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When threatened, the harvestman Egaenus convexus (Opiliones: Phalangiidae) ejects a secretion against offenders. The secretion originates from large prosomal scent glands and is mainly composed of two isomers of 4-hydroxy-5-octyl-4,5-dihydro-3 H -furan-2-one ( 1 ), a β-hydroxy-γ-lactone. The compounds were characterized by GC-MS of their microreaction derivatives, HRMS, and NMR. After the synthesis of all four possible stereoisomers of 1 , followed by their separation by chiral-phase GC, the absolute configurations of the lactones in the Egaenus secretion was found to be (4 S ,5 R )- 1 (90%) and (4 S ,5 S )- 1 (10%). Hydroxy-γ-lactones represent a new class of exocrine defense compounds in harvestmen.

Harvestmen have a pair of scent glands that open through ozopores. The literature suggests a link between the morphology of the ozopore area and the emission of a defensive secretion. A previous study on a species that aggregates in open areas, where individuals are probably more easily spotted by predators, showed that this defensive secretion causes conspecifics to flee. However, it is unknown whether this behavior occurs in species that aggregate in sheltered areas, where prey are harder to find. Herein, we describe the morphology of the ozopore area, the mode of emission of the defensive secretion, and its chemical composition in the harvestman Discocyrtus pectinifemur. We also tested if the defensive secretion is used as an alarm pheromone. We found that D. pectinifemur releases the defensive secretion in different ways, one of them being as a jet. Emission as a jet contrasts with that known for all congeners previously studied, and is in accord with the expected morphology of the ozopore. We found that the defensive secretion of D. pectinifemur does not function as an alarm pheromone. The composition of the defensive secretion, a mixture of quinones, is congruent with those already described for the clade that includes Discocyrtus. Our results support the link between the morphology of the scent glands area and the emission behavior of the defensive secretion, and they suggest that the alarm pheromone function in harvestmen may be dependent on ecological factors.

Four species of gonyleptid harvestmen, Acanthogonyleptes pulcher, Gonyleptes saprophilus (Gonyleptinae), Sodreana barbiellini, and Sodreana leprevosti (Sodreaninae), were examined by GC-MS and ¹³H NMR. All of these species release vinyl ketones, and three of them produce the corresponding pyranyl ketones, which are presumed hetero-Diels-Alder (HDA) dimers. The vinyl ketones 5-methyl-1-hexen-3-one, rac-4-methyl-1-hexen-3-one, and (S)-4-methyl-1-hexen-3-one were synthesized. Natural 4-methyl-1-hexen-3-one is present as a single stereoisomer and has the R-configuration. Vinyl ketone dimers (HDA dimers) were also observed in the scent gland exudate and characterized by HRMS, ¹³C NMR, and ¹H NMR chemical shifts of the pyranyl moiety.

The scent gland secretion of Austropurcellia forsteri was analyzed by gas chromatography-mass spectrometry, providing the first description of the secretion chemistry in the cyphophthalmid family Pettalidae. The secretion contained a total of 21 compounds: About 60% of the whole secretion consisted of a series of saturated, mono-unsaturated and doubly unsaturated methylketones, from C11 to C15, with a cluster of saturated and mono-unsaturated C13-methylketones dominating. A second fraction included several naphthoquinones such as 1,4-naphthoquinone (ca. 20% of secretion), 6-methyl-1,4-naphthoquinone (ca. 17%), and minor amounts of chloronaphthoquinones (ca. 2%). When compared with scent gland compositions of other representatives of cyphophthalmids (e.g. from families Sironidae and Stylocellidae), a highly conservative chemistry of cyphophthalmid secretions is apparent, based on a restricted number of methylketones and naphthoquinones.

The exocrine secretions from prominently developed prosomal scent glands in four species of the European laniatorean harvestman genus Holoscotolemon (Laniatores, Travunioidea, Cladonychiidae) were analyzed by gas chromatography - mass spectrometry. Two major alkaloidal compounds were detected: Nicotine accounted for more than 97% of the secretion in Holoscotolemon jaqueti and H. oreophilum, whereas the chemically related nicotinoid alkaloid anabaseine was the major compound in H. lessiniense. In addition, a series of minor nitrogen-containing components was found, namely 3-(1-methyl-2-piperidinyl)-pyridine and anabasine, in H. jaqueti and H. oreophilum, and anabasine together with 2,3'-bipyridyl in H. lessiniense. By contrast, extracts of adult H. unicolor did not show any components. In one juvenile specimen of H. unicolor, however, low amounts of alkyl pyrazines (dimethyl-isobutyl- and dimethyl-isopentylpyrazines) were detected. Nitrogen-containing components previously were found in Sclerobunus robustus (an American travunioid harvestman), so scent gland-derived alkaloids may be widespread or even common in the Travunioidea. Alkaloids have not been reported for other opilionid scent gland secretions outside the Travunioidea, and we hypothesize that they may be the phylogenetically ancestral allomones in the Laniatores, having been reduced and replaced by a phenol- and benzoquinone-rich chemistry in the more derived grassatorean taxa.

