Chiral methyl-branched pheromones.

Insect pheromones are some of the most interesting natural products because they are utilized for interspecific communication between various insects, such as beetles, moths, ants, and cockroaches. A large number of compounds of many kinds have been identified as pheromone components, reflecting the diversity of insect species. While this review deals only with chiral methyl-branched pheromones, the chemical structures of more than one hundred non-terpene compounds have been determined by applying excellent analytical techniques. Furthermore, their stereoselective syntheses have been achieved by employing trustworthy chiral sources and ingenious enantioselective reactions. The information has been reviewed here not only to make them available for new research but also to understand the characteristic chemical structures of the chiral pheromones. Since biosynthetic studies are still limited, it might be meaningful to examine whether the structures, particularly the positions and configurations of the branched methyl groups, are correlated with the taxonomy of the pheromone producers and also with the function of the pheromones in communication systems.

Synthesis and field evaluation of stereoisomers and analogues of 5-methylheptadecan-7-ol, an unusual sex pheromone component of the lichen moth, Miltochrista calamina.

Females of the lichen moth, Miltochrista calamina (Arctiidae, Lithosiinae), were previously shown to produce 5-methylheptadecan-7-ol (1) as a sex pheromone. In field tests, males were attracted only by the (5R,7R)-isomer of the four stereoisomers that were prepared by separation from two mixtures of diastereoisomers. A new route to (5R,7R)-1 starting from (S)-propylene oxide was developed utilizing the SN2 reaction of an optically active secondary tosylate and the Jacobsen hydrolytic kinetic resolution of an epoxide intermediate as key steps. Enantioselective HPLC analysis of the product and the antipode synthesized from (R)-propylene oxide confirmed their high enantiomeric excess (> 99 %). Using this stereospecific synthesis, six analogues with the same configuration as (5R,7R)-1 but with different alkyl chain(s) connected to the stereogenic centers were prepared in order to obtain GC/MS data and to examine the ability of M. calamina males to discriminate between them. The mass spectra of the synthetic analogues revealed characteristic fragment ions derived by cleavage around the methyl group in addition to that at the hydroxyl group. In field trapping tests, five out of the six compounds were attractive to male M. calamina moths, indicating that the males distinguished the configurations of methyl and hydroxyl groups but were less able to perceive differences in the lengths of the two alkyl chains in the pheromone.

Characterization of posticlure and the structure-related sex pheromone candidates prepared by epoxidation of (6Z,9Z,11E)-6,9,11-trienes and (3Z,6Z,9Z,11E)-3,6,9,11-tetraenes.

trans-11,12-Epoxy-(6Z,9Z)-6,9-henicosadiene (posticlure) has been identified from a pheromone gland of the lymantriid species, Orgyia postica. Since the diversity of Lepidoptera suggests that some species utilize the structure-related epoxy compound as a sex pheromone component, epoxydienes and epoxytrienes derived from (6Z,9Z,11E)-6,9,11-trienes and (3Z,6Z,9Z,11E)-3,6,9,11-tetraenes with a C19-C21 chain were systematically synthesized and the chemical data were accumulated in order to contribute to a new pheromone research. Peracid oxidation of each triene and each tetraene produced, respectively, a mixture of three epoxydienes (cis-6,7-epoxy-9,11-diene; cis-9,10-epoxy-6,11-diene; and trans-11,12-epoxy-6,9-diene) and four epoxytrienes (cis-3,4-epoxy-6,9,11-triene; cis-6,7-epoxy-3,9,11-triene; cis-9,10-epoxy-3,6,11-triene; and trans-11,12-epoxy-3,6,9-triene). While the 9,10-epoxy compounds were unstable and, interestingly, converted into 9-ketone derivatives after chromatography over SiO2, each positional isomer was isolated by HPLC equipped with an ODS column, and the chemical structure was determined by NMR analysis. On the GC-MS analysis with a DB-23 column, the positional isomers were also eluted separately and characteristic mass spectra were proposed. By comparing the spectral data of the epoxy compounds with a different carbon chain, diagnostic fragment ions reflecting the chemical structure were determined as follows: m/z 79, 109, 113, and M-114 for the 6,7-epoxydienes; m/z 69, 97, 111, 139, and M-111 for the 9,10-epoxydienes; m/z 57, 79, 109, 136, M-151, and M-111 for the 11,12-epoxydienes; m/z 79, 91, 105, and 119 for the 3,4-epoxytrienes; m/z 79, 124, M-124, M-96, and M-69 for the 6,7-epoxytrienes; m/z 79, 95, 109, 137, and M-108 for the 9,10-epoxytrienes; and m/z 79, 134, M-149, M-109, and M-95 for the 11,12-epoxytrienes.

