Conditions, alkane equivalences

If favourable crude oil inversion conditions are observed it is possible to calculate alkane equivalences based on either optimal salinity or PIT data. 

The conditions for hydrogenation of alkynes are similar to those employed for alkenes In the presence of finely divided platinum palladium nickel or rhodium two molar equivalents of hydrogen add to the triple bond of an alkyne to yield an alkane... 

In aqueous DMF, the reaction can be applied to the formation of C-C bonds in a solid-phase synthesis with resin-bound iodobenzoates (Eq. 6.33).80 The reaction proceeds smoothly and leads to moderate to high yield of product under mild conditions. The optimal conditions involve the use of 9 1 mixture of DMF-water. Parsons investigated the viability of the aqueous Heck reactions under superheated conditions.81 A series of aromatic halides were coupled with styrenes under these conditions. The reaction proceeded to approximately the same degree at 400°C as at 260°C. Some 1,2-substituted alkanes can be used as alkene equivalents for the high-temperature Heck-type reaction in water.82... 

The use of stronger acid conditions provides somewhat better synthetic yields of alkanes from alkynes. A useful method consists of treatment of the substrate with a combination of triethylsilane, aluminum chloride, and excess hydrogen chloride in dichloromethane.146 Thus, treatment of phenylacetylene with 5 equivalents of triethylsilane and 0.2 equivalents of aluminum chloride in this way at room temperature yields 50% of ethylbenzene after 1.5 hours. Diphenylacetylene gives a 50% yield of bibenzyl when treated with 97 equivalents of triethylsilane and 2.7 equivalents of aluminum chloride after 2.8 hours. Even 1-hexyne gives a mixture of 44% n -hexane and 7% methylpentane of undisclosed structure when treated with 10 equivalents of triethylsilane and 0.5 equivalent of aluminum chloride for 0.5 hour.146... 

Fig. 16.32 Alkane degradation under aerobic conditions, showing incorporation of oxygen from molecular oxygen into the aliphatic compound, producing a fatty acid. Fatty acids are oxidized further by p-oxidation [H] indicates reducing equivalents that are either required or formed in the reaction step. (Bouwer and Zender 1993)...

Under high-pressure conditions, volatile species, such as hydrogen, carbon dioxide, and in some cases olefins or alkanes, are accumulated on the anode surface, which may affect the product distribution [33,36]. An aqueous Kolbe electrolysis of an alkanoic acid (in the range C4-C6) tends to give higher yields of the Kolbe dimers when run at elevated pressure (100 kPa) than an equivalent experiment at atmospheric pressure. 

The retention index value represents the retention characteristics of that compound as being equivalent to the retention characteristics of a hypothetical normal alkane containing the "retention index divided by 100" equivalent carbon atoms. For example, C12H26 would have values of 1,200 and C13H28 would have a value 1,300. A compound that eluted under identical conditions between C12H26 and C13H28 would be represented by a numerical value between... 

Figure 2.22 Graphical measurement of Kovats retention index (/= lOOn ) on a column in the isothermal mode. The number of equivalent carbons n, is found from the logarithm of the adjusted retention time t of X. The chromatogram corresponds to the injection of a mixture of 4 n-alkanes and two aromatic hydrocarbons. The values in italics match the retention times given in seconds. By injecting periodically this mixture the modifications to the Kovats indexes of these hydrocarbons permits the following of the column s performance. The calculations for retention indexes imply that the measurements were effected under isothermal conditions. With temperature programming they yield good results to the condition to adopt an adjusted formula, though this entails a reduction in precision.

Crude oils were found to behave as an equivalent alkane as far as the attainment of optimum formulation was concerned. The equivalent alkane carbon number or EACN was then introduced to characterise pure hydrocarbons or mixtures [26]. The EACN of an oil phase is defined as the ACN of the alkane that results in the satisfaction of the correlation in the same conditions of surfactant, salinity, alcohol and temperature. EACN has been experimentally determined for n-alkanes mixtures, resulting in a linear mixing rule on a molar fraction basis, namely... 

The controlled oxygenation of alkanes, alkenes, and aromatic hydrocarbons is one of the most important technologies for the conversion of crude oil and natural gas to valuable commodity chemicals. Biomimetic studies of metalloporpltyrins have led to important advances in practical catalysis, especially with ruthenium porphyrins. Reaction of wj-CPBA, periodate, or iodosylbenzene with Ru(II)(TMP)(CO) produced RuCVIjfTMPXOjj . Remarkably, Ru(VI)(TMP)(0)2 was found to catalyze the aerobic epoxidation of olefins under mild conditions. Thus, for a number of olefins including cyclooctene, norbomene, cis-, and trans- -methyl styrene 16-45 equivalents of epoxide were... 

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