Extracts of Paranemastoma quadripunctatum (Opiliones, Dyspnoi, Nemastomatidae) contained seven components, all of which likely originated from the secretion of well-developed prosomal scent glands. The two main components (together accounting for more than 90% of the secretion) were identified as 1,4-naphthoquinone and 6-methyl-1,4-naphthoquinone. The minor components were 1,4-naphthalenediol, two methoxy-naphthoquinones (2-methoxy-1,4-naphthoquinone, and 2-methoxy-6-methyl-1,4-naphthoquinone) and two anthraquinones (2-methyl-9,10-anthraquinone and a dimethyl-9,10-anthraquinone). While some chemical data on scent gland secretions of the other suborders of Opiliones (Cyphophthalmi, palpatorean Eupnoi, and Laniatores) already exist, this is the first report on the scent gland chemistry in the Dyspnoi. Naphthoquinones are known scent gland exudates of Cyphophthalmi and certain Eupnoi, methoxy-naphthoquinones and anthraquinones are new for opilionid scent gland secretions.

Two alkylated 1,4-benzoquinones were identified from the defensive secretion produced by the neotropical harvestman Goniosoma longipes (Gonyleptidae). They were characterized as 2,3-dimethyl-1,4-benzoquinone and 2-ethyl-3-methyl-1,4-benzoquinone. We tested the effectiveness of these benzoquinone secretions against several predator types, including invertebrates and vertebrates. Different predators were exposed to the harvestmen's gland secretion or to distilled water in laboratory bioassays. Our results indicate that secretions containing the 1,4-benzoquinones released by G. longipes can be an effective defense against predation, and that the effectiveness of the secretion is dependent on the predator type. The scent gland secretion repelled seven ant species, two species of large wandering spiders, and one frog species, but was not an effective defense against an opossum. Our study also demonstrates that the scent gland secretion of G. longipes can work as a chemical shield preventing the approach of three large predatory ants for at least 10 min. The chemical shield may protect the harvestman against successive attacks of the same ant worker and also allow the harvestman to flee before massive ant recruitment. Our data support the suggestion that chemical defenses may increase survival with some but not all potential predators. This variation in defense effectiveness may result from many interacting factors, including the attack strategy, size, learning ability, and physiology of the predators, as well as the chemical nature of the defensive compounds, type of emission, and amount of effluent released by the prey.

Gas chromatographic-mass spectrometric analyses of the scent gland secretions of Siro duricorius and S. exilis (Opiliones, Cyphophthalmi, Sironidae) revealed a set of 24 components, comprising a series of saturated and unsaturated methyl ketones (C11-C15) and four naphthoquinones. Whereas the scent gland secretions of S. duricorius, collected in Austria, and S. exilis from USA were qualitatively nearly indistinguishable (with the exception of acetophenone that was specific to S. duricorius), they distinctly differed in their relative quantitative compositions: major components of the secretion of S. duricorius were 7-tridecen-2-one, tridecan-2-one, undecan-2-one, 1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone (tentatively identified only), and 4-chloro-1,2-naphthoquinone. In contrast, in S. exilis a compound tentatively identified as 6-methyl-4-chloro-1,2-naphthoquinone was present in large amounts (in S. duricorius a trace component), whereas undecan-2-one only occurred in minor quantities. Secretion profiles of juveniles and adults (both sexes) of each species showed high correspondence. This is the first report on the chemistry of scent gland secretions of the opilionid suborder Cyphophthalmi. 4-Chloro-1,2-naphthoquinone was identified as a new exocrine product of arthropods, whereas 1,4-naphthoquinone and the tentatively identified 6-methyl-1,4-naphthoquinone are known constituents of exocrine secretions from one species of palpatorid opilionids, Phalangium opilio. In contrast, all ketones identified were new for opilionid scent glands, although similar ketones are characteristic of scent gland secretions of palpatorid genera Leiobunum and Hadrobunus. With regard to the near-basic position of Cyphophthalmi in currently proposed phylogenetic trees of Opiliones, naphthoquinones and ketones from Siro may represent the condition ancestral to the (derived) naphthoquinone- and ketone-rich secretions in phalangid Palpatores.