Aromaticity classification

Heavy aromatic solvent naphtha Heavy aromatic solvent naphtha (petroleum) Petroleum distillates, intermediate catalytic cracked (Polyethyl) benzenes Solvent naphtha, heavy aromatic Solvent naphtha (petroleum), heavy aromatic Classification Petroleum hydrocarbon Definition Complex combination of hydrocarbons obtained from distillation of aromatic streams consists of predominantly C9-16 aromatic hydrocarbons... 

FIGURE 14.20 A flow chart of the hydrocarbon classification emphasizing the aromatic classification to be discussed next in the text. 

The official boundary between aromatic/anti-aromatic classification is a matter of convention, agreed upon between the users. One possibility is to consider A = 1/2 as the boundary of aromatic/anti-aromatic classification for the following reasons If structures with A = 0 and A < 0 c/o not exist, because they would be unstable, while a structure close to A = 1/2 appears to hover at the borderline between olefinic, aromatic, and antiaromatic classification", then the boundary A = 1/2 appears a plausible alternative choice. However, from a theoretical point of view, the case A = 0, which occurs for RE = 0, appears as a natural boundary between the aromatic and the anti-aromatic species. In the case of the compounds shown in Figure 2, which gradually change from aromatic to anti-aromatic, we see from Table 34 that RE for the compound which is in the middle of the list, cycloocta[c/e/ biphenylene, is close to zero, as one would like to be the case. Although anti-aromatic compounds are elusive and often hypothetical, it may become possible to have a truly anti-aromatic compound by forcing a non-planar... 

There are a total of eighteen different hydrocarbon series, of which the most common constituents of crude oil have been presented - the alkanes, cycloalkanes, and the arenes. The more recent classifications of hydrocarbons are based on a division of the hydrocarbons in three main groups alkanes, naphthanes and aromatics, along with the organic compounds containing the non-hydrocarbon atoms of sulphur, nitrogen and oxygen. 

A more general classification considers the phase of the total electronic wave function [13]. We have treated the case of cyclic polyenes in detail [28,48,49] and showed that for Hiickel systems the ground state may be considered as the combination of two Kekule structures. If the number of electron pairs in the system is odd, the ground state is the in-phase combination, and the system is aromatic. If the number of electron pairs is even (as in cyclobutadiene, pentalene, etc.), the ground state is the out-of-phase combination, and the system is antiaromatic. These ideas are in line with previous work on specific systems [40,50]. 

A more detailed classification of chemical reactions will give specifications on the mechanism of a reaction electrophilic aromatic substitution, nucleophilic aliphatic substitution, etc. Details on this mechanism can be included to various degrees thus, nucleophilic aliphatic substitutions can further be classified into Sf l and reactions. However, as reaction conditions such as a change in solvent can shift a mechanism from one type to another, such details are of interest in the discussion of reaction mechanism but less so in reaction classification. 

We will show here the classification procedure with a specific dataset [28]. A reaction center, the addition of a C-H bond to a C=C double bond, was chosen that comprised a variety of different reaction types such as Michael additions, Friedel-Crafts alkylation of aromatic compounds by alkenes, or photochemical reactions. We wanted to see whether these different reaction types can be discerned by this... 

The imides, primaiy and secondary nitro compounds, oximes and sulphon amides of Solubility Group III are weakly acidic nitrogen compounds they cannot be titrated satisfactorily with a standard alkaU nor do they exhibit the reactions characteristic of phenols. The neutral nitrogen compounds of Solubility Group VII include tertiary nitro compounds amides (simple and substituted) derivatives of aldehydes and ketones (hydrazones, semlcarb-azones, ete.) nitriles nitroso, azo, hydrazo and other Intermediate reduction products of aromatic nitro compounds. All the above nitrogen compounds, and also the sulphonamides of Solubility Group VII, respond, with few exceptions, to the same classification reactions (reduction and hydrolysis) and hence will be considered together. 

The classification of hydrocarbons as aliphatic or aromatic took place m the 1860s when It was already apparent that there was something special about benzene toluene and their derivatives Their molecular formulas (benzene is CgHg toluene is C7Hj ) indicate that like alkenes and alkynes they are unsaturated and should undergo addition reac tions Under conditions m which bromine for example reacts rapidly with alkenes and alkynes however benzene proved to be inert Benzene does react with Bi2 m the pres ence of iron(III) bromide as a catalyst but even then addition isn t observed Substitu tion occurs instead ... 

Classification of Substituents in Electrophilic Aromatic Substitution Reactions... 

The triaryknethane dyes are broadly classified into the triphenyknethanes (Cl 42000—43875), diphenylnaphthyknethanes (Cl 44000—44100), and miscellaneous triphenylmethane derivatives (Cl 44500—44535). The triphenyknethanes are classified further on the basis of substitution in the aromatic nuclei, as follows (/) diamino derivatives of triphenylmethane, ie, dyes of the malachite green series (Cl 42000—42175) (2) triamino derivatives of triphenylmethane, ie, dyes of the fuchsine, rosaniline, or magenta series (Cl 42500—42800) (J) aminohydroxy derivatives of triphenylmethane (Cl 43500—43570) and (4) hydroxy derivatives of triphenylmethane, ie, dyes of the rosoHc acid series (Cl 43800—43875). Monoaminotriphenyknethanes are known but they are not included in the classification because they have Httie value as dyes. 

Table 2. Classification of Food Flavors Depending on Perception of Main Aromatic Note ...

