Authors investigated the reaction of n-octanol with diethyl amine as a model synthetic experiment of higher amine by the reaction between higher alcohol and lower amine. In the case of copper-chromium oxide as a catalyst, the reaction proceeded at 200300°C for a short time and approx. 30 percent of octyl ethyl amine and 30 percent of octyl diethyl amine were obtained. The copper chromium oxide catalysts were reduced into metallic copper during the reaction. The exchange reaction of alkyl groups proceeded at a lower temperature than that of the dehydration reaction between alcohol and amine. In the case of the metallic copper powder as a catalyst, the higher reaction temperature was required than the case of copper chromium oxide catalyst. The amines obtained were, in every case, mixed amines and solitary tertiary amine could not be synthesized.
Although the olefin hydrogenation by dicobalt octacarbonyl is now well known as the side-reaction of oxo-reaction so far as the olefin has any conjugated structure, the investigation devoted only to hydrogenation has not yet been reported. In this present investigation conducted at 120190°C in 2530 atm. of hydrogen with unsaturated fatty acid methyl esters, it was found that the unconjugated double bond as well as conjugated can also be reduced more rapidly to monoene than the case of iron pentacarbonyl and monoene component remained entirely unchanged. But catalyst decomposition by ester group was also faster and all the cobalt carbonyl added was converted to cobalt soap. To elucidate these results the following reaction procedure was assumed; Co-ordinately unsaturated hydride of HCo(CO)3 is formed in the first place and its hydrogen-cobalt bond adds to double bond and makes carbon-cobalt bond, simultaneously its unfilled d-orbital catches the π-electrons of adjacent double bond and makes π-bonded complex, which has tautomeric structure of π-allyl-complex, then the scission of the cobalt-carbon bond is accomplished by the homolytically activated hydrogen already in the orbital through a displacement of π-electrons, and with consequent regeneration of HCo(CO)3. The unconjugated will be hydrogenated through conjugation process caused by addition-elimination of HCo (CO)3. Catalyst decomposition would be explained by nucleophilic attack of oxygen of ester group on the unfilled orbital.
Hygroscopicity and agglomerativity of sodium dodecylbenzenesulfonate-sodium sulfate system were determined at 35°C, and 48.592.0, and 80.090.0% relative humidities respectively. The seven sulfonates containing various structures, described in the previous report were used, and the test materials were prepared by spray-drying with sodium sulfate. The hygroscopicity increases as the aromatic nucleus is located near the center of the alkylchain, or as the side chain is more branch d. The agglomerating rate which was determined by specialy designed appratus has the same trend as the hygroscopicity. It was shown that there is a correlation between hygroscopicity and agglomerativity of the dodecylbenzenesulfonate-sodium sulfate systems.
Polyvinyl alcohol (PVA) was esterified by formic acid, acetic acid and propionic acid in the homogeneous system contained water using hydrochloric acid as catalyst and the surface tension of these esterified PVA was measured. The lowering of the surface tension with esterified PVA were great in the order of formic acid<acetic acid<propionic acid. It was presumed that the surface chemical properties of the aqueous solution of partially saponified polyvinyl ester became more active with increase in the hydrophobic property of the ester group, if the residual ester content and the distribution of ester groups in a polymer chain were the same.