Reactions of fluorinated organic peroxides with various nucleophiles, mainly aromatic, unsaturated, and heteroaromatic compounds, have been described in comparison with those of non-fluorinated organic peroxides, especially arenesulfonyl peroxides and nitrobenzoyl peroxide, which possess electron-withdrawing substituents similar to those of fluoroalkyl groups. The HOMO (nucleophiles) -LUMO (peroxides) interactions have been described in detail. Finally, it has been demonstrated that fluorinated organic peroxides are useful reagents for the introduction of various fluoroalkyl groups to nucleophiles.
The antioxidant effects of a mixed tocopherols concentrate (m-Toc), L-ascorbyl stearate (AS) and lecithin (LE) on the preservation of β-carotene in fully hardened palm kernel oil were investigated by storage at 15°C and 60°C. The hardened oil containing 10% of stripped safflower oil was also used as a substrate. 1) During storage at 15°C, the acid value markedly increased and the color changed to bluish green in the fully hardened palm kernel oil samples except those to which LE had been added. Such changes were not observed during storage at 60°C. The peroxide value of each sample was zero. 2) In storage at 15°C, β-carotene in samples with no antioxidants was lost more rapidly than that in storage at 60°C. After 60 days of storage, AS clearly inhibited the loss of β-carotene, so that it remained at about 4050% the added amount. However, m-Toc hardly showed such an effect, with hardly any change occurring in its amount, as was also noted for dibutyl hydroxytoluene (BHT). The addition of LE almost totally inhibited the loss of β-carotene. 3) In storage at 60°C, m-Toc and BHT slightly inhibited the loss of β-carotene, with loss being only slight for the former but considerable for the latter. LE showed a clear effect on the loss of β-carotene, and its addition along with m-Toc was the most effective. However, AS had no effect and was rapidly lost.
The synergistic effects of condensed phosphates along with a mixed tocopherols concentrate (m-Toc) on the oxidative deterioration of margarine with iron (III) were investigated. Margarine was prepared from the aqueous phase with iron (III) chloride and condensed phosphates, and lard with vitamin A, β-carotene and m-Toc. Its stability toward oxidative deterioration was evaluated on the basis of change in POV and content of vitamin A and β-carotene during storage at 25°C. 1) The addition of sodium pyrophosphate by 0.05% inhibited the oxidation of margarine with iron (III) to some extent, and synergistically enhanced the antioxidant effect of m-Toc. However, further addition of it did not affect the antioxidant effect. Similar results were also obtained by adding sodium metaphosphate or sodium polyphosphate. 2) The condensed phosphates inhibited almost entirely the accelerating effect of iron (III) on the oxidative decomposition of vitamin A and β-carotene in margarine. 3) The remnant percentages of tocopherols in margarine indicated condensed phosphates to prevent the decomposition of tocopherols through their action as masking reagents for metallic ion.
The reactions of styrene oxide (1) with acetone, the isomerization of oxides, and reactions of (1) with alcohols in the presence of H-form ion-exchange resins (Dowex 50W-X8, Dowex 50 W-X4, Diaion PK 216, Amberlyst 15 and Nafion NR 50) were studied. The following results were obtained : 2, 2-Dimethyl-4-phenyl-1, 3-dioxolane was synthesized in a high yield (isolated yield 93%) by a simple reaction of (1) with acetone catalyzed by Amberlyst 15 or Nafion NR 50. Phenylacetaldehyde was obtained (isolated yield 91%) by the isomerization of (1) catalyzed by Amberlyst 15 or Nafion NR 50. 2-Phenyl-2-methoxyethanol was obtained in a high yield by the reaction of (1) with methanol catalyzed by ion-exchange resins.
Adhesion and removal phenomena in aqueous solutions were investigated using spherical polyethylene particles and a quartz plate. The experimental results are discussed and explained on the basis of the heterocoagulation theory, using ζ-potentials of the particles and the quartz plate as determined by micro-electrophoresis. The magnitude of the energy barrier preventing particle adhesion was found to be about 4000 κT for particles of 4-5μm in diameter. The Hamaker constant (A11) of a polyethylene particle was estimated by the adhesion and removal phenomena and was determined as 6.06.8×10-13ergs from curves of interaction energy plotted against separation.
Quaternary ammonium salts which have two long-chain alkyl groups are widely used as softening agents, antistatic agents, hair conditioners, fungicides, and so forth. These quaternary ammonium salts are derived from tertiary amines having two long-chain alkyl groups. Extensive research has been carried out to develop amination catalysts by which tertiary amines can be produced from the corresponding alcohols, and many amination catalysts have been made. Most, however, do not possess sufficient catalytic activity and selectivity for industrial use. A pathway for the amination of aliphatic alcohols has also been the objective of considerable research. It is considered that there are three steps in the production of tertiary amines from the corresponding alcohols : dehydrogenation, amine addition, and hydrogenolysis. Amine addition is considered to occur without any catalyst and thus dehydrogenation and hydrogenolysis are carried out in place of a catalyst. The present authors used copper for dehydrogenation catalyst and nickel for hydrogenolysis and indicated in a previous report the copper-nickel catalyst to have very high activity and selectivity in a reaction of dodecyl alcohol with dimethylamine to produce N, N-dimethyldodecylamine. The present paper demonstrates how this catalyst is used to produce N, N-di (long-chain alkyl) methylamine [DAMA] from a higher alcohol and methylamine. The effects of the flow rates of hydrogen and methylamine on the conversion of alcohol and selectivity to DAMA were examined. The higher flow rate of H2 and lower rate of methylamine make possible the more effective production of N, N-di (long-chain alkyl) methylamine. The catalytic properties of the recovered copper-nickel catalyst were also examined and even after several times of use, its activity and selectivity were found essentially unchanged.
We have developed a new method for analyzing lipid hydroperoxide (linoleic acid hydroperoxide, LOOH) at picomole levels using the chemiluminescence system. This system consists of a cypridina luciferin analog such as 2-methyl-6-phenyl-3, 7-dihydroimidazo [1, 2-a] pyrazin-3-one (MPI) or 2-methyl-6- (p-methoxyphenyl) -3, 7-dihydroimidazo [1, 2-a] pyrazin-3-one (MMPI), the peroxide, and cerium (III) acetylacetonato. In MPI-dependent chemiluminescence, a linear relationship was observed between the amount of LOOH and chemiluminescence intensity. A similar linear relationship was also noted in MMPI-dependent chemiluminescence. The chemiluminescence intensity of the latter was about four times that of the former.