A classification based first on ion specificity, then on stmctural features has been suggested for the polyethers (7). Another method uses the presence of unsaturation or of aromatic groups in the molecular skeleton (8). In this review the compounds are classified based on the number of carbons in the backbone according to the numbering system proposed in reference 9. The carbon backbone or skeleton refers to the longest chain of contiguous carbons between the carboxyl group and the terminal carbon. 

Following the classification of Chapter 4.01, three classes will be considered, (a) Compounds isomeric with aromatic compounds (6), (7) and (8). The quaternary, non-aromatic salts (Scheme 7, Chapter 4.01) will be discussed only in connection with protonation studies which lead to the conclusion of their non-existence. The carbonyl derivatives (9), (10), (13) and (14) will also be included here because it is possible to write an aromatic tautomer for each one, (9 )-(14 ), even if it is energetically unfavoured, (b) Dihydro compounds. In this class not only pyrazolines (15), (16) and (17) but also pyrazolidinones (18) and pyrazolinediones like (1) are included, (c) Tetrahydro compounds. Besides the pyrazolidines (19), the pyrazolidinetriones (2) are included here. 

Saccharin does not comply with the normal 4n + 2)ir-electron rule for aromaticity, but in view of the fact that it has been shown earlier to have a degree of ir-electron delocalization through the sulfur atom, and for convenience of classification of its chemical reactions, it will be considered to be aromatic in the subsequent sections dealing with its chemistry. 

The selection rules for cycloaddition reactions can also be derived from consideration of the aromaticity of the transition state. The transition states for [2tc -f 2tc] and [4tc -1- 2tc] cycloadditions are depicted in Fig. 11.11. For the [4tc-1-2tc] suprafacial-suprafacial cycloaddition, the transition state is aromatic. For [2tc -F 2tc] cycloaddition, the suprafacial-suprafacial mode is antiaromatic, but the suprafacial-antarafacial mode is aromatic. In order to specify the topology of cycloaddition reactions, subscripts are added to the numerical classification. Thus, a Diels-Alder reaction is a [4tc -f 2 ] cycloaddition. The... 

Hydrocarbons are divided into two main classes aliphatic and aromatic. This classification dates from the nineteenth century, when organic chemistry was devoted almost entirely to the study of materials from natural sources, and terms were coined that reflected a substance s origin. Two sources were fats and oils, and the word aliphatic was derived from the Greek word aleiphar meaning ( fat ). Aromatic hydrocarbons, ine-spective of their- own odor, were typically obtained by chemical treatment of pleasantsmelling plant extracts. 

The use of light olefins, diolefins, and aromatic-based monomers for producing commercial polymers is dealt with in the last two chapters. Chapter 11 reviews the chemistry involved in the synthesis of polymers, their classification, and their general properties. This book does not discuss the kinetics of polymer reactions. More specialized polymer chemistry texts may be consulted for this purpose. 

The reactions of some aromatic metal carboxylates are on the borderline of classification as solid-state processes. While there is no evidence of liquefaction, rates of decomposition in the poorly crystallized or vitreous reactant obey kinetic expressions more characteristic of reactions proceeding in a homogeneous phase. 

In discussing base catalysis it will prove convenient to adopt, at the outset, a distinction first proposed by Bunnett and Garst22, who noted that the observed cases of catalysis in nucleophilic aromatic substitution could be broadly divided into two categories. The classification was in terms of the relative rates of the catalyzed and uncatalyzed reactions. Since all of the systems could be accommodated empirically by eqn. (4),... 

In any heterolytic reaction in which a new carbon-carbon bond is formed one carbon atoms attacks as a nucleophile and the other as an electrophile. The classification of a given reaction as nucleophilic or electrophilic is a matter of convention and is usually based on analogy. Although not discussed in this chapter, 11-12-11-28 and 12-14-12-19 are nucleophilic substitutions with respect to one reactant, though, following convention, we classify them with respect to the other. Similarly, all the reactions in this section (10-93-10-123) would be called electrophilic substitution (aromatic or aliphatic) if we were to consider the reagent as the substrate. 

Figure 18.2 Representative receiver operator curves to demonstrate the leave n out validation of K-PLS classification models (metabolite formed or not formed) derived with approximately 300 molecules and over 60 descriptors. The diagonal line represents random. The horizontal axis represents the percentage of false positives and the vertical axis the percentage of false negatives in each case. a. Al-dealkylation. b. O-dealkylation. c. Aromatic hydroxylation. d. Aliphatic hydroxylation. e. O-glucuronidation. f. O-sulfation. Data generated in collaboration with Dr. Mark Embrechts (Rensselaer Polytechnic Institute).

Most substances which appear in the examples of this chapter are analysed In Part Two and their enthalpy of decomposition determined experimentally. This is because most of them are considered hardly stable. This is one of the reasons for assigning no Tow risk in the suggested classifications. But it is also indisputable that criterion Cf overestimates the instability risk. It is the case for all aromatic compounds that are generally very stable. In the examples above, N-methylaniline, dichlorobenzene... 

The results obtained using this criterion are very close to reality. Two of the compounds that are known to be unstable and appear in this series, ie nitroaniline and ammonium nitrate, which have an expiosophoric group without necessarily being noted for being explosive, are classified medium risk . There are still two anomalies the far too severe classification for 1,2-dichiorobenzene, which is obviously due to the endothermic nature of the aromatic cycle Crt would be better to analyse 1,2-dichlorocyclohexane using the technique mentioned before) and on the other hand, the underestimated risk of ammonium dichromate, which is, incidentally, overestimated in the regulations as will be seen later. 

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