Transition Structures of the Electrocyclic Reactions of cis,cis,cis-1,3,5-Cyclooctatriene

The electrocyclic reactions of cis,cis,cis-1,3,5-cyclooctatriene have been studied using ab initio molecular orbital theory. cis,cis,cis-1,3,5-cyclooctatriene can undergo an electrocyclic ring opening in a conrotatory fashion to form cis,cis-1,3,5,7-octatetraene and a disrotatory electrocyclization to form bicyclo[4.2.0]octa-2,4-diene. The transition structures for these electrocyclic reactions have been located. Geometry optimizations employed restricted Hartree-Fock calculations and the 3–21G and 6–31G* basis sets. Electron correlation energies were calculated using second-order, and in some cases fourth-order, Møller-Plesset theory. Scaled RHF/6–31G* force constants were employed in the prediction of secondary deuterium isotope effects for the conrotatory ring opening. The ground state of cis,cis,cis-1,3,5-cyclooctatriene exists in a twist-boat conformation with staggering at the saturated linkage. The transition structure for the conrotatory electrocyclic ring opening to form cis,cis-1,3,5,7-octatetraene has a helical structure, which has implications for the stereoselectivities of ring closure of 1-substituted-cis,cis-1,3,5,7-octatetraenes. The disrotatory transition structure for the electrocyclization to form bicyclo[4.2.0]octa-2,4-diene is strongly distorted from C_s symmetry, in contrast to the transition structure for the disrotatory electrocyclization of cis-1,3,5-hexatriene. This distortion is caused by staggering about the saturated linkage.     

Synthesis and Characterization of Diepoxyalkenes Derived from (3Z,6Z,9Z)-Trienes: Lymantriid Sex Pheromones and Their Candidates

All stereoisomers of three diepoxyalkenes derived from (3Z,6Z,9Z)-trienes with a C₂₁, C₁₉, or C₁₈ straight chain, lymantriid sex pheromones and their candidates, were synthesized by MCPBA oxidation of optically active epoxyalkadienes. Their chromatographic behaviors were examined with GC and LC equipped with achiral and chiral columns. Detailed inspection of the mass spectra of these epoxides indicated the following diagnostic ions for determining the chemical structures: m/z 128, 167, M-87 and M-85 for (Z)-cis-3,4-cis-6,7-diepoxy-9-enes; m/z 111, M-125 and M-69 for (Z)-cis-6,7-cis-9,10-diepoxy-3-enes; and m/z M-125 and M-139 for (Z)-cis-3,4-cis-9,10-diepoxy-6-enes. Mass chromatographic analysis that monitored these fragment ions revealed the existence of a new pheromonal compound with a C₂₁ chain in an extract from virgin females of a lymantriid species, Perina nuda F. The three diepoxyalkenes were converted into the corresponding DMDS adducts, which showed characteristic ions from fragmentation between the two thiomethyl groups, reflecting the position of an original double bond.     

Identification of Sex Pheromone Components of a New Zealand Geometrid Moth, the Common Forest Looper Pseudocoremia suavis, Reveals a Possible Species Complex

Gas chromatography–electroantennographic detection analysis of sex pheromone gland extracts of the common forest looper Pseudocoremia suavis (Lepidoptera: Geometridae), a polyphagous defoliator of introduced Pinaceae and many New Zealand trees, revealed four compounds that elicited antennal responses. The two major active compounds (6Z)-cis-9,10-epoxynonadec-6-ene and (3Z,6Z)-cis-9,10-epoxynonadeca-3,6-diene were identified by comparison with known standards. Of the two minor active compounds, one was tentatively identified as (3Z,6Z)-cis-9,10-epoxyhenicosa-3,6-diene, whereas the other could not be identified because of insufficient amounts in extracts. (6Z)-cis-9,10-Epoxynonadec-6-ene, (3Z,6Z)-cis-9,10-epoxynonadeca-3,6-diene, and (3Z,6Z)-cis-9,10-epoxyhenicosa-3,6-diene were present in P. suavis gland extracts from Eyrewell Forest, a Pinus radiata plantation in the South Island of New Zealand, in a ratio of 35:65:5, respectively. Trapping trials in Eyrewell Forest established that (6Z)-cis-9,10-epoxynonadec-6-ene attracted male P. suavis. However, addition of (3Z,6Z)-cis-9,10-epoxyhenicosa-3,6-diene to the lure at <10% of (6Z)-cis-9,10-epoxynonadec-6-ene reduced capture of male moths, suggesting that one of its enantiomers was acting as a behavioral antagonist. During January–March of 2005, a blend trial involving single, binary, and ternary mixtures of the three components at Eyrewell Forest and at three other sites (two in the South Island and one in the North Island) revealed the existence of a second taxon of P. suavis at the three additional sites that was attracted to lures containing (3Z,6Z)-cis-9,10-epoxynonadeca-3,6-diene, either singly or in binary and ternary mixtures with (6Z)-cis-9,10-epoxynonadec-6-ene and (3Z,6Z)-cis-9,10-epoxyhenicosa-3,6-diene. This second taxon was not attracted to lures loaded solely with (6Z)-cis-9,10-epoxynonadec-6-ene.     

