Pheromones isolation

Bowers, W.S., Nault, L.R., Webb, R.E. and Dutky, S.R. (1972) Aphid alarm pheromone isolation, idenfication, synthesis. Nature 177, 1121-1122. 

Sex Pheromones Isolated and Identified from Tortricid Females... 

The synthesis of (2 5, 6R, 8 S)-2,8-dimethyl-l,7-dioxaspiro[5,5]undecane (868), one of the spiroacetal components of the pheromone isolated from the olive fruit fly, hinges on a dialkylation of tolylmethyl isocyanide with bromide 866. The bromide is obtained from 845b by sequential reduction of the olefin and ester followed by conversion of the resulting alcohol to bromide. Acidic hydrolysis of dialkylated product 867 provides the pheromone 868 directly... 

One enantiomer of a volatile pheromone isolated from urine of the male mouse of the species Mus musculus has been synthesized fi om (i ,7 )-tartaric acid via acetonide 88. Grignard addition and subsequent Wacker oxidation of the resulting olefin provides ketone 138. This is converted in four steps to (l S, 5i ,7iS)- xo-7-ethyl-5-methyl-6,8-dioxabicy-clo[3.2.1]oct-3-ene (139). Similarly, R,5S,lR)-exo- is prepared from (5, 5)-tartaric acid. The enantiomeric purity of both enantiomers corresponds to 100% ee [55] (Scheme 32). 

Fig. 19.6 HPLC analysis of the female-produced sex pheromone isolated from female conditioned seawater (Hardege, unpublished data). The chromatogram shows the HPLC analysis of female C. maenas urine at 2-day post-moult (black line), and synthetic pheromone, UDP (red line). HPLC conditions used were Phenomenex RP Fusion column (4.6 x 250 mm) mobile phase 0.2 M KH2PO4 buffer, pH 5.5 1 mL min-1. Synthetic pheromone UDP (for structure see insert) was at a concentration of 10-5 M. The unresolved shoulder peak in the female sample at 3.3 min represents both tautomeric forms of UDP...

C,H,202, Mr 152.19, a pheromone isolated from the feces of the desert locust Schistocerca gregaria that influences aggregation (formation of swarms) and is supposed to have other physiological activities. However, in recent studies, the substance could not be detected, at least in S. gregaria, instead a mixture of various phenols and phenylacetonitrile (CgH7NO, Mr 133.15) was reported. For general information on the pheromones of grasshoppers, see Ut . 

Amphibian pheromones have been previously isolated fh>m newt and salamander species, however, this peptide, which we have named splendipherin, is the first pheromone isolated fiom any anuran species. The delivery method of those previously isolated amphibian species are very clear. Sodefiin, the ten-residue peptide pheromone of Cynops pyrrhogaster and silefiin, the ten residue peptide pheromone of Cynops ensicauda are both sent through the water by the male newts by a vigorous shaking movement of the tail (Kikuyama et al., 1995 Yamamoto et al., 2000). The 20 kDa proteinaceous male courtship pheromone of Plethodon jordani is applied to the female s sldn by direct contact (Rollman et al., 1999). 

Michael, R.P., Keveme, E.B. Bonsall, R.W. 1971. Pheromones Isolation of male sex attractants from a female primate. Science, 172, 964—966. 

A component of pheromones isol. from female tsetse fly Glossina morsitans morsitans. 

Vittatalactone [105] Vittatalactone (192) is a pheromone isolated in 2005 from the striped cucumber beetle Acalymma vittatum [103]. This natural product presents a unique structure bearing a trawi-p-lactone and a deoxypropionate side chain. In 2009, Breit and coworkers assigned both its relative and absolute configurations [104]. 

Z)-9-tetradecenyl acetate, which is used in the blends of 223 lepi-dopteran species and (Z)-ll-tetradecenyl acetate (Figure 3.23) used by 214 species. Some further examples of lepidopteran pheromones are shown in Figure 3.23. Bombykol, the sex pheromone of the silkworm moth Bombyx mori (Plate 2) was the first pheromone isolated and identified, in an effort that took many years of work (Butenandt, Beckmann, Stamm and Hecfcer, Zeitschrift fur Naturforschung, 1959,14b, 283). It is not easy to see how bombykol could be biosynthesized by use of a A11-desaturase. Indeed it is made in the insect from palmitic acid, which is converted to (Z)-ll-hexadecenoic acid, and then an unusual 10,12-desaturase converts that into (10 , 12Z)-10,12-hexadecadienoic acid. 

Coke and Richon have constructed the 8-lactone framework of n-hexadecalactone, the proposed pheromone isolated from Vespa orientalis, through lactonization of a hydroxy acid intermediate [39] (Scheme 3). The optically pure amino alcohol 22 obtained by resolution was converted to the optically active epoxide 23 by quatemization, followed by Hofmaim elimination. Addition of the dianion of propiolic acid to epoxide 23, and subsequent reduction of the resulting acetylenic hydroxy acid with hydrogen and palladium, provided the saturated hydroxy acid 25, which spontaneously cycUzed to afford 8-lactone 12. In a similar way, the enantiomer of amino alcohol 22 was also transformed into the antipode of lactone 12. Furthermore, using this method, any terminal epoxide can easily be converted to the corresponding saturated 8-lactone in two steps. 

The second part of this sequence was also used for the total synthesis of dendrolasin, a pheromone isolated from the ant Lusius (Dendrolasius) Juliginosus latr (Scheme 5-84). ° ... 

Klun, J. A., and G. A. Junk Iowa European com borer sex pheromone isolation and identification of four Cu esters. J. Chem. Ecol. 3,447—459 (1977). 

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