Z-9-Hexadecenal

The female sex pheromone of the cranberry root grub, Lichnanthe vulpina Hentz (Coleoptera Glaphyridae), was identified as ( )-7-hexade-cenol and (Z )-7-hexadecenal. Both compounds captured males although it was observed that the alcohol was slightly more effective than the aldehyde. ... 

The constituents responsible for the musk odor of the oil are (Z)-7-hexadecen-16-olide [123-69-3] (ambrettolide) and (Z)-5-tetradecen-14-olide [63958-52-1]. ... 

The analyses of the H. subflexa ovipositor extracts (171 revealed eight major components coinciding in retention times on SP-2340 and p-chloro cholesteryl cinnamate capillary columns (Figure 9) with 16 A1, Z9-16 A1, Z11-16 A1, (Z -7-hexadecen-l-ol acetate, (Z7-16 Ac), (Z)-9-hexadecen-l-ol acetate (Z9-16 Ac), (Z)-ll-hexadecen-l-ol acetate, (Zll-16 Ac), Z9-16 OH, and Z11-16 0H. Several other peaks were also variably present but, when present, each composed less than 1% of the total mixture. Mass spectral data confirmed the identity of the major components. 

The blend of pheromone components identified from H. subflexa female gland extracts has two components in common with H. virescens, Z9-16 A1 and Z11-16 A1 and three not found in H. virescens, (Z)-7-hexadecen-l-ol acetate (Z7-16 Ac), ( >-9-hexa-decen-l-ol acetate (Z9-16 Ac) and (Z)-ll-hexadecen-l-ol acetate (Zll-16 Ac). Field studies (Table III) indicate that at the very least, the two aldehydes plus Zll-16 Ac are of importance to the capture of male H. subflexa. Hence, the absence of these three acetate components from the H. virescens pheromone ( 10), and different ratios of Z9-16 A1 to Z11-16 A1 probably account for the semiochemical isolation between H. subflexa males and H. virescens females. However, the release of pheromone components by female H. virescens such as 14 A1 and Z9-14 A1 may be disorienting to male H. subflexa and cannot be discarded as a possible mechanism for reproductive isolation. 

Zea mays Helico verpa zaa (Z)-3-Hexenyt Acetate (Z)-11 -hexadecenal, (Z)-11 -hexadecenol, (2)-9-hexadecenal, (Z)-7-hexadecenal, hexadecanal 12191... 

Ci6H2g02, Mt 252.40, is not reported as being found in nature, in contrast to (Z)-7-hexadecen-16-olide, which occurs in ambrette seed oil (see p. 182) and which is also referred to as ambrettolide. It is a colorless to slightly yellow liquid, re 0 0.949 -0.957, re 0 1.477-1.482, with an intense and powerful musk odor. It is prepared by treating aleuritic acid (9,10,16-trihydroxyhexadecanoic acid) with trimethyl... 

Tea mays Heticoverpa zea (Z)-3-Hexenyi Acetate (/,)-11 -hexadecenaL, (Zyl 1-hexadecenol, (Z>9-hexadecenal, (Z)-7-hexadecenal, hexadecanal 219 ... 

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).

Compounds isolated from the seed oil include ambrettolide, (Z)-7-hexadecen-16-olide), am-brettolic acid, and farnesol as well as 12,13-epoxyoleic acid, malvalic acid, sterculic acid, and C10-C18 acids (oleic, palmitic, Cio, C12, Ci4, C16, Cis). (Z)-5-Tetradecen-14-olide, (Z)-5-dodecenyl acetate, and (Z)-5-tetradece-nyl acetate were isolated from the absolute in yields of 0.5%, 0.01%, and 0.4%, respectively in addition, 2-fra j, 6-ira j -famesylacetate, 2-cw,6-fra 5-famesylacetate, andoxacyclono-nadec-lO-en-2-one (an ambrettolide homo-logue) were found in the seed coat. The floral musky odor of the oil is primarily the result of ambrettolide and (Z)-5-tetradecen-14-olide. ... 

Com earworm moth, Helicoverpa zea, females emit a blend of hexade-canal and (Z)-7-, (Z)-9-, and (Z)-ll-hexadecenal (16) that is a highly... 

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) ...

The sex attractant of the eastern spruce budworm, Choristoneura fumiferana, is (E)-ll-tetradecenal (73). A probable precursor, (E)-ll-tetradecen-l-ol, is produced in the sex attractant gland (74), but this compound, which inhibits the male response to the aldehyde, does not appear to be released by the calling female. The (Z)-isomer of tetradecenal has been identified as one of the sex pheromones of the tobacco budworm, Heliothis virescens it is accompanied by (Z)-ll-hexadecenal (75, 76)7 Similarly, the female of the striped rice borer secretes two alkenals--(Z)-ll-hexadecenal and (Z)-13-octadecenal as its sex pheromone blend (77). 

