Quantitative investigation of the ozonolysis reaction. VIII. On the direction of cleavage of primary ozonides of selected unsymmetrical olefins

Fliszár, Sándor; Granger, M.M.

doi:10.1021/ja01040a039

Cited by 30 publications

(14 citation statements)

References 1 publication

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“…It has been shown, in all cases studied, that in the presence of enough methanol (or ethanol) the zwitterions are quantitatively trapped to give the corresponding alkoxyhydroperoxides (16,17).3 It has been also shown that the ozonolysis of 1 mole of olefin, in the presence of excess alcohol, results in the production of a total of 1 mole of the mixture of carbonyl compounds. This is in complete agreement with the stoichiometry of Criegee's mechanism (Scheme 1) (12,16,18). …”

supporting

confidence: 87%

“…These amounts were measured by iodometry, as described previously (18). The analyses made under these conditions were very reproducible, providing they were carried out shortly after completion of the ozonolysis; the values found for the amounts of hydroperoxides decreased by only a few per cent 1 h after ozonolysis.…”

Section: Amoltnts Of Hydroperoxides (Active Oxygen)mentioning

confidence: 99%

“…Hence, only a poor precision can be obtained in using isolation techniques. Precision has been considerably improved by the use of non-destructive analytical methods for determining the amounts of reaction products, and because of this detailed studies on the factors governing the distribution of the paths of cleavage became possible (12,16,18,22). PI 1% [xl(l -4 1 = -(AGO,R* -AG0,b*)/2.3RT + (PR -pblo Equation [2], which is derived from eq.…”

mentioning

confidence: 99%

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Quantitative investigation of the ozonolysis reaction. XIV. A simple carbonium ion stabilization approach to the ozone cleavage of unsymmetrical olefins

Fliszár¹,

Renard²

1970

Can. J. Chem.

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The direction of ozone cleavage of selected unsymmetrical olefins RlR2C=CR3R4 to give (a) RlR2C0 + R3R4CCOO-and (b) RIR,CCOO-+ R3R4C0 has been measured, with particular emphasis on the mode of participation of alkyl substituents in distributing the reaction paths a and b. The interpretation, in terms of substituent effects in stabilizing potential zwitterionic carbo-cations in the transition states corresponding to paths a and b, considers (i) the "hyperconjugative stabilization" of positive sites, where the stabilizing abilities of the substituents are in the order CH, > C2H5 > i-C3H7 > tert-C4H9, and (ii) the participation of inductive effects. The latter appear to be particularly important when the substituents on the two C atoms of the primary ozonide act in the same direction in favoring its electrocyclic cleavage. In the ozonolysis of monosubstituted ethylenes the inductive effects are predominant, i.e. the R-C+HOO-formation is favored by the R groups in the order tert-C4H9 > i-C3H7 > C2H: > .CH3, whereas in trans-and cis-l,2-disubstituted ethylenes "hyperconjugation" governs the dlrectlon of cleavage. The cleavage of selected 1,l-disubstituted, tri-, and tetrasubstituted ethylenes is also studied.

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supporting

confidence: 87%

Section: Amoltnts Of Hydroperoxides (Active Oxygen)mentioning

confidence: 99%

mentioning

confidence: 99%

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Quantitative investigation of the ozonolysis reaction. XIV. A simple carbonium ion stabilization approach to the ozone cleavage of unsymmetrical olefins

Fliszár¹,

Renard²

1970

Can. J. Chem.

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“…= Ϫ 1·25 vs ). 21 These results revealed that the selectivity was affected mostly by the relative stability of the resulting carbonyl oxides. Carbonyl oxide formation was still one of the major pathways in the 1 O 2 oxidation of diazoalkanes with electron-withdrawing groups, i.e.…”

Section: Photooxidation Of Diazo Compoundsmentioning

confidence: 95%

Novel aspects of carbonyl oxide chemistry

Ishiguro

Nojima

Sawaki

1997

J. Phys. Org. Chem.

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The structural and chemical properties of 1,3-dipolar peroxidic species (X-O-O) such as ozone (X = O) and carbonyl oxides (X = R 2 C) depend significantly on the nature of X. Although cyclic O 3 is thermodynamically unstable, dioxiranes, cyclic isomers of carbonyl oxides, are isolable and have been fully characterized. In contrast to the well known electrophilic nature of ozone, carbonyl oxides usually act as a nucleophilic oxygen transfer agent, but their reactivity could be altered by substituents. It is expected that the chemistry of R 2 C-O 2 species will provide a good starting point for a better understanding of dioxygen complexes (X-O 2 ) with various Xs. Interesting aspects of carbonyl oxide chemistry are discussed, including methods of generation, cyclization to dioxiranes and the nature of their oxygen transfer activities.

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“…This reaction is simple and has been extensively studied. [8][9][10][11][12][13][14] Despite its simplicity this reaction is a good model for ozonolysis steps in the synthesis of important active pharmaceutical ingredients.…”

Section: Introductionmentioning

confidence: 99%

On-Line Analysis of a Continuous-Flow Ozonolysis Reaction Using Raman Spectroscopy

2007

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We describe the use of an on-line Raman analyzer to quantitatively track the levels of trans-stilbene, benzaldehyde, and alpha-methoxybenzyl hydroperoxide in a continuous flow ozonolysis reactor. Quantitative analysis is carried out using spectral stripping in order to overcome baseline artifacts inherent in simple peak area determinations and to incorporate prior knowledge into the analytical model. The performance of spectral stripping is compared to partial least squares (PLS) analysis. The effect of two process variables, feed flow rate and ozone concentration, are also explored. Finally, the benefit of utilizing an on-line technique is illustrated by demonstrating the bias introduced by sampling for off-line analysis.

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Quantitative investigation of the ozonolysis reaction. VIII. On the direction of cleavage of primary ozonides of selected unsymmetrical olefins

Cited by 30 publications

References 1 publication

Quantitative investigation of the ozonolysis reaction. XIV. A simple carbonium ion stabilization approach to the ozone cleavage of unsymmetrical olefins

Quantitative investigation of the ozonolysis reaction. XIV. A simple carbonium ion stabilization approach to the ozone cleavage of unsymmetrical olefins

Novel aspects of carbonyl oxide chemistry

On-Line Analysis of a Continuous-Flow Ozonolysis Reaction Using Raman Spectroscopy

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