Toluene and derivs

More detailed description will be given under TOLUENE AND DERIVATIVES Refs 1) Clift Fedoroff, Vol t, Lefax, Inc (1942), Chap 5, pp 5 19 2) Urbariski 1... 

Di (methy lot) methy I benzene Di (methy lol )-phenylmethane or Di(methylol)-toluene and Derivatives... 

Dinitrcfclwenes. They a redescribed under TOLUENE and DERIVATIVES... 

Dimethoxy toluene and derivs 5 D1305 dinitrodimethoxytoluer.es 5 D1305 mononitrodimethoxytoluenes 5 D1305 trinitrodimethoxytoluenes 5 D1305... 

Diphenylmethylamines and derivs see Anilino-toluene and derivs 1 A438—A440... 

Di-Oil. One of the names for crude DNT (Dinitrotoluene), CHa-CgHgCNOg) which will be described under TOLUENE AND DERIVATIVES... 

Enthaplies of Solution, Enthalpies of Reaction of Organolanthanide Compounds with Iodine in Toluene, and Derived Bond Disruption... 

It is also to he noted that ortho and para substitution often occur together in the same molecule, so that the group R enters the para and also both the ortho positions thus both aniline and phenol on bromination readily give symmetric (2,4,6) tribromo-compounds (p. 165), while both toluene and phenol on nitration readily give the symmetric trinitro-derivatives (p. 170). 

Give benzoyl and toluene-/>-sulphonyl derivatives (Schotten-Baumann reaction) (p. 243) also benzene-sulphonyl derivatives. 

Benzene-sulphonylotion. Benzene-sulphonyl chloride, which can be used in place of toluene-/>-sulphonyl chloride, is liquid at room temperature and consequently reacts rapidly when the reaction mixture (as in 3(a)) is vigorously shaken. In general, however, the toluene-/>-sulphonyl derivatives crystallise even more readily than the benzene-sulphonyl analogues, and have lower solubilities and higher m.ps. 

C) Benzoyl and Toluene-sulphonyl Derivatives. Proceed as in (3) above, using benzoyl or toluene p-sulphonyl chlorides benzene"Sul-phonyl chloride can be similarly used (see 3 above). (M.ps., pp. 550 -551.)... 

Note. PRIMARY ALIPHATIC AMINES. The lower amines are gases or low-boiling liquids (b.ps. CHjNH, 7 CiHjNH, 17 CH,(CH2,>,NH 49 (CHg)jCHNHa, 34 ) but may be encountered in aqueous or alcoholic solution, or as their crystalline salts. They are best identified as their benzoyl, or toluene-/>-sulphonyl derivatives (c/. (C) above), and as their picrates when these are not too soluble. This applies also to benzylamine, CjHsCHjNH, b.p. 185 also to ethylenediamine, usually encountered as the hydrate, NHj (CHj)j NH2,HjO, b.p. 116 , for which a moderate excess of the reagent should be used to obtain the di-acyl derivative. (M.ps., pp. 55 55 )... 

Benzoyl and Toluene -sulphonyl derivatives. Proceed as in 3 (p 374)- benzene sulphonyl derivatives can be similarly prepared. 

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 ... 

Partial rate factors may be used to estimate product distributions in disubstituted benzene derivatives The reactivity of a particular position in o bromotoluene for example is given by the product of the partial rate factors for the corresponding position in toluene and bromobenzene On the basis of the partial rate factor data given here for Fnedel-Crafts acylation predict the major product of the reaction of o bromotoluene with acetyl chlonde and aluminum chloride... 

Large-scale recovery of light oil was commercialized in England, Germany, and the United States toward the end of the nineteenth century (151). Industrial coal-tar production dates from the earliest operation of coal-gas faciUties. The principal bulk commodities derived from coal tar are wood-preserving oils, road tars, industrial pitches, and coke. Naphthalene is obtained from tar oils by crystallization, tar acids are derived by extraction of tar oils with caustic, and tar bases by extraction with sulfuric acid. Coal tars generally contain less than 1% benzene and toluene, and may contain up to 1% xylene. The total U.S. production of BTX from coke-oven operations is insignificant compared to petroleum product consumptions. 

