The paper is based on the article that qualified for the 1999 Japan Oil Chemists' Society Award. Novel methods for obtaining triacylglycerols (PUFA-TG) and glycerophospholipids (PUFA-PL) having functional polyunsaturated fatty acids such as docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA) are first reviewed. Physiologically beneficial PUFA-TG with 90% PUFA was prepared through triplicate transacylation of tuna orbital oil with PUFA at 60°C for 7.5h with immobilized lipase from Rhizomucor miehei in combination with ethyleneglycol or propyleneglycol as alternatives for essential water indispensable for enzyme activation. PL with 38% PUFA content was prepared with 83% recovery by 4 repeated transacylations of soy PL with polyunsaturated monoacylglycerol (PUFA-MG) using microbial lipase from Candida cylindracea. PUFA-MG could be used in place of essential water for inducing enzyme activity and also as a polyunsaturated acyl donor.
Study was made of the antioxidative and synergistic effects of amino compounds for autoxidation of PUFA-TG. Amino compounds such as nitrogen-containing PLs, alkylamines and spermine were found to possess but little antioxidative activity compared to the tocopherol mixture. The remarkable synergistic activity of primary amino group toward tocopherols was detected in the autoxidation of PUFA-TG in non-aqueous or emulsifying systems. Primary amino hydrogen in amino compounds may possibly function quite well as hydrogen radical donors for regenerating tocopherols.

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This paper reviews a recent method for the synthesis of fluorine-containing compounds using high-valency metal fluorides or plasma-polymerization. Regioselective fluorination is examined through use of semi-empirical and ab initio molecular orbital calculations. Differences in calculated energy levels in transition states or reaction intermediates were found consistent with experimental regioselectivity of fluorination reactions.

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A method was established for the synthesis of long chain ketones by reactions of 3, 4-unsaturated carboxylic esters with alkyl and alkenyl Grignard reagents. Grignard reaction of ethyl (E) -3-hexenoate (1b) with n-pentylmagnesium bromide (2a) gave 3-dodecen-6-one (3b) and 6-n-pentyl-3-dodecen-6-ol (5b). Subsequent to reactions in the presence of Et₃N at 253K, greater ketone selectivity was noted. Reactions of other 3, 4-unsaturated carboxylic esters (1b-d) and acids (1a'-c') with Grignard reagents (2a-c) gave ketones (3b, c, d, f) in good yields under the same conditions. Dialkylmonohomoallyl alcohols (5b, f-i), produced as by-products, readily underwent conversion to symmetrical ketones (6b, f-i) by thermolysis. With trihomoallyl alcohols (5q, r, t), diallylic ketones (3q, r, t) were obtained. The ketones quickly underwent isomerization to conjugated ketones (7q, t) by treatment with acid catalysts. By these reactions, various unsaturated ketones including ar-turmerone (8h) could be prepared selectively from 1, 4-addition reaction of conjugated ketones with Grignard reagents.

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Bis-quaternary ammonium salts [C_m-Bis (N-C_n)], possessing two equivalent ammonium groups substituted with one long-alkyl chain and two methyl groups and a connecting alkanediyl chain, were synthesized. Alkyl chains with 10 to 16 carbon atoms (n) and connecting chains with 2 to 6 carbon atoms (m), were examined for surface-active properties in water. The Krafft point decreased with increase in m. Critical micelle concentration decreased with increase in alkyl chain length n but was little affected with increase in connecting chain m and was about one order of magnitude lower than that of conventional mono-quaternary ammonium salts. Bis-type amphiphiles were more efficient, for m≤4, than corresponding monomeric surfactants in lowering the surface tension of water and surface area per molecule at air-water interface increased with n and m. The aggregation number of micelles increased with n but decreased with increase in m.
Variation in connecting chain m had significant influence on adsorption at the air-water interface and micelle formation in aqueous media of bis-type amphiphiles.

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The behavior of vitamin K₁ in the refining of vegetable oil, and vitamin K₁ content of commercial vegetable oils were examined.
(1) Vitamin K₁ in vegetable oil decreased considerably in deodorization in proportion to period of deodorization, furthermore vitamin K₁ decreased more at 260°C than at 230°C in deodorization.
(2) The behavior of vitamin K₁ in the refining was similar to that of tocopherol.
(3) Vitamin K₁ content of commercial grape seed oil was 72500μg/100g, which exceeds that in the other commercial vegetable oils.
(4) In each vegetable oil, Vitamin K₁ content of commercial oils greatly differ according to brand.

