Article No : a13_227 Hydrocarbons KARL GRIESBAUM, Universit€at Karlsruhe (TH), Karlsruhe, Federal Republic of Germany ARNO BEHR, Henkel KGaA, Dusseldorf,€ Federal Republic of Germany DIETER BIEDENKAPP, BASF Aktiengesellschaft, Ludwigshafen, Federal Republic of Germany HEINZ-WERNER VOGES, Huls€ Aktiengesellschaft, Marl, Federal Republic of Germany DOROTHEA GARBE, Haarmann & Reimer GmbH, Holzminden, Federal Republic of Germany CHRISTIAN PAETZ, Bayer AG, Leverkusen, Federal Republic of Germany GERD COLLIN, Ruttgerswerke€ AG, Duisburg, Federal Republic of Germany DIETER MAYER, Hoechst Aktiengesellschaft, Frankfurt, Federal Republic of Germany HARTMUT Ho€KE, Ruttgerswerke€ AG, Castrop-Rauxel, Federal Republic of Germany 1. Saturated Hydrocarbons ............ 134 3.7. Cumene ......................... 163 1.1. Physical Properties ................ 134 3.8. Diisopropylbenzenes ............... 164 1.2. Chemical Properties ............... 134 3.9. Cymenes; C4- and C5-Alkylaromatic 1.3. Production ....................... 134 Compounds ...................... 165 1.3.1. From Natural Gas and Petroleum . .... 135 3.10. Monoalkylbenzenes with Alkyl Groups 1.3.2. From Coal and Coal-Derived Products . 138 >C10 ........................... 166 1.3.3. By Synthesis and by Conversion of other 3.11. Diphenylmethane .................. 167 Hydrocarbons . .................. 139 4. Biphenyls and Polyphenyls .......... 168 1.4. Uses ............................ 140 4.1. Biphenyl......................... 168 1.5. Individual Saturated Hydrocarbons ... 142 4.2. Terphenyls....................... 171 2. Olefins .......................... 144 4.3. Polyphenyls ...................... 172 2.1. Monoolefins ...................... 144 5. Hydrocarbons from Coal Tar ........ 172 2.1.1. Properties . ...................... 145 5.1. Acenaphthene .................... 172 2.1.2. Production of Higher Olefins . ......... 145 5.2. Indene .......................... 174 2.1.2.1. Production from Paraffins . ......... 146 5.3. Fluorene......................... 175 2.1.2.2. Oligomerization of Lower Olefins . .... 149 5.4. Fluoranthene ..................... 176 2.1.3. Uses of Higher Olefins. ............. 154 5.5. Phenanthrene..................... 177 2.1.4. Economic Aspects of Higher Olefins .... 157 5.6. Pyrene .......................... 178 2.2. Dienes and Polyenes................ 157 6. Toxicology and Occupational Health ... 179 2.2.1. Low Molecular Mass 1,3-Dienes . .... 157 6.1. Alkanes ......................... 179 2.2.2. Synthesis of Dienes and Polyenes by 6.2. Alkenes ......................... 180 Oligomerization. .................. 158 6.3. Alkylbenzenes .................... 180 2.2.3. Synthesis of Dienes and Polyenes by 6.4. Biphenyls and Polyphenyls .......... 181 Metathesis. ...................... 159 6.5. Hydrocarbons from Coal Tar ........ 181 3. Alkylbenzenes .................... 160 6.5.1. Biological Effects .................. 181 3.1. Trimethylbenzenes................. 160 6.5.1.1. Carcinogenicity and Mutagenicity . .... 181 3.2. Tetramethylbenzenes ............... 161 6.5.1.2. Mammalian Toxicity and Toxicokinetics . 182 3.3. Penta- and Hexamethylbenzene ....... 162 6.5.1.3. Ecotoxicology . .................. 182 3.4. Diethylbenzenes ................... 162 6.5.2. Safety Regulations.................. 182 3.5. Triethylbenzenes and More Highly References ....................... 182 Ethylated Benzenes ................ 162 3.6. Ethylmethylbenzenes (Ethyltoluenes)... 163 Ó 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/14356007.a13_227 134 Hydrocarbons Vol. 18 1. Saturated Hydrocarbons oxidation, sulfoxidation, halogenation, sulfochlor- ination, and nitration. Industrial ionic reactions of The class of saturated hydrocarbons comprises a saturated hydrocarbons are restricted to acid- myriad of individual compounds. A large number catalyzed processes with strong acids. Such reac- of the theoretically possible saturated hydrocar- tions are employed mainly in the processing of bons is known [1], although only a limited num- petroleum by catalytic cracking, isomerization, and ber of individual saturated hydrocarbons are used alkylation; they yield complex mixtures of products. as raw materials in the chemical industry. Other ionic reactions of saturated hydrocarbons can becarriedoutwith superacids(e.g., FSO3H–SbF5, HF – SbF5): the alkylation of alkanes by alkanes 1.1. Physical Properties [3], alkylation of benzene by alkanes [3], and ionic chlorination [5] and bromination [6] of alkanes have Saturated hydrocarbons are colorless nonpolar been explored, but are not used industrially (see also substances, immiscible with polar solvents, but ! Acylation and Alkylation). miscible with many nonpolar organic solvents. Reactions of saturated hydrocarbons, because