Cyclopinolenic acids: Synthesis,derivatives and thermal properties

The two isomeric cyclopinolenic acids (CP-1 and CP-2), components of distilled tall oil, have been synthesized by means of an intramolecular Diels-Alder reaction of isomers of 5,10,12-octadecatrienoic esters, themselves synthesized in a stereocontrolled manner. The 5cis,10-trans,12trans isomer cyclizes at 200°C to a 1:3 mixture of esters of CP-1 and CP-2. At 200°C, the 5cis,10trans,12cis isomer is unreactive, but at 240°C it gives the same CP-1 + CP-2 ester mixture, presumably by way of prior isomerization to the 5cis,10trans,12trans isomer. A subambient thermal study of CP-1 and CP-2 and their derivatives shows that the compounds, excluding CP-1, lack crystalline structures or melting points, and display glass transitions only, below −80°C for esters and below −50°C for the carboxylic acids.     

cis-5,cis-9,cis-12-octadecatrienoic and some unusual oxygenated acids inXeranthemum annuum seed oil

Seed oil ofXeranthemum annuum (family Compositae) contains a number of unusual fatty acids in addition to palmitic, stearic, oleic, linoleic and linolenic. These acids includecis-5,cis-9,cis-12-octadecatrienoic, 5%;cis-9-l,10-l-epoxyoctadecanoic, 3%;cis-9-l,10-l-epoxy-cis-12-octadecenoic (coronaric), 8%; andcis-12-d,13-d-epoxy-cis-9-octadecenoic (vernolic), 2%; as well as a mixture of two hydroxy acids, 11%. The absolute configurations of the two 9,10-epoxy acids are established for the first time. Presented in part at the AOCS Meeting in Cincinnati, October 1965. No. Utiliz. Res. Dev. Div., ARS, USDA.     

Differences in Oxidation Kinetics Between Conjugated and Non-Conjugated Methyl Linoleate

The oxidation kinetics of conjugated methyl linoleate was compared with that of non-conjugated methyl linoleate under mild oxidation conditions (30 °C in the dark). Samples of methyl 9-cis,11-trans-linoleate, methyl 10-trans,12-cis linoleate and methyl 9-cis,12-cis linoleate were assayed separately and in mixtures. For comparative purposes, methyl α-linolenate and methyl oleate were also used. Two complementary analytical approaches were selected to monitor the progress of oxidation, (1) the traditional follow-up of residual substrate by gas liquid chromatography, and (2) an analytical procedure by high-performance size-exclusion chromatography (HPSEC) for direct measurement of the oxidation compounds formed. The HPSEC method enabled us to quantitate oxidized monomers, dimers and polymers concomitantly in a rapid and direct analysis. Results showed that conjugated methyl linoleate samples oxidized later than their non-conjugated counterparts, and showed a very different oxidation pattern. Thus, formation of oxidized monomers was negligible and the first and major compounds formed were polymerization products. Also, under the conditions used, non-conjugated and conjugated methyl linoleate samples in 1:1 mixtures led to decreased oxidation rate of non-conjugated methyl linoleate and increased oxidation rate of conjugated methyl linoleate. This study supports the view that oxidation kinetics of conjugated dienes differ substantially from that of methylene-interrupted dienes.     

