A convenient synthesis of 3-methyl-2-cyclopenten-2-ol-1-one (IIIa), a constituent of coffee aroma and maple flavor, is described. Condensation of diethyl glutarate with diethyl oxalate in N, N-dimethylformamide gave diketodiester I ; methylation in methyl ethyl ketone or in acetonitrile in the presence of potassium carbonate produced doubly methylated compound IIa which was hydrolyzed and decarboxylated to afford IIIa by refluxing with concentrated hydrochloric acid in acetic acid. Other allied compounds were also synthesized.
Following the previous studies on the lipids of micronektonic fishes and shrimps, the present paper deals with those of marine zooplanktons, which are fed by the micronekton and play an important role in the food chain. Most of the specimens were collected in the Japan Sea, Sagami and Suruga Bays. They consisted of two species belonging to the order Amphipoda (A), three species beloging to the order Euphausiacea (B) and five species belonging to the order Calanoida (C). Besides them the zooplankters were also caught from various depths off the Kii Channel and examined. The lipid contents of crustaceans based on the wet weight were 1.4% to 3.2% in A, 1.1% to 7.7% in B, and 4.8% to 15.7% in C. The wax esters in their lipids ranged from 63.8% of Calanus sinicus to 87.9% of Pareuchaeta elongata in C, from 37.2% of Parathemisto japonica to 49.0% of Printno macropa in A, and less than 10% in B. Generally the spring specimens contained larger amounts of the lipids than the autumn ones. However, the wax contents in the lipids indicated the opposite relation. Although the wax esters cover the carbon chain-length C30 to C46, the major esters range C34 to C44 with even numbered carbons, and also a trace amounts of odd numbered esters exist. The wax esters of Parathemisto japonica and Calanus cristatus composed of rather longer esters and their composition was similar to that of micronektonic shrimps, while the wax esters of Thysanoessa longipes, Pareuchaeta elongata and Euphausia pacifica were rich in shorter ones as observed in micronektonic fishes. These differences resulted from the composition of fatty acid and fatty alcohol moieties. The former type consists dominantly of monoenoic fatty acids and alcohols such as C20 : 1 and C22 : 1, whereas the latter one contains highly unsaturated fatty acids such as C20 : 5 and C22 : 6 and rather shorter alcohols such as C16 : 0 and CC18 : 1 as major components By analyzing the lipids of mixed zooplankters obtained from the different depths, 5m, 100m, 300m, 500m and 1, 000 m, it was recognized that the deeper zooplankton contained larger amounts of wax esters and less triglycerides, and vice versa for these lipid classes of the shallower one. An attempt to test the incorporation of 14C labelled substrates into the lipid classes by the intact zooplankters caught from 1, 000 m depth was carried out. In the case of [1-14C] -cetyl alcohol 42.2% were measured in the class of wax esters, in [1-14C] -palmitic acid 18.7% and in [1-14C] -acetate 14.3% as percentage radioactivity. Considerable amounts of radioactivity were also detected in the classes of aldehydes and alcohols, suggesting the bioreduction of the donated fatty acid to them before ester formation. Finally, the analyses of amino acid composition of crustacean plankton proteins revealed that they were quite alike each other, rich in ten essential amino acids, and excellent as natural diet for fishes from the viewpoints of nutrition of proteins as well as lipids which contain abundant essential fatty acids of linolenic family (w3).
In the course of the study on the lower order molecular association of oligosoap and polysoap in aqueous solution, the aggregation and solution properties of potassium caprylate (KC8) were investigated since its structure is simple and contains the same (polar) functional group, i. e, carboxylate, on those of oligosoap and polysoap. (1) The cmc values were measured by various methods. They were clearly observed and in good agreement each other. (2) The pre-cmc aggregation of KC8 may be probable in aqueous solution from the fact that reduced intensity vs, concentration plot shows a gradual ascent with increasing the concentration up to the cmc, and that the solubilization of the dye vs, concentration plot has two inflexion points. Further. (3) lower order molecular association of KC8, (4) effective micellar charge and (5) polydispersity of the micelle size have been discussed. The characteristics of (2), (3) and (5) of KC8 seem to be similar to those of oligosoap.
