Hydrocarbons aliphatic, oxidative substitution

The oxidation by Cr(VI) of aliphatic hydrocarbons containing a tertiary carbon atom has been studied by several groups of workers. Sager and Bradley showed that oxidation of triethylmethane yields triethylcarbinol as the primary product with a primary kinetic isotope effect of about 1.6 (later corrected by Wiberg and Foster to 3.1) for deuterium substitution at the tertiary C-H bond. Oxidations... 

Reactions of Ph" radicals (12h) formed at anodes yield styrene (30), biphenyl (31), p-terphenyl (32), insoluble hydrocarbon of high molecular weight and, in smaller amounts, benzene (33) as well as ethanol (19). 30 was the main product for substituted reagents 5q and 5r but for unsubstituted 5e only if the current efficiency, Teu was low. For higher Y i values 31 became the chief organic product. However, in contrast to aliphatic Grignard reagents, except methyl, the current efficiency was always much below 100%. In order to explain the above results the possibility of another route of anodic oxidation, different... 

The photoinduced oxidation with TCB is among the most selective C-H substitutions of aliphatic compounds. For example, oxidation of cyclohexane (7) with TCB in acetonitrile gave 8 as the sole product [14]. Many saturated acyclic hydrocarbons have been oxidized with moderate to good selectivity [14]. Oxidation of adaman-... 

Effect of Oxidants, Kharasch has shown that, in the presence of benzoyl or other organic peroxides, sulfuryl chloride selectively chlorinates the side chain and not the nucleus of alkyl-substituted benzene. The reaction, which is carried out in the dark, is also useful for the chlorination of aliphatic compounds such as acyclic hydrocarbons, cycloparaflSns, carboxylic acids, and their acid halides. ... 

Toluene. The oxidation of hydrocarbons having an aromatic nucleus and one or more side chains may be effected in the side chain without marked rupture of the ring itself, since each component behaves more or less as it would if it alone constituted the major part of the molecule. Thus, the ring component exhibits the characteristic stability of the aromatic compounds, and the aliphatic substituent shows the relatively greater ease of oxidation of the aliphatic hydrocarbons. Under specific conditions, oxidation of such substituted aromatic hydrocarbons may be controlled to give satisfactory yields of the side-chain products viz., toluene may be oxidized to benzaldehyde or benzoic acid o-xylene, to phthalic anhydride ethylbenzene, to benzoic acid etc. 

Organic aerosols formed by gas-phase photochemical reactions of hydrocarbons, ozone, and nitrogen oxides have been identified in both urban and rural atmospheres (Grosjean, 1977). Most of these species are di- or poly-functionally substituted alkane derivatives. These compounds include aliphatic organic nitrates (Grosjean and Friendlander, 1975), di-carboxylic acids (adipic and glutaric acids) (O Brien et al., 1975), carboxylic acids derived from aromatic hydrocarbons (benzoic and phenylacetic acids), polysubstituted phenols, and nitroaromatics from aromatic hydrocarbons (Kawamuraet al., 1985 Satsumakayashi et al., 1989, 1990). Some species that have been identified in ambient aerosol and are be-... 

Reduction of the double bond Pt>lynicri/.ation Nilroacctyicncs Ptdynitro aliphatic compounds Nitration of hydrocarbons Substitution of halogen Electrolytic methods Addition reaction Michael addition Diels-Alder addithm Oxidative dimerizatum a, to-Dinitroalkanes gem-Dinitroalkancs Iriniiromclhane (nitroform) derivatives Properties of nitroform Manufacture of nitroform... 

It is also used as a source material in the preparation of inorganic bromides. Hydrogen bromide serves as a catalyst in alkylation reactions. It has also been reportedly used in the controlled oxidation of aliphatic and ali-cyclic hydrocarbons to peroxides, ketones, and acids. In organic synthesis, hydrogen bromide is used to substitute bromine for aliphatic chlorine in the presence of aluminum catalyst. 

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