Methyl 10-undecenoate and mercuric acetate were reacted in methanol to give methyl methoxyacetoxy mercury-undecanoate. The mercurial adduct was then reacted with phenol, o-cresol, m-cresol, p-cresol and o-tert-butylphenol in 1: 5 mole ratio each at 60 °C for one hour in the presence of perchloric acid as a catalyst, giving methyl 10, 11-diaryl undecanoates corresponding to the respective phenols. The reaction of the mercurial adduct and 2, 6-di-tert-butylphenol gave methyl 11- (hydroxy, di-tert-butylphenyl) 9-undecenoate instead of methyl 10, 11-diaryl undecanoate. The mercurial adduct was then reacted with methyl benzoate, dimethyl phthalate, and methyl acetylsalicylate at the same reaction condition for 2 hours, giving methyl 11-methoxycarbonylphenyl-9-undecenoate, methyl 11-dimethoxycarbonylphenyl-9-undecenoate, and methyl 11-acetoxymethoxycarbonylphenyl-9-undecenoate. All diaryl undecanoates listed above showed antioxidant activity for methyl oleate at 40 °C and 100 °C. However, their activities are somewhat less than the activity of BRA. They were found effective as corrosion inhibitors by the water-dip method with a sample of turbine oil and test pieces o mild steel, aluminium, zinc and brass at the concentrations of 0.2, 0.4, 0.6 and 0.8%. Especially, the derivatives from p-cresol and o-cresol were excellent as corrosion inhibitors. Methyl 11-methoxycarbonylphenyl-9-undecenoate, methyl 11-dimethoxycarbonylphenyl-9-undecenoate and methyl 11- (acetoxy, methoxycarbonylphenyl) -9-undecenoate were converted to its sodium, calcium, strontium and barium soaps, and their activity as corrosion inhibitors was tested with a sample of turbine oil and test pieces of mild steel at the concentrations of 0.2, 0.4, 0.6 and 0.8% by the water-dip method. Regerding the acid components, the activity was ranked in the order of 11- (hydroxy, carboxyphenyl) -9-undecenoic acid>11-dicarboxyphenyl-9-undecenoic acid>11-carboxyphenyl-9-undecenoic acid. As for the base components, strontium and barium soaps were very effective followed by calcium soaps, sodium soaps being slightly less effective.
The anthers previously reported that Fe-Cu-O catalyst had high activity to catalytic hydrogenolysis of higher fatty ester to higher alcohol. After that, it was found that Fe-Cu-AI-O catalyst had higher activity when proper amount of Al was contained as third component. Hydrogenolysis of methyl ricinoleate to 1, 12-octadecanediol was studied using the catalyst. The yield was 77%. But when triglyceride was used as raw material, the yield was 50%. Preparation of unsaturated higher alcohol using Fe-Cu-Cd-O, which was prepared newly, was studied, but 65% of unsaturation on the product vanished when 93% of the ester was hydrogenolzyed. From the study of X-ray defraction on these catalysts before and after the reduction, it was recognized that, as to Fe, Fe304 was of active from in the reduction.
Degree of alkyl chain branching of various commercially available detergent alkylates, including straight chain type, branched chain type and mixture thereof, was studied by means of high-resolution nuclear maenetic resonance. and an explicit correlation between alkyl chain branching ofdetergent alkylates and biodegradability of their sulf onates was obtained. The degree of alkyl chain branching in detergent alkylates is expressed by a parameter HCH3-6 ΣH-5, which is obtained by a combination of NMR and gaschromatography, where HCH3 and Σ H - 5 denote the number of methyl hydrogens and the total number of hydrogens in the alkyl chain, respectively. A plot of this parameter for the alkyl chain branching of detergent alkylates against biodegradability of their sulfonates was found to be almost linear as in Fig.-3. Use of Hω, which denotes the number of total methyl hydrogens in the alkyl chain, instead of HCH3 in the parameter leads to a lack of the linearlity of the plot of the alkyl chain branching against the biodegradability of sulf onates as in Fig.-4. Whereas, biodegradability of alkylbenzene sulfonates can be more rapidly predicted, since Hω, can be derived only from NMR spectra of hydrogens in the alkyl chain in detergent alkylates.
Lauryl sarcosinate (L) -egg albumin (EA) -and lauryl sarcosinate-bovine serum albumin (BSA) complexes (EL, BL) were prepared by mixing each component dissolved in water at pH 7.07.5, respectively, Each complex comprising 10 mg of protein in the ratio L/protein=3 was twice injected in rabbits with Freund's Adjuvant method followed by thrice subcutaneous injections with 1 mg of each complex comprising 1 mg of protein in the ratio of L/protein=3, respectively. According to the ordinary precipitin reaction, we found only 1 or 2 positive reactions both in EAanti EL-and BSA-anti BL systems against 3 or 4 positive reactions in EA-anti EA-and BSA-anti BSA systems. On the other hand, we found only 1 positive reactions in the cases of EL-anti-EL-and BL-anti BL systems, respectively. The titers of antibody were 1 : 1 or 1 : 4 in EA-anti EL-against 1 : 64 or 1 : 128 in that of EA-anti EA systems, and 1 : 4 or 1 : 8 in BSA-anti BL-against 1 : 32 in BSA-anti BSA systems. Arthus phenomenon showed moderate reaction for BSA-anti BL-and severe reaction (necrose) in BSA-anti BSA systems.
Effect of metal chlorides on the autoxidation of methyl oleate was investigated by observing the changes in peroxide value, iodine value, saponification value and refractive index at 80°C. VCl4 and PdCl2 accelerate markedly the peroxide-decomposition, while BiCl3 and ZrCl4 showed less effect, and.AlC3 and SiCl4 showed no effect. In the addition of MoCl5, TiCl4 or WCl5 the changes in peroxide value, saponification value, acid value and refractive index wereless but decrease in the iodine value was great, and the oxidation reaction in the presence of such chloride seemed to occur by another mechanism rather than usual. SbCl5, GeCl4, InCl3 and SnCl4 inhibited the autoxidation.