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. 

A number of insect species, including corn earworm, Heliothis zea (Boddie), and tobacco budworm, Heliothis virescens (F.), contain and C,g aldehydes (C al and C al) in their pheromone blends (22, 23). The release rate of a C. al would be expected to be higher than that of a Cj al because of the molecular weight difference. A mixture containing 10% n-tetradecanal (CjA°al) in Z)-ll-hexadecenal [(J0-Il-Cj al] was formulated in four laminates, each made from a different type of polymeric membrane as the top and bottom layers vinyl, Mylar -coated vinyl, acrylic, and rigid vinyl film. (The saturated C,.°ol was used as a model because of availability.) The total alaehyde content was approximately 2.3 mg per cnr of laminate 0.7% (of the pheromone weight) of 2,6-di-tert-butyl-4-methylphenol (BHT) was added as an antioxidant. Table II gives the thickness of the polymers. 

Hexadecene, 14-methyl-, (E)-2-Hexadecene, 15-methyl-, (Z)-2-Hexadecene, 15-methyl-, (E)-4-Hexadecene, 3-methylene-7,11,15-trlmethyl-... 

Macrocyclic lactones such as ambrettolide (= 7-hexadecen-l,16-olide) (19), 15-pen-tadecanolide (20), hexadecanolide (21), and so on, as well as coumarin (22), dihydro-coumarin (23), bergaptene (24) nepetalactones (25) phthalides such as 3-butylphthahde (26), sedanolide (27), (Z)-ligustilide (28), 3-butyhdene-4,5-dihydrophthalide (29), and... 

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. 

The sex attractant produced by the female clover cutworm, Scoto-gramma trifolii, is a mixture of (Z)-ll-hexadecenyl acetate and (Z)-ll-hexadecenol 288). A mixture of these two compounds containing about 10% Zll-16 OH has proved to be most attractive 289, 290) while 20—25% Z11-16 OH decreases the catch of males appreciably 290). Adult males of the glassy cutworm, Crymodes devastator, are attracted by traps baited with equal parts of (Z)-ll-hexadecenyl acetate, (Z)-ll-hexadecenal and (Z)-7-dodecenyl acetate 291). No other species were trapped by this mixture. The addition of small quantities of either (Z)-11-hexadecenol or (Z)-9-tetradecenyl acetate completely inhibited attrac-tancy in the field. As a result of field tests, Underhill et al. 292) have recently found that alkenals may be as important in lepidopteran sex attractants as the acetates and alcohols. 

Steck, W., E. W. Underhill, B. K. Bailey, and M. D. Chisholm A sex attractant for male moths of the glassy cutworm Crymodes devastator (Brace) a mixture of Z-ll-hexadecen-l-yl acetate, Z-ll-hexadecenal and Z-7-dodecen-l-yl acetate. Environ. Entomol. 6, 270—273 (1977). 

The silylated methyl ester was then a-methylated with lithium diisopropylamide and methyl iodide in tetrahydrofuran. Reduction of methyl 10-( erl-butyldimethylsilyloxy)-2-methyldecanoate with DIBAL in ether at -78°C afforded the corresponding aldehyde. The 10- tert-butyldimethylsilyloxy)-2-methyldecanal was subsequently coupled in a Wittig reaction with 1-hexyltriphenylphosphonium bromide and n-butyllithium affording (Z)- and ( )-1 -(teri-butyldimethylsilyloxy)-9-methyl-10-hexadecene in a 9 1 ratio, respectively. Deprotection with tetrabutylammonium fluroride (TBAF) in tetrahydrofuran and final oxidation with pyridinium dichromate (PDC) in dimethylformamide resulted in a 9 1 mixture of (Z)- and ( )-9-methyl-10-hexadecenoic acid as shown in Fig. (7). As was also the case with acid 6, the stereochemistry at C-9 in 7 is not known. The key step in the synthesis of the allylic methyl group was a-methylation of a methyl ester, followed by reduction to the corresponding aldehyde, which was used in the subsequent Wittig reaction. 

The importance of trace chemicals in reproductive isolation was demonstrated by Klun and coworkers 459-461) for Heliothis zea and H. virescens. Both species produce relatively large amounts of 11-Z-hexadecenal (7) with traces of 9-Z-hexadecenal (6), 7-Z-hexadecenal (5) and hexadecanal (4). H. virescens females differ from H. zea because they also release tetradecanal (123), 9-Z-tetradecenal (124) and 11-Z-hexadecenol (125) as trace compounds. In both Heliothis species, trace... 

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