Synthesis and surface properties of chemodegradable anionic surfactants: Diastereomeric (2-n-alkyl-1,3-dioxan-5-yl) sulfates with monovalent counter-ions

Sodium, potassium and ammonium cis- and trans-(2-n-alkyl-1,3-dioxan-5-yl) sulfates 6–8 (alkyl: n-C₉H₁₉, 6a–8a, and n-C₁₁H₂₃, 6b–8b) were synthesized in a reaction of aliphatic aldehydes 1a,b with glycerol 2 followed by separation in high yields of individual geometric isomers of cis-and trans-2-n-alkyl-5-hydroxy-1,3-dioxanes, cis-3a,b and trans-3a,b, followed by sulfation with sulfur trioxide-pyridine complex, and finally neutralization with NaOH, KOH, and NH₄OH, respectively. Physical data of the compounds and some surface properties of 2-n-nonyl derivatives, such as critical micelle concentration (CMC), effectiveness of aqueous surface tension reduction (Π_CMC), surface excess concentration Γ_CMC, and the surface area demand per molecule (A_CMC), were determined. It was shown that the surface activity of these compounds is influenced both by their geometric structure and by the monovalent counter-ion.     

Synthesis and surface properties of chemodegradable anionic surfactants: Sodium (2-n-alkyl-1,3-dioxan-5-yl)sulfates

In the reaction of cis- and trans-2-n-alky-5-hydroxyl-1,3-dioxane mixtures with SO₃ · pyridine complex, followed by neutralization with sodium hydroxide or sodium carbonate, a new group of anionic surfactants, i.e., sodium cis- and trans-(2-n-alkyl-1,3-dioxan-5-yl)sulfates were obtained. The hydrophobic intermediates used in the sulfation reaction were obtained in high yields from four-component glycerol acetals by the process of transacetalization and selective crystallization of 1,3-dioxane derivatives. The physical data of the new compounds and some of their surface properties, such as critical micelle concentration (CMC), effectiveness of water surface tension reduction π_CMC, standard free energies of adsorption and micellization, ΔG _ads ^o and ΔG _CMC ^o , surface excess concentration, Γ_CMC, and the surface area demand per molecule, A_CMC, were determined. It was shown that the surface activity of the standard anionic surfactant sodium dodecyl sulfate should be similar to the surface activity of sodium (2-n-decyl-1,3-dioxan-5-yl)sulfate. Part XXX in the series: Chemical Structure and Surface Activity. Part XXIX: Sokołowski, A., B. Burczyk, and H.-R. Holzbauer, Adsorption of n-butyloligooxypropylene-pentaoxyethylene block copolymers at the aqueous solution-air interface, Collid Surfaces, in press.     

Alkoxyalkyl-substituted glycerol acetals: New hydrophobic intermediates for surfactant synthesis

In acid-catalyzed, one-step reactions of monofunctional alcohol (I) and glycerol mixture with a simple α,β-unsaturated carbonyl compound (acrolein, crotonaldehyde or methylvinyl ketone), four component glycerol acetals [mixtures ofcis-+trans-2-(2-alkoxyalkyl)-substituted derivatives of 4-hydroxymethyl-1,3-dioxolanes and 5-hydroxy-1,3-dioxanes] or two component glycerol ketals [mixtures ofcis-+trans-2-(2-alkoxyethyl)-2-methyl-4-hydroxymethyl-1,3-dioxolanes] were obtained, respectively. These compounds may be used as a new group of hydrophobic intermediates for synthesis of chemodegradable surfactants, which rapidly hydrolyze to nonsurfactant compounds in acidic aqueous solutions. Methods of synthesis, yields, compositions and chemical structures of components of reaction products, and products of their chemical degradation have been discussed. Part XX in the series: Acetals and Ethers. Part XIX, A. Piasecki,Polish J. Chem. 62:579 (1988).     

