- I snromol Gener ~rrgm: UnO /I ISSN: 0171-8177

New Sex Attractants for Species of the Zygaenid Subfamily Procridinae (Lepidoptera: Zygaenidae)

Received: 2010-02-0312010-04-17 Accepted: 2010-05-30

SUBCHEV M [Inst Zool, Bulg Acad Sci, BG-IWO Sofia], EFETOV K A [Crimean State Medic Univ, UA-95006 Simferopoll, TOSHOVA T [Inst 2001, Bulg Acad Sci, BG-1000 Sofia], PARSHKOVA E V [Crimean State Medic Univ, UA-95006 Simferopol], MIKL~S T ~ T H [Plant Protect lnst Hung Acad Ssci, H-I022 Budapest] & FRANCKE W [Org Chem, Hamburg Univ, D-20146 Hamburg]: New Sex Attractants for Species of the Zygaenid Subfamily Prouidinae (Lepidoptera: Zygaenidae). - Entomol Gener 32 (4): 243-250; Smttgart 2010-10. --- [Adele]

Both (R)- and (S)- enantiomers of 2-butyl(7Z)-dodecenoate and 2-butyl(9Z)-tetradecenoate, recentlv identified as sex nheromone comoonents of llliberis (Primiiliberisl mnrrulnta Jordan 1907. and their mixtures were screened in the field'in Bulgaria, ~kraine (Crimeaj, and Hungary in 2004-2007. As a result, sex attractants for five species of the subfamily Procridinae were discovered. (2R)-Butyl (7Q-dodecenoate alone or in combinations with other compounds, attracted numerous males of Jordanita (Tremewania) notata (Zeller 1847) in Bulgaria and Ukraine. Males of Adscita (Adrcira) - per?on (Hubncr 1813). All,.ila ITarmunndro) munnri (Ledercr 1x53, and Adrciro (AAura albanicrr I S d ~ ~ i b i k 1926) were recorded in traos baited with luresconwtnlna 29-burvl(7Z)dodecenoate. hlaler - , , , , ,

of Rhagades (Rhagades)pruni (Denis & Schiffermiiller 1775) were caught mainly in traps baited w~th (2R)-butyl(7Z)-dodecenoate as well as m traps baited with the latter compound and its enantiomer.

Key words: Illiberis (Primilliberis) rotundala Jordan 1907 - hocridinae - field screening - sex at- tractants - pheromone baits

Introduction

The zygaenid subfamily Procridinae consists of approximately 550 species [EFETOV 2004,2006; TARMANN 1984, 20041, worldwide. TARMANN 120031 listed 16 species of this subfamily as pests in Europe, Asia, and America.

Until 2004, sex pheromones were known only for two Procridinae species, H a r r i s i ~ metallica Stretch 1885 [MYERSON et all9821 and Theresimima ampellophaga (BayleBarelle 1808) [SUBCHEV et a1 19981. Very recently two sex pheromone components of a third species, Illiberis (Primilliberis) mtundata Jordan 1907.2-butyl(7Z)-dodecenoate and 2-butyl(9Z)- teuadecenoate, have been identified [SUBCHEV et a1 20091. Both (R)- and (9-enantiomers of the latter compounds were synthesized and used for further work with the target species and also for general field screenings in Bulgaria, Ukraine and Hungary.

Here are reported the results of this screening. ,

244 - MITKO SIIRCHEV et a1

2 Material and methods

The tested compounds, (2R)-butyl(7.Q-dodecenoate (R-7-12), (2R)-butyl(9Z)-tetradecenoate (R-9-14), (25')-butyl *Q-dodecenoatk (S-7-12) and (2s)-butyl (93-tetrademnoate (S-9-14) were svnthesized as described earlier ~SUBCHEV et al20091. Theenantiomeric vuritv of the comwundsused was: 94 %for R-7-12 and 92 % fors-7-12 as well as 93 %for R-9-14, anh 95 % fors-9-li. Batches of R-7-12 and R-9-14 used for our work in 2007, contained only 1.5 %of the corresponding enantiomer. Isopmpyl tetradecanoate (1~0141, found in the sex pheromone glands of Rhagades (Rhagades) pntni (Denis & Schiffermiiller 1775) [FRANCKE et al, unpublished] was synthesized by standard methods.

