Gas chromatographic behaviors of various 4- and 6-methyl sterols with cholestane, campestane, β-sitostane or stigmastane side chains at C-17 position were studied. From the retention times for these sterols and for their oxo, acetoxy, trimethylsiloxy and trifluoracetoxy derivatives at C-3 position, the increment of the retention times due to the introduction of an alkyl group at C-4 or C-6 position in the steroid skelton and at C-24 position in the side chain was expressed as retention factors, respectively. Moreover, interaction between functional group at C-3 and methyl group at C-4 or C-6 was expressed in terms of ΔR-values, which are ratios of the retention times for steryl derivatives to those for the cor responding free sterols. Main results obtained were as follows. 1) In spite of the variations of the side chain structures, no influences on the retention factors of 4- or 6-methyl group were observed. Whereas, the retention factors of C-24 alkyl group for methyl sterols were identical with those for non-methylated sterols, and were not affected by the natures of C-3 functional groups and liquid phases (SE-30, OV-17, DEGS). 2) It was observed that the ΔR-values for sterols examined differed from one another depending upon number, stereochemical configuration, position and the presence or absence of methyl groups adjacent to C-3 functional group, whereas, within a homologous series, were idetical. Thus, the ΔR-values decreased in the following order : non-methylated>4α-methyl>4β-methyl≅4, 4-dimethyl sterols on the ΔRAC-values (retention times of steryl acetate vs. the corresponding free sterol), 4α-methyl>non-methylated>4, 4-dimethyl>4β-methyl sterols on the ΔRTMS-values (retention times of the steryl trimethylsilyl ether vs. the corresponding free sterol), respectively. Changes of liquid phases were not affected on the orders of the ΔR-values described above. On the 6α-, 6β- and 6-methyl sterols, in general, the ΔR-values were approximately equal to each other because their methyl groups at C-6 are more apart from C-3 functional group compared to methyl group at C-4. It is, hence, concluded that the differentiation of sterol type can be easily carried out from their ΔRAC and ΔRTMS-values. The characteristics of these retention factors and ΔR-values shown in this study may be especially useful for the structural elucidation of unknown sterols.
In the previous papers, the authors reported that tocopherol showed the effect to reduce the toxicity of thermally oxidized oil (TO) in rats. The present paper deals with the comparison of nutritive values among TO with or without tocopherol (Toc) and fresh oil without tocopherol. Soybean oil was heated at 180°C for 50 hours, and TO with or without Toc and/or fresh oil (FO) from which Toc was removed by active alumina column chromatography were fed to rats in a diet contained 15% of test oils. The results indicated that the rats fed with TO showed growth depression as reported in the previous papers. On the other hand better growth was observed when the rats were fed with the Toc free FO. The weight and lipid content in liver and kidney of rats fed with TO were higher than those of rats fed FO or Toc free FO. On the contrary, the decrease of weight, lipid and Toc content in testicle of rats fed with TO or Toc free FO was observed. Feeding of TO and Toc free FO reduced the percentage of C18 : 2 in liver, kidney, testicle and blood lipids, but they were increased by the addition of Toc in the diets. Hemolysis rates of erythrocyte of rats fed with TO was higher than those of rats fed with free FO or the TO with Toc.
Unsolvated Grignard reagents with WCl6 are effective cocatalysts in the olefin metathesis. Activity of WCl6-BuMgI in benzene medium is comparable with those derived from BuLi. The optimum ratio of BuMgI to WCl6 was 2.0, and products of Friedel-Crafts reaction were less than 3% when the ratio was more than 1.5. The addition of 1% ethylether to the benzene medium deactivated the catalyst essentially. The mechanism of the deactivation was discussed.