Synthesis and field bioassay of some analogs of sex pheromone of citrus mealybug,Planococcus citri (Risso)

A series of structural analogs of (s+)-cis-(1R)-3-isopropenyl-2,2-dimethylcyclobutanemethanol acetate, sex pheromone of the citrus mealybug,Planococcus citri (Risso), was synthesized. The analogs were tested in a field bioassay in order to determine the structure-activity relationships of the pheromone. All changes in structure reduced the activity of the test compounds, to various degrees. The most active analog tested was the homolog (+)-cis-(1R)-3-isopropenyl-2,2-dimethylcyclobutaneethanol acetate (IV), whose activity, at a higher dosage, was comparable to that of the pheromone. The alcohol (+)-cis-(1R)-3-isopropenyl-2,2-dimethylcyclobutanemethanol was tested in mixtures with the pheromone and found to be neither an inhibitor nor a Synergist. The results show that all functional groups of the pheromone molecule are essential for optimal biological activity.Homoptera: Coccoidea: Pseudococcidae.Contribution from the Agricultural Research Organization (ARO), The Volcani Center, Bet Dagan, Israel, No. 1667-E, 1986 series.Levi Eshkol Postdoctoral Fellow, 1984–1986.     

High-performance liquid chromatography and spectroscopic studies on fish oil oxidation products extracted from frozen atlantic mackerel

The formation of stable hydroxy derivatives from hydroperoxides produced during the oxidation of linoleic acid methyl ester and fish oil were studied by reverse-phase high-performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS) and ¹³C nuclear magnetic resonance (NMR) spectroscopy. The oxidation products identified were mixtures of four isomeric hydroxy derivatives: 13-hydroxy-9-cis,11-trans-octadecadienoic, 13-hydroxy-9-trans,11-trans-octadecadienoic, 9-hydroxy-10-trans,12-cis-octadecadienoic, and 9-hydroxy-10-trans,12-trans-octadecadienoic acids. The presence of hydroxy compounds was confirmed by ¹³C NMR, which gave rise to a hydroxy carbon peak at 87 ppm, and by GC-MS, which showed three peaks corresponding to isomeric mixtures of trimethylsilyl ethers of the oxidized linoleic acid methyl ester. The mass spectra scans of the three peaks showed that they represent isomers of molecular weight 382 and are consistent with the molecular formula C₂₂H₄₂O₃Si. In oil extracted from stored frozen mackerel, 13-hydroxy-9-cis,11-trans-octadecadienoic acid was more prominent compared to the model lipid systems. HPLC offered a sensitive means of detection of hydroxy compounds produced both in the initiation and latter stages of oxidation. The effect of antioxidants added to the fish mince prior to storage can also be monitored by HPLC. Thus, the monitoring of lipid oxidation hydroxy derivatives by HPLC is of practical value in the efficient processing and quality control of fish, fish oils, and other fatty foodstuffs in order to enhance the acceptability, nutritional, and safety aspects.     

Synthesis of methyl 11,14,17-eicosatrienoate-3,3,4,4,8,8,9,9-d 8

For use in metabolic studies, methyl 11,14,17-eicosatrienoate-3,3,4,4,8,8,9,9-d ₈ was prepared by Wittig coupling of 3,6-nonadienyltriphenylphosphonium iodide with methyl 11-oxoundecanoate-3,3,4,4,8,8,9,9-d ₈ in the presence of butyl lithium. Theall cis isomer was separated by high-pressure liquid chromatography using a reverse-phase column. An unexpected by-product, methyl 10,13,16-nonadecatrienoate-2,2,3,3,7,7,8,8-d ₈, was also isolated. The structures and the configurations of the compounds were confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.     

Synthesis of 18-octadecanolide,a major constituent of dufour’s gland secretion ofColletes bees

18-Octadecanolide, a major constituent of Dufour’s gland secretion ofColletes bees, was synthesized by polymerization followed by depolymerization of 18-hydroxyoctadecanoic acid which in turn was obtained by hydrogenation of kamlolenic acid (18-hydroxy, 9-cis, 11-trans, 13-trans-octadecatrienoic acid) isolated fromMallotus philippinensis seed oil. The structures of the intermediates as well as the final lactone were established by infrared, proton nuclear magnetic resonance and mass spectrometric methods.     

