Thermal reactions of alkyl acetates (methyl, ethyl, propyl, butyl, and heptyl) with iodides of alkali and alkaline earth metals at various reaction temperatures were carried out. The reactions resulted in the formation of alkyl iodides and metal salts of acetic acid. The formation of methyl iodide was easier than that in the case methyl oleate previously reported. The maximum yields of methyl iodide in the reactions with lithium, calcium, and strontium iodides were as follows : lithium iodide 95%, calcium iodide 91%, strontium iodide 91%. Moreover, the yields of alkyl iodides from alkyl acetates were poor except methyl iodide.
The structures of oil globule membranes of 30% milk fat water emulsions containing monoglyceride (MG), sorbitan fatty acid ester (SE) and caseinate (CA) were studied by measuring electrophoretic mobilities (EM) of their dispersed oil globules at different pH. EMs were influenced by the hydrocarbon chain length of sorbitan ester (HCL). EM vs HCL pattern of the oil globules coated with SE was quite different from that of the oil globules coated with MG+SE. This fact means that the outer layer of oil globule membranes consited of neither MG nor SE exclusively. Thus, a mosaic model of MG-SE at the oil globule membrane, where MG and SE is supposed to form certain molecular association, can be assumed. EM vs HCL pattern of the oil globules coated with SE and MG+SE, had a resemblance to EM vs HCL pattern of those coated with SE+CA and MG+SE+CA respectively, This behavior seems that SE and MG+SE layers at the oil-water interface could be covered coasely by CA layer. The relation between EM and the rate of globule coalescence for the emulsions containing MG+SE+CA showed good linearity, However, EM appers to have little correlation with stability against coalescence, unless those oil globule membranes have a similar strength.
The reaction of 1, 2-epithiodecane with acetyl chloride gave a mixture of S- [1- (chloromethyl) nonyl] thioacetate (1) and S- (2-chlorodecyl) thioacetate (2), and a polymer. The ratio of the yields of (1) and (2) was little changed with the reaction conditions such as reaction temperature, reaction time, and kinds of solvents, and it was about 6 : 4. The yields of (1) and (2), however, became higher when polar solvents such as acetone, ethyl methyl ketone, DMF, acetonitrile, acetic anhydride, and acetic acid were used. The reaction of 1, 2-epithiooctane, 1, 2-epithiododecane, and 1, 2-epithiotetradecane with acetyl chloride gave similar results to the reaction of 1, 2-epithiodecane with acetyl chloride. The reaction is presumed to be attack of chloride ion of acetyl chloride to 1, 2-epithioalkanes.
Autoxidation of benzaldehyde (BA) in aqueous solutions of nonionic surfactants has been investigated. Oxidation process was followed by GC while the determination of the site of BA within micelles was made by UV spectroscopy and solubility measurement. It was found that the autoxidation of BA in aqueous solution was inhibited more strongly by nonionic surfactants, and that the site of BA within micelles was a deep penetration into the palisade layer. From the fact that dissolved oxygen participates the oxidation of BA, rates of oxygen absorption were examined in paraffin and in aqueous poly (ethylene) glycol solutions as micelle-core and micellepalisade model substances, respectively. Amounts of oxygen absorbed were less in aqueous poly (ethylene) glycol solutions than in water or paraffin. Based on the experimental results, it could be ascertained that the inhibition of BA oxidation in aqueous solutions of nonionic surfactants was caused by the inhibiting actions against oxygen absorption of the palisade layer of the micelle.
It was found that cyclopentene oxide (CPO) and 3, 4-epoxycyclopentene (5) were isomerized by gas-phase reaction with use of solid acid-base catalyst. The reaction conditions for isomerization of CPO to cyclopentanone (1) and (5) to 2-cyclopentenone (4), respectively, were investigated. The products from CPO were (1), cyclopentanol, 2-cyclopentenol, (4), cyclopentene, and cyclo_pentadiene. When Cu-Zn was used as a catalyst, (1) was obtained in about 51% yield. In case of isomerization of (5) with use of Cu-Zn catalyst under reduced pressure, only (4) was produced. When SiO2-Al2O3 (Al2O3 : 28wt%) catalyst was used instead of Cu-Zn catalyst, (4) was obtained in about 90% yield. Activity and selectivity of SiO2-Al2O3 catalyst for the formation of (4) were excellent.
Separation and determination of linear alkylbenzene sulfonates (LAS), α-olefin sulfonates (AOS), and alkanesulfonates (SAS) were studied by TLC, GLC, and NMR. The studies of LAS-AOS and LAS-SAS mixture were already reported4), 5). This paper describes about AOS-SAS and LAS-AOS-SAS mixture. 1) AOS-SAS. The mixture of AOS (hydrogenated), a primary sulfonate, and SAS, a secondary sulfonate, was esterified and separated by the same procedure we previously reported about a mixture of LAS and AOS. Isolated AOS from TLC plate was converted to trimethylsilyl derivative and analyzed by GLC with a 2% OV-17 0.5m column. The quantity of AOS in the mixture was calculated from the peak area of AOS in comparison to that of dodecyl pentaoxyethylene ether, a internal standard added before TLC separation. SAS was converted to thiol derivative and also analyzed by GLC with an OV-101 40m glass capillary column. 2) LAS-AOS-SAS. These components were divided into AOS and (LAS+SAS) by TLC in a form of methyl ester. (LAS+SAS) was converted to alkylphenol and olefin by alkali fusion, respectively, and was separated by column chromatography. Isolated LAS, AOS, and SAS were analyzed as alkylphenol (acetate), TMS and olefin derivative, respectively, by the GLC method already described. Quantitation of the three components was carried out by comparing the ratio of LAS to (AOS+SAS) before TLC separation, and the ratio of LAS to SAS after TLC separation by NMR. Analytical results of alkyl homolog distributions and the ratios of each component were both satisfactory.
The effect of added water on the decreasing in the transition point and the elevation of the melting point of higher alcohols were studied. Their crystal structure was analysed by using an X-ray diffractometer. It was suggested from experimental results, that the formation of the strong hydrogen-bonding networks of the hydroxyl groups between two alcohol and one water molecules is responsible for the changes in transition or melting points.
A mixture of β-caryophillene and formic acid was refluxed to give a mixture of 4, 4, 8-trimethyl-2-formyl-tricyclo [6.3.1.01.5] dodecane (3a) and β-caryophillene formate (4a) in yield of 80%. Hy drolysis of these formates gave their corresponding alcoholic compounds, (3c) and (4c). Oxidation of 4, 4, 8-trimethyltricyclo [6.3.1.01.5] dodecane-2-ol (3c) gave a new ketone, 4, 4, 8-trimethyltricyclo [6.3.1.01.5] dodecane-2-one (5).