Three components of the male yellowfin Baikal sculpin pheromonal signal have been isolated from urine by diethyl ether extraction, thinayer chromatography (TLC), and high-performance liquid chromatography (HPLC). Using mass spectrometry, we have identified two of them as testosterone (T) and 11β-hydroxytestosterone (11HT). These steroids are synthesized in testes during full spermatogenesis, and they are excreted in male urine with milt. The third component is not a steroid. It is more likely to be a polyene alcohol (farnesol). 2Z,6E-Farnesol possesses behavioral activity.
The 170 chemical shifts have been measured for 51 a,&unsaturated and aromatic ethers. A good linear relationship is found between the "0 chemical shifts in a series of dialkyl and the corresponding alkyl vinyl ethers. Hence, the extent of p,m-interactions between the oxygen atom and the vinyl group in the latter series does not, apparently, depend upon branching at the a-carbon atom in the alkyl moiety of these ethers. The PhOBu' ether, however, as compared to the other alkyl phenyl ethers, shows signi6cantly weakened p,m-interaction, which is apparently related to the steric hindrance of this interaction. The effects of two unsaturated groups upon the "0 chemical shifts in the corresponding ethers are non-additive. This is undoubtedly a result of 'rivalry' between these groups for conjugation with the lone electron pairs on the ethereal oxygen. The "0 chemical shift ranges of substituted methyl and vinyl phenyl ethers are nearly equal (=30 ppm). An analysis of the "0 shielding for cyclopropyl ethers shows no observable p,a-conjugation in these compounds. Excellent correlations (r>O.99) between the values of 1 7 0 chemical shifts and the calculated (MO LCAO SCF, CNDO/Z) =-electron charges on the corresponding oxygen atoms look promising for experimental estimations of m-electron densities on the ethereal oxygen.
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