Synthesis and surface properties of chemodegradable anionic surfactants: Sodium salts of sulfated 2-n-alkyl-5-hydroxymethyl-5-methyl-1,3-dioxanes

In acid-catalyzed reactions of long-chain aliphatic aldehydes (Ia-d) (a,R=n-C₅H₁₁; b,R=n-C₇H₁₅; c,R=n-C₉H₁₉; d,R=n-C₁₁H₂₃) with 1,1,1-tris(hydroxymethyl)-ethane (II), 2-n-alkyl-5-hydroxymethyl-5-methyl-1,3-dioxanes (IIIa-d) were obtained. Then they were reacted with SO₃·pyridine complex in dry carbon tetrachloride solution, to obtain trisubstituted derivatives of 1,3-dioxane (IVa-d). They constitute a new group of chemodegradable, acetal-type anionic surfactants, which may readily hydrolyze and oxidize to nonsurfactant compounds. Physical data of the new compounds and some surface properties, such as Krafft point, critical micelle concentration (CMC), surface tension of aqueous solution near CMC (γ_CMC) and wetting and foaming properties, were determined. Sodium salts of sulfated 2-n-alkyl-5-hydroxymethyl-5-methyl-1,3-dioxanes (IVa-d) exhibit aqueous solution properties similar to those of the well-known sodium alkyloligooxyethylene sulfates. Presence of the 5-methyl-1,3-dioxane moiety in molecules of compounds IVa-d introduces hydrophobic character comparable to the effect of three oxyethylene groups (-CH₂CH₂O-) or of two methylene groups (-CH₂-) of the alkyl chain in sodium alkyl ether sulfates [R(OCH₂CH₂)_mOSO₃Na] with equal R value. Part XXV in the series: Chemical Structure and Surface Activity. Part XXIV: A. Sokołowski, B. Burczyk, H.-R. Holzbauer, M. Herbst,Colloids Surfaces 57: 307 (1991).     

Fatty acid composition of some pine seed oils

The fatty acid composition of seeds from seven species of the genusPinus (P. pinaster, P. griffithii, P. pinea, P. koraiensis, P. sylvestris, P. mughus, andP. nigra) was established. Pine seeds are rich in oil (31–68% by weight) and contain several unusual polymethylene-interrupted unsaturated fatty acids with acis-5 ethylenic bond. These are thecis-5,cis-9 18:2,cis-5,cis-9,cis-12 18:3,cis-5,cis-11 20:2, andcis-5,cis-11,cis-14 20:3 acids, with a trace ofcis-5,cis-9,cis-12,cis-15 18:4 acid. Their percentage relative to total fatty acids varies from a low of 3.1% (P. pinea) to a high of 30.3% (P. sylvestris), depending on the species. The majorcis-5 double bond-containing acid is generally thecis-5,cis-9,cis-12 18:3 acid (pinolenic acid). In all species, linoleic acid represents approximately one-half the total fatty acids, whereas the content of oleic acid varies in the range 14–36% inversely to the sum of fatty acids containing acis-5 ethylenic bond. The easily available seeds fromP. koraiensis appear to be a good source of pinolenic acid: their oil content isca. 65%, and pinolenic represents about 15% of total fatty acids. These values appear to be rather constant.Pinus pinaster, which is grown on several thousand acres in the southwest of France, is an interesting source ofcis-5,cis-11,cis-14 20:3 acid (7% in the oil, which isca. 35% of the dehulled seed weight), an acid sharing in common three double bonds with arachidonic acid. Apparently,P. sylvestris seed oil contains the highest level ofcis-5 double bond-containing acids among pine seed oils that have ever been analyzed.     

Estolides from meadowfoam oil fatty acids and other monounsaturated fatty acids

The formation of estolides was detected during the studies on dimerization of meadowfoam oil fatty acids. By adjusting the reaction conditions, it was possible to produce monoestolides with little dimer or trimer formations. Estolides have potential use in lubricant, cosmetic and ink formulations and in plasticizers. This paper reports the conditions for production of estolides from mixed meadow-foam fatty acids, commercial oleic acid, high-oleic sun-flower oil fatty acids,cis-5,cis-13-docosadienoic acid, petroselinic acid and linoleic acid.     

