Functional groups, classification reactions

Skill 29.1 Identify the functional group classification and nomenclature of organic compounds and the general characteristics and reactions of each group. 

A wider variety of reaction types involving reactions at bonds to oxygen atom bearing functional groups was investigated by the same kind of methodology [30]. Reaction classification is an essential step in knowledge extraction from reaction databases. This topic is discussed in Section 10.3.1 of this book. 

Compendium of Organic Synthetic Methods, Vo/ume 9 contains both functional group transformations and carbon-carbon bond forming reactions from the literature appearing in the years 1993,1994 and 1995. The classification schemes used for volumes 6-8 have been continued. Difunctional compounds appear in Chapter 16. The experienced user of the Compendium will require no special insructions for the use of Volume 9. Author citations and the Author Index have been continued as in Volumes 6-8. 

In addition to the classification of inhibitors according to their mechanisms of the action on oxidation, they can be classified into consumable and long-lived inhibitors. A consumable inhibitor is irreversibly consumed in its reactions with free radicals (R or RCV) or hydroperoxide. The stoichiometric coefficient of inhibition of such inhibitors is typically equal to one or two per inhibitory functional group. However, in some systems (for example RH 02 InH), an inhibitor can act cyclically so that, getting repeatedly regenerated, the... 

The above classification of detoxication reactions has been developed for the metabolism of synthetic pesticides In plants. However, the same reactions can occur with natural exocons, such as allelopathic compounds, that have the same functional groups as synthetic pesticides. Most allelopathic chemicals contain functional groups that can be conjugated by Phase II reactions. Thus, detoxication of allelopathic compounds can be expected to proceed by conjugation with the omission of Phase I reactions. The remainder of this review will be concerned with the conjugation of allelopathic compounds. 

It should not be taken for granted that all polymers that are defined as condensation polymers by Carothers classification will also be so defined by a consideration of the polymer chain structure. Some condensation polymers do not contain functional groups such as ester or amide in the polymer chain. An example is the phenol-formaldehyde polymers produced by the reaction of phenol (or substituted phenols) with formaldehyde... 

Classification by Chemical Constitution Classification of solvents according to chemical constitntion allows certain qualitative predictions. In general, a compound dissolves far more easily in a solvent possessing related functional groups than in one of a completely different nature (see table 3.11). A proper choice of solvent, based on the knowledge of its chemical reactivity, helps to avoid undesired reactions between solute and solvent. 

The nature of the azo bond is such that only a very limited number of possible functional groups can be considered to have the necessary features to serve as starting materials for reductive methods of preparation. In a sense, the Bogo-slovskii reaction [17, 18] may be considered a reduction of a diazonium salt by copper(I) ions. However, because the reaction resembles the other condensations of diazonium salts, its classification among the condensation reactions seems appropriate. The direct reduction of azoxy compounds as such is of minor preparative importance except as a method of identification of an azoxy compound. However, in the various bimolecular reduction procedures of aromatic nitro compounds, it has been postulated that an azoxy intermediate forms in the course of the reaction. This intermediate azoxy compound is ultimately reduced to an azo compound. 

It is with logic of this kind — inferring chemical behavior from structural analogies —that much of organic chemistry can be understood. There are other logical classification schemes, however, and one of these depends more on types of reactions than on functional groups. 

The rationale of classification by reaction types is that different functional groups may show the same kinds of reactions. Thus, as we have just seen, alcohols, carboxylic acids, and amines all can accept a proton from a suitably strong acid. Fortunately, there are very few different types of organic reactions — at least as far as the overall result that they produce. The most important are acid-base, substitution, addition, elimination, and rearrangement reactions. Some examples of these are given below, and you should understand that these are descriptive of the overall chemical change and nothing is implied as to how or why the reaction occurs (also see Section 1-11). 

Classification and Organization of Reactions Forming Difunctional Compounds. This chapter considers all possible difunctional compounds formed from the groups acetylene, carboxylic acid, alcohol, thiol, aldehyde, amide, amine, ester, ether, epoxide, thioether, halide, ketone, nitrile, and olefin. Reactions that form difunctional compounds are classified into sections on the basis of the two functional groups of the product. The relative positions... 

Upon reaction with an adsorptive in aqueous solution (which then becomes an adsorbate), surface functional groups can engage in adsorption complexes, which are immobilized molecular entities comprising the adsorbate and the surface functional group to which it is bound closely [18]. A further classification of adsorption complexes can be made into inner-sphere and outer-sphere surface complexes [19]. An inner-sphere surface complex has no water molecule interposed between the surface functional group and the small ion or molecule it binds, whereas an outer-sphere surface complex has at least one such interposed water molecule. Outer-sphere surface complexes always contain solvated adsorbate ions or molecules. Ions adsorbed in surface complexes are to be distinguished from those adsorbed in the diffuse layer [18] because the former species remain immobilized on a clay mineral surface over time scales that are long when compared, e.g., with the 4-10 ps required for a diffusive step by a solvated free ion in aqueous solution [20]. Outer-sphere surface complexes formed in the interlayers of montmorillonite by Ca2+ or Mg2+ are immobile on the molecular time scale... 

Since classification schemes tend to be rather boring, a few words are necessary to explain why this Section has been included. In the first place, the philosophy behind the synthetic use of organic redox processes in which electrons are transferred stoichiometrically is entirely different from that used in conventional synthesis. There is a risk—and anyone who has dealt with the thankless task of propagating the virtues of organic electrosynthesis can attest to it—that a redox reaction is only considered to be a way of transforming diverse functional groups into each other. This is not so ... 

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