GAS-PHASE INFRARED-SPECTROSCOPY FOR DETERMINATION OF DOUBLE-BOND CONFIGURATION OF SOME POLYUNSATURATED PHEROMONES AND RELATED-COMPOUNDS

Gas-phase Fourier transform infrared spectroscopy allows the determina tion of the geometric configuration of disubstituted carbon-carbon dou ble bonds present in linear polyunsaturated compounds on the basis of the characteristic absorptions observed in the 3036-3011 and 982-947 c m(-1) regions. Although the 3036-3011 cm(-1) band, attributable to a = CH stretch vibration, is conventionally considered to be unreliable fo r cis/trans determinations, data obtained from a large number of mono- and polyunsaturated acetates show that many useful deductions can be based on this absorption, Double bonds of the RCH=CHR' type separated by at least two methylene groups, present in polyunsaturated compounds , give rise to an absorption at 3013-3011 cm(-1) if the double bonds a re not proximal to a functional group or a terminal methyl group, Cis dienes whose double bonds are separated by only a single methylene gro up show the cis =CH stretch band at 3017 cm(-1). For methylene-interru pted polyenes, this band shows a gradual hypsochromic shift as the uns aturation increases, Furthermore, a band at 1391 cm(-1) was recognized to represent the deformation vibration of the CH2 groups located betw een the double bonds, The intensity of this band is proportional to th e number of skipped methylene groups. I None of the isolated or methyl ene-interrupted dienes bearing only trans double bonds showed any sign ificant absorptions above 3000 cm(-1). However, spectra of trans-trans conjugated compounds show a =CH stretch band at 3016-3012 cm(-1) as a well-defined shoulder on the high-frequency side of the CH2 asymmetri c stretch band, in addition to the wag absorption observed at 984-982 cm(-1), which is highly characteristic for trans-trans conjugated comp ounds, The spectra of cis-trans or trans-cis conjugated compounds are virtually identical and show a characteristic ''fingerprint'' consisti ng of two bands of similar intensity at 978-976 and 949-946 cm(-1), in addition to the =C-H stretch band observed at 3021-3017 cm(-1), inter estingly, not only are the spectra of conjugated cis-cis compounds dev oid of any significant absorption in the 982-947 cm(-1) region, but al so the =CH stretch band is broad and appears as a poorly defined shoul der on the high-frequency edge of the CH2 asymmetric stretch band.