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HLB-temperature was found to change greatly with the number of glycerol (or hydroxyl) groups of polyglycerol nonionic surfactants based on examination of the phase inversion temperature (HLB-temperature) of emulsions. Change in HLB in polyglycerol nonionic surfactants was much more extensive compare to polyoxyethylene surfactants, and thus when using polyglycerol surfactants, suitable HLB by mixing is required. HLB of polyglycerol nonionic surfactants changed greatly compared to usual polyoxyethylene surfactants, the extent depending on the hydrocarbons (oils) used. The properties of polyglycerol nonionic surfactants were noted to be little affected by temperature.

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The anti-inflammatory drug, β-glycyrrhizinic acid 20-methyl ester (GMe), was converted to cationic variants (CGRs) by derivatizing diglucronic carboxyl groups with 2- (N-ethyl-, N-butyl- and N-benzyl-N, N-dimetylammonio) ethylamines. Critical micellar concentrations, ranging from 0.40.7mM, were essentially independent of solution pH from 5 to 9 and approximated that of GMe (0.3mM at pH 57.4). Transferability (%) of CGRs from water to 1-octanol phase at higher-than-neutral pH was much more than that of GMe or β-glycyrrhizinic acid (GL) : CGBu (55) >CGBn (20) >CGEt (15) >GMe (10) >GL (0). CGRs remarkably accelerated the release of the carboxyfluorescein (CF) trapped inside DPPC vesicles with no costing significant damage to cell membranes. The CF-releasing mechanism was examined kinetically by differential scanning calorimetory, light-scattering and electron microcopy.

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Automatic interfacial tension measurement apparatus based on the drop volume method was developed so as to determine interfacial tension between two liquid phases rapidly and accurately. By this apparatus, for pure water and oil, constant values of equilibrium interfacial tension were obtained. Interfacial tension between aqueous solutions of surfactant and oil, and oil solutions of surfactant and water was measured. In all cases, the equilibrium tension values were determined with high reproducibility and reliability of their absolute values was confirmed.
Interfacial tension between two liquid phases could be determined rapidly and automatically with high accuracy, and thus the present apparatus should prove quite using for examining various interfacial phenomena.

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Multi-alkylated surfactants of partially-quaternized 2-vinylpyridine telomers having 2-4 alkyl chains (xR_n-2VPQ; x and R_n mean the number of lipophilic alkyl chains and alkyl chain length, respectively) were derived from telomers with polymerization degree (Pn) ca. 5 obtained as salts of hydrochloric acid. Surface activitiy was voted to be highly affected by alkyl chain length and number of chains. Surface tension of 3.9R₈-2VP⁺Q and 3.4R₁₂-2VP⁺Q with Pn ca. 5 solutions (pH 2) was 28-29mN m^-1 at critical micellar concentration. Surface activity was affected by Pn of telomers and xR_n-2VP⁺Q having 3-4 octyl or dodecyl chains with Pn ca. 5 showed greater surface activity than xR₁₂-2VP⁺Q having 3-6 dodecyl chains with Pn 10-20.

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A new triterpenoid, (17α, 20R) -dammara-12, 24-dien-3β-ol, was isolated (as the acetate) from the fruits of Clusia guaviarensis and was identified by spectroscopic and chemical methods. This is the first example of a naturally occurring triterpenoid with a (17α, 20R) -dammarane skeleton.

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Study was made to determine the structures of three minor 5α-steroidal 3-ones detected in the seeds of foxtail millet (Setaria italica Beauv.). For this purpose, 24-ethyl-5α-cholest-24 (28) Z en-3-one and its carbon-carbon double bond isomers were synthesized from isofucosterol. Based on direct GC-MS comparison with the synthetic samples, one steroid was found here for the first time to have the structure, 24-ethyl-5α-cholest-24 (28) Z-en-3-one. Two other minor steroids were identified as 24ξ-ethyl-5α-cholesta-7, 22E-lien-3-one and 24ξ-ethyl-5α-cholest-7-en-3-one.

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