Synthesis of estolide esters from cis-9-octadecenoic acid estolides

Oleic acid (cis-9-octadecenoic acid) was converted in excellent yield to the estolide, which was then esterified with 2,2-dimethypropan-1-ol (neopentyl alcohol), cis-9-octadence-1-ol (oleyl alcohol), and 2-propanol to generate the corresponding estolide esters. Higher-formula mass estolide esters were synthesized by reaction of the parent estolide with 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 1,5-pentanediol to give the corresponding diesters of oleic estolide, thus doubling the molecular size of the parent estolide. Pour points and viscosities were determined in order to evaluate these products for possible industrial application.     

Distribution of Δ5-olefinic acids in the triacylglycerols fromPinus koraiensis andPinus pinaster seed oils

Purified triacylglycerols (TAG) fromPinus koraiensis andP. pinaster seed oils, which are interesting and commercially available sources of Δ5-olefinic acids (i.e.,cis-5,cis-9,cis-12 18:3 andcis-5,cis-11,cis-14 20:3 acids) were fractionated by reversed-phase high-performance liquid chromatography, and each fraction was examined by capillary gas-liquid chromatography for its fatty acid composition. A structure could be assigned to more than 92% of TAG from both oils. In both instances, ca. 48% of the TAG were shown to contain at least one δ5-olefinic acid. In the great majority of TAG, our data showed that there is only one molecule of δ5-olefinic acid per molecule of TAG. This is compatible with theoretical calculations based on the proportion of total δ5-olefinic in the oils. Thecis-5,cis-9,cis-12 18:3 acid (14.2 and 8.6% of total fatty acids in the seed oils ofP. koraiensis andP. pinaster, respectively) and thecis-5,cis-11,cis-14 20:3 acid (1.1 and 8.1% of total fatty acids in the seed oils ofP. koraiensis andP. pinaster, respectively) are preferentially associated with two molecules of linoleic acid, and to a lesser extent, to one molecule of linoleic acid and one molecule of oleic acid, or two oleic acid molecules. However, several other combinations occur, each in low amounts. The distribution of δ5-olefinic acids in TAG is evidently not random. Combining these results with the known preferential esterification of δ5-olefinic acids to the 1,3-positions of TAG would suggest that most of these acids are present at only one of these positions at a time.     

Biotransformation of saturated monohydroxyl fatty acids to 2-tetrahydrofuranyl acetic acid derivatives: Mechanism of formations and the biological activity of 5-n-hexyl-tetrahydrofuran-2-acetic acid

Transformation of 12-hydroxyoctadecanoic acid (12-HOA) to 5-n-hexyl-tetrahydrofuran-2-acetic acid (5-HTFA) byBacillus lentus NRRL B-14864 (B-14864) was carried out in the presence or absence of oligomycin, 2-bromooctanoic acid (2-BA), or sodium azide. In addition, several saturated and monounsaturated monohydroxyfatty acids, saturated monooxofatty acids, and monounsaturated fatty acid were used as substrates for transformation reactions by B-14864 or corynebacterium FUI-2. Methyl esters of the transformation products were analyzed by gas chromatography and gas chromatography/mass spectroscopy. Various γ-lactones and tetrahydrofuran fatty acid derivatives were conversion products when saturated monohydroxyfatty acids were used as substrates; the production of 5-HTFA from 12-HOA by B-14864 cells was completely inhibited in the presence of high concentration of oligomycin, 2-BA, or sodium azide; and fatty acid β-oxidation metabolic intermediates, 6-hydroxydodecanoic, 4-oxododecanoic, and 4-oxodecanoic acids were products when 12-HOA, 10-oxo-, and 12-oxooctadecanoic acids were used as substrates. Our results suggest that the production of 5-HTFA from 12-HOA by B-14864 was through the fatty acid β-oxidation pathway. Three-day-old driedfruit beetle pupae were topically treated with 5-HTFA to test for juvenile hormone activity, and 5-HTFA was found to possess juvenile hormone-like activity in pure form but not when it was diluted to 10%. Presented in part at the 37th West Central States Biochemistry Conference Annual Meeting, Columbia, Missouri, Oct. 1994.     

