Lily of the valley

Whiffs of peppermint and lily of the valley improve the alertness of people engaged in monotonous tasks. 

As early as 1967, IFF chemists (11), in an in-depth study of jasmin absolute, identified an ultratrace amount of one of the key compounds in the entire fragrance repoitoire, hydroxycitroneUal [107-75-7] (21). This chemical has been used for many years in almost every "white flower" fragrance to give a very diffusive and lasting lily-of-the-valley and jasmin note, but this represents the only known identification of the compound in nature. This illustrates that the human nose can often predict the presence of a molecule well before the instmmentation becomes sufficiently sensitive to detect it. 

The sulfur dioxide can be recovered and recycled. The myrcenol, after purification by distillation, can condense with acrolein to produce Lyral [31906-04-4], an important aldehyde with a strong-lasting odor similar to Lily-of-the-valley (92). 

Epoxidation of diliydromyrcenol gives an iatemiediate epoxide that can be hydrogenated to hydroxycitronellol. Treatment of the diol with acid can also give the a-,P-citroneUol and the a-citroneUol can be isomerized to the P-citroneUol (27) (110). The diol, hydroxycitronellol, is also useful for produciag hydroxycitroneUal, a lily-of-the-valley fragrance material. 

Uses. Cinnamyl alcohol and its esters, especially cinnamyl acetate, are widely employed in perfumery because of their excellent sensory and fixative properties. They are frequently used in blossom compositions such as lilac, jasmine, lily of the valley, hyacinth, and gardenia to impart balsamic and oriental notes to the fragrance. In addition, they ate utilized as modifiers in berry, nut, and spice flavor systems. The value of cinnamyl alcohol has also been mentioned in a variety of appHcations which include the production of photosensitive polymers (49), the creation of inks for multicolor printing (50), the formulation of animal repellent compositions (51), and the development of effective insect attractants (52). 

This alcohol appears to be almost odourless, but when a dilute solution in alcohol is allowed to evaporate slowly, a very fine lily-of-the-valley odour is developed, together with the suggestion of cedar-wood oil. 

Linalyl Propionate.—This ester is also produced by condensing the free alcohol and the free acid by means of sulphuric acid. It has a somewhat fruity odour recalling that of bergamot, and is especially suitable for perfumes of the lily of the valley type. It is a colourless oil, boiling at 115° at 10 mm. pressure. 

Azetidine-2-carboxylic acid, the lower homolog of proline, has been isolated from Convallaria majalis (lily of the valley) 40,44), Polygonatum officinalis (Solomon s seal) 153), and Polygonatum multiflorum 45). Fowden and Steward 47) surveyed plants from 56 genera for nitrogenous compounds and found azetidine-2 -carboxylic acid to be restricted to members of the Liliaceae. In some species it was identified in leaf, stem, and root but was more commonly found in the seed. In Polygonatum, azetidine-2-carboxylic acid accounted for 75% or more of the total nonprotein nitrogen in the rhizome 45). There was no evidence that it occurred as a constituent of protein. 

Fig. 1 Chromatogram of a lily of the valley extract - left before and right after treatment with Jensen s reagent, photographed in long-wavelength UV light (X = 365 nm) [13].

Fig. 1 Chromatograms of reference substances (A) and of a lily of the valley extract (B) 1 g-strophanthin, 2 = convallatoxin, 3 = k-strophanthin...

Kobayashi, S. J0rgensen, K. A. (Eds.) Cycloaddition Reactions in Organic Synthesis, Wiley-VCH, Weinheim, Germany, 2002 Carmichael, A. J., Earle, M. J., Holbrey, J. D. et al. The Heck reaction in ionic liquids a multiphasic catalyst system, Org. Lett., 1999, 1, 997-1000 Forsyth, S. A., Gunaratne, H. Q. N. Hardacre, C. et al. Utilisation of ionic liquid solvents for the synthesis of Lily-of-the-Valley fragrance beta-Lilial (R), 3-(4-t-butylphenyl)- 2-methylpropanal, J. Mol. Catal. A-Chem., 2005, 231(1-2), 61-66. 

Some of the most well-known cardenolides include digitoxin from Digitalis purpurea (foxglove), convallarin from Convallaria (lily-of-the-valley), ouabain from Strophanthus and Acocanthera, many digitoxin-like cardenolides from... 

Foxglove, lily-of-the-valley, Digitalis poisoning - cardiovascular... 

About 300 different non-protein amino acids occur in plants. They may be incorporated into proteins in place of the correct amino acids. If they are incorporated into enzymes, they can prevent them from functioning. This often leads to death of the animal. For example, azetidine 2-carhoxylic acid in lily-of-the-valley, Comallaria majalis, and several legumes interferes with synthesis or utilization of structurally similar proline (Fig. 11.9). 

Emberger and ITopp and Werkhoff and ITopp reported that there are significant sensory differences between the eight menthol and the four menthone enantiomers. (5)(-)-7-Hydroxy-6, 7-dihydrocitronellal has a lily-of-the-valley odor, while the odor of its enantiomer is weaker and has green, leaf like and minty notes.The enantiomers of cis- and trans-Tose oxide have closely similar odors with slight but detectable quality differences. ... 

Properties. (zb)-Linalool [22564-99-4] is, like the individual enantiomers, a colorless liquid with a flowery-fresh odor, reminiscent of lily of the valley. However, the enantiomers dilfer slightly in odor [33]. Together with its esters, linalool is one of the most frequently used fragrance substances and is produced in large quantities. 

Uses. Linalool is used frequently in perfumery for fruity notes and for many flowery fragrance compositions (lily of the valley, lavender, and neroli). Because of its relatively high volatility, it imparts naturalness to top notes. Since linalool is stable in alkali, it can be used in soaps and detergents. Linalyl esters can be prepared from linalool. Most of the manufactured linalool is used in the production of vitamin E. 

Uses. Because of its fine, flowery odor, hydroxydihydrocitronellal is used in large quantities in many perfume compositions for creating linden blossom and lily of the valley notes. It is also used in other blossom fragrances such as honeysuckle, lily, and cyclamen. 

Uses. Cinnamic alcohol is valuable in perfumery for its odor and fixative properties. It is a component of many flower compositions (lilac, hyacinth, and lily of the valley) and is a starting material for cinnamyl esters, several of which are valuable fragrance materials. In aromas, the alcohol is used for cinnamon notes and for rounding off fruit aromas. It is used as an intermediate in many syntheses (e.g., for pharmaceuticals such as the antibiotic Chloromycetin). 

The compound is more stable than cyclamenaldehyde and is a popular component of flower compositions, particularly lily of the valley and linden types, because of its mild, pleasant, blossom fragrance. Large quantities are used in soap and cosmetic perfumes. 

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