Monomorium ants

T73 Trinervitermes bettonianus,575 Cubitermes umbratus,576 termites, Monomorium, ants 577... 

Figure 9.7 Alkyl- and alkenyl-pyrrolines, -pyrrolidines and N-methylpyrrolidines of unknown origin from Solenopsis thief ants and some Monomorium ants...

Mori reported an improved synthesis of (3S,4P,6 ,10Z)-faranal (37), the trail pheromone of the Pharaoh s ant (Monomorium pharaonis) [84]. As summarized in Scheme 55, the key-reaction was the coupling of iododiene A with iodide E. The geometrically pure A was prepared by the zirconocene-mediated carbo-alumination reaction, and E was prepared from B by the asymmetric cleavage of its epoxy ring to give C (77% ee), which could be purified via its crystalline 3,5-dinitrobenzoate D. 

Besides piperidine alkaloids, a total of 19 pyrrolidines have been found in the secretions of thief ants and fire ants of the genera Solenopsis and Monomorium. Among these, compounds 80-84 are simple pyrrolidines with two saturated linear all-carbon side chains only in Solenopsis latinode is there a secondary amine (82) and its methylated analog (85). One or two terminal unsaturations are present in compounds 86-91, which all possess a (hex-l-en)-6-yl chain and a 5-, 7-, or 9-carbon saturated chain. Compounds 93, 94, 96, 97, and 98 are the A-l-pyrrolines corresponding to pyrrolidines 80, 82, 90 (93 and 96 corresponding to 80, 94 to 82, and 97 and 98 to 90). 

E)- and (2Z)-Farnesylamine (123) (Fig. 20) were detected in the extracts of the myrmicine ant Monomorium fieldi from Australia. Their structures were established by comparison with synthetic material. This is the first report of a farnesylamine derivative from a natural source [129]. 

Workers of pharaoh s ant, Monomorium pharaonis, utilize their poison gland secretion as an effective repellent in the same way as that of thief ants, Solenopsis (Diplorhoptrum) species, in order to steal brood from the nests of other... 

The structure of monomorine I (16a), isolated from the extract of workers of the thief ant, Monomorium pharaonis, by gas-liquid chromatography (Table II), has been revealed to be 3-butyl-5-methyloctahydroindolizidine on the basis of mass and H-NMR spectra. The mass spectmm shows characteristic peaks at m/z 180 (345 M - CH3) and m/z 138 (346 M - Bu, a base peak), indicating the presence of methyl and butyl group attached to the a carbons of an amine, in addition to a molecular ion at m/z 195. The fact that the (M — 1) peak is higher than the M peak indicates a cyclic amine. The H-NMR spectmm shows two methyl groups (triplet at 8 0.88, CH3—CH2 doublet at 8 1.18, CH3CH—N) and three methines adjacent to nitrogen (8 2.13, 2.27, and 2.52). 

The principal component of the secretion of the poison gland of the European thief ant (Solenopsis fugax) is rrarcs-2-n-butyl-5-n-heptylpyrrolidine, identified by mass spectrometry and synthesis.5 The reductive amination of 1,4-diketones with sodium cyanoborohydride and ammonium acetate has yielded various 2,5-dialkyl-pyrrolidines that occur in the poison glands of ants of Monomorium spp.6... 

We end with an example that includes methods from this chapter as well as some revision and a reminder of stereochemistry. Monomorine I 71 is the trail pheromone of Pharaoh s ant (Monomorium pharaonis). These ants are pests in hospitals as they spread infections and they follow a trail of monomorine as they go about their evil work. Synthetic monomorine might be... 

Trail Pheromones. Tumlinson et al. (133) identified methyl 4-methyl pyrrole-2-carboxylate (XXXVT as the major trail pheromone of the ant, Atta texana. Another poison gland product, 3-butyl-5-methyloctahydroindolizine (XXXVI) has been reported to be the dominant releaser of trail following for workers of Monomorium pharaonls (134).In contrast to these cyclic releasers... 

In a review of current work on the trail pheromone of the Pharaoh s ant, Monomorium pharaonis, it is reported that natural monomorine III is the all-cw-... 

Certain 2,5-dialkyl-pyrrolidines, which are trail pheromones of the pharaoh ant (Monomorium pharaonis L.), have been synthesized by application of the Hofmann-Loffler reaction to 5-aminotridecane and 7-aminopentadecane. The same type of compound results from Seebach alkylation of TV-nitrosopyrrolidines.4... 

A few years ago the complete structure of periplanone-B, apart from its stereochemistry, was elucidated and published by our research team (32,33,34) with Persoons as the principal investigator, who included this work in his doctoral thesis (35), and shared the Royal Dutch Shell Prize for 1978 with Ritter for this work and the structure elucidation of faranal, the trail pheromone of the Pharaoh s ant, Monomorium pharaonis (36,37). 

Both possible isomers of the 2,5-dialkyl-1-pyrrolines have been identified in the venoms of Solenopsis and Monomorium species. These compounds generally accompany the corresponding dialkylpyrrolidines as venom constituents. The venom of 3. punctaticeps, an African species, contains both 61- and -pyrrolines (VII) (j3) as do the venoms of three North American Monomorium species (12 ). The latter dialkylpyrrolines (VIII) are distinguished by the presence of two terminally unsaturated side chains. The pyrrolines in the venom of M. latinode are distinctive in constituting the only 5-pyrrolines (IX) in ant venoms that are not accompanied by the 1-pyrrolines (6). 

