W. F. Steck

Structure-activity relationships in sex attractants for north American noctuid moths

Sex attractants known for 145 species of noctuid moths have many common features both as to chemical constituents and to their relationships in blends. The great majority of constituents are straight-chain (Z)-alkenols, -alkenals, or -alkenyl acetates of even carbon number (10 through 16). The unsaturation is nonterminal in odd-numbered positions (5 through 11). In effective lures, these components are blended in specific ratios and the components in a sex pheromone or sex attractant blend are structurally related by “one-change” steps. This means that any blend component differs from one or more other components by a single structural alteration, such as a change in double bond position, or a change in carbon chain length, or a change in the oxygen function. For the few multicomponent systems known in detail, the central place in the “one-change” framework is occupied by the predominant blend component. Different patterns of occurrence of lure components occur in the subfamilies Acronictinae, Noctuinae, Hadeninae, Cuculliinae, Amphipyrinae, Heliothidinae, Plusiinae, Acontiinae, and Pantheinae, and some subfamilies are as yet without known lures. Some guiding principles for elucidation of blend compositions for unstudied species are presented; these guidelines can also be used in improvement of some synthetic blends of unsatisfactory quality.

Coumarins and alkaloids from cell cultures of Ruta graveolens

Abstract Cells of Ruta graveolens L., grown in continuous light in liquid medium produced the coumarins umbelliferone, scopoletin, psoralen, xanthotoxin, isopimpinellin, rutamarin and rutacultin (6,7-dimethoxy- 3-(1,1-dimethylallyl)coumarin), a new natural product. Four alkaloids were also identified: skimmianine, kokusaginine, 6-methoxydictamnine and edulinine (1-methyl-4-methoxy-3-[2,3-dihydroxy-3-methylbutyl]-2-quinolone).

Triunsaturated hydrocarbons, sex pheromone components ofCaenurgina erechtea.

Abstract(Z,Z,Z)-3,6,9-Eicosatriene and (Z,Z,Z)-3,6,9-heneicosatriene have been identified as components of the sex pheromone of the noctuid,Caenurgina erechtea (Cramer), the forage looper. Structural assignments were made on the basis of spectroscopic and chromatographic data and were confirmed by comparison with synthetic material. Flight tunnel behavioral studies demonstrated that either component, when tested individually, would elicit wing fanning responses in males; however, mixtures of the two components increased this response and were essential for initiation of upwind flight and landing. In field experiments, traps baited with either component alone captured few or no adult forage looper males while those baited with both components captured several target males.

Novel sex pheromone components from the fall cankerworm moth, Alsophila pometaria

A sex pheromone extract from fall cankerworm moths,Alsophila pometaria, attracted conspecific males in field tests. Four EAG-active components were isolated from the extract and identified by GC-MS, highfield PMR spectroscopy, and microchemical techniques asn-nonadecane (I), (Z,Z,Z)-3,6,9-nonadecatriene (II), (Z,Z,Z,E)-3,6,9,11-nonadecatetraene (III), and (Z,Z,Z,Z)-3,6,9,11-nonadecatetrane (IV). Studies of the behavioral responses of male moths in a flight tunnel to the isolated components showed II, III, and IV were the major components of the sex pheromone. No sex pheromone behavioral responses were observed for I.

Field trapping of diamondback mothPlutella xylostella using an improved four-component sex attractant blend

In addition to three known sex lure components [(Z)-11-hexadecenyl acetate, (Z)-11-hexadecenal, and (Z)-11-hexadecenol], (Z)-9-tetradecenyl acetate was field-proven as a trace coattractant for malePlutella xylostella, with an optimal content below 0.01% in blends. This potent four-component lure for diamondback males also attractedCrymodes devastator males, and in this respect is not different in its attractancy from virgin diamondback females. Replacement of (Z)-9-tetradecenyl acetate in the four component lure with (Z)-9-tetradecen-1-ol, at the level of 10% of the total lure mixture, did not alter its attractancy for diamondback males, but it did inhibit attraction ofCrymodes devastator. The status of biologically active components as possible sex pheromones or para-pheromones is discussed.

Formation of edulinine and furoquinoline alkaloids from quinoline derivatives by cell suspension cultures of Ruta graveolens

Abstract The formation of furoquinoline alkaloids and of edulinine, elaborated by cell suspension cultures of Ruta graveolens , was found to occur by way of 4-hydroxy-2-quinolone. Other substrates transformed to furoquinolines included 4-hydroxy- and 4-methoxy-3-(3-methyl-2-butenyl)-2-quinolone, known earlier as natural precursors in studies with whole plants. Involvement of dictamnine as a natural precursor of 8-methoxydictamnine (γ-fagarine) and skimmianine was proved using 14 C-labelled compounds. Edulinine in the cell suspensions was formed from such substrates as 4-hydroxy- N -methyl-2-quinolone, 4-hydroxy-3-(3-methyl-2-butenyl)- N -methyl-2-quinolone and its 4- methyl ether; this is probably the natural biosynthetic sequence. Changes in alkaloid yields were noted upon prolonged subculturing.

Metabolism of cinnamic acid in plants: Chlorogenic acid formation☆

Abstract Rapid, efficient synthesis of chlorogenic acid from cinnamate was observed in leaves of plants of several genera. Use of labelled cinnamate, p-coumarate and caffeate showed two pathways were operative in this synthesis in tobacco. Trapping experiments indicated the major route to be: cinnamic acid → p-coumaric acid → p-coumaroylquinic acid → chlorogenic acid, and the secondary route cinnamic acid → p-coumaric acid → caffeic acid → chlorogenic acid. The metabolism of chlorogenic acid is discussed.

Sex pheromone components of fall cankerworm moth,Alsophila pometaria : Synthesis and field trapping.

Abstract(Z,Z,Z,E)-3,6,9,11-Nonadecatetraene and (Z,Z,Z,Z)-3,6,9,11-nonadecatetraene, sex pheromone components ofAlsophila pometaria, were synthesized by stereoselective Wittig reactions and found to be spectroscopically and chromatographically identical to isolated natural material. Flight-tunnel bioassays and field-trapping experiments confirmed that the two tetraenes together with (Z,Z,Z)-3,6,9-nonadecatriene are sex pheromone components. While traps baited with either tetraene individually captured conspecific males in field-trapping experiments, addition of the triene, which captured no males by itself, to either tetraene resulted in synergistic responses.

Leaf furanocoumarins of Heracleum lanatum

Abstract Sphondin is the principal furanocoumarin of Heracleum lanatum leaves; pimpinellin, isopimpinellin, bergapten, xanthotoxin, isobergapten, psoralen and angelicin were also identified. At least eleven other furanocoumarins were present.

Synthesis of sex pheromone components of the forest tent caterpillar, Malacosoma disstria (Hubner) and of the western tent caterpillar, Malacosoma californicum (Packard).

All four geometrical isomers of 5,7-dodecadien-1-ol have been stereoselectively synthesized by using Wittig condensation reactions. (5 Z,7E)-5,7-Dodecadien-1-ol and its corresponding aldehyde are components of the sex pheromone of the forest tent caterpillar. (5 E,7 Z)-5,7-Dodecadienal is a component of the pheromone of the western tent caterpillar. These compounds have been successfully tested in the field.