Polyene hydrocarbons

Millar, J. G. (2000). Polyene hydrocarbons and epoxides a second major class of lepidopteran sex attractant pheromones. Annual Review of Entomology 45 ... 

Two general classes of pheromone compound have been identified in moths, and these have some broad, although not uniform, associations with certain taxa. The polyene hydrocarbons and epoxides of various chain lengths are pheromones found in some subfamilies of the Geometridae and Noctuidae, and in the Arctiidae and Lymantridae (Millar, 2000). These compounds are probably derived from dietary Unoleic and linolenic acids. The other major class of pheromone compounds includes acetate, alcohols, and aldehydes, which are found in the Tortrici-dae, Pyralidae, Gelechiidae, Sessiidae, and Noctuidae. This class of compounds is derived from the insect s fatty acid synthesis pathway, with enzymatic modifications discussed above. Both classes of pheromone are broadly represented in the Noctuidae but are typically found in different subfamilies (Am et al., 1992,2003). 

Examples are the sulfonating of polyethylene film with chloro-sulfonic acid (60) the sulfonating of sheets of phenolformaldehyde resin (77) the treatment of a film consisting of polystyrene and polyvinylchloride with concentrated sulfuric acid (4) the sulfonating of films consisting of aliphatic vinylpolymers with chlorosulfonic acid (125) the sulfonating of copolymers of a monovinyl- and a polyvinyl compound (30). Also are used copolymers of aromatic monovinyl-compounds and linear aliphatic polyene hydrocarbons (3) copolymers of an unsaturated aromatic compound and an unsaturated aliphatic compound (76), and of reaction products of poly olefines and partially polymerized styrene (173). 

Polyene hydrocarbons, epoxides, and related compounds as components of lepidopteran pheromone blends... 

Subfamily, genus, species Polyene hydrocarbons Polyene epoxides Aldehydes Other References... 

Table 18.2 Polyene hydrocarbons, epoxides, and related compounds known or suspected as sex pheromones for geometrid moths. Compounds in bold have been found in pheromone gland extracts or aeration extracts and have been shown to be active in behavioral bioassays or field trials, compounds in normal font have been found in pheromone gland or aeration extracts, compounds in italics have been shown to attract males infield screening trials, and underlined compounds have been shown to be antagonistic.

J. H. (1987). Polyenic hydrocarbons as sex attractants for geometrids and amatids (Lepidoptera) found by field screening in Hungary. Z. Naturforsch., 42c,... 

Szocs, G Toth, M., Francke, W Francke, S. and Plass, E. (1996). Homologous polyenic hydrocarbons in the sex pheromones of winter geometrids (Lepidoptera). Abstracts o f the 13th Annual Meeting, International Society for Chemical Ecology, Prague, 18-22 August, 1996 p. 178. 

Identification of polyenic hydrocarbons from the northern winter moth, Operophtera fagata, and development of a species specific lure for pheromone traps. Chemoecology, 14, 53-58. 

Very recently, polyenic hydrocarbons were found as a new class of sex pheromones in the family of Geometridae (Lepidoptera) 206>207>. From this class (3Z,6Z,9Z)-... 

Strong arguments have been presented by Honig and co-workers (48,88) favoring identification of the 280-run band as due to the Ag state (53,89). Such a state has been well established by Zechmeister (90) in polyene hydrocarbons, where it is allowed in cis, but not in trans isomers. Although this selection rule is... 

First, we will take up cyclopropyl group formation by the rearrangement of carbon skeletons via cationic intermediates encountered in various mono- and sesquiterpenes, and also examine the illudin biosynthesis where contraction of a cyclobutyl cation to a cyclopropane has been invoked. We will then discuss the head-to-head condensation of isoprenoid alcohols at the C15 or C20 level to generate the cyclopropyl intermediates, presqualene pyrophosphate and prephytoene pyrophosphate, on the way to the C30 and C40 polyene hydrocarbons, squalene and phytoene respectively. Conversion of 2,3-oxidosqualene via common intermediate protosterol cation to cycloartenol or lanosterol represents an important pathway in which the angular methyl group participates in the three-membered ring formation. The cyclopropanation outcome of this process has been carefully studied. 

In theoretical interpretations of their electronic [Gouterman (85), Simpson (160), Weiss (199)] and pmr spectra [Jackman (105)] porphyrins have often been treated as cyclic polyene hydrocarbons, and it has recently been demonstrated that the (16)-annulene n dianion (which has 18 n electrons, is planar and aromatic) does indeed perfectly reproduce the spectra of porphyrin species with D,m symmetry [Oth (137)]. The analogy between aromatic hydrocarbons and the porphyrins stands on solid experimental and theoretical ground, and redox potentials together with any coupling constants from esr experiments should yield equally straightforward correlations. Zeeman effect measurements also support this conclusion [Malley (126)]. 

Allylstarch can be blended with lower alkyl itaconates in the ratio from 2 1 to 10 1 and then copolymerized with a variety of coating materials to enhance coating plasticity, drying, and hardening.1028 Allylstarch can be polymerized into insoluble products using either sulfur chloride or disulfur dichloride.1029 The reaction product of allylstarch with propylene oxide was utilized as a dispersant for petroleum emulsions.1030 Novel resinous materials have been obtained from adducts of unsaturated esters of dienophilic dioic acids and cyclic polyenic hydrocarbons with mono- and di-allyl starch.1031... 

Finally, we should mention the work on conjugated polyene hydrocarbons, which are not polyhexes, but have been counted" with a treatment similar to the one we just described for catafusene. The counting series for polyene hydrocarbons is... 

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