Alkanes deuterated—

The fumarate pathway for the metabolism of alkanes under sulfate-reducing conditions was examined using fully deuterated hexadecane (Callaghan et al. 2006). Identification of the metabolites including labeled methylpentadecylsuccinate and 4-methyloctadecanoate... 

Warshel, Levitt, and Lifson derived a partially optimised consistent force field for amides and lactams (25). It is composed of an alkane part and an amide-part. The former was taken over from analogous earlier calculations for saturated hydrocarbons (17). The potential constants of the amide-part were optimised with the help of a large number of experimental frequencies (taken from TV-methylform amide, acetamide, iV-methylacetamide, and several deuterated species) as well as experimental geometry data for 7V-methylacet-amide. The resulting force field was used for the calculation of vibrational and conformational properties of 2-pyrrolidone, 2-piperidone and e-caprolactam. 

A very different neutrally charged complex for alkane activation has been reported recently and is shown in Scheme 34(A). The compound is a hydridoplatinum(II) complex bearing an anionic ligand based on the familiar nacnac-type, but with a pendant olefin moiety (97).This complex is extremely soluble in arenes and alkanes and activates C-H bonds in both types of hydrocarbons. This is indicated by deuterium incorporation from deuterated hydrocarbon into the substituents on the arene of the ligand and into the Pt hydride position (A A-d27, Scheme 34). The open site needed for hydrocarbon coordination at Pt(II) is created by olefin insertion instead of anion or solvent substitution (97). 

Rather large kH/kD isotope ratios (29) have been reported in model studies of dehydrocyclization using deuterated vs. normal alkanes, particularly when one considers the high temperatures being used, but the origin of these effects is difficult to sort out. In contrast to catalytic dehydrocyclization reactions, the dehydrocyclization reactions of the observable p-H-bridged cyclodecyl cations are much more amenable to mechanistic studies, albeit difficult because of the low temperatures involved. Examination of the dehydrocyclization transition... 

Further, a large number of examples with simple alkyl substituents [168, 171, 176-184], cyclic alkanes [185], aryl substituents [177, 186-192], olefmic substituents [78, 177, 193-196], deuterated compounds [172], thioether groups [171], ester groups [197], orthoesters [198, 199], acetals [168, 182, 200-204], silyl-protected alcohols [198, 205-211], aldehydes [212], different heterocycles [213-217], alkyl halides [218, 219] and aryl halides [192, 220-223] have been reported. A representative example is the reaction of 92, possessing a free hydroxyl group, an acetal and a propargylic ether, to 93 [224] (Scheme 1.40). 

The effect of steric hindrance on the rates and kinetic isotope effects for reactions of l-nitro-l-(4-nitrophenyl)alkanes and their deuterated analogues with two bicyclic guanidines of comparable basicity (l,5,7-triazabicyclo[4.4.0]dec-5-ene, TBD, and its 7-methyl derivative, MTBD) in THF has been studied. The results disagree with the notion that deuterium kinetic isotope effects are enhanced by steric hindrance, since for the reactions of MTBD with various carbon acids the KIEs decrease with steric hindrance in the carbon acid but the converse is true for reactions of TBD. 

Hydrodesulfurization of certain hydroxy-437 and methoxy-sub-stituted615 alkybenzo[6]thiophenes is a useful means of preparing some otherwise inaccessible alkyl-substituted phenols [e.g., Eq. (15)].015 Various p-methoxyphenylbenzo[6]thiophenes have been employed similarly to prepare the corresponding hydroxydiphenyl-alkanes.464 Catalytic hydrodesulfurization of a-alkyl-/ -(3-benzo[6]-thienyl)propionic acids affords a convenient method of preparing a,y-disubstituted y-phenylbutyric acids.636 Treatment of / -(3-benzo[6]thienyl)acrylic acid with Raney nickel alloy, sodium meth-oxide, and deuterium oxide affords the deuterated acid (366).667... 

Calculated and Measured Values of Quenching Cross Sections of Some Deuterated Alkane Molecules for Hg 6(3Pi) Atom1 -1... 

The pattern of apparent alkane losses from specifically deuterated oarboxylate ions is most easily rationalized by invoking a 1,2-elimination mechanism (see Equation 1)... 

Quantitation. Pristane and phytane concentrations (/xmol/kg bitumen) were obtained by integration of their peak areas and that of the deuterated C22 anteisoalkane (I, Table II) standard in the FID chromatograms. The concentration of the other compounds in the saturated hydrocarbon fraction were obtained by integration of appropriate peaks in mass chromatograms of m/z 57 (n-alkanes, standard), m/z 367 (extended hop-17(21)-enes), m/z 191 (hopanes), m/z 217 (steranes). Because of differences in yield of these ions for different classes of compounds the values for hop-17(21)-enes, steranes and hopanes are approximate. 

Under the same conditions, several types of hydrocarbon are also converted to fully deuterated compounds. The results are summarized in Table 1. Cydooctene was also transformed into fully deuterated cydooctene without a skeletal rearrangement. As shown in entries 2 and 3, saturated hydrocarbons have also been transformed into fully deuterated compounds. As described above, an interaction between allylic C-H bonds and palladium hydride induces the H-D exchange reaction for alkenes. H-D exchange in alkanes, however, cannot be explained in this way. Direct C-H activation without assistance from any functional group may be a route to the formation of fully deuterated alkanes. 

Fig. 35 Temperature dependence of lamellar spacing (upper half) and angle of chain tiltwith respect to the lamellar normal (lower half) for extended-chain crystals of end-deuterated alkane C216H385D49 grown from toluene solution at 70 °C. SAXS spectra were recorded during heating from 60 °C to the melting point. Data for heating at 1 °C/min (solid diamonds) and 6 °C/min (open squares) are shown for comparison (from [84] by permission of American Chemical Society)...

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