Linalool acetate

SYNS ACETIC ACID LINALOOL ESTER BERGAMIOL 3,7-DIMETHYL-l,6-OCTADIEN-3-OL ACETATE 3,7-DIMETHYL-l,6-OCTADIEN-3-YL ACETATE FEMA No. 2636 LICAREOL ACETATE LINALOL ACETATE LINALOOL ACETATE... 

There are many compounds closely related to natural products that are associated with novel syntheses. Dehydrated linalool oxide 891, for example, is conveniently made by chlorination of linalool acetate (28 acetate) with calcium hypochlorite, then cyclization of the allyl chloride 892 with sodium hydroxide and Aliquat 336 in methanol. Once obtained 891 was converted to the dehydrogenated lilac alcohols 893 (R = H). The monoepoxides (on the isopropenyl group) were transformed in a mixture of diacetates that were pyrolyzed to the acetates 893 (R = Ac). Linalool oxide epoxides (894) have... 

Acetic acid linalool ester AI3-00941 Bergamiol Bergamol Bergamot mint oil Dehydrolinalool, acetate 3,7-Dimethyl-1,6-octadien-3-yl acetate EINECS 204-115-4 EINECS 254-806-4 Ex bois de rose (synthetic) FEMA No. 2636 HSDB 644 Licareol acetate Linalol acetate Linalool acetate Lynalyl acetate NSC 2138 1,6-Octadien-3-ol, 3,7-dimethyl-, acetate Phanteine, Found in volatiie oils such as bergamot and lavendar oils. Used in perfumery. Liquid bp 220° d = 0.895 insoluble in H2O, solubie in organic solvents, Bush Boake Allen IFF. 

Linaiooi 95] Linaiooi 925. See Linalool Linalool acetate. See Linalyl acetate Linalool isobutyrate. See Linalyl isobutyrate Linalool oxide... 

Used as a source of natural linalool or linalool acetate, which are extensively used in perfumery. Acetylated bois de rose oil is reportedly used in soaps, detergents, creams, lotions, and perfumes, with maximum use level of 1.2% in perfumes. ... 

Aroma chemicals are isolates, or chemically treated oils or components of oils. Some components are removed physically, others chemically. In most cases, they are further purified by distillation. For example, Bois de Rose (rosewood) oil may be distilled to isolate linalool, which may be then further treated chemically to yield derivatives such as linalyl acetate, an important fragrance ingredient and a primary component in its own right of lavender and lavandin oils. Vetiver oil Haiti, although containing only 70% alcohols, is treated with acetic anhydride, then carefully distilled to include valuable odor components in the distillate, even though they may not be esters. 

Bois de Rose. Bois de rose oil is obtained by steam distillation of wood chips from South American rosewood trees, Aniba rosaeodora. The tree, a wild evergreen, grows mainly in the Amazon basin. The oil is used as obtained in perfumery for its sweet, woody-floral odor and as a source of linalool [78-70-6] (3), which it contains to the extent of 70%. Linalool distilled from bois de rose oil is also used directly in perfumery and for conversion to esters, eg, the acetate (1). 

L v ndin. Lavandin, Lavandula hjbrida as a plant species is of recent origin, unknown until the late 1920s. It is a hybrid of two common lavenders, l vandula officinalis and l vandula latifolia. Lavandin is cultivated mainly ia southern France and has become one of the most produced and used natural perfumery materials. The flowering tops of the shmb are used to produce a concrete, an absolute, and a steam-distilled oil the last is by far the most used. Low cost and refreshing odor quaUty allow lavandin to be employed ia a wide variety of perfume appHcations and at high concentrations. Chemically it is comprised of 30—32% linalool (3) and linalyl acetate (1), along with numerous other substances, mosdy terpenic. 

Linalool can also be made along with nerol and geraniol via the hydrochlorination of myrcene. After conversion of the chlorides to acetates followed by saponification of the acetates, the mixture of alcohols is obtained. Fractionation of the mixture gives linalool in about 95% purity, but the presence of close boiling impurities prohibits manufacture of a perfiimery-quahty product. 

Uses ndReactions. Linalool can be estetified to linalyl acetate by reaction with acetic anhydride. Linalyl acetate [115-95-7] has a floral-fmity odor, reminiscent of bergamot and lavender. The price of the acetate in 1995 was 14.30/kg (45). Linalool is subject to dehydration and to isomerization to nerol and geraniol during the esterification. However, if the acetic acid formed during the esterification is removed in a distillation column, the isomerization can be minimized and good yields of the acetate obtained (130). 

In detergent perfumes, the stabiUty of vanillin is not always certain. It depends on the association made with other raw materials, eg, with patchouli, frankincense, cloves, most of the animal notes, and such chemicals as amyl saUcylate, methyl ionones, heflotropin, gamma undecalactone, linalool, methyl anthrarulate, benzyl acetate, phenyl ethyl alcohol, cedar wood derivatives, oak mosses, coumarin, benzoin. Pern balsam, and cistus derivatives. In some cases, these mixtures can cause discoloration effects. 

