WERKWIJZE VOOR HET BEREIDEN VAN ALKADIENYLACETATEN MET GECONJUGEERDE DUBBELE BINDINGEN MET LOKSTOF WERKING VOOR INSEKTEN, WERKWIJZE VOOR HET BEHEERSEN VAN INSEKTEN.

摘要

1435621 Tetradeca-9,11-dienyl acetate NATIONAL INSTITUTE OF AGRICULTURAL SCIENCES MINISTRY OF AGRICULTURE & FORESTRY 2 Nov 1973 [14 May 1973] 51083/73 Heading C2C [Also in Division A5] The invention comprises tetradeca-9,11-dienyl acetate and methods of obtaining separate isomers thereof. In Method I, a compound of formula CH#C(CH 2 ) 8 OY, (A), where Y is trimethylsilyl, tetrahydropyran-2-yl (exemplified) or the latter substituted by a C 1 -C 5 alkyl group, is reacted with an alkylmagnesium halide (e.g. C 2 H 6 MgBr) and then with butyraldehyde to give the latter is esterified with p-toluenesulphonyl chloride and acid split off (e.g. with KOH/ ethanol) to give CH 3 CH 2 CH = CHC#C(CH 2 ) 8 OY which is treated with inorganic acid in an alcohol (e.g. H 2 SO 4 in methanol) and then acetylated (with acetic anhydride/pyridine or acetyl chloride/acetic acid) to yield a mixture of the cis and trans isomers of this is hydrogenated using, for example Lindlar's catalyst to give a mixture of the 9-cis/11-cis and 9-cis/11-trans isomers of the claimed compound. The two isomers may be obtained separately by separation by gas chromatography before or after hydrogenation. In Method 2, a compound of formula X1Mg(CH 2 ) 7 OY2 (B), where X1 is a halogen atom (e.g. Br) and Y is as before (e.g. tetrahydropyranyl), is reacted with where X11 is halogen (e.g. Br) to obtain a mixture of the cis and trans isomers of which is hydrogenated as before to give a mixture of the 9-cis/11-cis and 9-trans/11-cis isomers of the claimed compound, the separate isomers being obtainable by separation by gas chromotography before or after hydrogenation. By Method III the trans-9/trans-11 isomer is obtained by isomerizing the other isomers, separately or mixed, using, for example as catalyst iodine + sunlight, and separating the product by gas chromatography. Starting material were prepared as follows: A was obtained by the sequence suberic acidmethyl suberate - octanediol - 1 - bromo - 8- hydroxy - octane - 1 - bromo - 8 - tetrahydropyranyl-octane-A. C was obtained by the sequence butyne + acrolein - CH 3 CH 2 C# CHOHCH = CH 2 -C. B was obtained by the sequence -# 1,7 - dihydroxyheptane -# 1- bromo 7 - hydroxy - heptane - 1 - bromo 7- tetrahydroxypyranyl heptanes-B. The compounds are sex-attractants for insects.