Sex pheromone components of three species ofSemiothisa (Geometridae), (Z,Z,Z)-3,6,9-heptadecatriene and two monoepoxydiene analogs

Adult males ofSemiothisa signaria dispuncta (Walker) were attracted to field traps baited with (Z,Z,Z)-3,6,9-octadecatriene and (Z,Z)-6,9-cis-3,4-epoxy-octadecadiene. However, analyses of sex pheromone gland extracts of females of this species by GC-MS and by GC in combination with an electroantennograph detector (GC-EAD) showed the pheromone to be comprised of a mixture of the next lower homologs: (Z,Z,Z)-3,6,9-heptadecatriene and (Z,Z)-6,9-cis-3,4-epoxy-heptadecadiene. Blends of these two C₁₇ compounds were subsequently found to be more attractive to males in the field than the corresponding C₁₈ mixtures. Sex pheromones of two otherSemiothisa species were also found to contain C₁₇ components. (Z,Z,Z)-3,6,9-Heptadecatriene, detected by GC-EAD analysis of a female abdominal tip extract ofS. bicolorata (Fabricius), attracted conspecific males, and this attraction was significantly reduced by additions of (Z,Z)-6,9-cis-3,4-epoxyheptadecadiene, the major pheromone component ofS. signaria dispuncta, to the lure. (Z,Z)-3,9-cis-6,7-Epoxy-heptadecadiene was detected by GC-EAD analysis as the primary male antennal stimulatory component present in abdominal tip extracts ofS. ulsterata (Pearsall), and males of this species were attracted to traps baited with this epoxide. Each of these three C₁₇ compounds constitute previously unknown lepidopteran sex pheromone components. Blends of (Z,Z, Z)-3,6,9-heptadecatriene and (Z,Z)-3,9-cis-6,7-epoxyheptadecadiene attracted males of a fourth species,S. delectata Hulst, but no females of this species were obtained to permit analysis of its sex pheromone. The occurrence of (Z,Z,Z)-3,6,9-heptadecatriene inS. neptaria (Guenee) females was indicated by GC-MS analysis of an abdominal tip extract; however, no males were attracted to any of the fielded mixtures containing this hydrocarbon.     

Abraxas grossulariata L. (Lepidoptera: Geometridae): Identification of (3Z,6Z,9Z)-3,6,9-heptadecatriene and (6Z,9Z)-6,9-cis-3,4-epoxyheptadecadiene in the female sex pheromone

(3Z,6Z,9Z)-3,6,9-Heptadecatriene and (6Z,9Z)-6,9-cis-3,4-epoxyheptadecadiene have been identified in female sex pheromone gland extracts ofAbraxas grossulariata L. (Lepidoptera: Geometridae). The compounds were detected by gas chromatography with electroantennographic detection (GC-EAD) and identified by GC-mass spectrometry (GC-MS). The amounts of hydrocarbon and epoxide were 0.13 and 0.42 ng/female, respectively. These identifications were confirmed by synthesis; the absolute configuration of the epoxide remains to be determined. Another isomeric epoxide, (3Z,6Z)-3,6-cis-9,10-epoxyheptadecadiene, was tentatively identified in small amounts (0.04 ng/female). Racemic (6Z,9Z)-6,9-cis-3,4-epoxyheptadecadiene elicited the largest electroantennogram response within a series of heptadecadiene and nonadecadiene monoepoxides and the corresponding trienic hydrocarbons and, in field tests, attracted maleA. grossulariata into traps. Addition of 10% (3Z,6Z,9Z)-3,6,9-heptadecatriene to this epoxide enhanced attractiveness; addition of (3Z,6Z)-3,6-cis-9,10-epoxyheptadecadiene had no effect at low proportions while higher proportions caused a reduction in the numbers of males caught.     

Identification of 11,15-octadecadienoic acid from beef and mutton tallow

By means of gas liquid chromatography and thin layer chromatography on Silica gel G/AgNO₃ we isolated some isolinoleic acids from beef and mutton tallow, which by their chromatographical behavior, IR analysis and by double bond determination by ozonolysis are mainly stereo-isomeric 11,15-octadecadienoic acids and in a smaller amount stereo-isomers of 10,15-octadecadienoic acids. 4-Cis- and 4-trans-heptenals, 2-trans,6-cis- and 2-trans,6-trans-nonadienals have been isolated from the DNPH mixture obtained from the volatile decomposition products of an oxidized synthetic mixture of stereo-isomeric 11,15-octadecadienoic acids. Presented in part by G. Hoffmann at the 7th ISF Congress, Hamburg, October 1964.     