Pheromone baits were prepared by applying solutions of the test compounds in n-hexane (Merck, GC grade) onto rubber caps. Delta traps with sticky layers covered with Tanglefoot@ insect glue were used in all the tests.

Field screening tests were canied out at several sites in Bulgaria, Ukraine (Crimes), andHungary in 2004-2006. The baits used in 2004-2005 contained single compounds: R-7-12, S-7-12, R-9-14 and S-9-14 as well as corresponding 2-component mixtures. lbo tests designed for Rh prmi (Denis & Schiffermiiller 1775) were organized in 2006. First R-7-12, S-7-12, and a racemic mixture thereof were tested. For the second test, different ratios of these two compounds were prepared. A bait con- taining R-7-12 and S-7-12 and also isopropyl tetradecenoate was added to the test, because the latter compound was found in the extracts of females sex pheromone glands of this species [FRANCKE et al, unpublished data]. The distance between the traps in a replicate was 5-10 m, and between the replicates 3W500 m in Bulgaria, 5&200 m in Ukraine, and 5&100 m in Hungary. Other details for each test are given in the titles to the Tables.

An additional test including R-7-12 and R-9-14 of higher purity was organized in Ukraine (Mt. Chatyr-Dag) in 2007. The aim of this test was to reinvestigate (and c o n h ) the results obtained in 2004-2006 for some of the species, avoiding to some extent the possible effect caused by the enmtio- menc impurity of the compounds used in the earlier tests. Apart from the newly synthesized R-7-12, R-9-14 and a mixture thereof, the less enantiomerically pure samples of S-7-12, S-9-14 and a mixture thereof, which had been tested in 2004-2006, were also screened in these bioassays, which were conducted in three replicates during 28.06.-20.07.2007, with checks on June 30, July 6, and July 20.

All collected specimens have been determined by K A Efetov.

3 Results

Catches of five Procridinae species were recorded in field screening tests: a) Adscita (Adscita) gelyon (Hiibner 1813). The main catches of this species in both Bul-

garia and Ukraine in 2004-2005 were recorded in traps baited with S-7- 12 and traps with baits containing this compound (Tab 1). Further assays carried out in Ukraine in 2006, when only dodecenoates were tested, confirmed S-7-12 to be the compound that attracted males of this species, although seven males of A gelyon were caught in a trap baited with R-7-12 only ( I s b 2). The other test with different ratios of R-7-12 and S-7-12, carried out in the same year, confirmed previous results (Tab 3). Six moreA geryon males were caught in traps baited with S-7-12 only and one in a trap baited with S-7-12+S-9-14 in Ukraine in 2007.

b) Adscita (Tarmnnita) mannii (Lederer 1853). In field tests during 20W2005, three males of this species were caught in traps baited with S-7-12, one male in a trap baited with a mixture of this compound with S-9-14 and one male in a trap baited with R-7-12 (Tab 1). Two more males of this species were caught in Bulgaria in 2006 in traps baited with S-7-12 only and a three component mixture (R-7-12+S-7-12+iso14) respectively (Tab 3).

'Ihb 1: Species of Procridinae and total number of male moths caught by traps baited with R-7-12, S-7-12, R-9-14. and S-9-14 (doses of 50 pg) and their combit~ations (]:I) in: I. Botanic garden, Sofia, Bulgaria, 20.06.47.07.2004, two replicates; 11. Kresna, Bulgaria, 18.06.-23.07.2004, two replicates; 111. Botanic garden, Sofia, Bulgaria, 16.06~l8.07.2005, two replicates; IV. Kresna, Bulgaria, 16.05.-28.07.2005, two replicates; V. Kokaliane, Bulgaria, 10.07.-11.08.2005, two replicates; VI. Budakeszi, Hungary, 27.06.44.07.2005, VII. Simferopol, Ukraine (Crimea), 15.05.4'3.07.2005, one replicate and VIII. Mt. Chatyr-Dag, Ukraine (Crimea), 15.05.43.07.2005, one replicate. Only sites with catches for a cenaiu species are included in the Table.

