The methods for the introduction of trifluoromethyl and other fluoroalkyl groups into aro-matic compounds have been described in detail. Furthermore, it has also been demonstrated that the various aromatic compounds containing fluoroalkyl groups are applicable to the water-oil repellent and optical usage.
Two types of phase behavior were observed in a water/nonionic surfactant/triglyceride sys-tem. One type was the same as that noted in a water/nonionic surfactant/hydrocarbons system in which a surfactant phase, D, coexists with excess water and oil phases at a certain temperature. The other type was typically observed in a water/nonionic surfactant/amphiphilic oil such as long-chain alcohols. That is, a lamellar liquid crystal coexists with an oil phase at lower tem-perature. With increase in temperature, liquid crystals melt and the melted phase (another sur-factant phase, D') forms a three-phase region together with the water and oil phases. Each of these two types of phase behavior is dependent on the types of surfactant and triglycerides and can be changed by addition of propanol.
Two kinds of 2-alkyl-3-hydroxy fatty acids having definite alkyl chain lengths (carbon number=16 and 24) were synthesized as they have similar chemical structures to those of natural-ly-occurring corynomycolic acids as microbial biosurfactants from a hydrocarbon-assimilat-ing microorganisms. Their surface-active properties were very good, particularly in regard to surface and interfacial tension lowering, and penetrating and emulsifying acition. These acids were compared for their alkyl chain lengths. The membrane fluidity of hydrocarbon-assimilat-ing microorganism (Candida bombicola) was found to increase on adding of corynomycolic acids (4a, 4a-Na, 4b, and 4b-Na) using the ESR spin probe method. Aqueous solutions of corynomycolic acids wetted remarkably polymer surfaces such as polyethylene terephthalate (critical surface tension=43mN/m) as microbial surface models. From these results, hydroca-rbon-assimilating microorganism may be concluded to take in small droplets of hydrocarbon emulsions inside their cells in close contact with emulsions through the mediation of corynomyc-olic acids.
Nine fungi of Mortierella genus were cultivated batchwise in a 30L-fermenter in high con-centration glucose medium (100-200g/L). As a result, four strains attained a γ-linolenic acid (GLA) productivity exceeding 2g/L. The strain content of GLA in the fatty acids of the lipids obtained was from 6.6-7.8%. Using M. ramanniana var. angulispora IFO 8187, one of the four strains, the effects of various cultivation conditions on GLA productivity were investigated. Culti-vation at a higher content of GLA in the total lipids was generally noted in strains with lower lipid productivity, thus giving lower GLA yield. Consequently, cultivation to obtain high GLA yield is possible in a cultivation of high lipid productivity rather than high GLA content. Two types of repeated batch cultures with one and two fermenters, respectively, were made to obtain higher lipid productivity. A maximum lipid productivity of 13.9g/L/d was realized in the 2nd fermenter with a double stage repeated batch culture. GLA yield in the repeated batch culture increased with lipid productivity.
In the course of studies on the iodine-sensitized photoconjugation of 1, 4-diene compounds, the effects of terminal functional groups on this reaction were investigated. Linoleic acid and its related compounds, such as methyl linoleate, linoleyl alcohol, linoleyl acetate and cis-6, cis-9-octadecadiene derived from linoleic acid, were used as samples. Based on the results of sensitized isomerization, the carboxyl group was without any effect whatsoever. Linoleic acid reacted at the same rate as 6, 9-octadecadiene, or faster than that of methyl linoleate, so that maximum equilibrium was attained within 1h. Moreover, the photo-conjugation of linoleyl acetate occurred more slowly than that of methyl linoleate. The amounts of the conjugated compounds were about as much as 80% in either case. With linoleyl alcohol, isomerization was quite slow, the yield being about 10% after 8h. This is in agreement with the finding that this sensitized conjugation does not proceed in a polar solvent such as ethanol. Therefore, the reactivities of the end-groups on this iodine-sensitized reaction decrease in the following order : CH3≥COOH>COOCH3>CH2OCOCH3>>CH2OH. This reaction apparently occurs through a radical mechanism involving a bridged iodoalkyl radical as an intermediate. The products mainly consisting of cis, trans- and trans, trans-conjugated dienes were thus obtained at a ratio of about 3 : 7.
The procedure for the synthesis of γ-jasmolactone from methyl 3-farmyl propionate is pre-seated, as shown in Scheme-1. Methyl 7, 7-diethoxy-4-oxoheptanoate (2), prepared from methyl 3-formylpropionate (1) and acrylaldehyde diethyl acetal by radical addition reaction in a 64% yield, was converted to 7, 7-diethoxy-4-heptanolide (3) in 86% yield. The lactone (3) was treated with 1% acetic acid under reflux to give 6-formyl-4-hexanolide (4) in 86% yield, on which the Wittig reaction was subse-quently conducted to give γ-jasmolactone (5) in 77% yield. Methyl 6-formyl-4-oxohexanoate (6) was prepared from compound (2) by refluxing with 1% acetic acid in 82% yield. γ-Jasmolactone (5) was synthesized from compound (6) in the 55% yield, according to the published method.