Male-Produced Sex Attractant Pheromone of the Green Stink Bug, Acrosternum hilare (Say)

Sexually mature virgin adult males of the green stink bug, Acrosternum hilare attracted sexually mature virgin adult females in laboratory bioassays using a vertical Y-tube. There was no indication that males attracted other males, or that females attracted either sex. These results suggested that A. hilare males produce a sex pheromone. Extracts of odors collected from sexually mature males contained compounds that were not present in extracts from females or sexually immature males. (4S)-Cis-(Z)-bisabolene epoxide ((4S)-cis-Z-BAE) was the major sex-specific component of the extract. The crude extract was attractive to female A. hilare, but when separated into four fractions, only the portion containing (4S)-cis-Z-BAE and the minor component (4S)-trans-Z-BAE was attractive to females. This fraction was as attractive as the crude extract, suggesting that the former contained all the pheromone components. Neither synthetic (4S)-cis-Z-BAE nor (4S)-trans-Z-BAE alone was attractive to females, but a 95:5 cis:trans blend, mimicing the ratio naturally produced by males, was attractive to females in Y-tube bioassays. Bioassays in a field cage showed that significantly more A. hilare females were attracted to cotton string lures treated with 1 mg of a 95:5 blend of (4S)-cis-Z-BAE and (4S)-trans-Z-BAE placed inside a bouquet of alfalfa than to an alfalfa bouquet containing a pentane-treated control. In field cage studies, attraction of females was greatest during the late afternoon and evening hours, and female A. hilare approached the synthetic pheromone source almost exclusively by walking.     

Conformational behavior of 3,3-dimethyl-3-silathiane 1-oxide and its diastereomeric 2-methyl derivatives

The conformational behavior of 3,3-dimethyl-3-silathiane 1-oxide 3 and its trans-4 and cis-4 2-methyl derivatives has been studied by ¹H and ¹³C NMR. The equatorial conformer 3-eq for 3 and the diequatorial isomer trans-4-eq for trans-4 predominate (>95%) in CDCl₃ solution. In contrast, the cis-4-ax conformer is the more preferred form of cis-4. The conformational free energy (ΔG°) in the equilibrium cis-4-ax???cis-4-eq was determined to be about +0.01 and +0.52?kcal?mol^?1 at 26 and ?120°C, respectively. The Gibbs free energy of activation (ΔG ^?) for the inversion cis-4-ax?→?cis-4-eq was estimated to be 8.1?kcal?mol^?1 at ?100°C.     

Application of a GC-MS method using deuterated fatty acids for tracingcis-vaccenic acid biosynthesis in kaki pulp

A gas chromatographic-mass spectrometric method using [2,2-²H₂]fatty acids has been developed to trace the biosynthesis ofcis-vaccenic (cis-11-octadecenoic) acid in higher plants. The deuterated fatty acids and other unlabeled fatty acids in the biosynthetic reaction mixture were converted into bis(methylthio) derivatives and analyzed by mass chromatography. The principle of this method was based on the shift of key fragment ions (containing two deuterium atoms) due to the cleavage between the methylthio-substituted carbons. The labeled compounds were detected by the m/z values which shifted 2 mass units from those of the corresponding unlabeled compounds and estimated by a calibration curve based on the peak areas of the key fragment ions. For metabolic experiments, a homogenate fraction was prepared from the pulp part of maturing kaki (Diospyros kaki) fruit and incubated with ammonium [2,2-²H₂]palmitoleate (cis-9-hexadecenoate) or [2,2-²H₂]palmitoleoyl-CoA. The incubation resulted in the formation of detectable amounts of isotopically-labeledcis-vaccenic acid containing two deuterium atoms at the carbon chain between the double bond and the carboxyl group. This experimental evidence proved thatcis-vaccenic acid was formed from palmitoleic acid by chain elongation.     

Analysis of the geometric isomers of methyl linoleate by gas chromatography

The four geometric isomers of methyl linoleate have been quantitatively determined by gas chromatography on Apiezon L and DEGS polyester capillary columns. Three peaks were eluted from the Apiezon L column: (a) the 9-cis, 12-cis isomer; (b) the 9-cis, 12-trans isomer; and (c) the 9-trans, 12-cis and 9-trans, 12-trans isomers combined. The DEGS polyester column also resolved three peaks: (a) the 9-trans, 12-trans isomer; (b) the 9-cis, 12-cis and 9-cis, 12-trans isomers combined; and (c) the 9-trans, 12-cis isomer. Since the separation of isomers was different on each column, the content of each of the four isomers could be determined from the combined results. Quantitative results agreed closely with the per centtrans bonds as determined by infrared analysis. Presented at the fall meeting of the American Oil Chemists' Society, Chicago, Illinois, October 30-November 1, 1961. Supported in part by a grant from Cargill, Ineorporated.     