Propionates and acetates of chiral secondary alcohols: novel sex pheromone components produced by a lichen moth Barsine expressa (Arctiidae: Lithosiinae).

Females of a lichen moth, Barsine expressa (Arctiidae, Lithosiinae), which inhabit Iriomote Island in Japan, were captured by a black-light trap, and the pheromone gland extract was analyzed by gas chromatography (GC) with an electroantennographic (EAG) detector, and by GC coupled with mass spectrometry. The females produced several EAG-active esters, and the mass spectrum of a major component indicated the mixture consists of propionates derived from C(17)-saturated secondary alcohols, which were inseparable on the capillary GC column. In addition to these main components, the pheromone glands included two acetate derivatives of C(17) alcohols, and other propionates of C(16) and C(15) alcohols. The crude extract was treated with K(2)CO(3), and a 1:1 mixture of C(17) alcohols with a C(6)- or C(7)-chain moiety was obtained. The two alcohols were uniformly converted into monodeuterated n-heptadecane by mesylation and succeeding LiAlD(4) reduction. This result revealed a straight-chain structure of the C(17) alcohols with the acyl groups located at the 7- or 8-position. Field tests on Iriomote Island showed that the synthetic esters were behaviorally active. A 1:1 mixture of racemic 7-propioxyheptadecane and 8-propioxyheptadecane, which were prepared from the secondary alcohols synthesized by a Grignard coupling reaction, attracted male moths. Furthermore, propionates of the alcohols synthesized enantioselectively by using a hydrolytic kinetic resolution with Jacobsen's catalyst were evaluated. Only the traps baited with a mixture of the two esters with the same S-configuration significantly attracted B. expressa males. In the Tokyo area, the propionate mixture attracted a closely related species, Barsine aberrans aberrans.

Characterization of epoxytrienes derived from (3Z,6Z,9Z)-1,3,6,9-tetraenes, sex pheromone components of arctiid moths and related compounds.

Cis-9,10-epoxy-(3Z,6Z)-1,3,6-henicosatriene has been identified from a pheromone gland of arctiid species, such as Hyphantria cunea. Since the diversity of lepidopteran species suggests that structurally related compounds of the 9,10-epoxide are also utilized as a sex pheromone components, epoxytrienes derived from (3Z,6Z,9Z)-1,3,6,9-tetraenes with a C(19)-C(21) chain were systematically synthesized and characterized. While 1,2-epoxy-3,6,9-triene was not obtained, peracid oxidation of each tetraene produced a mixture of three cis-epoxides (3,4-epoxy-1,6,9-triene, 6,7-epoxy-1,3,9-triene, and 9,10-epoxy-1,3,6-triene), which were separable by LC as well as GC. Detailed inspection of the mass spectra of the C(19)-C(21) epoxides indicated the following diagnostic ions for determining the chemical structures: m/z 79, M-70, and M-41 for the 3,4-epoxytrienes; m/z 79, 95, 109, and 149 for the 6,7-epoxytrienes; and m/z 79, 106, 120, M-121, and M-107 for the 9,10-epoxytrienes. Resolution of two enantiomers of each C(21) epoxytriene was accomplished by HPLC equipped with a chiral column, and analysis of the pheromone extracted from virgin females of H. cunea revealed the 9S,10R configuration of the natural epoxytriene as the same configuration of C(21) 9,10-epoxydiene, a main pheromone component of this species. GC-EAD analysis of the optically pure epoxides showed that the antennae of male H. cunea were stimulated more strongly (>100 times) by the (9S,10R)-isomers than the antipodes.

Female sex pheromone of Cystidia couaggaria couaggaria (Lepidoptera: Geometridae): identification and field attraction.

