 80' of 1 .O, 0.07, and 0.001 respectively. As measures of the stability of the derived bridgehead free radicals, the rates span a range much narrower than that for carbonium ion formation at these strained positions. The results are consistent with suggestions that free radicals have smaller force constants for out-of-plane bending than do the corresponding carbonium ions.

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Section: Discussionmentioning

confidence: 99%

Bridgehead free radical stability. The decomposition of t-butylperoxyesters of the 1-adamantyl, 1-bicyclo[2•2•2]octyl, and 1-norbornyl systems

Humphrey¹,

Hodgson²,

Pincock³

1968

Can. J. Chem.

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“…It has convincingly been argued that tert-butyl peroxypivalate decomposes by a concerted twobond scission (1,2,(5)(6)(7)14). The criteria used, the magnitude of the activation parameters, and the high yields of carbon dioxide produced, have been taken with some modification (1,4,6) as indications of a concerted two-bond scission.…”

Section: Meclzanistic Conclusionmentioning

confidence: 99%

“…The thermal decompositions of the simple peresters have been proposed to proceed by two mechanistically distinct pathways, one-bond scission (reaction 1) and twobond scission (reaction 2). Kinetic criteria for distinguishing between the two paths has been established by Bartlett and Hiatt by comparing the activation parameters of a series of peresters and by correlating these comparisons with the chemical information available for these systems (2). Although these criteria have been somewhat modified, the analysis of the problem has been well supported (I).…”

Section: Introductionmentioning

confidence: 99%

“…A study of the decomposition of tert-butyl &,a-dimethylperpropionate 1 and its P-substituted analogues affords a method for the study of the substituent effect on the decomposition of a perester which has been considered as decomposing via the two-bond scission process [2] (2,(5)(6)(7)(8). Homolytic cleavage of the P-substituted peresters can in theory proceed through a variety of possible transition states (I-IV).…”

Section: Introductionmentioning

confidence: 99%

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Kinetic studies on the mechanism of the decomposition of a number of β-substituted tert-butyl α, α -dimethylperpropionates

Tanner¹,

Yabuuchi²,

Lutzer³

1977

Can. J. Chem.

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Can. J. Chem. 55, 612 (1977). A series of terf-butyl peresters having a general forn~ula corresponding to I were synthesized.The thermally initiated rates of decomposition of these peresters were determined at several temperatures and the activation parameters for these thermolyses were calculated. The rates of decomposition were relatively insensitive to the substituents and followed the order I > C2H, > C6H5S > H > Br > C1. The activation parameters and product studies were consistent with a simple two bond scission mechanism and no evidence could be found for neighboring group participation in these homolyses.

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“…The rates of decomposition of many peroxides yielding some acids and esters as products were determined by infrared spectrophotometry. 5 The products of the decomposition were analyzed as follows. The polystyrene film was dissolved in benzene.…”

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confidence: 99%

Decomposition of Peroxides in Polystyrene and Some Solid Arenes

Minato

Kato

Mori

1976

Polym J

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ABSTRACT:In order to cinnamoyloxylate polystyrene, cinnamoyl peroxide was decomposed in polystyrene film. The rates and products of the decomposition were determined. Products were cinnamoyloxypolystyrene, cinnamic acid, and a mixture of cinnamic acid esters (mainly styryl cinnamate). It was found that 0.11 mol cinnamoyloxy group per mol of cinnamoyl peroxide was attached to the polystyrene nuclei. The results were compared with those for the decomposition of benzoyl peroxide in polystyrene. The rates of decomposition of peroxides in some solid aromatics were then studied. The decompositions in solid biphenyl were slow, but those in phenanthrene were very fast. The results were interpreted in terms of the ionization potentials of the aromatics.KEY WORDS Cinnamoyl Peroxide I Benzoyl Peroxide 1 Polystyrene I Decomposition in Solids I Cinnamoyl groups are light-sensitive, and the introduction of Ph-CH=CH-COO-groups into polystyrene is of interest since the polymers thus formed are expected to cross-link upon irradiation with light. A convenient method for the introduction of cinnamoyloxy groups into polystyrene appeared to be the decomposition of cinnamoyl peroxide in polystyrene. Such an investigation has been carried out, and the results are described in this paper. Decompositions of benzoyl peroxide in polystyrene, phenanthrene and biphenyl have also been investigated, and the results are compared. EXPERIMENTAL MaterialsPolystyrene was prepared by the emulsion polymerization of styrene at looc with a redox system of polyamine-iron-hydroperoxide. 1 Viscosity-average molecular weight was 126,000.Cinnamoyl peroxide was prepared by the method described by Sana, Nandi, and Palit. [P 0] are the concentrations of peroxide at time t and time 0), the plots were on a straight line at least until 50-% decomposition. Haas determined the rates of decomposition of benzoyl peroxide in polystyrene films by iodometry, 3 and then by infrared spectrophotometry, 4 and the results of the two methods were in fair agreement. The rates of decomposition of many peroxides yielding some acids and esters as products were determined by infrared spectrophotometry. 5

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A Series of Tertiary Butyl Peresters Showing Concerted Decomposition

Cited by 214 publications

References 2 publications

Bridgehead free radical stability. The decomposition of t-butylperoxyesters of the 1-adamantyl, 1-bicyclo[2•2•2]octyl, and 1-norbornyl systems

Bridgehead free radical stability. The decomposition of t-butylperoxyesters of the 1-adamantyl, 1-bicyclo[2•2•2]octyl, and 1-norbornyl systems

Kinetic studies on the mechanism of the decomposition of a number of β-substituted tert-butyl α, α -dimethylperpropionates

Decomposition of Peroxides in Polystyrene and Some Solid Arenes

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