Electrophysiological and chemical analysis of sex pheromone communication system of the mottled umber,Erannis defoliaria (Lepidoptera: Geometridae)

(Z,Z,Z)-3,6,9-nonadecatriene (Z3,Z6,Z9–19Hy) and (Z,Z)-3,9-cis-6,7-epoxy-nonadecadiene (Z3,Z9-cis-6,7-epo-19Hy) were identified in pheromone gland extracts from femaleErannis defoliaria. The two components were found in a 13 ratio, with the main component,Z3,Z9-cis-6,7-epo-19Hy present at an amount of about 1.5 ng per female. The components were identified by means of gas chromatography-mass spectrometry, gas chromatography-electroantennography and gas chromatography-single sensillum recordings. Single sensillum measurements on the male antenna showed two physiological types of sensilla. One type was characterized by a large spike amplitude cell responding toZ3,Z9-cis-6,7-epoxy-19Hy and a small spike amplitude cell responding toZ3,Z6,Z9–19Hy. A second type responded only with a large spike amplitude cell to the epoxide, and this cell was inhibited by the triene. Of the two pheromone components, the epoxide gave the higher response in the EAG tests. Preliminary field tests support the identification of the pheromone components. The epoxide was also found to be present in the extract of the pheromone gland ofColotois pennaria, and males ofC. pennaria andAgriopis marginaria were trapped by the mixture of the identified compounds.     

Preparation of methylcis-9,cis-12,cis-15-octadecatrienoate-15,16-d 2 and methylcis-9,cis-12,cis-15-octadecatrienoate-6,6,7,7-d 4

Methylcis-9,cis-12,cis-15-octadecatrienoate-15,16-d ₂ was obtained from Wittig coupling of methyl 12-oxo-cis-9-dodecenoate,18, and 3,4-dideutero-cis-3-hexenyltriphenylphosphonium bromide,16. Compound18 was obtained by periodic acid oxidation of methyl 12,13-dihydroxy-cis-9-octadecenoate,17, obtained fromVernonia oil. Compound18 also was synthesized from methyl oleate as the starting material. The deuterated fragment,16, was prepared from 3-hexynol and using Lindlar's catalyst and deuterium gas to introduce the deuterium atoms. Methylcis-9,cis-12,cis-15-octadecatrienoate-6,6,7,7-d ₄ was prepared by Wittig coupling of 3,6-nonadienyltriphenylphosphonium iodide,5, with methyl 9-oxononanoate-6,6,7,7-d ₄,11. Deuterium atoms were introduced during the synthesis of11 from 3-butynol and 5-bromopentanoic acid with deuterium gas in the presence of [Ph₃P]₃-RhCl. For the preparation of5, the 3,6-nonadiynol intermediate was reduced to 3,6-nonadienol with P-2 Nickel and hydrogen. The final products were separated from isomers formed during the synthetic sequences by silver resin chromatography.     

X-Ray diffraction study of sodium soaps of monounsaturated and polyunsaturated fatty acids

X-Ray powder diffraction patterns of the sodium soaps of 14 monounsaturated and polyunsaturated fatty acids were obtained at room temperature. The patterns of the soaps of 9,12-trans,trans-octadecadienoic acid, 11,14-cis,cis-eicosadienoic acid 11,14,17-allcis-eicosatrienoic acid and 5 monounsaturated fatty acids were typical of the crystalline lamellar phase. The patterns of the soaps of 9,12-cis,cis-octadecadienoic, allcis-9,12,15-octadecatrienoic, allcis-8,11,14-eicostrienoic, allcis-5,8,11,14-eicosatetraenoic, allcis-5,8,11,14,17-eicosapentaenoic and allcis-4,7,10,13,16,19-docosahexaenoic acids were indicative of the less ordered forms reported for sodium oleate at elevated temperature. The diffraction data from the less ordered soaps are consistent with the melted form of the hydrocarbon chains of the unsaturated acids at room temperature.