The plum cankerworm moth, Cystidia couaggaria couaggaria (Geometridae: Ennominae), is a defoliator of Chinese plum trees (Prunus mume). The pheromone components of the female were analyzed by gas chromatography (GC) with an electro-antennographic (EAG) detector and GC coupled with mass spectrometry. The crude pheromone extract included several EAG-active components, i.e., trienyl, dienyl, and saturated hydrocarbons, with a C21-C25 straight chain. The characteristic mass spectra indicated the unsaturated hydrocarbons to be (3Z,6Z,9Z)-3,6,9-trienes and (6Z,9Z)-6,9-dienes. In the fields, mixtures of the synthetic C<21 and C<23 trienes in a ratio of 2:3 and 1:4 successfully attracted males of this diurnal species during daytime. While the male antennae responded to the C25 triene and saturated hydrocarbons, their synergistic effects were not observed on the male attraction in the fields. Addition of the C21 diene interestingly inhibited the activity of the triene mixture. Males of Cystidia truncangulata, a sympatric diurnal congener of C. c. couaggaria, showed similar EAG responses to the unsaturated hydrocarbons, but no C. truncangulata males were attracted by the lures tested for C. c. couaggaria males, indicating that the identified hydrocarbons comprised the species-specific pheromone of C. c. couaggaria females.

Biosynthetic pathways of the sex pheromone components and substrate selectivity of the oxidation enzymes working in pheromone glands of the fall webworm, Hyphantria cunea.

The fall webworm, Hyphantria cunea Drury (Lepidoptera: Arctiidae), is a harmful polyphagous defoliator. Female moths produce the following four pheromone components in a ratio of about 5:4:10:2; (9Z,12Z)-9,12-octadecadienal (I), (9Z,12Z,15Z)-9,12,15-octadecatrienal (II), cis-9,10-epoxy-(3Z,6Z)-3,6-henicosadiene (III), and cis-9,10-epoxy-(3Z,6Z)-1,3,6-henicosatriene (IV). Although ¹³C-labeled linolenic acid was not converted into trienal II at the pheromone glands of H. cunea females, GC-MS analysis of an extract of the pheromone gland treated topically with ¹³C-labeled linolenyl alcohol showed the aldehyde incorporating the isotope. Other C18 and C19 fatty alcohols were also oxidized to the corresponding aldehydes in the pheromone gland, indicating a biosynthetic pathway of IIvia linolenyl alcohol and low substrate selectivity of the alcohol oxidase in the pheromone gland. On the other hand, epoxydiene III was expected to be produced by specific 9,10-epoxidation of the corresponding C21 trienyl hydrocarbon, which might be biosynthesized from dietary linolenic acid in oenocytes and transported to the pheromone gland. The final biosynthetic step in the pheromone gland was confirmed by an experiment using deuterated C21 triene, which was synthesized by the chain elongation of linolenic acid and LiAlD4 reduction as key reactions. When the labeled triene was administered to the female by topical application at the pheromone gland or injection into the abdomen, deuterated III was detected in a pheromone extract by GC-MS analysis. Furthermore, the substrate selectivity of epoxidase and selective incorporation by the pheromone glands were examined by treatments with mixtures of the deuterated precursor and other hydrocarbons such as C19-C23 trienyl, C21 dienyl, and C21 monoenyl hydrocarbons. The 9,10-epoxy derivative of each alkene was produced, while the epoxidation of the C21 monoene was poorer than those of the trienes and diene. The low selectivity indicated that the species-specific pheromone of the H. cunea female was mainly due to the critical formation of the precursor of each component.

Novel components of the sex pheromones produced by emerald moths: identification, synthesis, and field evaluation.

