Alicyclic hydrocarbons reactions

The effect of adding large quantities of acetic acid to the medium is more complicated. The acceleration of the oxidation rate of isopropanol was ascribed initially to a shift of the esterification equilibrium to the right (reaction 29). However, RoCek found that acceleration by acetic acid occurs for oxidations which cannot involve a pre-equilibrium esterification, e.g. those of aliphatic and alicyclic hydrocarbons. The obvious alternative, i.e. that acetic acid combines with chromic acid, viz. 

The reactivity of hydrogens at various positions of aliphatic and alicyclic hydrocarbons and their derivatives in various reactions is successfully interpreted by the theoretical indices, Dr and /r, mentioned in Chap. 6. Most of the results obtained were reviewed in reference 16 and are not repeated here. 

As pointed out previously, controlled degradation reactions are very difficult with aliphatic or alicyclic hydrocarbons, and most of the relabeling work has been concentrated on aromatic reaction products. Procedures have been extensively described by Pines and co-workers (e.g., 97, 96, also 87, 89-98, 95, 98). For the present purpose, it suffices to note that the 14C contents of the methyl side-chains and the rings in aromatic reaction products are readily estimated by oxidation of the methyl to carboxyl, followed by decarboxylation, while ethyl side-chains may be oxidatively degraded one carbon atom at a time. Radiochemical assays may be made on CO2 either directly in a gas counter, or after conversion to barium carbonate, while other solid degradation intermediates (e.g., benzoic acid or the phthalic acids) may be either assayed directly as solids or burned to CO2. Liquids are best assayed after burning to CO2. 

Peroxyl radicals can undergo various reactions, e.g., hydrogen abstraction, isomerization, decay, and addition to a double bond. Chain propagation in oxidized aliphatic, alkyl-aromatic, alicyclic hydrocarbons, and olefins with weak C—H bonds near the double bond proceeds according to the following reaction as a limiting step of the chain process [2 15] ... 

Nitroalkanes can be formed from the direct nitration of aliphatic and alicyclic hydrocarbons with either nitric acid ° or nitrogen dioxide in the vapour phase at elevated temperature. These reactions have achieved industrial importance but are of no value for the synthesis of nitroalkanes on a laboratory scale, although experiments have been conducted on a small scale in sealed tubes. 

Hydroxylatiott. Tertiary C—H bonds of alicyclic hydrocarbons are oxidized to the corresponding alcohols by p-nitroperbenzoic acid. Unlike the oxidation with trifluoroperacetic acid (7, 281-282), the reaction occurs regioselectively and with practically complete retention of configuration, and thus is comparable to dry ozonation (6,440). 

Although aliphatic and alicyclic hydrocarbons react with most sul-fonating agents, the reactions are not suitable for the preparation of the pure sulfonic acids. " Certain olefins react with sulfur dioxide-dloxane complex to give olefinic sulfonic acids In this way, cyclohexene is converted to l-cyclohexene-3-sulfonic acid, whereas with concentrated sulfuric acid in a mixture of acetic acid and acetic anhydride the main product is 2-hydroxycyclohexanesuIfonic acld. 1-Propene-l-sulfonic acid is obtained in low yield by the action of oleum on n- or isopxopyl alcohol. ... 

With certain very important and interesting exceptions, alicyclic hydrocarbons undergo the same reactions as their open-chain analogs. 

The reactions of and recoil atoms with simple aliphatic and alicyclic hydrocarbons investigated in gaseous and liquid phase have been reviewed by St5ck-... 

The Freund reaction refers to the formation of alicyclic hydrocarbons by the reaction of sodium on open chain dihalo compounds. ... 

The alicyclic secondary alcohol, cycZohexanol, may be dehydrated by concentrated sulphuric acid or by 85 per cent, phosphoric acid to cyciohexene. It has a higher boiling point (82-83°) than amylene and therefore possesses some advantage over the latter in.the study of the reactions of unsaturated hydrocarbons. 

For a review of bridgehead reactivity in nucleophilic substitution reactions, sec Muller Marcda. in Olah Cage Hydrocarbons Wiley New York. 1990, pp. 189-217. For a review of reactions at bridgehead carbons, see Fort Schleycr Adv. Alicyclic Chem. 1966, /. 283-370. 

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