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Other Reactions involving Ring Fission

On the other hand, in cyclic ethers (alkene oxides, oxetans, tetrahydrofuran) and formals the reaction site is a carbon-oxygen bond, the oxygen atom is the most basic point, and, hence, cationic polymerization is possible. The same considerations apply to the polymerization of lactones Cherdron, Ohse and Korte showed that with very pure monomers polyesters of high molecular weight could be obtained with various cationic catalysts and syncatalysts, and proposed a very reasonable mechanism involving acyl fission of the ring [89]. [Pg.135]

A similar ring-fission occurs when apomorphine is heated with acetic anhydride and hydrochloric acid [71] and when the mono- and dimethyl ethers are heated with benzoyl chloride [72], Another reaction that involves fission of the nitrogen ring is the reaction between diben-zoylapomorphine and cyanogen bromide, which results in [xii] [73]. Other tetrahydroisoquinoline derivatives also suffer ring-fission with this reagent [74-76]. [Pg.305]

As in these last examples, the descriptions of diastereoselective epoxidations were accompanied already by details on their subsequent use in ring fission reactions, we shall now switch to the various options of controlled regioselective and diastereoselective epoxide transformations. The nucleophilic opening of epoxides shows a strong dependence on substrate structure, nature of the nucleophile, and the catalyst involved, similarly to nucleophilic substitutions. Lastly, one has to consider the solvent and other details of the reaction conditions including the transition state conformation. [Pg.222]

Mechanisms involving glycol bond fission have been proposed for the oxidation of vicinal diols, and hydride transfer for other diols in the oxidation of diols by bromine in acid solution.The kinetics of oxidation of some five-ring heterocyclic aldehydes by acidic bromate have been studied. The reaction of phenothiazin-5-ium 3-amino-7-dimethylamino-2-methyl chloride (toluidine blue) with acidic bromate has been studied. Kinetic studies revealed an initial induction period before the rapid consumption of substrate and this is accounted for by a mechanism in which bromide ion is converted into the active bromate and hyperbromous acid during induction and the substrate is converted into the demethylated sulfoxide. [Pg.231]

Pincock and his co-workers have studied the photochemical fragmentation reactions of the esters (31). This system has an in-built electron accepting sensitiser. When (31a-c) are irradiated in methanol the principal reaction is fission to yield the styrene (32) and p-cyanobenzoic acid. The other products formed from the reactions are the styrene addition products (33)-(35). The authors propose that the Norrish T) e II process in this instance involves a proton transfer and this occurs within the zwitterionic biradical formed as the primary intermediate on electron transfer. Further proof of the authenticity of this mechanism was obtained by irradiation of the deuteriated derivatives (31 d, e). The results of a study of the photochemical decomposition of benzyl phenylacetate, as a suspension in water over Ti02, have been reported. Bond fission is the result of irradiation of (36) in cyclohexane/ethyl acetate. A Norrish Type II hydrogen abstraction occurs with the elimination of the enone moiety. This affords a path to the CD ring system (37) of vitamin D. [Pg.51]

The isotope effect in the bromination of 7V,iV-dimethylaniline in aqueous acid implies dissimilar mechanisms for the ortho and the para substitution. The rate-determining step could well involve, among other factors, fission or lengthening of the C—H bond in ortho bromination, but this is unlikely in para bromination. The di-methylamino group and bromine are believed to form an intermediate complex in these reactions, which appears to decrease the velocity of substitution with additional electrophile. Recent quantitative measurements, in electrophilic bromination , have reached the conclusion that the NMe2 group activates the para position of the ring ten times more than the ortho position. [Pg.548]


See other pages where Other Reactions involving Ring Fission is mentioned: [Pg.114]    [Pg.114]    [Pg.341]    [Pg.556]    [Pg.210]    [Pg.24]    [Pg.96]    [Pg.138]    [Pg.242]    [Pg.81]    [Pg.427]    [Pg.32]    [Pg.446]    [Pg.648]    [Pg.104]    [Pg.240]    [Pg.184]    [Pg.240]    [Pg.1042]    [Pg.532]    [Pg.416]    [Pg.818]    [Pg.225]    [Pg.226]    [Pg.283]    [Pg.77]    [Pg.218]   


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Ring fission

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