9-Tetradecenal

Z) 5 Tetradecen 4 olide (sex pheromone of female Japanese beetle)... 

Notice that (Z) 5 tetradecen 4 olide IS a cyclic ester Recall from Section 19 15 that cyclic esters are called lactones and that the suffix olide is char acteristic of lUPAC names for lactones... 

C10H22S BUTYL-HEXYL- -201.497 8.4742E-01 1.4603E-04 64.31 602 C14H28 1-TETRADECENE -213.140 1.2035E+00 9.1571 E-05 154.77... 

A gas chromatographic method is described in this work for the analysis of tetradecane-l,4-sultone (C14 5-sultone) and the combination of 2-chloro-tetradecane-l,3-sultone (C14 2-chloro-y-sultone) and l-tetradecene-l,3-sultone (C14 unsaturated y-sultone) in neutral oils isolated from alkenesulfonate. Samples of the neutral oil are diluted in hexane and injected directly into the gas chromatograph. Quantitative data are obtained by comparison to known amounts of the respective sultones. Through the use of silica gel column chromatography followed by GC of collected fractions, separation and individual quantitation of the 2-chlorotetradecane-l,3-sultone and l-tetradecene-l,3-sultone can be obtained. 

Enantiomerically pure japonilure [(4JR,5Z)-5-tetradecen-4-olide, 26] is commercially important to attract the Japanese beetle (Popillia japonica), because only pure (4.R,5Z)-26 is bioactive, while ( )-26 is totally inactive. Synthesis of (4 ,5Z)-26 via enzymatic resolution of racemic intermediates was first reported by Sugai [63], and then further studied by Fukusaki [64] to establish the process as summarized in Scheme 39. Lipase PS (Amano) from Pseudomonas sp. and lipase OF (Meito) from Candida cylindracea were shown to be the enzymes of choice. 

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. 

Larvae of the tenebrionid beetle Hypophloeus versipellis were shown to possess an unpaired defensive gland reservoir with an opening situated at the anterior border of the ninth tergite [ 126]. The secretion contains methyl- 1,4-ben-zoquinone 7, ethyl-1,4-benzoquinone 8, ethylhydroquinone, and acetophenone as well as 6-methyl-1,4-naphthoquinone 177,6-ethyl-1,4-naphthoquinone 178, and 6-propyl-1,4-naphthoquinones 179. Several alkenes (probably 1-alkenes) like 1-tridecene, 1-tetradecene, 1-pentadecene (main constituent), 1-hexa-decene, and 1-heptadecene may function as solvents for the solid biologically active compounds. 

Metathesis of 1-octene leads cleanly to ethene and 7-tetradecene, but as the reaction proceeds also 2-octene is formed and metathesis products derived from the isomerisation reaction. It was found that after prolonged reaction times decomposition of the ruthenium alkylidene catalyst occurs. At least eight different products were formed and several of them have been identified [37], Figure 16.22 shows the identified compounds derived from Grubbs 1st generation catalyst (the 2nd generation gives basically the same result [38]). 

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