I I Soecies. number of moth cauaht - Site J notata A geryon A mannll Rh pmni

I I II 1 111 1 IV I V I Total I I 1 111 1 VII I Vlll I Total I I 1 111 1 V I Total 1 111 1 VI I Total

Tab 2: Species of Procridinae and total number of male moths caught by traps baited with R-7-12. $7-12 (doses of LOO pg), and their combinations (ratio 'J

]:I) in: I. Simferopol, Ukraine (Crimea), 30.04.-21.06.2006, two replicates, 11. Belogorsk, Ukraine (Crimea), 7.05.-21.06.2006, two replicates and "1. Mt. Chatyr-Dag, Ukraine (Crimea), 17.06.-15.07.2006, two replicates. -

: *r of moth i t

BaiffSite J notata A geryon Rh pruni A albanica .. m .. .. m ... . m m

C) Jordanita (Tremewania) notata (Zeller 1847). Main catches of this species were recorded in Bulgaria in 2004-2005 in traps baited with R-7-12 and traps with baits containing this compound. The only exception was one male of J notata caught in a trap baited with a mixture of S-7-12 and S-9-14 (Tab 1). Additional tests in Ukraine in 2006, confirmed these results (Tab 5 3) and proved S-7-12 to have no significant effect on the attractiveness of R-7-12 to J notata males. The number of moths of this species caught in traps baited with R-7-12 alone was the same as the number caught in traps baited with a mixture of R-7-12 and S-7-12 in Belogorsk (Tab 2).

d) Rhagades (Rhagades) pruni. In our 200&2005 field tests, males of this species were caught only in traps baited with a mixtureof R-7-12 and S-7-12in Bulgariaand Hungary (Tab 1). However, in 2006, in a test, designed especially for this species, the number of males in traps baited with R-7-12 alone was similar to the number caught in traps baited with various mixtures of R-7- 12 and S-7- 12 in both Ukraine (Crimea) and Hungary (Tab 2,3). A total number of eleven Rh pruni males was caught in traps baited with R-7-12. Using (R)-configured compounds of higher enantiomeric purity, during bioassays carried out in 2007 at Mt. Chatyr-Dag, Crimea, Ukraine, one male of this species was caught in traps baited with R-7-12+R-9-14. In these tests, the attractivity of R-7-12 alone was not compared with mixtures of R-7-12 and S-7-12.

e) A single male of Adscita (Adscita) albanica (Naufock 1926) was caught in a trap baited with a mixture of R-7-12 and S-7-12 in Ukraine (Crimea) in 2006 (Tab 2). One more male of this species was caught in a trap baited with a mixture of S-7-12 and S-9-14 in Ukraine in 2007.

4 Discussion

Hmetallica was the first Procridinae species for which the sex pheromone was identified. In female extracts of this species MYERSON et al [I9821 found 2-butyl(7.Q-tetradecenoate and activity of the (8-enantiomer of the latter compound as an attractant for the males of this s~ecies in the field. In field tests. this (S)-enantiomer attracted also H ~uatemalena (Druce ~,

1'884) and Acoloitus novaricus Barnes & McDunnough 1913, while thi (R)-enantiomer at- tracted H americana (GuBrin-M6neville 1884) and A falsarius Clemens 1861 [SODERSTROM et a1 1985; LANDOLT et al 1986; LANDOLT & HEATH, 19911.

From the results of the here mentioned field work, it can be concluded that males of A geryon and A mannii are attracted by S-7-12 while males of J notata and Rh pruni are attracted by R-7-12. However, because of the relatively low enantiomeric purity of the tested compounds we cannot exclude that the corresponding enantiomers are involved in the pheromone system of these species, i e that defined enantiomeric compositions are nec- essary for a maximum attractivity. As a rule, the non-natural enantiomer did not influence the attractiveness of the natural pheromone in Procridinae species. This was shown for H americana and A falsarius [LANDOLT et a1 19861 and H guatemalena [LANWLT &HEATH 1991), for which even the racemic mixture attracted a number of these species. Special experiments with Th ampellophaga in the field also showed that the (8-enantiomer did not inhibit the attractiveness of the natural sex pheromone of the species (2R)-butyl(72)- tetradecenoate [SUBCHEV et a1 20041. On the other hand, both pairs A geryon and A mannii as well as Jnotata and R h p m i are sympatric. So, for each pair using the same attractant, some additional reproductive isolation mechanism should occur. One of the possibilities is a more complex pheromone system in these species - secondary component(s) acting as either synergist(s) for conspecific males or inhibitor(s) for wrong males.

