Aromatic Hydrocarbons and Aryl Halides

This test for the presence of an aromatic ring should be performed only on compounds that have been shown to be insoluble in concentrated sulfuric acid (Sec. 25.3). The test involves the Friedel-Crafts reaction (Sec. 15.2) between an aromatic compound and chloroform in the presence of anhydrous aluminum chloride as a catalyst. The colors produced in this reaction are often characteristic for certain aromatic compounds, whereas aliphatic compounds give little or no color with this test. Some typical examples are tabulated below. Often these colors change with time and ultimately yield brown-colored solutions. 

The chemistry of the test involves a series of alkylation reactions (Sec. 15.2) for benzene, the ultimate product is triphenylmethane (Eq. 25.32). 

The colors arise because species such as triphenylmethyl cations, (C HjljC, form and remain in the solution as their tetrachloroaluminate, AlCl4, salts ions of this sort are highly colored owing to the extensive delocalization of charge that is possible throughout the three aromatic rings. 

The test is significant if positive, but a negative test does not rule out an aromatic structure some compounds bearing electron-withdrawing groups are so unreactive that they do not readily undergo Friedel-Crafts alkylation reactions. 

Positive tests for aryl halides are difficult to obtain directly, and some of the best evidence for their presence involves indirect methods. Elemental analysis indicates the presence of halogen. If both the silver nitrate and sodium iodide-acetone tests are negative, the compound is most likely a vinyl or an aromatic halide, both of which are very unreactive toward silver nitrate and sodium iodide. Distinction between a vinyl and an aromatic halide can be made by means of the aluminum chloride-chloroform test. 

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Stilbenes, photocyclization of, 30, 1 StiUe reaction, 50, 1 Stobbe condensation, 6, 1 Substitution reactions using organocopper reagents, 22, 2 41, 2 Sugars, synthesis by glycosylation with sulfoxides and sulfinates, 64, 2 Sulfide reduction of nitroarenes, 20, 4 Sulfonation of aromatic hydrocarbons and aryl halides, 3, 4 Swem oxidation, 39, 3 53, 1... 

Aromatic hydrocarbons and aryl halides can be converted into sulfinic acids in yields averaging 80% if the reaction is carried out at low temperature, if, as in the Gattermann aldehyde synthesis, reaction is initiated by passing in dry hydrogen chloride, and if the tetrachloroaluminum sulfinate formed is decomposed, not by acid, but by alkali, and acid is used for the first time to decompose the alkali sulfinites thus formed.240 Aryl ethers give sulfinic acids even in the cold, but reaction readily proceeds further to give sulfoxides and sulfonium compounds 241... 

Two types of derivatives are used to characterize aromatic hydrocarbons and aryl halides. These are prepared by nitration (Eq. 25.33) and side[Pg.873]

Sulfonation with Sulfuric Acid and Sulfur Triozide. Various mechanisms for the reaction of aromatic hydrocarbons or aryl halides with sulfuric acid or with sulfur trioxide have been proposed. Since.the reaction is heterogeneous, it is not favorable for experimental study. Solvents that dissolve sulfuric acid or sulfur trioxide form addition compounds with the reagent hence any conclusion drawn from a homogene ous sulfonation might not be applicable to the ordinary sulfonation. One possibility is that an electrophilic reagent such as sulfur trioxide with its relatively positive sulfur atom or an ion such as HOaS" " in the case of sulfuric acid attacks the negative center of the polarized form of the hydrocarbon, as illustrated for benzene. 

Practically any aromatic hydrocarbon or aryl halide can be sulfonated if the proper conditions are chosen. As the compound becomes more complex, however, the tendency toward the production of by-products and mixtures of isomers is increased. It is usually difficult to prevent polysubstitution of a reactive hydrocarbon. For example, even when phenanthrene is sulfonated incompletely at room temperature, some disulfonic acids are formed. The sulfonation of anthracene follows such a complex course that the 1- and 2-sulfonic acid derivatives are made from the readily available derivatives of anthraquinone. The foUowii sections include comments.on the accessibility of the reaction products of the commonly available hydrocarbons and aryl halides. The examples cited and still others are listed in Tables I-XIII. 

The palladium(O) complex undergoes first an oxydative addition of the aryl halide. Then a substitution reaction of the halide anion by the amine occurs at the metal. The resulting amino-complex would lose the imine with simultaneous formation of an hydropalladium. A reductive elimination from this 18-electrons complex would give the aromatic hydrocarbon and regenerate at the same time the initial catalyst. 