The disubstituted pyrrolidines and piperidines have been demonstrated to be excellent repellents for ants under field conditions. Workers of Monomorium pharaonis effectively repel other species of ants with venom droplets which accumulate on the tip of the sting (37), a strategy that is used with equal success by workers of North American Monomorium species ( 38.) and the European thief ant, Solenopsis fugax (37). The venom of the latter species contains a single alkaloid, trans-2-butyl-5-heptylpyrrolidine (I, m=3, n=6) (1 ), and the... 

Disubstituted indolizidines, unlike many classes of amphibian alkaloids, are not unique to amphibians. 3,5-Disubstituted indolizidines such as monomorine I [(5Z,9Z)-195B] occur in ants of the genera Monomorium and Solenopsis (125,129,134). Some of the ant indolizidines are as follows (5Z,9Z)-3-n-butyl-5-methylindolizidine (monomorine I), (5Z,9Z)-3- -ethyl-5-methylindolizidine, (5Z,9Z)-3-hexyl-5-methylindolizidine, and (5 ,9Z)-3-butyl-5-(4-pentenyl)indolizidine. A series of 5-substituted indolizidines, the piclavines, were reported recently from a marine tunicate (Clavelina picta) (135). 

The 2,5-disubstituted pyrrolidines (and pyrrolines) are well known as constituents of ant venoms, particularly ants of the myrmicine genera Solenopsis, Monomorium, and Megalomyrmex 158). More than 20 such compounds have been identified in myrmicine ants 134,149,158-161). These include the /rans-pyrrolidine 197B. Incidentally, all ant pyrrolidines so far detected are of the trans configuration. A trans-2-n-butyl-5-n-heptylpyrrolidine (cf. 225C) occurs in ants, but a 2,5-di-/i-butylpyrrolidine (cf. 183B) has not been reported. 

S,4R,6E,10Z)- F- aranal C l 10 Pharaoh s ant Monomorium pharaonis) T Zirconoceire- mediated carboaluminalion reaction [167]... 

All the currently known indolizidine and quinolizidine alkaloids isolated from ants are illustrated in Fig. 6. (+ )-Monomorine I (427), the well-studied trail pheromone constituent of the Pharaoh ant Monomorium pharaonis), and the analogs 428-431 were described in the earlier volumes in this series. These five compounds are 3,5-disubstituted indolizidines bearing short saturated or mono-unsaturated hydrocarbon chains. The relative stereochemistry in monomorine VI (430) still remains unknown, while that of 431 was atypical for the class at the time of its isolation 380). The structural resemblance of fiiis group of alkaloids to the... 

In 1977, Ritter and coworkers in the Netherlands isolated and identified faranal (95, Figure 4.46), the trail-following pheromone of the workers of the Pharaoh s ant (.Monomorium pharaonis). The detection threshold of 95 is about 1 pg/cm of a trail. This remarkable bioactivity of 95 attracted the attention of... 

New 2,6-dialkylated piperidines (207-210) have been isolated as cis/trans mixtures from the ant venom of Monomorium delagoense [487], Their structures were determined using MS, catalytic hydrogenation to the hydrocarbons, and methoxymercuration-demercuration followed by MS analysis. The structures of 207-209 were confirmed by synthesis of the cis/trans mixtures from the corresponding dialkyl pyridines. The major venom component, cis/trans 207, displayed potent insecticial activity against Reticulitermes worker termites (LD50 = 150 pg/g termite). In addition, 207 was a potent repellent for the ants Pheidole and Iridomyrmex [487],... 

Following the initial discovery of alkyl-substituted piperidines in Solenopsis venom, a very large number of structurally related alkaloids were identified in the venom from ants of the subfamilies Myrmicinae and Pseudomyrmicinae, all of which share a carbon skeleton based on a single unbranched chain. Analyses of ants from the genera Solenopsis, Monomorium, and Diplorhoptrum revealed 2,5-dialkylated pyrrolidines,... 

The ant venom alkaloids occurring in the genera Solenopsis and Monomorium have been reviewed briefly. The venoms of iMy latinode and M subopacum contain an array of 2,5-dialkylpyrro-lidines (1), and the pyrrolines (2) are also present. All were identified by gas-chromatographic separation followed by mass spectrometry. ... 

A trail substance of the Pharaoh ant, Monomorium pharaonis (L), has been identified as a 3-butyl-5-methyloctahydroindolizine of unknown stereochemistry. The four isomers (6a—d) have now been prepared by methods which allow the stereochemistry at C-3, C-5, and C-9 to be assigned. Reaction of 2,6-lutidine (7) with n-butyl-lithium and 1,2-epoxyhexane gave the alcohol (8), which on treatment... 

Monomorine (664), isolated from the cosmopolitan ant Monomorium pharaonis (L.) as a major component displaying attracting and trail-initiating activity, is another example in which stereoselective hydride addition to a prochiral ketone creates easy access to cmcial stereogenic centers. L-Selectride reduction of 647 affords, with high syn selectivity, alcohol 662 (98 2). This is similarly converted in six steps to the (25, 5i )-pyrroline 663 which, after... 

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