The subfamily Geometrinae (Lepidoptera: Geometridae) includes many species called emerald moths. Based on our recent finding of novel polyenyl compounds, including a double bond at the 12-position from two geometrine species, Hemithea tritonaria and Thalassodes immissaria intaminata, (6Z,9Z,12Z)-6,9,12-trienes and (3Z,6Z,9Z,12Z)-3,6,9,12-tetraenes with a C(17)-C(20) straight chain were synthesized and analyzed by GC-MS. The 6,9,12-trienes, which were prepared by a double Wittig reaction between two alkanals and an ylide derived from (Z)-1,6-diiodo-3-hexene, characteristically produced fragment ions at m/z 79, 150, and M-98. The 3,6,9,12-tetraenes, which were prepared by a coupling between (Z)-3-alkenal and an ylide derived from (3Z,6Z)-1-iodo-3,6-nonadiene, showed fragment ions at m/z 79, 148, and M-96. These diagnostic ions were useful to distinguish these compounds from other known polyenyl pheromones, such as 4,6,9- and 6,9,11-trienes and 1,3,6,9-tetraenes. With reference to the GC-MS data, pheromone extracts of other species in Geometrinae inhabiting the Iriomote Islands were analyzed, and the 6,9,12-trienes were identified in the pheromone gland extracts of Pamphlebia rubrolimbraria rubrolimbraria and Maxates versicauda microptera. Furthermore, a field evaluation of the synthetic polyenes in a mixed forest of Tokyo revealed the following new male attractants for emerald moths: Idiochlora ussuriaria by a C(17) 6,9,12-triene and Jodis lactearia by a C(20) 3,6,9,12-tetraene, indicating the characteristic chemical structures of Geometrinae pheromones. On the other hand, through reexamination of the pheromone extract of H. tritonaria, (3E,6E)-α-farnesene was identified as an electrophysiologically active component in addition to the C(17) 6,9,12-triene. The binary mixture attracted more males than the single component lure baited with the triene in the Iriomote Islands.

Female sex pheromone of a lichen moth Eilema japonica (Arctiidae, Lithosiinae): components and control of production.

Seven candidates for components of the female sex pheromone of Eilema japonica (Arctiidae, Lithosiinae) were detected in an extract of pheromone glands with a gas chromatograph-electroantennographic detector. The compounds were identified as (Z,Z)-6,9-icosadiene (D20), (Z,Z)-6,9-henicosadiene (D21), (Z,Z,Z)-3,6,9-henicosatriene (T21), (Z,Z)-6,9-docosadiene (D22), (Z,Z,Z)-3,6,9-docosatriene (T22), (Z,Z)-6,9-tricosadiene (D23), and (Z,Z,Z)-3,6,9-tricosatriene (T23). Assays using synthetic lures in a wind tunnel showed that D21 (proportion, 0.39), T21 (0.08), D22 (0.27), and T22 (0.26) are important for evoking full behavioral responses from the males. Titers of the pheromone components did not show clear temporal fluctuations. Moreover, decapitation of the female moth had no effect on the titers of pheromone components in the pheromone gland, suggesting that cephalic endocrine factors such as pheromone biosynthesis activating neuropeptide (PBAN) are not involved in the control of pheromone biosynthesis in this species.

Positions and stereochemistry of methyl branches in the novel sex pheromone components produced by a lichen moth, Lyclene dharma dharma.

Female moths of Lyclene dharma dharma (Arctiidae, Lithosiinae) produce three sex pheromone components (I-III), for which we assigned the following novel chemical structures; 6-methyl-2-octadecanone (1) for I, 14-methyl-2-octadecanone (2) for II, and 6,14-dimethyl-2-octadecanone (3) for III. In the Iriomote Islands where the insects were collected, a lure including racemic 1 and 2 attracted the male moths without mixing 3. In this study for further confirmation of the plane structures, the positional isomers with a methyl branch at the 4-, 5-, 7-, 13-, or 15-position (4-8, respectively) were synthesized. The GC-MS analyses revealed that natural components I and II were best fitted with those of 1 and 2, respectively, among the methyl-2-octadecanones examined, indicating the usefulness of this analytical instrument and authentic standards for the determination of the positions of methyl branches. In field trapping tests, 4-8 could not substitute for 1 or 2, nor did these compounds inhibit the active binary lure of 1 and 2, indicating that the males strictly recognized the 2-ketones with a methyl branch at the 6- or 14-positions. Next, the absolute configurations of I and II were determined by HPLC with a normal-phased chiral column (Chiralpak AD-H), which could separate the enantiomers of both 1 and 2. The chiral HPLC analysis of a crude pheromone extract indicated that the females exclusively produced (S)-1 and (S)-2. Furthermore, a field evaluation of each enantiomer revealed that (S)-1 and (S)-2 were bioactive but (R)-1 and (R)-2 were not.

Improved synthesis of three methyl-branched pheromone components produced by the female lichen moth.

