Cyclic mechanism

The formation of 1-and 2-aIkenes can be understood by the following mechanism. In the presence of formate anion, the 7r-allylpalladium complex 572 is converted into the 7r-allylpalladium formate 573. The most interesting feature is the attack of the hydride from formate to the more substituted side of the (T-allylic system by the cyclic mechanism shown by 574 to form the 1-alkene 575[367]. The decarboxylation and hydride transfer should be a concerted... 

Decarboxylation is not a general reaction of carboxylic acids. Rather, it is unique to compounds that have a second carbonyl group two atoms away from the —COoH. That is, only substituted malonic acids and /3-keto acids undergo loss of CC>2 on heating. The decarboxylation reaction occurs by a cyclic mechanism and involves initial formation of an enol, thereby accounting for the need to have a second carbonyl group appropriately positioned. 

Figure 9. Proposed cyclic mechanism for ATP synthesis by complex V involving all three catalytic sites of F,. In this scheme only the a and p subunits of F, are shown these are connected by a short stalk to F, in the inner membrane. Proton translocation through Fq driven by the proton motive force (AP) causes sequential conformational changes in each of the p-subunits and ATP synthesis as described in the text hexagons, high-affinity sites semicircles, low affinity sites parallelepipeds, intermediate-affinity sites (with no movement of F,).

A cyclic mechanism has been tentatively proposed for the reaction involving trialkyltin halides. 

Addition-elimination (12-14) and cyclic mechanisms (12-38) are also known. 

The names for these mechanisms vary throughout the literature. For example, the Sgi mechanism has also been called the Sp2, the Se2 (closed), and the Se2 (cyclic) mechanism. The original designations, Se 1, Se2, and so on, were devised by the Hughes-Ingold school. It has been contended that the SeI mechanism violates the principle of conservation of orbital symmetry (p. 1068), and that the Se2 (back) mechanism partially violates it Slack, D.A. Baird, M.C. J. Am. Chem. Soc., 1976, 98, 5539. 

Addition to conjugated systems can also be accomplished by any of the other three mechanisms. In each case, there is competition between 1,2 and 1,4 addition. In the case of nucleophilic or free-radical attack, the intermediates are resonance hybrids and behave like the intermediate from electrophilic attack. Dienes can give 1,4 addition by a cyclic mechanism in this way ... 

In the above-mentioned reactions with hydrazine and hydroxylamine, the actual reducing species is diimide (NH=NH), which is formed from N2H4 by the oxidizing agent and from NH2OH by the ethyl acetate.The rate of this reaction has been studied.Although both the syn and anti forms of diimide are produced, only the syn form reduces the double bond, at least in part by a cyclic mechanism ... 

It must be emphasized once again that the rules apply only to cycloaddition reactions that take place by cyclic mechanisms, that is, where two s bonds are formed (or broken) at about the same time. The rule does not apply to cases where one bond is clearly formed (or broken) before the other. It must further be emphasized that the fact that the thermal Diels-Alder reaction (mechanism a) is allowed by the principle of conservation of orbital symmetry does not constitute proof that any given Diels-Alder reaction proceeds by this mechanism. The principle merely says the mechanism is allowed, not that it must go by this pathway. However, the principle does say that thermal 2 + 2 cycloadditions in which the molecules assume a face-to-face geometry cannot take place by a cyclic mechanism because their activation energies would be too high (however, see below). As we shall see (15-49), such reactions largely occur by two-step mechanisms. Similarly. 2 + 4 photochemical cycloadditions are also known, but the fact that they are not stereospecific indicates that they also take place by the two-step diradical mechanism (mechanism... 

This reaction is reversible and suitable p-hydroxy alkenes can be cleaved by heat (17-34). There is evidence that the cleavage reaction occurs by a cyclic mechanism (p. 1351), and, by the principle of microscopic reversibility, the addition mechanism should be cyclic too. Note that this reaction is an oxygen analog of the ene... 

H2O may be replaced by any acid, HA, and a cyclic mechanism for the breakdown of the ester is quite feasible. For oxidation in alkali the fractional order in hydroxide ion, the low kjkjy and low degree of oxygen-transfer from oxidant are taken as symptomatic of a free-radical chain reaction of the type... 

It is clear then that more than one mechanism is operative for glycol fission. In the case of c -cyclopentanediols and camphanediols a cyclic ester is a necessary intermediate. For tra/js-decalin-9,10-diol a non-cyclic mechanism must operate which cannot function for cholestane-3/ ,6j8,7a-triol and is inefficient for /rans-camphanediols. It is pertinent that while the fission of glycols capable of forming cyclic esters proceeds several hundred times faster in benzene than in acetic acid, the reactions of trans-decalin-9,10-diol and tra/ij-hydrindane-l,6-diol are 4-5-fold slower in benzene . ... 

