Deer lactone

Humans and insects can discriminate enantiomers of the same compound (Friedman and Miller, 1971 Russell and Hills, 1971) (Table 2.1). Blacktailed deer Odocoileus hemionus columhianus) discriminate between the two geometric isomers and somewhat between the enantiomers of the deer lactone (Fig. 2.2) (Brownlee eta/., 1969 Muller-Schwarzeeta/., 1976,1978a). Young male Asian elephants have more (+) than (-) enantiomer of frontalin in their temporal secretion. Their secretion and(+)-frontalin affect conspecifics little. However, the nearly recemic enantiomer mix from mature bulls attracts ovulating females and repels males (Greenwood etal., 2005)... 

FIGURE 2.2 The deer lactone (Z)-4-hydroxydodec-6-enoic acid lactone. 

Miiller-Schwarze, D., Ravid, U., Claesson, A., et al. (1978a). The deer lactone source, chiral properties, and responses by black-tailed deer. JoarnaZo/C/jcm/ca/Eco/cgy4,247-256. 

From the tarsal tuft, Brownlee et al. (296) isolated a substance identified as 4-hydroxy-6-dodecenoic add lactone (68) or deer lactone. Deer can discriminate between the geometric isomers, responding to the Z-isomer only (297). Urine is the source of the lactone which is deposited on the tarsal tuft by rub-urination (298). 

U. Ravid, a. Claesson, A.G. Singer, R.M. Silverstein, C. Muller-Schwartze, N.J. Volkman, K.F. Zemanek, and R.G. Butler The Deer-Lactone . Source, Chiral Properties, and Responses by Black-Tailed Deer. J. Chem. Ecol. 4, 247-256... 

When the natural product source contains racemic mixtures (of isomeric forms), then clearly the assignment of signal value to either or both variants of a compound needs to be determined. Alterations in receptor detection of chirality can change sensitivity to the geometrically alternate compound over the range 101 to 106. Of the lactones passed into urine and deposited on tarsal hairs of Black-tailed deer (Odocoileus... 

Molan, A. L., Duncan, A. J., Barry, T. N. and McNabb, W. C. (2003). Effects of condensed tannins and crude sesquiterpene lactones extracted from chicory on the motility of larvae of deer lungworm and gastrointestinal nematodes . Parasitology International, 52, 209-218. 

Musks are important ingredients of fragrance formulations, but almost all the musks used are polycyclic aromatics produced chemically from petrochemi-cally derived raw materials. Naturally occurring musks include the macrocyclic lactones found in some plants, such as ambrette seedoil and galbanum, and the keto musks produced by some animals, such as musk deer and civet cats. 

In addition to mating-disruption pheromones, there are a number of naturally occurring, nonpheromonal attractants and repellents. Many are typically used as food additives or in cosmetics or perfumes, and are derived from diverse plant and animal sources. Capsaicin [44], the spicy component of chili peppers, is used in several bird, deer, and rodent repellents. Maple lactone [45], a common food additive and flavoring, is used in traps to attract cockroaches with its stale beer odor. Methyl... 

Figure 7. Pheromones from R or S lactone acid for beetles dermestids (y-capro-lactone), Pityogenes chalcographus (L.), Japanese beetle (I, Fig. 1), ambrosia beetle, and lesser grain borer beetle gypsy moths and block-tailed deer.

Derivation (Natural) Secretion from preputial follicles of the musk deer. Synthetic (1) Ketones and lactones with 15- or 16-carbon rings, structurally resembling the odoriferous principles of natural musk, civet, and musky-type plants. Among these are ambrettolide, civetone, muscone, exaltolide. (2) Nitrated compounds, usually nitrated ferf-butyl-tol-uenes or xylenes or related compounds. The three most commonly used in perfumery are musk am-brette, musk ketone, and musk xylene. 

A number of mammalian pheromones are combinations of low-molecular-weight carboxylic acids. In other mammals, steroids, sulfur-containing compounds, amines, and alcohols play pheromonal roles some of these compounds also are derived from carboxylic acids (Albone, 1984 Harbome, 1982). Macrocyclic lactones such as civetone (77) and mus-cone (78) are the active odor compounds of the civet cat and the musk deer, respectively. 

Anyone who has owned a female cat or dog knows that sex pheromones are not limited to insects. Female cats or dogs widely advertise, by odor, their sexual availability when they are "in heat." This type of pheromone is not uncommon to mammals. Some persons even believe that hiunan pheromones are responsible for attracting certain sensitive males and females to one another. This idea is, of course, responsible for many of the perfumes now widely available. Whether or not the idea is correct cannot yet be established, but there are proven sexual differences in the ability of humans to smell certain substances. For instance, Exaltolide, a synthetic lactone of 14-hydroxytetradecanoic acid, can be perceived only by females or males after they have been injected with an estrogen. Exaltolide is very similar in overall structure to civetone (civet cat) and muskone (musk deer), which are two naturally occurring compounds believed to be mammalian sex pheromones. 

Enantiomerically pure lactonic pheromones 607-611, of the carpenter bee, blacktailed deer, Japanese beetle, rove beetle, and Oriental hornet, respectively, have been synthesized from racemic cyano alcohols of type 612. The key to the success of the overall approach is the facile separation of diastereomeric carbamates derived from cyano alcohols of type 612 by automated multigram LC. The chosen approach also facilitates the assignment of absolute configurations to the lactone enantiomers and their precursors. In the case of 607, direct determination of enantiomeric purity and absolute configuration is also possible using the chiral solvating agent 2,2,2-trifluoro-l-(9-anthryl)ethanol [439]. 

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