Z-9-Tetradecenal

Identification of compounds in volatiles collected from hunting M. cornigera revealed three common components of moth sex pheromone blends (Z)-9-tetradecenal, (Z)-9-tetradecenyl acetate, and (Z)-ll-hexade-cenal [while there was insufficient material for mass spectrometry, gas chromatographic retention time evidence suggests that (Z)-ll-hexadece-... 

FIGURE 2 Relative proportions of three identified components of M. comigera spider volatiles (47). The variation in the ratios suggests that spiders change the moth-attracting blends they produce. Z11-16 AL, (Z)-ll-hexadecenal Z9-14-.AC, (Z)-9-tetradecenyl acetate Z9-14 AL, (Z)-9-tetradecenal. 

The selective hthiation of 2-hexanone phenylaziridinyl-lEl-hydrazone 127 with LDA and subsequent alkylation with 8-(tert-butyldimethylsilyloxy)octyl bromide gave (Z)-hydrazone 128 in 65% yield. Its LDA-catalyzed selective decomposition followed by hydrolysis of the silyl ether yielded (Z)-9-tetradecen-l-ol, which was acetylated to afford the target compound 129 in 80% yield with a complete regioselectivity and a cisitrans ratio of 99.6/0.4. 

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-tetradecenal (with (Z)-11-hexadecenal) [53939-27-8] CH3CH2CH2CH2CH=CH(CH2)7CHO tobacco budworm, Heliothis virescens... 

Caro, J.H. Glotfelty, D.E. Freeman, H.P. (Z)-9-Tetradecen-l-ol formate Distribution and dissipation in the air within a corn crop after emission from a con-trolled-release formulation. Presented at the American Chemical Society/Chemical Society of Japan Chemical Congress (PEST 081), Honolulu, April 1-6, 1979. 

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. 

In an earlier investigation of the H. virescens sex pheromone we identified two compounds, (Z)-ll-hexadecenal and (Z)-9-tetradecenal in a ratio of 16 1, respectively, from ether washes of calling female bodies ( 1). These compounds were also identified as H. virescens sex pheromones by Roelofs ejt al. (9) However, field evaluation of crude extracts and synthesized pheromone led us to speculate that other pheromone components might be present. Subsequently Klun et al. (10) identified seven components in the ovipositor rinses of H. virescens females by capillary GC. Our analysis of H. virescens ovipositor washes by methods similar to Klun s gave results consistent with his data. The seven components and the relative amounts found were tetradecanal (14 A1) (1.61, (Zl-9-tetradecenal (Z9-14 A1) (21, hexadecanal (16 A11 (9.51, (Zl-7-hexadecenal (Z7-16 A1 (11, (Zl-9-hexadecenal (Z9-16 A1 (1.31, (Z)-ll-hexadecenal (Z11-16 AU (81.41, and (Z)-ll-hexadecenol (Z11-16.-OH) (3.21. 

The behavior of two other formulations, microcapsules and small plastic laminate flakes, containing tetradecenol formate, were compared in applictions to plots of mature corn at Beltsville, in August 1980. (8) The Z-9-tetradecen-1-ol formate (TDF) is a mating disruptant, rather than a true pheromone, of the Heliothis species of moths. It was selected in these experiments because reliable analytical methods were available (9) and its behavior was expected to be similar to that of the actual pheromones, whose chemical structures and properties are also similar. The two formulations were polyurea-polyamide microcapsules 5-microns in diameter supplied by ICI at Bracknell, Berkshire, England, and a small (3 mm side) plastic laminate formulation supplied by the Herculite Corporation of York, PA. The microcapsules were applied at 300 g of TDF per hectare and the flakes at 285 g/h. Both formulations were applied by air to mature corn 240-270 cm in height in clear, hot weather with a daily maximum temperature of 39°C. 

Colton, tobacco, tomato Heliothis virescens (Z)-3-Hcxcnyl Acetate (Z)-1 1-hexadecenal, (Z)-9-tetradecenal, hcxadccanal, tetradecanal [2261... 

Figure 1. Gas chromatographic analysis (Column - 30m x 0.25mm id Supelcowax 10) of the extract of the pheromone gland of a 3-day-old virgin female of Heliothis virescens obtained 1 h after injection of 0.5 pmoles of synthetic PBAN in 10 /xl of water during the photophase (upper), compared to the extract of a gland obtained 1 h after injection of 10 /il of water during the third photophase. Pheromone components are tetradecanal (14 AL, (Z)-9-tetradecenal (Z9-14 AL), hexadecanal (16 AL), (Z)-7-hexadecenal and (Z)-9-hexadecenal (Z7/Z9-16 AL) (no resolution), (Z)-11-hexadecenal (Zll-16 AL) and (Z)-11-hexadecen-l-ol (Z11-16 0H).

In addition to the 5-lactones of structure (41), other lactonic aroma components with a saturated ring are known, the structure of which, however, is somewhat different from that of the n-series represented by (41). These are 6-hydroxy-5-hexanolide (42), identified in tomato (557), and three cyclic compounds carrying an unsaturated chain in position 5, viz. (Z)-7-decen-5-olide (jasmine lactone) (44) 712), identified in the flavor of black tea (50) together with methyl jasmonate (779). (Z)-9-dodecen-5-olide (45) and (Z)-9-tetradecen-5-olide (46), the latter two lactones having been isolated from butter flavor (50, 725). On the other hand, lactone (43) was isolated from milk where it is present in a quantity of 10 pg/kg (0.001 ppb) (247) this quantity, however, is probably much lower than the threshold value. 

A three-layer plastic flake has been prepared as one form of a matrix entrapped polymer relying on a physical diffusion of the active agent.22 The outside layers were a vinyl plastic. The inside layer was any one of several pheromones of the pink bollworm, Pectinophora gossypiella (Saunders) including gossyplure, TF, virelure, or Z-9 TDF pheromones. Gossyplure is a 1 1 mixture of the Z,Z and Z,E isomers of 7,11-hexadeca-dienyl acetate. TF is 1-tetradecenal formate. Virelure is a 16 1 mixture of (Z)-11-hexadecenal and (Z)-9-tetradecenal. Z-9-TDF is (Z)-9-tetra-decen-l-ol formate. 

Z)-ll-Hexadecenal has been isolated from the female moth, Heliothis armigera, and is a potent olfactory stimulant for males in laboratory and field tests (657). The olfactometer response of laboratory-reared males of H. virescens to its pheromones, (Z)-ll-hexadecenal and (Z)-9-tetra-decenal and the inhibitor (Z)-9-tetradecen-l-ol formate has been studied 658). 

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