The following improvements were made to eliminate the complexity of the experimental technique for determining a wave length and a diameter of issued jet. 1) The photograph of the jet waves can be taken easily by using the photographing apparatus as shown in Fig. -2. 2) By introducing a correction factor, the diameter of issued jets can be determined without experimental measurement which applicability was checked and tested. A comparison between the result determined by the present method and Burcik's data on sodium dodecyl sulfate solution gives very good agreement as shown in Fig. -5. Furthermore, the order of the dynamic surface tension of sodium dodecyl benzene sulfonate solution was determined and the equation as shown in Fig. -5. was obtained.
Solution copolymerization of styrene (St) with maleic anhydride (Man) was carried out using 1-dodecanethiol (RSH) -benzene as solvents and benzoyl peroxide (BPO) as an initiator. The chemical structure of the obtained co-telomer was determined by molecular weight, elementary analysis IR spectrum and is as follows; _??_ From these results, it was made clear that the obtained co-telomer was the alkyla ted alternating copolymer. These co-telomers were treated with ammonia in acetone to obtain the corresponding ammonium salts. The surface active properties of these ammonium salts such as surface tension, dispersing power (CaCO3) and foaming power were measured, and the results are as follows; γ_??_40dyne/cm (0.1wt%), cmc=0.0030.004wt%. on dispersing power, they showed good values at the low concentration. The effect of Pn on the surface active properties of these co-telomers (Pn510) was hardly recognized.
The amounts of polyoxyethlene (20) sorbitane laurate SL (EO) remained on the fruit and vegetables such as strawberry, cabbage, cucumber and spinach washed by the detergent solution of SL (EO) have been determined by means of the radiotracer method using SL (EO) labeled with radioisotope 14C. Further studies on sodium dodecylbenzene sulfonate (DBS) and sodium triethyleneglycol dodecylether sulfate (ES) have been carried out and compared with SL (EO). The measurement was chiefly made for cabbage leaf under the various conditions. Under the condition of dipping in 0.1% detergent solution for ten minutes at 1618°C, following by rinsing twice with 100ml of water for 20sec., the amout of residual SL (EO) observed were 0.18γ/cm2 for the surface and 0.54γ/cm along the section of cabbage leaf. The amount of SL (EO) remained on cucumber and strawberry were nearly the same as that on cabbage, but that on cabbage, and spinach were four or five times larger than that on cucumber and strawberry when compared in the unit of the amount of residual SL (EO) per weight. The tendency for the amount of the various surface active agents in this study was about the same between fruit and vegetables, and the residual amount of DBS, SL (EO) and ES decreased in that order listed.
Critical micelle concentration (cmc) values of salts of optically active and racemic N-acylamino acids were measured by a dye method and a conductivity method. And constant values (A and B) of a equation log cmc=A-BN (N : number of carbon atoms in the acyl radicals) were evaluated. The value B of salts of optically active N-acylamino acid was equal to that of racemic one. But the value A was different, that is, the value A of salts of optically active N-acylamino acid was smaller than that of racemic compound. The cmc values of the salts of N-acyl-L-amino acid (Ala, Phe) were smaller than those of DL-compounds. These phenomena suggest that the salts of optically active N-acylamino acids form micells more easily than the racemic ones.
The relation between hydrophobic structure and surface activity was investigated on the following oil-soluble organo boron surfactants. _??_ Bisglycerylborate (BGB) monoalkylate The lowering ability of interfacial tension of BGB monoisostearate with a blanched hydrophobic group was lower than those of BGB monoalkylates with a straight hydrophobic group in the lower concentration region, but the best in tested four surfactants in the higher concentration region. In case of the type with a straight hydrophobic group, BGB monooleate and BGB monolinoleate containing the unsaturated chain showed the better lowering ability of interfacial tension than BGB monostearate with the saturated alkyl group. The result was discussed on the basis of II-A curves and water numbers of these surfactants.
The thermal condensation of paraformaldehyde with Caryophyllene at 200°C in a stainless-steel autoclave gave an alcoholic compound, 2, 6-dimethylene-10, 10-dimethyl-5-hydroxy-methyl-bicyclo [7, 2, 0] undecane.