Quantitative determination of isomeric impurities contained in purified potassium 5, 8-diisopropyl-2-naphthalenesulfonate [KDNS] by means of NMR was investigated, after KDNS was converted to the methyl ester [MeDNS]. GLC methods were unsuitable for determining the isomeric impurities because of peaks of MeDNS and the isomer, separated from a mixture of methyl esters derived from side reaction products on KDNS preparation, were overlapped each other. On the other hand, NMR spectra observed in the aromatic ring proton range were suitable for these determinations, and lower limits of determination on the isomers contained in MeDNS were estimated as 0.5mol%. As the results, it was recognized that the purified KDNS, which have been used hitherto in our studies, was of purity over 99.5mol% with respect to the isomers.
The behavior of oily soil in a detergent solution was discussed in terms of the ζ-potential and the potential energy of interaction. Oleic acid and oleyl alcohol were used as a model of oily soil. The nonphosphate detergent (composed zeolite, 20%) was considered. The ζ-potentials of oleic acid and oleyl alcohol in each aqueous solution of sodium dodecyl sulfate, various builders (sodium tripolyphosphate, sodium silicate, sodium carbonate, sodium carboxymethyl cellulose, sodium sulfate), and the detergent were measured by a microelectrophoresis. The potential energies of interactions between the oily soil and each materials (nylon, cellulose, zeolite, clay, carbon black, carbon black coated with palmitic acid) were calculated by the use of the theory of heterocoagulation and that between oily soils by the use of the DLVO theory. From these results, it is suggested that also when sodium tripolyphosphate is not composed, oily soils are dispersed in the detergent solution well by the effect of sodium dodecyl sulfate and various builders, and do not redeposit onto fabrics.
Thermolytic reaction of 1, 8-terpin hydrate (1), 1, 4- and 1, 8-cineol (2) and (3) in the presence of ZnCl2/KCl/NaCl fused salts (chloride fused salts) or NaNO2/NaNO3/KNO3 fused salts (nitrate fused salts) were carried out at different temperatures and the salt effect on the products has been investigated. The results obtained are as follows: In the chloride fused salts, β- and α-terpineols (11), and (12) were obtained from (1) as main products, amounting to more than 70% of the thermolytic products. γ-Terpineol (10) and terpinene-4-ol (13) were obtained from (2) as main products with the highest conversion of 75% and 71%, respectively. In the nitrate fused salts, (11) were obtained from (1) as the main product, amounting to 80% of the thermolytic product under the optimal conditions. The thermolysis of (3) gave (12) as a major product (71%).
5-Alkyl-2-penten-5-olides (7) were prepared from dimethyl adipate (1). 2-Alkyl-2-(methoxycarbonyl) cyclopentanone (2) was obtained from (1) by Dieckmann condensation. Decarboxylation of (2) gave 2-alkylcyclopentanone (3). Oxidation of 2-hexylcyclopentanone (3, R=C6H13) with m-chloroperbenzoic acid afforded 5-hexyl-5-pentanolide (6). The compound (6) was treated with benzene-selenyl bromide followed by oxidation with hydrogen peroxide to give 5-hexyl-2-penten-5-olide (7).
Straight-chain saturated fatty acid was prepared with good conversion by the following procedure: a mixture (480ml) of α-olefin (200 mmol), di-t-butyl peroxide (50 mmol), and acetic acid was added into an autoclave containing 360g of acetic acid (150°C, 5kg/cm2) with a feeding rate of about 2ml/min. Fatty acids prepared by the procedure were octanoic, decanoic, lauric, myristic, palmitic, stearic, and icosanoic acids.