Pheromone queen substance

The consecutive addition of alkyl halide to activated olefins by photoelectrocatalysis (PEC) of hydroxocobalamin hydrochloride allows the construction of extended carbon chains as shown for the synthesis of pheromone queen substance 9. The mild conditions of the B12/PEC reaction are suited for the addition of primary alkyl halides 10 containing a potential leaving group. This is illustrated in the synthesis of endo- and exo-brevicomin (11) (Scheme 4). 

The best understood of the sexual pheromones of social insects is the queen substance of honeybees. Interestingly, the queen substance used for queen control inside the nest is also the substance used by virgin queens to attract drones for mating. Callow and Johnston (1960) and Barbier and Lederer (1960) identified 9-keto-2(E)-decenoic acid ([E]-9-oxodec-2-enoic acid) (9-ODA) as major components of the queen mandibular glands. 9-Hydroxy-2(E)-decenoic acid is also present (Callow et al., 1964) and together both attract drones. Additional components of the queen retinue pheromone have recently been identified (Keeling et al., 2003). 

Queen Substance. The queens of many hymenopterous species release primer pheromones in the colonial milieu and these compounds strongly influence the reproductive or endocrine systems of the workers. Butler et al. (139) identified ( )-9-oxo-2-decenoic as the compound that inhibits both ovarian development in workers (140) and queen cell construction (141). The queen substance of the Oriental hornet has been identified as 6-hexadecalactone (XXXVII) (142). 

One of the reported syntheses of ( )-9-oxodec-2-enoic acid 392, the queen substance of the honey bee Apis mellifera, uses two ylide reactions 222). Starting from pimelic acid 385 the resonance-stabilized ylide 386 is prepared by alkylation of methylene-triphenylphosphorane 209 and the former hydrolyzed to 7-oxooctanoic acid 387. Reduction of the corresponding thiol ester 389 and olefination of the resulting aldehyde 390 with phosphorane 67 gives the ( )-2-unsaturated ester 391. The latter was hydrolyzed to pheromone 392 222) (Scheme 69). 

Primer pheromones, which cause long-term behavioral changes, are harder to isolate and identify. One example, however, is the queen substance produced by queen honeybees. All the eggs in a colony are laid by one queen bee. If she is removed from the hive or dies, the worker bees are activated by the absence of the queen substance and begin to feed royal jelly to bee larvae to raise a new queen. The queen substance also prevents the development... 

A similar approach was applied in the study of the silkmoth bombykol pheromone receptor (Sakurai et al. 2004 Nakagawa et al. 2005), a receptor for honeybee queen substance p-oxo-2-decenoic acid (Wanner et al. 2007), and a ligand repertoire for Anopheles ORs (Lu et al. 2007). In these cases, however, coexpression of Ga15 was not necessary, but expression of one member of the Or83b family was absolutely necessary. The molecular mechanisms for signal transduction are discussed in Sect. 4. 

Butler, C.G., Callow, R.K. and Johnston, N.C. (1961). The isolation and synthesis of queen substance, 9-oxodec-fra s-2-enoic acid, a honeybee pheromone. Proc. R. Entomol. Soc. 155,417-432. 

Figure 10 summarizes some results of the lipid-oxidation system in basldlomycetes, leaves, fruits, vegetables, and cereals. It can be seen that there is a development with evolution and differentiation. The enzyme system is highly substrate specific to a (Z,Z)-1,4-pentadiene system converting linoleic- and linolenic acids into carbonyls and oxoacids which may undergo further isomerization (E3) and/or reduction (E4). Some of the components formed are very potent aromatics, pheromones, and wound hormones. Basidio-mycetes and Fungi produce (-)-1-octen-3-ol as their sensorial principle. 9-Oxodecanoic acid is known as queen substance and is the sex pheromone of honey bees. 

Queen substance originally a term for the entire mandibular gland secretion of the queen bee, which contains about 30 substances. It is now the trivial name for 9-oxo-trans-2-decenoic acid. This compound, together with 9-hydroxy-(ranr-2-decenoic acid, is very important as a pheromone for the maintenance of the division of labor within the hive. In the course of caring for the young, the worker bees lick the pheromone mixture off the queen. This causes their ovaries to shrink, and they are inhibited from building queen cells. Larvae in queen cells are not fed honey, but royal jelly, a mixture of pollen and secretions, which does not contain Q. Roy jelly is recommended as a health product, but its effeetiveness is disputed. 