Some physical properties are given in Table 1. of the lack of functional groups, are nonselective, The boiling points and, starting with C3, melting with respect to both the region of attack (regios- points of n-alkanes increase with increasing mo- electivity) and the number of reaction sites (de- lecular mass. At 20 C and atmospheric pressure, gree of substitution), unless the molecule pos- C1 to C4 n-alkanes are gases, C5 to C16 are liquid, sesses specific structural features, e.g., tertiary and from C17 solid. i-Alkanes do not display a hydrogen atoms. Such reactions frequently af- definite correlation between the number of car- ford mixtures of isomeric or structurally analo- bon atoms and their boiling- and melting points. gous compounds which can only be separated The boiling points of i-alkanes all are lower than with difficulty or not at all. those of the corresponding n-alkanes; this is also On the basis of free enthalpy of formation (see true for many of the melting points. Furthermore, Table 2) most of the saturated hydrocarbons are the boiling points of isomeric alkanes decrease thermodynamically unstable with respect to the with increasing degree of branching. The boiling elements carbon and hydrogen. They are, however, points and melting points of cycloalkanes are kinetically stable at ambient temperature. Thermal generally higher than those of n-alkanes having decomposition of saturated hydrocarbons proceeds the same number of carbon atoms (Table 1). stepwise by loss of hydrogen or hydrocarbon The density of the saturated hydrocarbons in fragments with concomitant formation of industri- the liquid state at 20 Cis<1 g/cm3 ; it varies ally useful unsaturated cracking products, such as from 0.6 g/cm3 for compounds with low carbon acetylene, olefins, or aromatic hydrocarbons. numbers to 0.8 g/cm3 for compounds with high On ignition, mixtures of saturated hydrocar- carbon numbers (Table 1). Additional physical bons and oxygen or air may lead to combustion or properties are compiled in Tables 2–5. explosion, depending on the ratio of hydrocarbon and oxygen. Such reactions can be initiated either by imposed ignition or, if the ignition tempera- 1.2. Chemical Properties ture of the mixture is exceeded, by self-ignition. These reactions are the basis for the use of Alkanes and cycloalkanes are saturated, nonpolar, hydrocarbons as heating- and engine fuel. Perti- and lack functional groups; such hydrocarbons can nent fuel properties of individual saturated hy- undergo reaction only after cleavage of CÀHor drocarbons are summarized in Table 4. CÀC bonds. Consequently, the scope of primary reaction steps is essentially limited to dehydroge- nation, substitution, and chain- or ring cleavage. 1.3. Production Saturated hydrocarbons cannot undergo addition reactions, which represent a versatile synthetic tool By far the largest amount of saturated hydrocar- for unsaturated hydrocarbons (see Chap. 2). Most bons is obtained from the natural sources natural industrial reactions involving saturated hydrocar- gas and petroleum, either by isolation or by bons are radical reactions, e.g., thermal cracking, suitable conversion reactions. Additional sources Vol. 18 Hydrocarbons 135 Table 1. Physical properties of saturated hydrocarbons [2] 20 Compound Empirical CAS registry mp, C bp, C h (20 C), r (20 C), nD formula number mPa Á s g/cm3 a Methane CH4 [74-82-8] À182.5 À161.5 a Ethane C2H6 [74-84-0] À183.27 À 88.6 a b Propane C3H8 [74-98-6] À187.69 À 42.1 0.5005 Cyclopropane C3H6 [75-19-4] À127.4 À 32.8 b b n-Butane C4H10 [106-97-8] À138.4 À 0.5 0.5788 1.3326 b a Cyclobutane C4H8 [287-23-0] À 90.7 12.5 0.6943 1.365 b 2-Methylpropane C4H10 [75-28-5] À159.6 À 11.7 0.5572 n-Pentane C5H12 [109-66-0] À129.7 36.1 0.234 0.62624 1.35748 Cyclopentane C5H10 [287-92-3] À 93.9 49.3 0.438 0.74538 1.40645 2-Methylbutane C5H12 [78-78-4] À159.9 27.9 0.224 0.61967 1.35373 b b 2,2-Dimethylpropane C5H12 [463-82-1] À 16.6 9.5 0.5910 1.342 n-Hexane C6H14 [110-54-3] À 95.3 68.7 0.3117 0.65937 1.37486 2-Methylpentane C6H14 [107-83-5] À153.7 60.3 0.65315 1.37145 3-Methylpentane C6H14 [96-14-0] 63.3 0.66431 1.37652 2,2-Dimethylbutane C6H14 [75-83-2] À 99.9 49.7 0.64916 1.36876 2,3-Dimethylbutane C6H14 [79-29-8] À128.5 58.0 0.66164 1.37495 n-Heptane C7H16 [142-82-5] À 90.6 98.4 0.4169 0.68376 1.38764 2-Methylhexane C7H16 [591-76-4] À118.3 90.1 0.67859 1.38485 3-Methylhexane C7H16 [589-34-4] 91.9 0.68713 1.38864 3-Ethylpentane C7H16 [617-78-7] À118.6 93.5 0.69816 1.39339 2,2-Dimethylpentane C7H16 [590-35-2] À123.8 79.2 0.67385 1.38215 2,3-Dimethylpentane C7H16 [565-59-3] 89.8 0.69508 1.39196 2,4-Dimethylpentane C7H16 [108-08-7] À119.2 80.5 0.67270 1.38145 d 3,3-Dimethylpentane C7H16 [562-49-2] À134.46 86.1 0.69327 1.39092 2,2,3-Trimethylbutane C7H16