Quantitative investigation of the ozonolysis reaction. XI. Effects of substituents in directing the ozone cleavage of trans-1,2-disubstituted ethylenes

Fliszár, Sándor; Granger, M.M.

doi:10.1021/ja00714a023

Cited by 28 publications

(18 citation statements)

References 4 publications

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“…Similar results are also obtained in the study (12) For the phenyl group, however, no constant group contribution AGR* is observed.…”

supporting

confidence: 90%

“…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: 88%

“…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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“…Similar results are also obtained in the study (12) For the phenyl group, however, no constant group contribution AGR* is observed.…”

supporting

confidence: 90%

supporting

confidence: 88%

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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“…This is in line with the previous experience that in the ozonolysis of unsymmetrically substituted olefins the carbonyl oxide fragment is preferentially formed at the carbon atom which is tied to the least electron deficient substituents (7). Thus, for 1-chloro-Zbutene and for 3-chloropropene the ozone cleavage was reported to afford the corresponding nonchlorinated carbonyl oxides in proportions of 89% and 83%, respective] y (8).…”

Section: Reaction Coilrsementioning

confidence: 99%

Ozonolysis of olefins containing monochloro substituted double bonds

Keul¹,

Griesbaum²

1980

Can. J. Chem.

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Ozone cleavage of 12 substituted vinyl chlorides (1) in methanol occurred such that the chlorinated moiety of the double bond afforded the carbonyl fragment (i.e. acyl chloride) and the nonchlorinated moiety afforded the carbonyl oxide fragment. All of these fragments underwent secondary reactions: formyl chloride gave carbon monoxide and hydrogen chloride; all other acyl chlorides yielded the corresponding methyl esters. The carbonyl oxides were converted into the corresponding methoxy hydroperoxides. Under the influence of hydrochloric acid unsubstituted and monosubstituted methoxy hydroperoxides were dehydrated to form the corresponding methyl esters, whereas the disubstituted methoxy hydroperoxide of acetone produced the cyclic trimeric peroxide of acetone.

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“…I Ozonolysis of aryl-substituted olefins results in the predominant formation of carbonyl oxides (ROO), in which substituents stabilize the positive charge on the C atom of the carbonyl oxide group, z~ In the case of atkyl-substituted olefins, the formation of ROO is controlled by polar and stefic factors. 4.s…”

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confidence: 99%

Electronic effects in the reaction of diphenylcarbonyl oxide with aldehydes

et al. 1999

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The reactivity of 14 aldehydes with diphenylcarbonyl oxide Ph~COO was characterized by the kn/k3! ratio. The values of /~33//r I vary from 1.3" 10 -2 (CrFsCHO) to 1.0 (p-Me2N--PhCHO), 70 ~ aeetonitrile as the solvent. A charge transfer complex (CTC) was suggested to be primarily formed during the reaction. The electronic effects of substituents in the reaction were analyzed using the published data. Carbonyl oxide reacts with aldehydes as a nucleophile (at the carbon atom of the --CHO fragment to form 1,2,4-trioxolane) and also as an electrophile (at the aromatic ring with the intennediate formation of CTC). The latter is transformed into either 1,2,4-trioxolane or the products of oxidation of the phenyl ring.

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Quantitative investigation of the ozonolysis reaction. XI. Effects of substituents in directing the ozone cleavage of trans-1,2-disubstituted ethylenes

Cited by 28 publications

References 4 publications

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

Ozonolysis of olefins containing monochloro substituted double bonds

Electronic effects in the reaction of diphenylcarbonyl oxide with aldehydes

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