Interesting Dienes and Polyenes

Compounds with many n bonds are called polyenes. 

In the remainder of Chapter 16 we examine conjugated dienes, compounds having two double bonds joined by one o bond. Conjugated dienes are also called 1,3-dienes. 1,3-Butadiene (CH2=CH-CH=CH2) is the simplest conjugated diene. 

Three stereoisomers are possible for 1,3-dienes with alkyl groups bonded to each end carbon of the diene (RCH=CH-CH=CHR). 

Two possible conformations result from rotation around the C-C bond that joins the two double bonds. 

Keep in mind that stereoisomers are discrete molecules, whereas conformations interconvert. Three structures drawn for 2,4-hexadiene illustrate the differences between stereoisomers and conformations in a 1,3-diene  

---

Since then, the metathesis reaction has been extended to other types of alkenes, viz. substituted alkenes, dienes and polyenes, and to alkynes. Of special interest is the metathesis of cycloalkenes. This gives rise to a ring enlargement resulting in macrocyclic compounds and eventually poly-... 

Dienes and polyenes have been a subject of great interest due to their important role in biology, materials science and organic synthesis. The mechanism of vision involves cis-trans photoisomerization of 11 -civ-retinal, an aldehyde formed from a linear polyene. Moreover, this kind of molecule exhibits high linear and non-linear electrical and optical properties. Short polyenes are also involved in pericyclic reactions, one of the most important classes of organic reactions. 

Examples of the application of correlation analysis to diene and polyene data sets are considered below. Both data sets in which the diene or polyene is directly substituted and those in which a phenylene lies between the substituent and diene or polyene group have been considered. In that best of all possible worlds known only to Voltaire s Dr. Pangloss, all data sets have a sufficient number of substituents and cover a wide enough range of substituent electronic demand, steric effect and intermolecular forces to provide a clear, reliable description of structural effects on the property of interest. In the real world this is not often the case. We will therefore try to demonstrate how the maximum amount of information can be extracted from small data sets. 

Concerning special reactant gases used in Cl mass spectrometry of dienes and polyenes, some more recent results are also of interest. It is noted that the distinction of isomers bearing C—C double bonds using Cl mass spectrometry relies, in appropriate cases, on... 

Reduction of dienes and polyenes has attracted much attention since it is important from both practical and theoretical aspects. In these reactions the major interest is the selective reduction of a double bond in the presence of another. In general, saturation of all the multiple double bonds of nonaromatic compounds can be carried out with any of the catalysts which are suitable for low-pressure reductions or with some reducing chemicals. 

The photochemical reactivity of alkenes is also of great interest [1,2]. Studies in this area have led to an expansion of the synthetic utility of these substances. Typical photochemical reactions include cis-trans isomeriza-tions, inter- and intramolecular cycloadditions, photooxidations, and electrocyclic ring opening and closing of conjugated dienes and polyenes. Many of these photoreactions have thermal counterparts. In contrast,... 

We have already acknowledged our intent to use relevant estimation approaches to enthalpies of vaporization and sublimation to maximize the usefulness of the data available. That dienes and polyenes have multiple double bonds that are potentially hydrogenatable to the totally saturated aliphatic or alicyclic hydrocarbons allows the employment of two other assumptions. The first assumption argues that the enthalpy of hydrogenation, AHn measured in a nonpolar solvent is essentially equal to that which would be obtained in the gas phase. The second assumption, implicitly employing the first, legitimizes the use of estimation techniques and even molecular mechanics to derive the enthalpy of formation of the totally saturated species. From this last number, the enthalpy of formation of the unsaturated diene or polyene of interest can be derived by equation 3 and simple arithmetic. 

---