Preparation and properties of sulfonate salt-type cleavable surfactants with a 1,3-dioxane ring

A series of di-anionic cleavable surfactants were prepared by the condensation of aldehydes with 2,2-bis(hydroxymethyl)-1,3-propanediol, followed by reaction with 1,3-propanesultone in the presence of sodium hydride. Surfactant 5a had a different¹H nuclear magnetic resonance spectrum in D₂O than products 5b−d. This was rationalized by its different conformation, which originates from the self-coiling of its alkyl chain. The critical micelle concentrations, Krafft points and hydrolysis properties of these surfactants were determined.     

Microbial conversion of palmitoleic acid to 9,12-hexadecadienoic acid (16:2ω4) by Trichoderma sp. AM076

Trichoderma sp. AM076, isolated from a freshwater sample, was found to accumulate 9,12-cis-hexadecadienoic acid (16:2ω4), when grown with palmitoleic acid (16: 1ω7). Methyl myristate was the best carbon source for the conversion of palmitoleic acid to 16:2ω4. The mycelial 16:2ω4 content reached 17.4 mg/g dry mycelia (443 mg/L) when the fungus was grown in a medium that contained 2.0% methyl myristate, 1.5% yeast extract, and 2.0% methyl palmitoleate, pH 6.0, for 5 d at 28°C with shaking. In both nonpolar and polar lipids from the mycelia, 16:2ω4 was detected as one of the major fatty acids when 16:1ω7 was added. It is probable that 16:1ω7 is converted to 16:2ω4 through the Δ12 desaturation reaction.     

Conifer seeds: Oil content and fatty acid composition

The seed oils from twenty-five Conifer species (from four families—Pinaceae, Cupressaceae, Taxodiaceae, and Taxaceae) have been analyzed, and their fatty acid compositions were established by capillary gas-liquid chromatography on two columns with different polarities. The oil content of the seeds varied from less than 1% up to 50%. Conifer seed oils were characterized by the presence of several Δ5-unsaturated polymethylene-interrupted polyunsaturated fatty acids (Δ5-acids) with either 18 (cis-5,cis-9, 18∶2,cis-5,cis-9,cis-12 18∶3, andcis-5,cis-9,cis-12,cis-15 18∶4 acids) or 20 carbon atoms (cis-5,cis-11 20∶2,cis-5,cis-11,cis-14, 20∶3, andcis-5,cis-11,cis-14,cis-17 20∶4 acids). Pinaceae seed oils contained 17–31% of Δ5-acids, mainly with 18 carbon atoms. The 20-carbon acids present were structurally derived from 20∶1n-9 and 20∶2n-6 acids. Pinaceae seed oils were practically devoid of 18∶3n-3 acid and did not contain either Δ5-18∶4 or Δ5-20∶4 acids. Several Pinaceae seeds had a Δ5-acid content higher than 50 mg/g of seed. The only Taxaceae seed oil studied (Taxus baccata) had a fatty acid composition related to those of Pinaceae seed oils. Cupressaceae seed oils differed from Pinaceae seed oils by the absence of Δ5-acids with 18 carbon atoms and high concentrations in 18∶3n-3 acid and in Δ5-acids with 20 carbon atoms (Δ5-20∶3 and Δ5-20∶4 acids). Δ5-18∶4 Acid was present in minute amounts. The highest level of Δ5-20∶4 acid was found inJuniperus communis seed oil, but the best source of Δ5-acids among Cupressaceae wasThuja occidentalis. Taxodiaceae seed oils had more heterogeneous fatty acid compositions, but the distribution of Δ5-acids resembled that found in Cupressaceae seed oils. Except forSciadopytis verticillata, other Taxodiaceae species are not interesting sources of Δ5-acids. The distribution profile of Δ5-acids among different Conifer families appeared to be linked to the occurrence of 18∶3n-3 acid in the seed oils.     

Synthesis and Surface Properties of Dicephalic Surfactants with a 1,3-Dioxane Ring

A new group of surface active dicephalic derivatives of 1,3-dioxane, i.e., 2-alkyl-5,5-bis{[3-(N,N-dimethylamino)propyl]amido}-1,3-dioxane-di-N-oxides, were synthesized with high yields by the reaction of an appropriate 2-alkyl-5,5-bis-(carboxyethyl)-1,3-dioxane with an excess of N,N-dimethyl-1,3-propanediamine followed by oxidation with an aqueous solution of hydrogen peroxide. Structures and purity of all intermediates and final di-N-oxides were confirmed by means of ¹H-NMR and ESI-MS spectroscopy. Synthesized compounds showed high surface activity with low values of critical micelle concentration and high effectiveness of surface tension reduction (γ _CMC). However, only derivative with the longest 2-alkyl substituent showed good foaming and moderate emulsifying properties.

