Linalool and linalyl acetate

Casabianca H, Graff JB, Faugier V, Fleig F, Grenier C, Enantiomeric distribution studies of linalool and linalyl acetate A powerful tool for authenticity control of essential oAs, J High Resol Chromatogr 21 107—112, 1998. 

Petitgrain oil Paraguay is obtained from an acclimatized variety of the bitter orange tree. Citrus aurantium L. subsp. aurantium, which is grown in Paraguay. It is pale yellow liquid with a characteristic, strong, pleasant odor, reminiscent of linalool and linalyl acetate. 

For hundreds of years the essential oil of lavender has been well appreciated for perfumery purposes [72]. Lavender oil is obtained by steam distillation from the fresh-flowering tops of Lavandula angustifolia Miller (Lavandula officinalis Chaix) [73]. It is a colourless or pale yellow, clear liquid, with a fresh, sweet, floral, herbaceous odour on a woody balsamic base [73, 74]. According to the European Pharmacopoeia, characteristic components of lavender oils are limonene, cineol, 3-octanone, camphor, linalool, linalyl acetate, terpinen-4-ol, lavandulyl acetate, lavandulol and a-terpineol. Adulterations commonly include blends of lavender oils with lavandin oil or spike oil, and the addition of synthetic linalool and linalyl acetate. In contrast, genuine lavender oils contain as main constituents (i )-linalyl acetate and (i )-linalool of high enantiomeric purity (Fig. 17.14). 

For that reason enantioselective analysis of linalool and linalyl acetate proved to be a powerful tool to detect adulterations with synthetic racemates of linalool and linalyl acetate, respectively [56, 75]. 

The determination of 5 Gv-pdb and d Hv sMow values of synthetic and natural linalool and linalyl acetate using IRMS has been reported by different authors [76-81]. With use of a pyrolysis interface, the determination of isotope... 

A reliable authenticity assessment is concluded from the simultaneous consideration of multielement IRMS and enantioselective analysis. The differences of the stable isotope ratios of linalool and linalyl acetate are depicted as a three-dimensional plot of A values (d values of linalool minus d values of linalyl acetate for oxygen, hydrogen and carbon) (Fig. 17.15). This plot shows that the commercial samples S1-S5 are different from all the other samples investigated. Linalool and linalyl acetate of S1-S5 definitely are not genuine lavender oil compounds. 

Table 17.7 Enantiomeric ratios of linalool and linalyl acetate from non-authentic samples [82] ...

Bilke S, Mosandl A (2002) Authenticity assessment of lavender oil i ing GC-P-IRMS H/ H-ratios of linalool and linalyl acetate. Eur Food Res Technol 214 532... 

Peana, A. T., D Aquila, P. S., Panin, F., Serra, G., Pippia, P., and Moretti, M. D. (2002). Anti-inflammatory activity of linalool and linalyl acetate constituents of essential oils. Phytomedicine 9, 721-726. 

Percentage of the Monoterpene Compounds, Linalool and Linalyl Acetate, in the Volatile Fraction Extracted from Aromatic Plant Species... 

The top note (14%) is a classic mixture of bergamot and rosewood, together with their naturally occurring ingredients linalool and linalyl acetate. 

In Casmir the same technique is used but in an oriental context. The formula is constructed around large amounts of Hedione (20%), Galaxolide and ethylene brassylate, a combination of Iso E super and Vertofix, and vanillin (14%), which together make up some 80% of the formula. In deference to the oriental character linalool and linalyl acetate are present to provide a top note with traces of rose, vetiver, and patchouli, in the background. A strong fruity note, characteristic of many modem American perfumes, is also included. 

Turysheva et al. (1989) showed that the oil from material with a high proportion of split fruits was suitable for obtaining the perfumery fractions of (-i-)-linalool and (+)-linalyl acetate. 

In lavender essential oils, linalool and linalyl acetate are sedative and antispasmodic compounds when lavender is used in blends with other essential oils, these effects can be enhanced. 

Linalool and linalyl acetate are the intensively studied chiral monoterpenoids. Their enantiomeric ratio had been investigated in the precious bergamot oil [36-38], lavender oils [39], and many other plants used as fragrance and flavour materials mainly fi-om Labiatae and Rutaceae families [40-42]. 

Depending on production time and growing area, the content of linalool and linalyl acetate varies [24-30]. Qualities from autumn production possess higher linalool values (15 -16%) than spring oils, while, on the other hand, the content of linalyl acetate increases with fruit maturity (up to 33%) [28, 31]. 

S. Hanneguelle, J.-N. Thibault, N. Naulet, G.J. Martin (1992) Authentication of essential oils containing linalool and linalyl acetate by isotopic methods. J. Agric. Food Chem. 42, 81-87... 

Also, the addition of copper plates in order to simulate the application of cupric vessels during lavender oil production does not influence the chiral stability of linalool and linalyl acetate. 

Comparative investigations on the enantiomeric purity of linalool and linalyl acetate in the essential oils of Lavandula angustrfolia MILLER leads to quick and simple techniques of gas chromatographic chirality evaluation of lavender oil compounds. Their usefulness in the authenticity control of lavender oil compounds is demonstrated in Lig. 6.39 [95]. 

Commercial lavandin oil (2) contains cineole, a blue zone directly above linalool, in almost equal concentration a.s linalool and linalyl acetate. 

Differences in linalool and linalyl acetate content were ascribed to the state of the plant material on distillation. In the USA and Italy, the plant material is freshly harvested, chopped and distilled within a few hours, whereas in France and the Russian countries, the harvested material is air-dried prior to distillation. The excess moisture which is associated with processing of fresh plant material could lead to the major constituent, linalyl acetate, hydrolyzing to linalool, probably facilitated by an increased pH of the medium during distillation [8]. The presence of a large amount of alpha-terpinyl acetate in the essential oil extracted from S. sclarea plants of Italian origin was reported [6]. 

The composition of the essential oil of the stems of A. giganteum was investigated by GC-MS [3]. Forty seven terpenes were identified. Linalool and linalyl acetate were the main components and these were responsible for the distinctive smell of the stems. From the stems of A. giganteum, three rare naturally occurring flavonol 3-methyl ethers were isolated together with chrysophanol, physcion, 2,6-dimethoxybenzoquinone and p-sitosterol [4]. The flavonol methyl ethers were identified as kaempferol... 

Enantioselective GC has found a wide variety of applications, for instance, studies of citronellol (Ravid et al., 1992) and a-terpineol (Ravid et al., 1995) in a variety of species and verbenone in rosemary oils (Ravid et al., 1997). Chiral phases were applied to the separation of linalool and linalyl acetate in a variety of plant species (Konig et al., 1992 Cassabianca et al., 1998), extracts of Angelica seeds and roots (Holm et al., 1997) and other monoterpenoids in geranium oils (Kreis Mosandl, 1993). Separation of monoterpenes in Scots pine and juniper oils (Hiltunen Laakso, 1995), Abies (Holm et al., 1994) and Picea (Persson et al., 1996) oils and limonene, linalool, citronellal and P-citronellol Cymbopogon winterianus)... 

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