Tetradecadienyl acetate

The sex pheromone of the South American tortricid moth, Argy-rotaenia sphaleropa, was identified as a mixture of (Z)-l 1-tetradecenal, (Z)-ll,13-tetradecadienal, (Z )-ll-tetradecenyl acetate and (Z )-ll,13-tetradecadienyl acetate in the ratio of 1 4 10 40. Best results for trapping were obtained with mixtures of (Z )-ll-tetradecenal and (Z )-ll,13-tetradecadienal in the ratio of 1 4 to 1 9. ... 

Kuwahara, Y., Kitamura, C., Takahashi, S., , H., Ishii, S. and Fukami, H. (1971). Sex pheromone of the almond moth and the Indian meal moth cis-9, trans-12-tetradecadienyl acetate. Science 171 801-802. 

Fig. 4.7. Volatiles identified from the bolas spider Mastophora cornigera and Mastophora hutchinsoni (15-19) and the pheromone components of Tetano-lita myenesalis (20, 21). 15, (Z)-9-Tetradecenal 16, (Z)-9-tetradecenyl acetate 17, (Z)-ll-hexadecenal 18, (Z)-ll-hexadecenyl acetate 19, (9Z,12F)-9,12-tetradecadienyl acetate 20, (3Z,6Z,9Z)-3,6,9-henicosatriene 21, (3Z,9Z)-(6S, 1R) ...

Z)-9-tetradecenyl acetate [16725-534] CH3(CH2)3CH=CH(CH2)8OOCCH3 southern armyworm, Spodoptera eridania (with (Z)-9,(E)-12-tetradecadienyl acetate) beet armyworm, Spodoptera exigua... 

Jurenka R. A. (1997) Biosynthetic pathway for producing the sex pheromone component (Z,E)-9,12-tetradecadienyl acetate in moths involves a delta-12 desaturase. Cell. Mol. Life Sci. 53, 501-505. 

Z, 9Z, 12Z, 15Z)-Pentacosapentaene and (9Z, n )-tetradecadienyl acetate attractant lure blend for Dioryctria ebeli (Lepidoptera Pyrallidae). J. Entomol. Sci., in press. 

On the other hand, the sex pheromones of both S. littoral is and S. litura were reported to consist of binary mixtures of (Z E)-9,11-tetradecadienyl acetate and (Z,E)-9,12-tetradecadien.yl acetate (90, 91). The presence of additional compounds in the sex pheromone blend is believed to be responsible for the sexual isolation of these two Spodoptera species from each other. 

Both the Indian meal moth, Plodia interpunctella, and the almond moth, Cadra cautella, utilize (, Ej-9,12-tetradecadienyl acetate as a primary sex pheromone (92, 93). In addition, (Z -9-tetradecen-l-ol has been identified as part of the sex pheromone of C. cautella (94). Significantly, attraction of almond moth males to their females is strongly inhibited in the presence of Indian meal moth females (95). These results emphasize the probable presence of secondary components in the sex pheromone blend that may play key roles in jamming the olfactory responses of closely-related and sympatric species. 

For the synthesis of (9Z,11 )-9,11-tetradecadienyl acetate the molecule, because its reversed geometry compared with the examples described above, its appropriately synthesized by a reversed sequence of olefmation steps. The reaction of ( )-2-pentenal with ylides of 9-substituted alkyl-triphenylphosphonium salts gives (9Z,11 )-9,11-tetradecadiene derivatives with 80-95 % isomeric purity 188,190,m 193). 

Z,5 )-3,5-Tetradecadienyl acetate 284 was recently presumed to be the pheromone of Prionoxystus robiniae on the basis of electronantennogram data it could be synthesized via Wittig reaction of ( )-2-undecenal 282 and the ylide 283. (3Z,5 )-3,5-tetradecadienyl acetate 284 was separated from its distillation residue [98% (3E,5E)-3,5-isomer] with 95 % purity by means of spinning ribbon-column distillation 196> (Scheme 52). 

From females of the beet armyworm, Spodoptera exigua, the (Z,E)- and (Z,Z)-tetradecadienyl acetates, the (Z)-9- and (Z)-l1-tetradecenyl acetates and tetra-decanyl acetate were isolated and identified. Synthetic mixtures of some of these components attract male moths in field tests. 

Brady and Ganyard identified (Z,E)-9,12-tetradecadienyl acetate in this moth (42), but trapping experiments with this compound, alone or in combination with (Z)-9-tetradecenyl acetate were unsuccessful (43,44). A joint effort to reinvestigate this problem was therefore started by research teams in Delft and Wageningen. 

While our most recent communication was in press (45), a publication on the same subject by Tumlinson, Mitchell and Sonnet appeared (46). They isolated 11 compounds from female Spodoptera exigua, but their field tests demonstrated that a mixture of only two of them, (Z,E)-9,12-tetradecadienyl acetate and the free alcohol, (Z)-9-tetradecenol, in a ratio of 5 4, were needed for attractancy. Such a mixture was equal in activity to live females,... 

The major component of the pheromone of S. littoralis is the conjugated diene (Z,P)-9,11-tetradecadienyl acetate which is very susceptible to degradation by heat and sunlight (5). The micro-encapsulated formulation of this diene had to be applied at the higher level of 40 gm a.i. per ha to achieve complete disruption (Fig. 10), although trials with improved formulations in 1981 have reduced this level. 

Figure 10. Communication disruption of Spodoptera littoralis in 0.01 ha plots in Egypt with microencapsulated (Z,E)-9,11-tetradecadienyl acetate applied at 40 g a.i./ha. Key control (O) and treatment (%).

Witting s cw-olefination could readily be used for the preparation of derivatives containing several double bonds of Z- and -configuration. Thus, for example, the reaction of the unsaturated phosphoran (9) with 9-acetoxynonanal yields (Z, )-9,12-tetradecadienyl acetate (10) (Vostrowsky et al., 1973). This compound is the sex attractant of several storehouse pests. 

Cuvigny T, Fabre JL, Du Penhoat CH, Julia M. Synthesis with sulfones. 31. The stereospecific reduction of 2-benzene-sulfonyl-1,3 dienes to conjugated Z,E-dienes-synthesis of (9Z,ll )-9,ll-tetradecadienyl acetate. Tetrahedron Lett. 1983 24(40) 4319 322. 

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