Tautomerism mechanisms

The intermediacy of enols or enolate anions may be demonstrated by hydrogen exchange reactions (see Section 4.11.2). Both acid-catalysed and base-catalysed tautomerism mechanisms involve removal... 

Those species related to C2B9HH (II-C4) 2,135,145), i.e., CBioHu 62, 72, 155) and BuHn 70), due to the presence of the seven-coordinate boron (violation of rule 4p) tend to scramble their borons on an NMR time scale via a valence bond tautomerism mechanism 142, 155) which possibly involves the transient and reversible opening of the eleven-vertex closo structure to the eleven-vertex nido structure 55, 96). 

In porphycene, the rates, barriers and the overall tautomerization mechanism seem to be completely different. Comparison of the reaction for 1 and 2 in the crystalline state was performed using i N CPMAS NMR (Fig. 8.5) [40, 68]. At elevated temperatures both molecules reveal only one peak, characteristic of a rapid inner hydrogen exchange. For porphyrin, lowering of the temperature from 356 to 192 K leads to line broadening and, finally, to the separation of =N- and NH... 

When this enol undergoes the reverse tautomerization mechanism, protonation of the planar enol can occur on either face, resulting in the formation of both enantiomers of the carboxylic acid (i.e., racemization). 

With terminal alkynes, hydration gives the ketone instead of the aldehyde, consistent with Markovnikov addition (Eq. 10.10). When alkynes are treated with strong acids, vinyl cations are formed. Nucleophilic attack by water and deprotonation first give a vinyl alcohol (enol), which ultimately tautomerizes to a ketone. The tautomerization mechanism will be given in the next chapter. 

In the first chapter, devoted to thiazole itself, specific emphasis has been given to the structure and mechanistic aspects of the reactivity of the molecule most of the theoretical methods and physical techniques available to date have been applied in the study of thiazole and its derivatives, and the results are discussed in detail The chapter devoted to methods of synthesis is especially detailed and traces the way for the preparation of any monocyclic thiazole derivative. Three chapters concern the non-tautomeric functional derivatives, and two are devoted to amino-, hydroxy- and mercaptothiazoles these chapters constitute the core of the book. All discussion of chemical properties is complemented by tables in which all the known derivatives are inventoried and characterized by their usual physical properties. This information should be of particular value to organic chemists in identifying natural or Synthetic thiazoles. Two brief chapters concern mesoionic thiazoles and selenazoles. Finally, an important chapter is devoted to cyanine dyes derived from thiazolium salts, completing some classical reviews on the subject and discussing recent developments in the studies of the reaction mechanisms involved in their synthesis. 

The aldehyde or ketone is called the keto form and the keto enol equilibration referred to as keto-enol isomerism or keto-enol tautomerism Tautomers are constitu tional isomers that equilibrate by migration of an atom or group and their equilibration IS called tautomerism The mechanism of keto-enol isomerism involves the sequence of proton transfers shown m Figure 9 6... 

Mechanism of the initial reaction, known as alkaline peeling, is shown in equation 4. EnoHzations and tautomerizations take place easily because of the contiguous hydroxyl groups. The hydroxyl or substituted hydroxyl on the second, ie, P-carbon, from a carbonyl group is released from the molecule by P-elimination. 

Photochromism Based on Tautomerism. Several substituted anils of saHcylaldehydes are photochromic but only in the crystalline state. The photochromic mechanism involves a proton transfer and geometric isomerization (21). An example of a photochromic anil is /V-sa1icylidene-2-ch1oToani1ine [3172-42-7] C H qCINO. 

Aromatic pyrazoles and indazoles, in the broad sense defined in Sections 4.04.1.1.1 and 4.04.1.1.2, will be discussed here. Tautomerism has already been discussed (Section 4.04.1.5) and acid-base equilibria will be considered in Section 4.04.2.1.3. These two topics are closely related (Scheme 10) as a common anion (156a) or a common cation (156b) is generally involved in the mechanism of proton transfer (e.g. 78T2259). For aromatic pyrazoles with exocyclic conjugation there is also a common anion (157) for the three tautomeric forms... 

Annular tautomerism does not occur in isothiazoles or benzisothiazoles. Substituent tautomers can sometimes be distinguished by chemical methods, but it is important that reaction mechanisms and the relative rates of interconversion of tautomeric starting materials or isomeric reaction products are carefully investigated. Physical methods only will be considered in this section, and references to original publications can be found in a comprehensive review (76AHC(S1)1). 

