Chemistry of venom alkaloids in someSolenopsis (Diplorhoptrum) species from Puerto Rico

Abstract

A number of 15-carbon alkaloids have been identified in venom extracts of four Puerto Rican species of ants in the genusSolenopsis (Diplorhoptrum). Workers of a species from El Verde produced thecis andtrans isomers of 2-methyl-6-nonylpiperidine with the latter isomer predominating. The same compounds were identified in queens of a species from Río Grande, but in this species no alkaloids were detected in worker extracts. Workers of aDiplorhoptrum species collected on Mona Island produced primarily atrans-2-methyl-6-(Z-4-nonenyl)piperidine,3, with smaller amounts of thecis isomer, whereas the major compound found in the queens of the same species on Mona Island was (5Z,9Z)-3-hexyl-5-methylindolizidine, identical with the alkaloid produced by queens of a species collected on Cabo Rojo. Surprisingly, workers of the Cabo Rojo species produced (5Z,9Z)- and (5E,9E)-3-butyl-5-propylindolizidine (4 and5, respectively) reported earlier as the 223AB indolizidines from skins of dendrobatid frogs. The possible significance of the qualitative and quantitative differences in the venom alkaloids synthesized by queens and workers is discussed as is the possibility that ants containing such alkaloids may serve as a dietary source for the skin alkaloids used by certain frogs in chemical defense.

Intraspecific and Intracolonial Variation in the Profile of Venom Alkaloids and Cuticular Hydrocarbons of the Fire AntSolenopsis saevissimaSmith (Hymenoptera: Formicidae)

“…A clear trend of ever-increasing relative amounts of venom cis-piperidinic alkaloids is perceived towards larger females, queens. Similar trend was observed with other species of fire ants, including S. invicta and S. geminata [4,22,29,37]. Venom alkaloids were not detected in the male body nor head extracts.…”

Workers and alate queens of Solenopsis geminata share qualitatively similar but quantitatively different venom alkaloid chemistry

“…Both cis-and trans-C9 have been reported from the venom of alate queens of S. geminata, S. richteri and hybrid S. richteri × S. invicta (MacConnell et al, 1974;Chen et al, 2012), from the venom of workers of Solenopsis (Diplohoptrum) species collected from Puerto Rico (Jones et al, 1982(Jones et al, , 1996Blum et al, 1985), and of S. conjurata Wheeler collected from Costa Rica (Jones et al, 1984). Chen and Fadamiro (2009a) also reported the detection of cis-C9 in the venom of S. richteri workers.…”

Syntheses, Crystal Structures, Spectroscopic Properties, and Catalytic Aerobic Oxidations of Novel Trinuclear Non‐Heme Iron Complexes

“…As neither a ylide nor a phosphonate with methylene spacer between the phosphorus and the ester moiety was amenable, ligand precursor 5b·HCl was prepared by adapting a procedure by Jones. [14] 2,6-Dimethylpyridine (6) was deprotonated with nBuLi in Et 2 O followed by treatment with homoallylic bromide to yield 2,6-dipentenylpyridine (7), which was submitted to ozonolysis in the presence of NaOH in MeOH/ CH 2 Cl 2 by utilizing a method by Marshall for the direct conversion of alkenes to methyl esters. [15] Final acid hydrolysis of the diester 4b gave the desired hydrochloride 5b·HCl in 89 % yield.…”