Certain types of corrosion are selective. Thus, corrosion cracking is observed primarily in the case of alloys and only when these are in contact with particular media. Corrosion is often enhanced by various extraneous effects. Stress corrosion cracking can occur under appreciable mechanical loads or internal stresses corrosion fatigue develops under prolonged cyclic mechanical loads (i.e., loads alternating in sign). 

In general, the elimination reactions are anti under acidic conditions and syn under basic conditions. This stereoselectivity is the result of a cyclic mechanism under basic conditions, whereas under acidic conditions an acyclic (3-elimination occurs. 

The reaction proceeds via a cyclic TS involving coordination of both the alcohol and ketone oxygens to the aluminum. Computational (DFT) and isotope effect studies are consistent with the cyclic mechanism.190 Hydride donation usually takes place from... 

Although recognizing the existence of the concerted cyclic mechanism, it has been proposed that most preparative pyrolyses proceed as surface-catalyzed reactions.336... 

Mixtures of alkenes are formed when more than one type of (3-hydrogen is present. In acyclic compounds the product composition often approaches that expected on a statistical basis from the number of each type of hydrogen. The E-alkene usually predominates over the Z-alkene for a given isomeric pair. In cyclic structures, elimination is in the direction that the cyclic mechanism can operate most favorably. 

Alkylation by allylic halides is usually a satisfactory reaction, and in this case the reaction may proceed through a cyclic mechanism.81 For example, when l-14C-allyl chloride reacts with phenyllithium, about three-fourths of the product has the labeled carbon at the terminal methylene group. 

The cyclic mechanism predicts that the addition reaction will be stereospecific with respect to the geometry of the double bond in the allylic group, and this has been demonstrated to be the case. The E- and Z-2-butenyl cyclic boronates 1 and 2 were synthesized and allowed to react with aldehydes. The F-boronate gave the carbinol with anti stereochemistry, whereas the Z-boronate resulted in the syn product.37... 

Mechanistic studies have been designed to determine if the concerted cyclic TS provides a good representation of the reaction. A systematic study of all the E- and Z-decene isomers with maleic anhydride showed that the stereochemistry of the reaction could be accounted for by a concerted cyclic mechanism.19 The reaction is only moderately sensitive to electronic effects or solvent polarity. The p value for reaction of diethyl oxomalonate with a series of 1-arylcyclopentenes is —1.2, which would indicate that there is little charge development in the TS.20 The reaction shows a primary kinetic isotope effect indicative of C—H bond breaking in the rate-determining step.21 There is good agreement between measured isotope effects and those calculated on the basis of TS structure.22 These observations are consistent with a concerted process. 

Addition reaction of peroxide-generated macroalkyl radicals with the reactive unsaturation in MA is shown in reaction scheme 4. The functionalised maleic-polymer adduct (II, scheme 4) is the product of hydrogen abstraction reaction of the adduct radical (I, scheme 4) with another PP chain. Concomitantly, a new macroalkyl radical is regenerated which feeds back into the cycle. The frequency of this feedback determines the efficiency of the cyclical mechanism, hence the degree of binding. Cross-linking reaction of I occurs by route c ( scheme 4). 

These considerations allow for a cyclic mechanism to occur in the formation of oxalic acid, where oxaloacetic acid yields either oxalate and acetate, which may be reoxidized, or pyruvate, which will then in turn yield acetate. This is illustrated in the following phase sequence of oxalate formation by these organisms ... 

The cyclic mechanism of free radicals generation in oxidation of aldehydes catalyzed by transition metal ions was demonstrated C. Bawn and J. Williamson [65]... 

The intermediate formation of the nitroxyl radical was detected in the oxidation of 2-propanol retarded by diphenylamine chain termination occurs by cyclic mechanisms involving both... 

Inhibition Coefficients f and Rate Constants k for the Reactions of Peroxyl Radicals with Aromatic Amines in Systems with a Cyclic Mechanism of Chain Termination (Experimental Data)... 

Cyclic chain termination with aromatic amines also occurs in the oxidation of tertiary aliphatic amines (see Table 16.1). To explain this fact, a mechanism of the conversion of the aminyl radical into AmH involving the (3-C—H bonds was suggested [30]. However, its realization is hampered because this reaction due to high triplet repulsion should have high activation energy and low rate constant. Since tertiary amines have low ionization potentials and readily participate in electron transfer reactions, the cyclic mechanism in systems of this type is realized apparently as a sequence of such reactions, similar to that occurring in the systems containing transition metal complexes (see below). 

Kinetic Characteristics of the Cyclic Mechanism of the Chain Termination on Nitroxyl Radicals in the Oxidation of Alcohols and Amines (Experimental Data)... 

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