Tetradecenoic acid

The starting acid must be 5-tetradecenoic acid. The stereochemistry of the double bond is not revealed by these experiments. 

Z11,E14-16 CoA, which is then chain shortened to Z9,E12-14 CoA, or alternatively Z1 l-16 CoA is chain shortened to Z9-14 CoA and then a A12 desaturase produces Z9,E12-14 CoA. Both pathways are possibilities based on the previous identification of a A14 desaturase in the Asian com borer (Zhao et al., 1990) and a A12 desaturase in some other insects (de Renobales et al., 1987). To differentiate between the two possible pathways, D9-Zll-16 acid (Z 11-[13,13,14,14,15, 15,16,16,16-2H9]hexadecenoic acid and D2-Z9-14 acid (Z9-[13,14-2H2] tetradecenoic acid) were applied to the glands. The results indicate that D9-Z11-16 acid was chain shortened to Z9-14 acid but was not converted to Z9,E12-14 CoA. This indicates that chain shortening occurs and incorporation of D2-Z9-14 acid into Z9,E12-14 CoA indicates that a A12 desaturase is present. The D9-Zll-16 acid was not incorporated into Z9,E12-14 CoAbecause of an isotope effect. This labeled compound had nine deuteriums on the methyl end where the desaturase enzyme would act, preventing the introduction of a double bond. Combined together, the labeling studies with precursors and intermediates indicate... 

Liu W., Jiao H., O Connor M. and Roelofs W. L. (2002) Moth desaturase characterized that produces both Z and E isomers of All-tetradecenoic acids. Insect Biochem. Mol. Biol. 32, 1489-1495. 

The fatty acid content of the ovipositor tips of a variety of Lepidopteran species were determined by acid methanolysis followed by gas-liquid chromatography (GLC) (4.). In each case, unusual fatty acids corresponding to pheromone components were identified. For example, the tufted apple bud moth, Platynota idaeusalis, uses (E)—11—tetradecenyl acetate and alcohol as pheromone components (5.) and also contains (E) -11—tetradecenoic acid in its ovipositor tip. In several species, the fatty acid content of the rest of the insect also was determined. In each instance, the unusual fatty acid components were found only in the ovipositor tip or in the pheromone-producing gland located in the tip. 

One insect proved to be of special interest and was studied in greater detail (5-6). The redbanded leafroller moth (RBLR), Argyrotaenia velutinana, uses (Z)- and (E) -11—tetradecenyl acetates as pheromone components in the ratio of 9 1. The pheromone glands of these insects also contained the corresponding acids, All-tetradecenoic acids, but the Z to E ratio was about 4 5. If these acids serve as precursors to the acetates, there must be strict stereochemical control exercised in the reactions that produce the final product in the 9 1 ratio. 

In the redbanded leafroller moth, treatment of intact glands with DMSO containing radioactive acetate led to the formation of radiolabeled 14, 16 and 18 carbon saturated acids as well as All-tetradecenoic acids and pheromone components (12). Cell-free preparations from redbanded leafroller pheromone glands also showed FAS activity when radiolabeled acetyl Co A, NADPH and malonyl Co A are supplied (21). The major products are the 16 and 18 carbon saturated acids, with the 18 carbon acid predominating. 

Rodriguez S, Clapes P, Camps F, Fabrias G. Stereospecificity of an enzymatic monoene 1,4-dehydrogenation reaction conversion of (Z)-ll-tetradecenoic acid into ( , )-10,12-tetradecadienoic acid. J. Org. Chem. 2002 67 2228-2233. 

C14H22aN02 1-chloro-3-adamantyl ethoxymethyi ketone 73599-94-7 496.15 43.514 1,2 27798 C14H2602 4-tetradecenoic acid 544-65-0 590.00 52.595 2... 

C14H22N2 p-amino-b-sec-butyl-N,N-dimethylphenethylami 33132-75-1 415.15 35.795 1.2 27800 C14H2602 9-tetradecenoic acid 13147-06-3 590.00 52.595 2... 

To prepare 9-decenoic and 13-tetradecenoic acid methylester, we used the transition-metal catalysed olefin metathesis [6, 7], actually applied in petro- and polymerchemistry in seven industrial processes [8], As stated first by C. Boelhouwer et al. [9, 10], this reaction is valid not only for olefins, but for unsaturated fatty acid esters, too. 

The reaction is highly influenced by the solvent therefore among others NMP, DMF, dioxane, methyl formamide, dimethyl acetamide and tetramethyl urea were tested. The best results were achieved in DMF and tetramethyl urea. Using these solvents and PdCl2/CuCl or RhCl3/FeCl3 [27] as catalysts, oxidations of 10-undecenoic acid methylester, 9-decenoic acid methylester and 13-tetradecenoic acid methylester were carried out on a preparative scale (Table 2). 

If 13-tetradecenoic acid was cleaved, the whole amount of dicarboxylic acid (brassylic/tridecanedioic acid) precipitated. Its purity was 90% caused by impurities in the educt. 

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