Benzene, toluene, and xylene are made mosdy from catalytic reforming of naphthas with units similar to those already discussed. As a gross mixture, these aromatics are the backbone of gasoline blending for high octane numbers. However, there are many chemicals derived from these same aromatics thus many aromatic petrochemicals have their beginning by selective extraction from naphtha or gas—oil reformate. Benzene and cyclohexane are responsible for products such as nylon and polyester fibers, polystyrene, epoxy resins (qv), phenolic resins (qv), and polyurethanes (see Fibers Styrene plastics Urethane POLYiffiRs). 

Table 9 is a summary of world toluene supply and demand for 1996. North America, Asia, and Western Europe dominated the world s toluene business ia 1996. The three regions together accounted for over 85% of world production, imports, exports, and actual consumption, respectively. North America led ia production and consumption, while Asia led ia imports and exports. Table 10 presents the world toluene supply and demand. The worldwide demand for toluene increased by 7% from 1993 to 1994 and from 1994 to 1995, consecutively, because of higher hydrodealkylation (HDA) and disproportionation (TDP) operations, plus strong demand for all other derivatives. Over 70% of toluene is derived from a single source, catalytic reformate. 

Petroleum-derived benzene is commercially produced by reforming and separation, thermal or catalytic dealkylation of toluene, and disproportionation. Benzene is also obtained from pyrolysis gasoline formed ia the steam cracking of olefins (35). 

Acetic acid (qv) can be produced synthetically (methanol carbonylation, acetaldehyde oxidation, butane/naphtha oxidation) or from natural sources (5). Oxygen is added to propylene to make acrolein, which is further oxidized to acryHc acid (see Acrylic acid and derivatives). An alternative method adds carbon monoxide and/or water to acetylene (6). Benzoic acid (qv) is made by oxidizing toluene in the presence of a cobalt catalyst (7). 

Processes for hydrogen gasification, hydrogen pyrolysis, or coking of coal usually produce Hquid co-products. The Hygas process produces about 6% Hquids as benzene, toluene, and xylene. Substitution of petroleum residuum for the coal-derived process oil has been used in studies of coal Hquefaction and offers promise as a lower cost technology (104). 

Benzene is a flammable liquid and its vapors are toxic and explosive. Low concentrations are dangerous on continued inhalation because benzene affects the blood forming function of the bone marrow and it is a cancirogen. Dermatitis may result from repeated skin contact. Alkyl derivatives such as toluene and xylenes are far less toxic and are, therefore, much safer than benzene for use in solvents. Some of the symptoms of benzene poisoning are dizziness, constriction of the chest, and tightening of the leg muscles. 

These esters were prepared from the phenol and the acid chloride, plus DMAP (or from the acid plus trifluoroacetic anhydride). Although the diisopropyl derivative can be cleaved with hot aqueous NaOH, the di-r-butyl derivatives could only be cleaved with NaOMe in a mixture of toluene and HMPA. The related... 

However, when the reaction was carried out in a mixture of ethylene glycol and toluene and followed by hydrolysis the 2-keto derivative 42 was obtained in 54% yield, presumably via the more stable ene-hydrazine intermediate 41. 

Benz[/]isoindole (125), recently prepared from the p-toluene-sulfonyl derivative (124), proved to be too unstable for isolation, but eould be trapped in solution as the Diels-Alder adduct (127). The corresponding 1-phenyl derivative (126) was also prepared and, aecording to spectral measurements, reacts with maleic anhydride to give the product (128) derived by additive substitution. This subsequently rearranged to the adduct (129). The same behavior is observed in the reaction of (126) with V-phenylmaleimide. This provides the first clear indication that substitution products from isoindole derivatives and dienophiles can be converted into the normal addition products. 

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