Aroylation of an aromatic system by reaction with phthalic anhydride under Friedel-Crafts conditions yields the o-aroylbenzoic acid. These readily available compounds have characteristic melting points which make them useful as derivatives in the characterisation of aromatic hydrocarbons and of aryl halides (Section 9.6.3, p. 1238). 

A9.6.4.7 The Nordic Council of Ministers issued a report (Pederson et al, 1995) entitled Environmental Hazard Classification, that includes information on data collection and interpretation, as well as a section (5.2.8) entitled QSAR estimates of water solubility and acute aquatic toxicity . This section also discusses the estimation of physicochemical properties, including log Kow For the sake of classification purposes, estimation methods are recommended for prediction of minimum acute aquatic toxicity, for ...neutral, organic, non-reactive and non-ionizable compounds such as alcohols, ketones, ethers, alkyl, and aryl halides, and can also be used for aromatic hydrocarbons, halogenated aromatic and aliphatic hydrocarbons as well as sulphides and disulphides, as cited in an earlier OECD Guidance Document (OECD, 1995). The Nordic document also includes diskettes for a computerized application of some of these methods. 

In the preparation of hydrocarbons an alkyl, aryl, or aralkyl halide is mixed with an excess of an aromatic hydrocarbon, and anhydrous aluminum chloride is added in small portions. The reagents must be free from moisture. If the reactants are not liquid or the reaction is very vigorous, a solvent is used. Benzene, nitrobenzene, carbon disulfide, or o-dichlorobenzene may be employed as solvents. When polyhalides are used, more than one molecule of the hydrocarbon may react. For example, benzene with chloroform yields triphenylmethane, and benzene with carbon tetrachloride gives triphenylmethyl chloride ... 

DPA, rubrene, fluorene and other fluorescent aromatic hydrocarbons are reported to yield chemiluminescence when electrolyzed together with alkyl and aryl halides such as (6) or (7)... 

AROMATIC HYDROCARBONS Aromatic hydrocarbons may be prepared by the following methods 1. Wurtz - Fittig reaction. The interaction of an aryl halide, alkyl hahde and sodium gives a reasonable yield of an alkyl aryl hydrocarbon, for example ... 

Chemiluminescence also occurs during electrolysis of mixtures of DPACI2 99 and rubrene or perylene In the case of rubrene the chemiluminescence matches the fluorescence of the latter at the reduction potential of rubrene radical anion formation ( — 1.4 V) at —1.9 V, the reduction potential of DPA radical anion, a mixed emission is observed consisting of rubrene and DPA fluorescence. Similar results were obtained with the dibromide 100 and DPA and/or rubrene. An energy-transfer mechanism from excited DPA to rubrene could not be detected under the reaction conditions (see also 154>). There seems to be no explanation yet as to why, in mixtures of halides like DPACI2 and aromatic hydrocarbons, electrogenerated chemiluminescence always stems from that hydrocarbon which is most easily reduced. A great number of aryl and alkyl halides is reported to exhibit this type of rather efficient chemiluminescence 155>. 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

Organohalides (Figure 1.17) exhibit a wide range of physical and chemical properties. These compounds consist of halogen-substituted hydrocarbon molecules, each of which contains at least one atom of F, Cl, Br, or I. They may be saturated (alkyl halides), unsaturated (alkenyl halides), or aromatic (aryl halides). The most widely manufactured organohalide compounds are chlorinated hydrocarbons, many of which are regarded as environmental pollutants or hazardous wastes. 

Considering what was said about stabilization energies in our previous discussion of thermochemical mimics, we now turn to aryl halides. There are several conceptual approaches to their thermochemistry one can take. The first is to consider halogenated derivatives of benzene, then of naphthalene, then of the isomeric anthracene and phenan-threne, etc. This approach, perhaps more appropriate for a study of generally substituted aromatic hydrocarbons, is immediately thwarted. Although there are many appropriate derivatives of benzene worthy of discussion, thermochemical data on halogenated naphthalenes are limited to the isomeric 1- and 2-monosubstituted derivatives, and halogenated derivatives of other aromatics remain thermochemically unstudied. 

The reductive photodehalogenation of aryl halides has been actively investigated in recent years. Special attention has been given to (poly)halobenzenes and (poly)halo-biphenyls. The reactions are of interest in view of their mechanisms, and because of the importance of chlorinated aromatic hydrocarbons as environmental pollutants and the possibility of their photoinduced degradation. The photochemistry of aryl halides and related compounds in general14 and the photochemistry of polyhaloarenes in particular18 have been reviewed. 

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