Hydrocarbons acyclic, isomerization

G.l.c. papers of interest include the classification of 22 acyclic monoterpenoid alcohols according to retention indexes, resolution of cyclic ketones [e.g. ( )-menthone, ( )-isomenthone] as diethyl (+)-tartrate acetals, and the use of lanthanide shift reagents to resolve non-terpenoid racemic epoxides.The occurrence and prevention of monoterpenoid hydrocarbon isomerization during silica gel chromatography has been examined and the separation of monoterpenoids and sesquiterpenoids by gel permeation chromatography is reported. Monoterpenoid hydrocarbons have been selectively extracted from essential oils using dimethylsilicone. ... 

Whereas the parent difluoro-vinylcyclopropane isomerizes to difluorocyclopentene under pyrolysis conditions, the corresponding alkyl compounds also lead to acyclic dienes. The activation energy for the difluoro-vinylcyclopropane isomerization is practically identical with that observed for the unsubstituted hydrocarbon [211, 212], If the alkyl group is oriented cis to the vinyl substituent, only dienes are isolated, and the process occurs at much lower, temperatures. Presumably these stereoisomers rearrange by a different mechanism (a 1,5-homodienyl hydrogen shift [213]). When the dichlorocyclopropane XVII is subjected to flash vacuum pyrolysis it isomerizes to 9,9-dichloro-bicyclo[5.3.0]dec-l(7)-ene [214],... 

Stereoisomers among the tetpenes are abundant and exceedingly important to the chemistry of the field. Stereochemical nomenclature therefore cannot be ignored in any complete scheme for systematizing terpene nomenclature for the present, however, the recommendations in this report provide only structural names for the simple acyclic, monocyclic, and bicyclic terpene hydrocarbons. Studies in various fields — e.g., steroids — on preferred methods of designating isomeric configurations are being made by other committees (1, 21, 25). 

In a formal way, the isomerization of acyclic hydrocarbons according to a cyclic mechanism may be represented as the succession of three consecutive steps ... 

While the first process is likely in the case of iridium, nickel, and cobalt, it should not be so easy on platinum, because of its competition with carbene-olefin isomerization (see Section III, Scheme 29). We believe that the only way of explaining why 1,2-dicarbenes may account for the hydrogenolysis of cyclic hydrocarbons (Scheme 34), but only for a minor part for the hydrocracking of acyclic hydrocarbons, is the competition, for the latter, between carbene-dicarbene formation and carbene-olefin isomerization. Carbene-olefin interconversions are unlikely in the case of cyclic hydrocarbons, since a dicarbene species cannot transform into a 1,1,2,3-tetraadsorbed species (l-carbene-2,3-olefin) and further into a 1,1,3-triadsorbed species without C-C rupturing. 

Diastereomers are also encountered in unsaturated acyclic compounds. When two C atoms are joined together by a double bond, all the remaining four single bonds to the two C atoms lie in the same plane as the C=C bond. If each of these two carbon atoms is bonded to a H atom and a hydrocarbon (alkyl) chain, the alkyl chains can be either on the same side of the C=C bond as each other or on opposite sides, and the resulting diastereomers (which used to be known as geometric isomers), shown in Fig. 2.2b, are termed cis and tram, respectively. Again, these diastereomers have different physical properties (see also Box 2.3). Optical isomerism is not possible about a C=C bond (the mirror images are superimposable). 

It is easy to list the various chemical and biological events influenced by flexibility, but unfortunately efforts to quantitate this structural attribute have been few. Mann analyzed the conformation of alkanes by modifying the number of gauche arrangements with Pitzer s steric partition function. Luisiranked alkanes on a. scale of conformational rigidity based on three-states rotational isomerism. Unfortunately, these schemes are designed for acyclic hydrocarbons and have no inherent capability to be adapted to heteroatomic molecules. 

K. Altenburg, Brennst.-Chem., 47, 100, 331 (1966). Dependence of the Boiling Point of Isomeric Hydrocarbons on the Form of the Molecules. I. Theoretical Basis and Applications to Isomeric Acyclic Alkanes. 

Reactions of acyclic hydrocarbons of various skeletal structures with CO in superacid media were recently studied by Yoneda and coworkers " as discussed in the previous section. Products obtained were only isomeric carboxylic acids with lower number of carbon atoms than the starting alkanes. Formation of the carboxylic acids were accounted by the reactions of parent, isomerized and fragmented alkyl cations with CO to form the oxocarbenium ion intermediates (Koch-Haaf reaction) followed by their quenching with water. No formylated products in these reactions have been identified. 

Investigations which concern the mechanisms of skeletal rearrangements of saturated hydrocarbons induced by heterogeneous transition metal catalysis are of great interest for industrial applications, e.g. for petroleum reforming processes The developments in this field were reviewed recently by Hejtmanek, and by Maire and Garin , who focussed on the probable reaction mechanisms which include bond-shift and cyclic mechanisms for the skeletal isomerization of acyclic alkanes. Scheme 1 summarizes the... 

Myosin see Muscle proteins Myrcene a triply unsaturated acyclic monoterpene hydrocarbon. M is a pleasant smelling liquid, M, 136.24, b.p.,2 55-56°C, p 0.8013, n 1.470. It is a component of many essential oils, and it is prepared for the perfumery industry by pyrolysis of p-pinene (from oil of turpentine). M. is al used commercially for the preparation of isomeric acyclic monoterpene alcohols and their acetates... 

The brief glinpse into the world of polycyclic hydrocarbons in Section 4-6 provides further examples of the divCTsity of the carbon frame in organic chemistry (see Table 2-4 for the number of possible isomeric acyclic alkanes). Wheneva- possible, such molecules adopt stractures in which cyclohexane rings exist in the chair configuration, for example, traws-decaUn. We constructed this molecule by fusing one cyclohexane ring to... 

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