Solution polymerization of methyl acrylate was carried out using 1-dodecanol (ROH), 1-chloro dodecane (RCl), 1-dodecanoic acid (RCOOH), 1-dodecyl amine (RNH2), or 1-dodecane thiol (RSH) as solvent and benzoyl peroxid (BPO) as an initiator. When ROH, RCl or RCOOH was used as solvent the degree of polymerization of telomers (LO, LC and LA series) obtained were 1022 and ROH was the most excellent solvent in point of yield and low degree of polymerization. On the other hand, use of RNH2 as solvent gave N, N'-didodecyl-β-amino propionamide (LN-A) and its polymer (LN-AA), while use of RSH as solvent yielded 1 : 1-addition product, disulfide and telomer (Pn=2.4). The chemical structures of these products were determined by their molecular weight, elementary analyses and IR spectra. These telomers were treated with water-acetone alkaline solution to obtain the corresponding polyacrylic acid. The surface active properties of these saponified telomers are as follows : Their surface tension generally showed a high value, but high saponified LO series had a low value (<30 dyne/cm). Relation between cmc and Pn of LO series was log cmc=0.0549PPn-1.80. Low saponified telomers showed good value on emulsifying, but bad on dispersing power.
The telomer indicated below was obtained by solution polymerization of methyl acrylate using 1-dodecanol as a solvent and benzoyl peroxide as an initiator. _??_ This telomer (Lo) was then treated with hydroxyl amine and sodium methoxide in benzene to obtain the corresponding polycarboxy-polyhydroxamic acid (LoHX series). Treatment of the telomer (LO) with water-acetone alkaline solution to obtain the corresponding partialy saponified ones (LoH series). LoH series were further treated with hydrazine hydrate or ethylenediamine to obtain the corresponding poly-carboxy-polyhydrazide (LoH HD series) or polycarboxy-polyamide (LoH EA series), respectively. _??_ _??_ These reactions proceed smoothly, and the chemical structures of these derivatives were determined by elementary analyses and IR spectra. These telomer type surfactants were easily soluble in water and capable of micelle formation. Further, they, especially LoHX series, formed water insoluble chelate complexes with various metal ions.
The new type of complexanes (Ia, b, c) having hydrophobic alkyl groups (decyl (a), dodecyl (b), hexadecyl (c)) were synthesized and their properties as surfactant were investigated. An aqueous solution of complexane (Ib) -copper chelate (5×10-3M) showed 0.40 in specific surface tension and 0.12 in specific interfacial tension (kerosene/water). The iron chelates of those complexanes had excellent dispersing power (TiO2/toluene) compared with commercial dispersants.
cis-4-Decenoic, trans-4-decenoic, and Rac.-3-hydroxydecanoic acids and their sodium salts had antiseptic effect on bacteria, yeast and mold Especially, cis-4-decenoic and trans-4-decenoic acids showed a remarkable effect than Rac.-3-hydroxydecanoic acid, sodium cis-4-decenoate, sodium trans-4-decenoate and sodium Rac.-3-hydroxydecanoate. The antiseptic property of these free fatty acids and their corresponding sodium salts were greater in the medium of low pH. For example, the minimum inhibitory concentration of cis-4-decenoic acid was 1/5000 for Bacillus subtilis, Bacillus megateriuna, Mucor praini, Rhizopus chinensis, Penicillium roqueforti, Aspergillus niger, Candida lipolytica and Saccharomyces cerevisiae on a glucose-peptone medium in pH 4.
1-Dialkylaminoalkylidenediphosphonic acids were obtained by the reaction of N, N-dialkylaliphatic acid amides with phosphorus trichloride, and subsequent treatment with acetic acid. The dissociation constants (pKa) of these aminodiphosphonic acids were determined from the titration curves. The behavior of dimethylaminomethylenediphosphonic acid and 1-dimethylaminoethylidene-diphosphonic acid toward metal ions was investigated, and it was found that these aminodiphosphonic acids could be utilized for chelating agents.