Female moths of Lyclene dharma dharma (Arctiidae, Lithosiinae) produce a novel sex pheromone composed of three methyl-branched ketones: 6-methyl-2-octadecanone (I), 14-methyl-2-octadecanone (II), and 6,14-dimethyl-2-octadecanone (III). Their structures were confirmed by syntheses accomplished by a different route for each component. In order to obtain a sufficient amount of the synthetic pheromone, we developed new routes via methyl-branched 1-alkenes: 6-methyl-1-octadecene (1), 14-methyl-1-octadecene (2), and 6,14-dimethyl-1-octadecene (3). Compound 1 was synthesized by coupling between a C(10)-chain bromide and a 3-methyl-branched C(8) unit (A) prepared from 3-methyl-1,5-pentanediol, 2, by coupling between a C(11)-chain bromide and a 3-methyl-branched C(7) unit (B) prepared from 2-hexanone, and 3, by connecting A and B, using propargyl alcohol as a C(3) linchpin. The use of 3-chloro-1-propanol and tert-butyl acetoacetate as the linchpin was also examined to connect the two synthetic blocks in the synthesis of 3. Components I-III were obtained by Wacker oxidation of the corresponding 1-alkenes 1-3 in good yields.

Synthesis of the deuterated sex pheromone components of the grape borer, Xylotrechus pyrrhoderus.

Adult males of the grape borer, Xylotrechus pyrrhoderus, secrete (S)-2-hydroxy-3-octanone [(S)-1] and (2S,3S)-2,3-octanediol [(2S,3S)-2] from their nota of prothoraces as sex pheromone components. Their structural similarity suggests that one of them is the biosynthetic precursor of the other component. In order to confirm the biochemical conversion, deuterated derivatives of both components were synthesized by starting from a Wittig reaction between hexanal and an ylide derived from D(5)-iodoethane and ending with enantiomeric resolution by chiral HPLC. The molecular ions of 1 and 2 could scarcely be detected by using a GC-MS analysis, and the labeled compounds showed similar mass spectra to the unlabeled pheromone components. However, several fragment ions, including four deuterium atoms, were observed in the mass spectra of their acetate derivatives, indicating that the conversion could be confirmed by examining a compound with the diagnostic ions after acetylation of the volatiles collected from insects treated with the labeled precursors.

Synthesis and field evaluation of methyl-branched ketones, sex pheromone components produced by Lithosiinae female moths in the family of Arctiidae.

Female moths of Lyclene dharma dharma (Arctiidae, Lithosiinae) produce a novel sex pheromone composed of three methyl-branched ketones (I-III) in a ratio of 2:1:1. In order to confirm the structure of III (6,14-dimethyl-2-octadecanone), a mixture of its four stereoisomers was synthesized via chain elongation by two Wittig reactions, starting from 1,7-hexanediol. GC-MS data of the synthetic III were satisfactorily coincident with those of the natural component. In addition to the racemic mixtures of I (6-methyl-2-octadecanone) and II (14-methyl-2-octadecanone), previously synthesized, the activity of III was evaluated in the Iriomote Islands, and effective male attraction was observed for the 2:1:1 mixture of I-III. This result indicates that the females do not produce only one stereoisomer for each component or that the response of the males is not disturbed by the other stereoisomers of natural isomers produced by the females. The field test also revealed that the two-component lure of I and II captured as many males as the mixture of I-III, while lures baited with two components in other combinations and with only one component scarcely exhibited any male attraction ability.

Instrumental analysis of terminal-conjugated dienes for reexamination of the sex pheromone secreted by a nettle moth, Parasa lepida lepida.

Conjugated dienyl compounds make one of the main groups of lepidopteran sex pheromones, and GC has been frequently used to determine the configurations of the double bonds. However, the separation of two geometric isomers of a terminal-conjugated diene, such as 7,9-decadien-1-ol secreted by a nettle moth Parasa lepida lepida (Limacodidae), is assumed to be difficult. In order to clarify the chromatographic separation of the terminal dienes, 7,9-decadienyl and 9,11-dodecadienyl compounds (alcohols, acetates, and aldehydes) were analyzed by GC and HPLC. On a capillary GC column, the (E)-isomers flowed out slightly faster than the corresponding (Z)-isomers, but their peaks almost overlapped. On the other hand, HPLC equipped with an ODS column completely separated the two geometric isomers examined and the (Z)-isomers eluted from the column faster than the (E)-isomers without dependence on a functional group. In addition to undergoing direct HPLC analysis without derivatization, the dienyl alcohols were converted into 3,5-dinitrobenzoates and analyzed by LC-ESI-MS operated under the same reversed-phase condition. The two separated geometric isomers were sensitively monitored by negative ions at m/z 211, M, M+1, M+17, and M+31, which were characteristically derived from the benzoates. Based on these results, a pheromone extract of P. l. lepida was examined, and it was confirmed that the female moths exclusively produced the (Z)-isomer of the 7,9-diene. Furthermore, a GC-EAD analysis and a field evaluation with both geometrical isomers indicated that the mating communication of P. l. lepida is predominantly mediated with the (Z)-isomer.