固载杂多酸催化合成2-甲基-2-(4-甲基-3-戊烯基)-1,3-二氧六环

以离子交换树脂固载磷钨酸为催化剂合成了 2 -甲基 - 2 - (4-甲基 - 3 -戊烯基 ) - 1 ,3 -二氧六环。考察了影响收率的因素。其最优条件为 :6 -甲基 - 5 -庚烯 - 2 -酮∶ 1 ,3 -丙二醇∶催化剂∶带水剂为 1mol∶ 1 .5 mol∶ 1 2 g∶ 2 0 0 m L,反应在回流温度下进行 ,反应时间 3 .0 h。收率可达 89.6 %,催化剂可重复使用。     

Triacylglycerols of winter butterfat containing configurational isomers of monoenoic fatty acyl residues. I. Disaturated monoenoic triacylglycerols

The triacylglycerols of winter butterfat were fractionated according to the type and degree of unsaturation into six fractions by silver ion high-performance liquid chromatography (Ag-HPLC). The acyl carbon number distribution of the triacylglycerols in each fraction was elucidated by reversed-phase HPLC and mass spectrometry (MS). The MS analysis of each fraction gave deprotonated triacylglycerol [M - H]⁻ ions which were produced by chemical ionization with ammonia. The daughter spectrum of each of the [M - H]⁻ ions provided information on its fatty acid constituents. Successful fractionation of triacylglycerols differing in the configuration of one fatty acyl residue by Ag-HPLC was important because geometrical isomers could not be distinguished by the MS system used. In addition to the fatty acid compositions, reversed-phase HPLC analysis demonstrated the purity of the collected fractions: molecules having acis-trans difference were separated nearly to the baseline. Triacylglycerols differing in the configuration of one fatty acyl residue were not equally distributed in relation to their acyl carbon numbers. This indicates that during the biosynthesis of triacylglycerols,cis- andtrans-fatty acids are processed differently. Although the fatty acid compositions of the corresponding molecular weight species of disaturatedtrans- and disaturatedcis-monoenoic triacylglycerols were similar, there may be differences in the amounts of different fatty acid combinations or in the distribution of fatty acids between the primary and secondary glycerol positions. In addition to the main components, it was possible to analyze minor triacylglycerols, such as molecules containing one odd-chain fatty acid, by the MS system used.     

Preparation,surface-active properties and acid decomposition profiles of a new “soap” bearing a 1,3-dioxolane ring

New soap-type surfactants bearing a 1,3-dioxolane ring were prepared in good yields by the acid-catalyzed condensation of 1-O-alkylglycerols (alkyl: decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, orcis-9-octadecenyl) with oxocarboxylic acid esters, followed by alkaline hydrolysis without any expensive reagent and special equipment. These surfactants were soluble in alkaline water at room temperature. Their critical micelle concentrations were much smaller than that of sodium dodecanoate. An alkaline solution of the octadecyl homologue was nonfoaming, but the other homologues, including thecis-9-octadecenyl derivative, showed high foaming ability in alkaline solutions. The structural effect of these compounds on the area per molecule at the surface is also discussed. Because these surfactants contain a 1,3-dioxolane ring, they can be utilized as a new acid-decomposable type of cleavable surfactant. At pH 1, they decompose almost completely into nonsurface-active species after 80 min.     

