J. SMOLANOFF, J. M. J

1,4-BENZOQUINONES IN AFRICAN MILLIPEDS1

BY J. SMOLANOFF, J. M. DEMAN(}E, J. MEINWALD, T. EISNEP.4

The defensive glands of millipeds have been the subject of con-siderable recent chemical and biological investigation. Compoundsidentified from the secretions have included hydrogen cyanide, ace-tate esters, aldehydes, phenols, 1,4-benzoquinones, quinazolinones, andnitrogen-containing terpenes (re.erences in Eisner et al., I975). Themost widespread o these components are the 1,4-benzoquinones whichhave been found in the secretion o. species of the orders Julida, Spiro-bolida, and Spirostreptida. We here report the isolation o 1,4-ben-zoquinones from three species oi: Spirostre’ptida from Africa: Archi-spirostreptus tumuliporus, Peridontopyge conani, and P. rubescens.The millipeds were collected in Senegal, in the region o Kaolack

(Sine-Saloum), where they are known to damage agricultural crops,particularly peanuts. Peridontopyge conani and P. rubescens can beespecially abundant. At the beginning o.f the rainy season the milli-peds swarm over the soil surface in large, numbers in search of ’foodand mates.

The animals were shipped live to. Ithaca., N. Y., where they were"milked" of secretions on arrival. Individual animals were handledand tapped gently with a small metal mallet, until the golden-brownsecretion oozed from their glands. The effluent was soak.ed up inpieces of filter paper, and transferred to carbon disulfide. Examina-tion of the secretion from the two ,species of Peridontopyge by gas-liquid chromatography (6 ft. column, 15% SE-3o, 2ooC) revealedthe presence o.f a single component. Comparison with an authenticsample (gas-liquid chromatography, infrared spectroscopy, protonmagnetic resonance spectroscopy) showed this component to be 2-

methyl-3-methoxy- 1,4-benzoquinone.The secretion from A. tumuliporus was .shown by gas-liquid chro-

matography to contain two components, which by chromatographicand spectroscopic comparison with authentic samples were shown to

1Paper No. XLIV of the series Defense Mechanisms of Arthropods.2Department of Chemistry, Spencer T. Olin Laboratory, Cornell Univer-

sity, Ithaca, New York 14853.aMus6um National d’Histoire Naturelle, Laboratoire de Zoologic, 61 Rue

de Buffon, Paris---Ve.4Section of Neurobiology and Behavior, Division of Biological Sciences,

Cornell University, Ithaca, New York 14853.Manuscript received by the editor April 3, 1975

78

1975] 8m,olanoff, Demange, Meinwald, & Eisner 79

be 2-methyl-3-methoxy- 1,4-benzoquinone and 2-methyl- 1,4-benzoqui-none. Gas-liquid chromatography indicated the presence o a thirdminor component, present as a shoulder on the downward side o the2-methyl- 1,4-benzoquinone peak.

Individual milkings rom males and emales o the three speciesshowed no qualitative sexual differ.ences in quinone content, althoughthe ratio oi: the two quinones in J. tumuliporus showed considerableindividual variability.The two quinones here identified .are the most .common ones o.und

in millipeds (reerences in Eisner et al., 1975). FiCteen spirostreptoidspecies have been previously studied. O these, eight resemble Arch-ispirostreptus tumuliporus in that they produce both quinones (,4rch-ispirostreptus gigas, Cambala hubrichti, Collostreptus [ulvus, Dora-togonus annulipes, Orthoporus lavior, O. punctilliger, Prionopetalum[rundsbergi, P. tricuspis) (Eisner et al., 1975; leriss6 and Salles,I97O; Wood, I974). One species resembles Peridontopyge conaniand P. rubescens in that it produces 2-methyl-3-methoxy-I,4-benzo-quinone o.nly (Orthoporus conifer) (Eisner et al., 1965). Five spe-cies, including two other Perid,ontopyge, produce only 2-methyl-I,4-benzoquinone (,4uglonopygus aculeatus, Peridontopyge aberrans, P.vachoni, 8pirostreptus multisulcatus, Rhapidostreptus (Spirostreptus)virgator) (Barbier, 1959; Barbier and Lederer, 1957). One speciesproduces the unsubstituted quinone, 1,4-benzoquinone (Spirostreptuscastaneus) (Barbier and Lederer, 1957).

This study has been supported by grants AI-o29o8 rom the Na-tional Institutes o Health and BYIS-74-I5O84 rom the. NationalScience Foundation.

REFERENCES CITED

BAIBIER, M.1959. S6parations de p-benzoquinones naturelles par chromatoplaques.

d. ChromatotTraphy 2, 649-651.BARBIER, M. AND LEDERER, E.

1957. On the benzoquinones of the venom of three species of myria-pods. Biokhimya 22, 221-225.

EISNER, T., ALSOP, D., HICKS, K., AND MEINWALD, J.1975. Defensive secretions of millipeds. In "Arthropod Veno.ms" (S.

Bettlni, ed.). Sprirger Verlag (in press).EISNER, T., HURST, J. j., KEETON, W. T., ,AND MEINWALD, Y.

1965. Defense mechanisms of arthrop0ds. XVI. Para-benzoquinonesin the secretion of spirostreptoid millipeds. Ent. Soc.5 8, 247-248.

80 Psyche [March

PRIssi, A. C. M., ASv SALLI$ C. A.1970. Estudo quimico de Diplopoda Brasilejros. III. Collostreptus

fulus (Schubert, 1960). ltlas $o’c. Biol. Rio de Janeiro 13,95-99.

Woofs, W. F.1974. Toluquinone and 2methoxy-3-methyl benzoquinone from the de-

fensive secretions of three African millipeds. lnn. Ent. $oc.lmer. 67, 988-989.

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J. SMOLANOFF, J. M. J