Alkanes and Related Compounds

Petroleum hydrocarbons are used as automotive fuels and as monomers for the production of a range of plastics. They provide the basis of the petrochemical industry and the halogenated derivatives, which are discussed in Part 2 of this chapter. 

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Table 9.10 Examples of microbial products produced from alkanes and related compounds. Ail the examples cited are the subject of patents.

IV. Oxidations of Alkanes and Related Compounds Involving Transition... 

CATALYSIS OF HYDROGEN-DEUTERIUM EXCHANGE IN ALKANES AND RELATED COMPOUNDS... 

OXIDATIONS OF ALKANES AND RELATED COMPOUNDS INVOLVING TRANSITION METAL COMPOUNDS... 

Kinetic data for H + CH4 and H + QHg have been critically analyzed [9, 50] and Tsang has reviewed H + CsHg [56] and H + isobutane [57]. Kerr and Moss [49] list uncritically Arrhenius parameters for a wide range of alkanes and related compounds. 

Figure 1.15 shows the product profiles for the mixture containing 2.5, 140 and 357.5 Torr of cyclohexane, H2 and O2 at 753 K. The results are typical of the quality of data obtained not only from cyclohexane but alkanes and related compounds in general. Primary and secondary products may be characterized from the shape of the profiles. Cyclohexane, 7-oxabi-cyclo(2,2,l)heptane (1,4 cyclohexane oxide), 1,2 epoxycyclohexane, CH2=CHCH2CH2CH2CH0 (hex-5-en-l-al), buta-1,3-diene and possible... 

Considerable interest arose during the 1970 s and 1980 s in the use of micro-organisms to produce useful fatty adds and related compounds from hydrocarbons derived from the petroleum industry. During this period, a large number of patents were granted in Europe, USA and Japan protecting processes leading to the production of alkanols, alkyl oxides, ketones, alkanoic adds, alkane dioic acids and surfactants from hydrocarbons. Many of these processes involved the use of bacteria and yeasts associated with hydrocarbon catabolism. 

PART 3 ALKANES, CYCLOALKANES AND RELATED COMPOUNDS WITH CHLORINE, BROMINE, OR IODINE SUBSTITUENTS... 

SEC-RI/UV has also been used to analyse some 26 thioorganotin compounds, organotin carboxylates and chlorides, essentially PVC stabilisers, and some of their main by-products and related compounds (thioesters and dithioesters, n-alkanes) [803]. Not all organotin chlorides were stable in the adopted analysis conditions. N, Ai -ethylene-bis-stearamide and -oleamide in common plastics (ABS, SAN, PUR, LDPE, PA6.6) can be analysed by SEC after derivatisation with trifluo-roacetic anhydride. SEC analysis of fatty alcohol ethoxy-lates (FAE), used as nonionic surfactants, has also been described [759]. 

Additives and a Database for H Abstraction by HO2 from Alkanes, Aromatics and Related Compounds. Combust. Flame, 129 365-377,2002. 

Treatment of diethyl malonate and related compounds with 1,2-dihaloethane in the presence of base constitutes a classical method of cyclopropane synthesis296"300. The reaction can be conveniently carried out under PTC conditions. An improved method utilizing solid-liquid phase transfer catalysis has been reported298. The reaction of dimethyl or diethyl malonate with 1,2-dibromoalkanes except for 1,2-dibromethane tends to give only low yields of 2-alkylcyclopropane-l, 1-dicarboxylic esters. By the use of di-tm-butyl malonate, their preparations in satisfactory yields are realized (equation 134)297. The 2-alkylcyclopropane derivatives are also obtained from the reaction of dimethyl malonate and cyclic sulfates derived from alkane-1,2-diols (equation 135)301. Asymmetric synthesis... 

Not only alkenes and arenes but also other types of electron-rich compound can be oxidized by oxygen. Most organometallic reagents react with air, whereby either alkanes are formed by dimerization of the metal-bound alkyl groups (cuprates often react this way [80]) or peroxides or alcohols are formed [81, 82]. The alcohols result from disproportionation or reduction of the peroxides. Similarly, enolates, metalated nitriles, phenolates, enamines, and related compounds with nucleophilic carbon can react with oxygen by intermediate formation of carbon-centered radicals to yield dimers (Section 5.4.6 [83, 84]), peroxides, or alcohols. The oxidation of many organic compounds by air will, therefore, often proceed faster in the presence of bases (Scheme 3.21). 

Simple alkenes, alkadienes, and related compounds Alkanes Conclusions References... 

A green fluorescent protein-based Pseudomonas fluorescens strain biosensor was constructed and characterized for its potential to measure benzene, toluene, ethylbenzene, and related compounds in aqueous solutions. The biosensor is based on a plasmid carrying the toluene-benzene transcriptional activator (Stiner and Halverson, 2002). Another microbial whole-cell biosensor, using Escherichia coli with the promoter luciferase luxAB gene, was developed for the determination of water-dissolved linear alkanes by luminescence (Sticher et al., 1997). The biosensor has been used to detect the bioavailable concentration of alkanes in heating oil-contaminated ground-water samples. 

Acid-Catalyzed Reactions and Rearrangements of Alkanes, Cycloalkanes, and Related Compounds... 

R. C. Wilhoit, B. J. Zwolinski G. K. Estok, G. B. Mahoney, and S. M. Dregne, Handbook of Vapor Pressures and Heats of Vaporization of Hydrocarbons and Related Compounds, Thermodynamics Research Center, Dept, of Chemistry, College Station, Texas, Texas A M University, 1971. Includes table of AHy p(29S) and Ai7vap(b.p.) for many hydrocarbons, including alkanes and cycloalkanes. 

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