Monomorium pharaonis

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. 

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). 

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... 

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). 

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... 

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... 

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... 

From the above survey of results the synthetic potential of the oxazinolactam intermediate 46 in hand, we envisaged to synthesize monomorine I (62) which constitutes of an extension of the methodology based on intramolecular nitroso Diels-Alder cycloaddition. The relative stereochemistry of this substance, isolated as one of the trail pheromones from Pharaoh ants (Monomorium pharaonis L.) (ref. 19), has been determined its relative stereochemistry by nonstereoselective synthesis (ref. 20). More recently, a stereospecific synthesis of racemic 62 (ref. 21) and a chiral synthesis of the (-)-enantiomer of natural 62 (ref. 22) were reported. 

Indolizidine alkaloids are produced by the Pharaoh ant, Monomorium pharaonis. This tropical ant is now a common... 

OZ)-3,4,7,11 -tetramethyltrideca-6,10-dienal (faranal), the trail pheromone of Pharaoh s ant, Monomorium pharaonis, In one approach, racemic (3S,47 /3/ ,45) faranal (54) was synthesised by a route in which stereospecific formation of a trisubstituted double-bond and a substituted vinyl iodide was controlled by addition of alkyl-copper complexes to terminal acetylenic derivatives. The relative configuration of the methyl groups at C-3 and C-4 was established by the use of c fs-4,5-dimethyl cycl ohexene as an important intermediate (Scheme 8). ... 

Fig. 15.10 Trail pheromones identified from myrmicine ants, indicating the diversity of structures encountered. ( l) Atta texana (Tumlinson et al., 1972) andcephalotes (Riley et al.y 1974b) (b) A. sexdens rubropilosa (Cross et aL, 1979) and Myrmica spp. (Ever-shed et al., 1981) (c) Lasius fuliginosus (Huwyler et al., 1975) (d) Monomorium pharaonis (Ritter et al., 1977) (e) Solenopsis invicta (Williams et a/., 1981 Vandermeer etal., 1981).

HOlldobler, B, (1973) Chemische Strategic beim Nahrungserwerb der Diebsameise Solenopsis fugax Latr.) und der Pharaoameise (Monomorium pharaonis L.). Oecologia, 11, 371-80. 

Ritter, F. J., Bruggeman-Rotgans, I. E. M., Verweil, P. E. J., Persoons, C. J. and Tal-man, E. (1977) Trail pheromones of the Pharaoh s ant, Monomorium pharaonis isolation and identification of faranal, a terpenoid related to juvenile hormone II. Tetrahedron Letters, 2617-18. 

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