Receptor cells specialized to pheromones have also been studied in other insect groups. In the honey bee. Apis mellifera, two separate cell types have been observed, one for queen substance and another for the alarm pheromone... 

Vareschi, 1971). The response spectra of these cells do not overlap. Furthermore, the cells keyed to the queen substance possess optical specificities (Kafka et al., 1973). The ant, Lasius fuliginosus, has a highly specialized cell type for the alarm pheromone, undecane (Dumpert, 1972) the cell was 1000 times less sensitive to decane and to dodecane (Kafka, 1974). 

Boch, R., Shearer, D. A. and Young, J. C. (1975) Honey bee pheromones field tests of natural and artificial queen substance. J. Chem. EcoL, 1, 133-48. 

The most important example of a primer pheromone is found in honeybees. A bee colony consists of one queen bee, several hundred male drones, and thousands of worker bees, or undeveloped females. It has recently been found that the queen, the only female that has achieved full development and reproductive capacity, secretes a primer pheromone called the queen substance. The worker females, while tending the queen bee, continuously ingest quantities of the queen substance. This pheromone, which is a mixture of compounds, prevents the workers from rearing any competitive queens and prevents the development of ovaries in all other females in the hive The substance is also active as a sex attractant it attracts drones to the queen during her "nuptial flight." The major component of the queen substance is shown in the figure. 

The dimerization of butadiene is a useful method for the synthesis of various natural products. Pellitorine, which is an insecticidal compound isolated from Amcydkm pyrethrum roots, queen substances, which are well-known honey bee pheromones, ds-dvetone, which is a naturally occurring unique symmetric 17-manbered cyclic ketone, and recifeiolide, which consists of a 12-membered lactone firamwork, can readily be synthesized from butadiene dimers. 

The pheromones of bees have important functions in the organization of the colony. The queen constantly gives off a substance which informs the members of the colony about her presence. This Queen-substance was isolated by Butler, Callow and Johnston . It is a relatively simple substance of the following constitution ... 

A synthesis of a Queen substance [35] and of the pheromone of Monarch butterfly [36] are additional examples of applications of this particularly useful process. 

The same telomer was used by Baker et al. to synthesize the dimethyl-pentadecari 2-ol, the pheromone of the pine sawfly [16]. Also the queen substance, a well-known honey bee pheromone, is formed starting from the malonate telomer, which has exactly the right carbon number and a suitable functionality for a facile synthesis of this natural product (Equation 16) [17]. 

Queen substance (338), the multi-purpose pheromone of the honey bee (Apis mellifera), was obtained from substituted 5-bromothiophenes by Tamaru et al. (640). 

This reaction provides a useful way of introducing a double bond next to a carbonyl group. Here it is in a synthesis by Barry Trost of the Queen Bee Substance (the compound fed by the workers to those bee larvae destined to become queens). The compound is also a pheromone of the termite and is used to trap these destructive pests. Trost started with the monoester of a dicarboxylic acid, which he converted to a methyl ketone by reacting the acyl chloride with a cuprate. The ketone was then protected as a dioxolane derivative to prevent it enolizing, and the sulfur was introduced by reacting the enolate of the ester with the sulfur electrophile MeSSMe. 

Queen butterfly pheromone, 79 Queen s substance, 217 Quinine, 80, 501 Quinol acetates, 314-315 QuinoUne, 383, 498, 619, 621 Quinoline—Acetic acid, 501 Quinolineearboxylic acids, 450 p-Quinols, 428-429 Quinomycin, 193 Quinones, 120, 121, 555, 556 Quinonimines, 513... 

Dicarboxylic esters are used to prepare polyesters and polyamides. The residual double bonds permit cross-linking of the polymer chains. Cross metathesis of methyl oleate with excess ethene affords methyl 9-decenoate, a key intermediate in the synthesis of queen bee substance , a honey bee pheromone. 

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