New Sex Attractants - 249

In this context it is worth mentioning that in Jordanita s u b s o h at least two butylest- ers of unsaturated fatty acids could be detected (structures yet undefined, FRANCKE et al, unpublished). Another possibility is a temporal isolation - non-overlapping seasonal ap- pearance or daily sexual activity. An example for such temporal isolation is the American pair of Procridinae species Harrisina arnericana and Acoloithus falsarius. The males of both species are attracted by (2R)-butyl(7Z)-tetradecenoate but the flight of H americana males occurs in the morning, while that of A falsarius males in the afternoon [LANDOLT & HEATH 19871. In the case of J notata and Rh pruni the seasonal flight period of the former species is earlier than that of the latter one.

5 References

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Acknowledgments - Danksagnng: This project was supported by Grant 120112002, Grant D002- 24412008 of the Bulgarian National Scientific Fund and OTKAgrant K81494 of HAS.

Authors' addresses - Ansebriften der Verfasser: Professor Dr Sci Mitko Snbchev & Dr Teodora Toshova Eksoerimentalna zooloeiva. Himicheska ekoloeiva na nasekomite. Institut w zooloeiva. -. -. Bul Tzar ~sioboditel 1, BG- 10%. Sofia; Bulgaria. Professor Dr Sci Konstantin A Efetov & Dr Ekaterina V ParsNrova, Krimskiv Gosudars!xeniv Medicinikiy Univcnitet. UA-riub6 Simferopol, Cnmea. l'kraine. Professor Dr h.111 Wluko Fmck,Organi~chr.Chemie, Un~\.irsitat Hamhum, D-20116 Hmburg,

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Das vodiegende Buch stellt FlieR- und Stillpewasser als Okosysteme vor, die sich durch die ~echselbeziehungen der Pflanzen mit ihrer belebten nnd unbelebten Umwelt charakterisieren las- sen. Gleichzeitie werden die momholo?ischen und okoloeischen Besonderheiten von Sumof- und - . " - Wasserpflanzen einsehend behandelt. Neben den Eigenheiten der aquatischen Okosysteme wird auch ihre ~eziehung zu den angrenzenden Uferzonen beleuchtet. ~ n t e r anderen werden folgende ~ h e m e n hesomchen: Anteile limnischer Svsteme am Wasserkreislauf - Entstehuns der OberRachen?ewLser - ~e\;assergrund als ~tandort-i-~akophyten als strukhubildende ~ l imente und ~tandortfaktoren - ~uellen-und jhnliche eraustrin us trine - ~ l ~ c ! 3 ~ e a ac.erveectation - Lebcn mir der Wassersnomt~ng -Die BedeutungderTrophie iur GewhserOkosysteme - GeuPsserAltemg a19 ndturlicherVorgang.

SCHWOERBEL J & BRENDELBERGER H: Einfiibrung in die Limnologie. 9. Aufl. - [VIII+340 S, zahh Abb + Tab, 170 x '?A0 mm, Ha~tka~t.Einbandl. - Publ: Spektmm, Elsevier Akademischer Verlag, Heidelherg-Miinchen 2005; ISBN: 3-8274-1498-9; PI: 8 34,50. --- [EGR-Nr 3.0001

Dieses Kurzlehrbuch der SiiSwasserkunde beschreibt die System-Eigenschaften der Gewasser und schildertdieZusammenhange zwischen den klimatischen, gwlogischen und physikalisch-chemi- schen Faktoren sowie dem Stofthaushalt und den aauatischen 'lier- und PflanzengemeinschaRen. Ein - umfangreiches Kapitel ist der angewandten Limnologie und ihren aktuellen Problemen (Abwasser- Behandlung, Gewasser-Belastung nnd GewLser-Therapie. Fln&Ausbau und Hocbwasser-Gefahr, Gewnsser-Versauem~, Okotoxikologie) pewidmet.

Das bew3ute&ndwissen des fehrbich-~lassiken vonJijRGEN SCHWOERBEL wurdevonHElNz BRENDEL~~RGER eriindlichdurcheesehen. aktualisiertundum einize Abschnine enveitert.Somit rich- - - - tet sich das Werk wiedemm an Studierende der Limnologie, Biologie, Hydmlogie, Wasserwirtschaft und Ingenienmissenschaften sowie an alle diejenigen, 61 die Kenntnisse der GewLserkunde von Bedeutung siod, um okologische Entscheidungen treffen zu konnen.