Mechanism The reaction of and A -steroids with nitrosyl fluoride to form ni trimines is best discussed in conjunction with the nitrosyl chloride reaction leading tothe5a-chloro-6 -nitro steroids (33). Since nitroso alkanes are oxidized with nitrosyl chloride to nitro alkanes it is believed that 5a-chloro-6j5-nitro steroids are formed in this way from an initially formed 5a-chloro-6 -nitroso adduct. The same is true for nitrosyl fluoride up to the stage of the nitroso fluoride (56). Since NOF is a weaker oxidizing agent than NOCl the nitroso fluoride tautomerizes to the fluoro oxime (57) at a rate... 

The mechanism of the Fiesselmann reaction between methylthioglycolate and a,P-acetylenic esters proceeds via consecutive base-catalyzed 1,4-conjugate addition reactions to form thioacetal Enolate formation, as a result of treatment with a stronger base, causes a Dieckmann condensation to occur providing ketone 8. Elimination of methylthioglycolate and tautomerization driven by aromaticity provides the 3-hydroxy thiophene dicarboxylate 9. 

The mechanism of this reaction is generally understood to consist of subsequent Claisen condensation reactions to produce an intermediate diketone 12, which readily tautomerizes to the fully conjugated dihydroxythiophene 13. ... 

Based on these observations, it is likely that the mechanism involves initial formation of thione 3 (X = O or S), which is followed by tautomerization to 4 and cyclization to 5. Aromaticity drives the facile elimination of either H2O or H2S resulting in the thiophene product. 

The mechanism for the redistribution in oxidation states begins similarly to that of the Paal thiophene synthesis. However, upon formation of dithione 38, nucleophilic addition of one thiocarbonyl into the other produces the intermediate zwitterion 39. A 1,3-tautomerization of hydrogen then gives... 

The proposed mechanism for the Conrad-Limpach reaction is shown below. Condensation of an aniline with a 3-keto-ester (i.e., ethyl acetoacetate 5) with loss of water provides enamino-ester 6. Enolization furnishes 10 which undergoes thermal cyclization, analogous to the Gould-Jacobs reaction, via 6n electrocyclization to yield intermediate 11. Compound 11 suffers loss of alcohol followed by tautomerization to give 4-hydroxy-2-methylquinoline 7. An alternative to the proposed formation of 10 is ejection of alcohol from 6 furnishing ketene 13, which then undergoes 671 electrocyclization to provide 12. 

This information coupled with the proposed mechanism of the Conrad-Limpach reaction, reasonably lead to the below proposed mechanisms. Conjugate addition of aniline and elimination of alcohol provides the P-anilinoacrylate 14, which upon heating to 180-320 °C gives species, like 34a,b, which undergo 6n-electrocyclization to 35 or 36, respectively. Loss of ethanol from 36 gives 35 and tautomerization provides 4-... 

On the basis of the dissociation constant values, it seems sensible to conclude that, in these moderately basic carbinolamines, the hydrogen atom of the hydroxyl group is suflQciently acid to be eliminated under the influence of an alkali and by its transfer to the nitrogen atom of the mesomeric anion, the formation of the amino-aldehyde form may result. Instead of the amino-aldehyde, however, the corresponding bimolecular ether (15a-c) can be obtained. " It can be concluded that the formation of the bimolecular ether (S l or 8 2 mechanism) and the formation of the amino-aldehyde (B-SeI or B-Se2 mechanism) are competitive reactions. It seems probable that where the first reaction can occur the latter one is pushed into the background. The triple tautomeric system postulated by Gadamer... 

Interconversion between two tautomeric structures can occur via discrete cationic or anionic intermediates (scheme 24, where T is an anion capable of reacting with a proton at a minimum of two distinct sites). Alternatively, interconversion can occur by simultaneous loss and gain of different protons (scheme 25, w here T has the same definition as in scheme 24). These mechanisms are well established for acyclic compounds, but they have been much less thoroughly investigated for heteroaromatic systems. The rate of interconversion of two tautomers is greatest when both of the alternative atoms to which the mobile proton can be attached arc hetero atoms, and isolation of the separate isomers is usually impossible in this case. If one of the alternative atoms involved in the tautomerization is carbon, the rate of interconversion is somewhat slower, but still fast. When both of the atoms in question are carbon, however, interconversion is... 

Methods of the first type have been used for both qualitative and quantitative investigation. An important limitation is that the rates of interconversion of the tautomeric forms must be small as compared with those of the test reaction (s). The method is further complicated since the test reactions are sometimes complex and it is difficult to be certain that only one tautomer is reacting. An even more fundamental objection is that much chemical evidence is based on incorrect reaction mechanisms. Thus, the formation of condensation products (30) with aldehydes has repeatedly been quoted as evidence for structures of type 31 and against type 32,. whereas if 31 does react with an aldehyde it must either first tautomerize to 32 or ionize to 33. 

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