A new stereospecific synthesis of sex pheromones of insects of the (Z)-alkenyl-1-acetate series based on selective ozonolysis of 1-methyl-1Z,5Z-cyclooctadiene

Partial ozonolysis of 1-methyl-1Z,5Z-cyclooctadiene gives 8-oxo-4Z-nonene-1-al, which is converted to Lepidoptera pheromones after subsequent transformations.     

Insect pheromones and their analogs. XIII. Synthesis of dodec-8E-enyl and dodec-8Z-enyl acetates — Components of the sex pheromones ofGrapholitha funebrana andGrapholitha molesta

A new route is proposed for the synthesis of dodec-8E-enyl and dodec-8Z-enyl acetates which is based on the reaction of the Grignard reagent from the readily accessible 1-bromo-5-(1-ethoxyethoxy)pentane with 1-bromohept-3-yne — the bromide obtained from product of the -hydroxyethylation of pent-1-yne with 2-chloroethylvinyl ether, hept-3-yn-1-ol, by a double decomposition reaction of its tosylate with lithium bromide. The key synthon — dodec-8-yn-1-ol — was converted with the aid of sodium in liquid ammonia into the stereochemical individual dodec-8E-enol, while its reduction with the aid of 9-borabicyclo[3.3.1]nonane (BBN) gave the steroisomeric alcohol exclusively with the Z configuration, as followed from the results of capillary GLC and the IR spectra of the corresponding acetates. The PMR spectra of the compounds synthesized are also given.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 398–400, May–June, 1985.     

Selective oxidation of aromatic substituents in alicyclic compounds by ozonolysis in an ester solvent

Conclusions A method was proposed for the selective conversion of aryl-substituted alicyclic compounds to cycloaliphatic carboxylic acids by ozonolysis in ethyl acetate, followed by conversion of the ozonolysis peroxide product on Lindlar catalyst in a hydrogen atmosphere.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2146–2148, September, 1979.The authors thank V. A. Smit and B. M. Lerman for supplying the samples for ozonolysis.     

Cyclocondensation of lower aliphatic aldehydes with arylamines and cyclopentadiene

Three-component condensation of lower aliphatic aldehydes (C₁-C₃) with arylamines and cyclopentadiene (the Povarov reaction) gave 3a,4,5,9b-tetrahydro-3H-cyclopenta[c]-quinolines. Ozonization of their N-trifluoroacetyl derivatives afforded the corresponding ozonides. Cyclocondensation of 4-fluoroaniline with formaldehyde and cyclopentadiene gave earlier unknown 2-fluoro-3b,6,6a,7,9,9a,10,12a-octahydrobenzo[i,j]dicyclopenta[b,g]quinolizine.