Identification of novel C(20) and C (22) trienoic acids from arctiid and geometrid female moths that produce polyenyl Type II Sex pheromone components.

Gas chromatography-mass spectrometry (GC-MS) and GC-electroantennographic detection (EAD) analyses of the sex pheromone extract from a wasp moth, Syntomoides imaon (Lepidoptera: Arctiidae: Syntominae), showed that virgin females produced (Z,Z,Z)-3,6,9-henicosatriene and (Z,Z,Z)-1,3,6,9-henicosatetraene with a trace amount of their C(20) analogs. Identification of the chemical structures was facilitated by comparison with authentic standards and the double-bond positions were confirmed by dimethyl disulfide derivatization of monoenes produced by a diimide reduction. In a field test in the Yonaguni-jima Islands, males of the diurnal species were captured in traps baited with a 1:2 mixture of the above-described synthetic C(21) polyenes. Lipids were extracted from the abdominal integument and its associated oenocytes and peripheral fat bodies. Following derivatization, fatty acid methyl esters (FAMEs) were fractionated by HPLC equipped with an ODS column, and methyl (Z,Z,Z)-11,14,17-icosatrienoate and (Z,Z,Z)-13,16,19-docosatrienoate were identified by GC-MS. These novel C(20) and C(22) acid moieties are longer-chain analogs of linolenic acid, (Z,Z,Z)-9,12,15-octadecatrienoic acid. They are presumed to be biosynthetic precursors of the S. imaon pheromone because the C(21) trienyl component might be formed by decarboxylation of the C(22) acid. On the other hand, the C(20) acid, but not the C(22) acid, was found in FAMEs of Ascotis selenaria cretacea (Lepidoptera: Geometridae), which secretes C(19) pheromone components, (Z,Z,Z)-3,6,9-nonadecatriene and the monoepoxy derivative, indicating that different systems of the chain elongation might play an important role in developing species-specific communication systems mediated with polyunsaturated hydrocarbons and/or epoxy derivatives, components of Type II lepidopteran sex pheromones.

Synthesis and chemical characterization of hydrocarbons with a 6,9,11-, 3,6,9,11-, or 1,3,6,9-polyene system, pheromone candidates in Lepidoptera.

Lepidopteran Type II sex pheromones are mainly composed of 6,9-dienes, 3,6,9-trienes, and their epoxy derivatives, which are biosynthesized from linoleic and linolenic acids by the species in some families of higher Lepidoptera. To investigate further structural modifications on this theme, we synthesized polyunsaturated hydrocarbons with a C(17)-C(21) chain, which included an extra double bond. Using the Wittig reaction, (Z,Z,E)-6,9,11-trienes and (Z,Z,Z,E)-3,6,9,11-tetraenes were synthesized from (E)-2-alkenals with appropriate carbon chains, and (Z,Z,Z)-1,3,6,9-tetraenes were synthesized from 3-hexyn-1,6-diol. The gas chromatography-mass spectrometry (GC-MS) analysis of each synthetic polyene, whose chemical structure was confirmed by (1)H NMR and (13)C NMR, revealed some characteristic fragment ions reflecting the positions of the double bonds, i.e., m/z 79, 110, 163, and M-85 of the 6,9,11-trienes, m/z 79, 108, and M-82 of the 3,6,9,11-tetraenes, and m/z 79, 91, 106, and M-54 of the 1,3,6,9-tetraenes. Because the determination of the unsaturated positions is difficult to accomplish by chemical derivatization with a limited amount of natural pheromones, these diagnostic ions found in authentic samples would help identify the hydrocarbons in a pheromone extract. Furthermore, we carried out field screening tests of these polyenes in forests in Japan, and documented the attraction of four geometrid species in Tokyo and one noctuid species in the Iriomote Islands.