Benzenes reaction with alkanes

Bergman has also reported an example of C-H addition to a zirconium-nitrogen double bond. The complex Cp2Zr(NHR)Me loses methane to generate an imido complex that can either be trapped with THF or reacted with benzene (Eq. 19). No reactions with alkanes were reported [86]. 

In some cases POMs can oxygenate hydrocarbons. For example, the oxidation of alkanes and benzene by poly vanadate in CF3COOH to produce alkyl (phenyl) trifluoroacetates and ketones is stimulated by light [85]. In fact, the alkane and benzene reactions with the vanadate virtually do not proceed in the absence of light. On the other hand, ethylbenzene and toluene are rapidly oxidized in the dark reaction, even at 10 °C. 

The study of exothermic gas phase reactions of laser descried Ln ions with various hydrocarbons with Fourier transform mass spectrometry has shown that the single and double dehydrogenations and the formation of the corresponding LnR cation species takes place in all cases [50-53]. The reactions of Sc , T", La and Gd" with cyclohexane and cyclohexene to produce the benzene derivatives Ln (QH5), which account for more than 99% of the total product distribution [51, 53]. The reaction of the scandium primary product ion Sc CQH ) with cyclohexene gives the bis(benzene)-scandium ion. Pr" and Eu" indicate lower activity than Gd " and Sc " in reactions with alkanes [51]. 

The alkanephosphonic acid dichlorides obtained by these methods are converted with amines, with all reactions carried out in solvents such as acetone, benzene, or diethyl ether at 10°C with triethylamine as HC1 captor. The conversion runs quantitatively followed by a purification with the help of column chromatography with chloroform/methanol in a ratio of 9 1 as mobile phase. The alkanephosphonic acid bisdiethanolamides could be obtained as pure substances with alkane residues of C8, C10, C12, and Ci4. The N-(2-hydroxyethane) alkanephosphonic acid 0,0-diethanolamide esters were also prepared in high purity. The obtained surfactants are generally stable up to 100°C. Only the alkanephosphonic acid bismonomethylamides are decomposed beneath this temperature forming cyclic compounds. 

The other 60% of the alkyl groups for LAS detergents are made through linear a-olefins. n-Alkanes can be dehydrogenated to a-olefins, which then can undergo a Friedel-Crafts reaction with benzene as described above for the nonlinear olefins. Sulfonation and basification gives the LAS detergent. 

Arenes can also be cleaved with peroxyacetic acid831 and permanganate.636,832 Ru04 effectively oxidizes arenes to cleavage products with the use of a cooxidant such as NaT04. Violent reaction with benzene and immediate oxidation of several other aromatics such as triphenylmethane and tetralin834 take place, but oxidation products could not be isolated. Since alkanes are resistant to Ru04,... 

In connection with reactions where a solvent is required, it must be noted that all transformations promoted by chiral Mo catalysts may be carried out in toluene (in addition to benzene) or various alkanes (e.g., n-pentane) with equal efficiency (see below for specific examples). Moreover, although 5 mol % catalyst is typically used in our studies, 1-2 mol % loading often delivers equally efficient and selective transformations. 

The Friedel-Crafts sulfonylation of aromatics with alkane- and arenesulfonyl halides and anhydrides has been studied (Eq. 9) [23]. In the reaction of pentafluorobenzenesul-fonyl fluoride with pentafluorobenzene, decafluorodiphenyl sulfone is formed with deca-fluorodiphenyl [23c]. Certain phenylacetylenes react with SO2 and benzene in the presence of SbFs to form benzothiophene 5-oxide [24]. (Eq. 10). Sulfinyl fluoride reacts similarly with arenes under SbFs catalysis to give sulfoxides (Eq. 11) [25]. 

The montmorillonite promoted alkylation of benzene with long chain primary and secondary alcohols gave mixtures of the 1- 2- and 3-phenyl alkanes. No 1-phenyl products were obtained when secondary alcohols were used. Reaction with tertiary alcohols gave a single alkylated product in better than 95% yield after about a five minute reaction at 80°C (Eqn. 22.6). ... 

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