SATURATED HYDROCARBONES – alkanes and cycloalkanes RADICAL REACTION Sulfochloration R – H + Cl2 + SO2 R – SO2Cl iniciation propagation Pay attention for inhibitors of radical reactions! They are able to stop reaction of propagation. Oxygen, for instance, is forming with radicals peroxyalkyl radical (which is less reactive) SATURATED HYDROCARBONES – alkanes and cycloalkanes Sulfoxidation R – H + SO2 + O2 R - SO3H alkaneperoxysulfonic acid alkanesulfonylperoxid radical iniciation propagation SATURATED HYDROCARBONES – alkanes and cycloalkanes Autoxidation R – CH2 - R + O2 R – CO – R + ( 2 R - CHO ) iniciation propagation termination SATURATED HYDROCARBONES – alkanes and cycloalkanes Autoxidation R – CH2 - R + O2 R – CO – R + ( 2 R - CHO ) Practical presentations Production of industrial products working up of isopropylbenzene (kumene) SATURATED HYDROCARBONES – alkanes and cycloalkanes Nitration - nitrogen oxides , diluted nitric acid (400o C) R – NO2 Reaction is accompanied by bonds C-C splitting The source of reagents for nitration is a mixture of nitrogen oxides Burning iniciation propagation source for further chain reactions SATURATED HYDROCARBONES – alkanes and cycloalkanes Radical reactions in atmosphere ozone when decomposes is protecting the earth against UV-light – radiation is transferred to heat hn ozonosphere – 25 km over surface of earth Freones – hydrocarbones with bond chlorine and fluorine (application in cooling systems, inert solvents, spray medium) iniciation propagation Decomposition of freone Crutzen, Molina, Rowland (1995 NP) SATURATED HYDROCARBONES – alkanes and cycloalkanes CRACKING - C-C bonds splitting DHC-C = 346 kJ/mol TERMINATION recombination – formation of smaller molecules than before cracking disproportionation HYDROCRACK (250 – 450o C + catalyst + H2 + pressure) 700 – 900o C SATURATED HYDROCARBONES – alkanes and cycloalkanes The source of saturated and nonsatureted hydrocarbons, aromates and compounds containing sulfur and nitrogen compounds are earth gas and oil Boiling point o C Number of carbon atoms Application under 30 2 - 4 Gassous components - heating 30 - 180 4 - 9 Gasoline - engines 160 - 230 8 - 16 Kerosene – heating, engines 200 - 320 10 - 18 Fuel oil – diesel engines 300 – 450 16 – 30 Heavy oil- heating higher Vax, asphalt , koke Oktano number: heptane 0 isooktan (2,2,4-trimethylpentan) 100 Ecologie of hydrocarbones STRUCTURE AND STEREOCHEMIE OF COMPOUDS WITH Csp3 Carbon atom in sp3 hybrid state (picture) Two carbon atoms in sp3 state, Fischer projection, perspektive projection, mutual transformation Configuration – Cahn, Ingold, Prelog rules for priority of substituents STRUCTURE AND STEREOCHEMIE OF COMPOUDS WITH Csp3 Cahn, Ingold, Prelog – rules for priority assesment of substituents (groups) 1 The higher proton number, the higher priority 2 When two atoms have the same proton numbers (isotopes), higher priority owns the atom with higher mass 3 When we are not able decide about priority applying the two rules above, we must compare proton numbers at neighbouring more distant atoms (at the second atoms from the stereogenic centrum) , and when we are not successful we must continue to the third and further atoms. 4 Atoms bound with multiple bonds are evaluated as the atom would be multiply bound by a single bond