A minor source of vernolic,malvalic, and sterculic acids inPithecollobium dulce (syn.Inga dulcis) seed oil

Pithecollobium dulce, Benth (syn.Inga dulcis, Willd) seed oil, belonging to the Leguminosae plant family, contains minor amounts of vernolic acid (12,13-epoxy-octadec-cis-9-enoic acid, 10.0%), malvalic acid [7-(2-octacyclopropen-1-yl)heptanoic acid, 3.2%], and sterculic acid [8-(2-octacyclopropen-1-yl)octanoic acid, 2.0%]. The other normal fatty acids are palmitic (12.1%), stearic (4.2%), behenic (10.6%), oleic (34.1%), and linoleic (23.8%). These fatty acids have been characterized by Fourier transform infrared,¹H nuclear magnetic resonance, mass spectrometry and gas-liquid chromatography techniques and by chemical degradations.     

Syntheses of 12-aminododecanoic and 11-aminoundecanoic acids from vernolic acid

12-Aminododecanoic acid and 11-aminoundecanoic acid, monomer precursors for nylon-12 and nylon-11, respectively, have been synthesized from vernolic (cis-12,13-epoxy-cis-9-octadecenoic) acid via a reaction sequence that includes the formation of 12-oxododecanoic acid oxime. Saponification of vernonia oil, followed by a low-temperature recrystallization at −20°C, gave 51% vernolic acid (97% purity, m.p. 23–25°C). Hydrogenation afforded cis-12,13-epoxystearic acid (m.p. 52–54°C, lit. m.p. 52–54°C), which upon oxidation with periodic acid in tertiary butyl alcohol gave 12-oxododecanoic acid with an isolated yield of 71.0%. Reaction of the oxoacid with hydroxylamine hydrochloride gave 12-oxododecanoic acid oxime, which was catalytically reduced to give 12-aminododecanoic acid with a yield greater than 85% and a melting point of 184–186°C (lit. m.p. 185–187°C). 11-Aminoundecanoic acid was prepared from the 12-oxododecanoic acid oxime via a three-step reaction sequence that involved a Beckmann rearrangement, Hofmann degradation, and hydrolysis. Thus, the aldoxime acid was hydrolyzed in the presence of nickel acetate tetrahydrate to give 11-carbamoylundecanoic acid (48% yield, m.p. 129–131°C, lit. m.p. 129–130°C). The amide was then treated with a solution of sodium methoxide and bromine at 70–80°C to give 11-(methoxycarbonylamino)undecanoic acid at 75% yield (m.p. 84–86°C; elemental analysis, calculated for C₁₃H₂₅NO₄: C, 60.19; H, 9.73; N, 5.40; O, 24.68%; found C, 60.02; H, 9.81; N, 5.26; O, 24.91%), which upon alkaline hydrolysis and subsequent neutralization gave 11-aminoundecanoic acid at 34% yield (m.p. 189–192°C, lit. m.p. 190°C). Mass spectrometric and ¹³C nuclear magnetic resonance data of the previously unreported 11-(methoxycarbonylamino)undecanoic acid is provided.     

Synthesis and Structural Analysis of Structured Triacylglycerols with CLA Isomers in the <Emphasis Type="Italic">sn</Emphasis>-2- Position

The present research deals with the chemical esterification of the sn-2- position of sn-1,3-diacylglycerol (sn-1,3-DAG) with 9cis,11trans (c9,t11) and 10trans,12cis (t10,c12) conjugated linoleic acid (CLA) isomers to obtain structured triacylglycerols (TAG); the sn-1,3-DAG substrates were produced from extra virgin olive oil by means of enzymatic reactions while CLA isomers were obtained using a three-step procedure based on alkaline hydrolysis of sunflower oil, urea purification of linoleic acid (LA) and alkaline isomerization of LA. The results showed good levels of CLA incorporation in structured TAG at the tested temperatures: 37.5% at 4 °C and 39.1% at 14 °C. To evaluate the incorporation of CLA isomers in sn-2- position of sn-1,3-DAG structural analysis of the newly synthesized TAG was carried out using an enzymatic and a chemical method. The results of the structural analysis also showed up the occurrence of acyl migration. The pancreatic lipase method allowed the direct determination of the fatty acid composition of TAG sn-2- position but this enzymatic method showed different results (p < 0.05) in respect to the chemical one; this occurrence could be due to an acylic specificity of the lipase. High incorporation of CLA isomers in sn-2- position of TAG was observed, 77.0% at 4 °C and 81.5% at 14 °C, considering the results of the chemical procedure.     

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.