The main components of Salvia mirzayanii were Linalool, Linalyl acetate, a-Tei pinyl acetate, 5-Cadinene, Spathulenol, Cubenol and a-Cadinol. The extraction yield, based on hydrodistillatin was 2.2% (v/w), and based on the SFE varied in the range of 0.65-10.59% (v/w) under different conditions. 

The north-south gradient was also evident in the concentration of the most abundant chemotype, which was shown to consist of linalool [19] and its acetate. Most frequent in Greenland, Iceland, and Norway (90-100%), it was present in only 40% of plants collected in Scotland, and in only ca. 5% of plants from southern sites. This finding paralleled the observations of Stahl-Biskup and Laakso (1990) that a similar north-south trend exists in the oils of Thymus ser-pyllum subspecies serpyllum and tanaensis in Finland. The opposite trend was observed with y-terpinene, which was present in southern populations but absent from those from the northern sites. 

S)-3,7-Dimethyl-2-oxo-6-octene-l,3-diol (39) was recently identified as the aggregation pheromone of the Colorado potato beetle (Leptinotarsa decem-lineata), and synthesized by Oliver et al., starting from (S)-linalool [86]. An improved synthesis of (S)-39 by Mori is shown in Scheme 57 [87]. Enzymatic acetylation of ( )-2,3-epoxynerol (A) with vinyl acetate and lipase PS gave B together with C. The acetate B was converted to a multi-gram quantity of (S)-39 according to Oliver [86]. 

Linalool, 3 231, 232, 233 24 477, 495, 496, 500-503, 546 acid treatment of, 24 502 epoxidation of, 24 502 main producers of, 24 501 Linalool oxide, 24 502 Linalyl, 24 479 Linalyl acetate, 24 501 Linalyl alcohol, 24 500 Linalyl esters, 3 231 Linalyl oxide, 24 503 Lincomycin, registered for use in aquaculture in Japan, 3 221t Lincosamide, bacterial resistance mechanisms, 3 32t Lindane, 13 145-147... 

Optically pure trans- and czs-linalool oxides, constituents of several plants and fruits, are among the main aroma components of oolong and black tea. These compounds were prepared from 2,3-epoxylinalyl acetate (9) (Scheme 17) [102]. The key step consist of a separation of the diastereomeric mixture of 9 by employing an epoxide hydrolase preparation derived from Rhodococcus sp. NCIMB 11216, yielding the product diol and remaining epoxide in excellent diastereomeric excess (de>98%). Further follow-up chemistry gave both linalool... 

Another heterocyclization is presented by Panifilow et al. Cyclic acetals and ethers are obtained by electrochemical oxidation of the terpenoid alcohol linalool 57 in methanol containing alkaline and sodium methoxide as electrolyt [102]. Anodic oxidation of the C(6)-C 7) double bond of linalool leads to the radical cation 58. In addition to direct methoxylation of the radical cation an attack on the hydroxyl group takes place. After a second one-electron oxidation and following methoxylation the regioisomeric cyclic acetal and a subsequent 1,2-hydride shift, the cyclic acetal 60 and the cyclic ether 61 are finally formed in yields of 16 and 24%, respectively (Scheme 13). As shown by Utley and co-workers bicyclic lactones 65 and 66 can be synthesized by anodic oxidation... 

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. 

The 1-pro-7 -hydrogen is lost on oxidizing geraniol with a cell-free extract from Cannabis sativa (Vol. 7, p. 9, ref. 96), asymmetric microbial reduction of ( )-citronellal to (-)-citronelloI is reported, and callus cultures of Nicotiana tabacum selectively hydroxylate linalool, dihydrolinalool, and the derived acetates at the -methyl group [e.g. to give (59)]. ... 

In the presence of acids, linalool isomerizes readily to geraniol, nerol, and a-terpineol. It is oxidized to citral by chromic acid. Oxidation with peracetic acid yields linalool oxides, which occur in small amounts in essential oils and are also used in perfumery. Hydrogenation of linalool gives tetrahydrolinalool, a stable fragrance material. Its odor is not as strong as, but fresher than, that of linalool. Linalool can be converted into linalyl acetate by reaction with ketene or an excess of boiling acetic anhydride [34]. 

Synthesis from (3-Pinene. For a description of this route, see under Geraniol. Addition of hydrogen chloride to myrcene (obtained from /3-pinene) results in a mixture of geranyl, neryl, and linalyl chlorides. Reaction of this mixture with acetic acid-sodium acetate in the presence of copper(I) chloride gives linalyl acetate in 75-80% yield [37]. Linalool is obtained after saponification. 

However, the lower fatty acid esters (particularly the acetates) of the acyclic terpene alcohols geraniol, linalool, and citronellol are extremely important both as fragrance and as flavor substances. The acetates occur in many essential oils, sometimes in rather high amounts. Formates, propionates, and butyrates occur less frequently. As a result of the development of large-scale production processes for terpenes, the esters of acyclic terpene alcohols are nearly always made synthetically. All acyclic terpene esters that are used as fragrance and flavor materials can be prepared by direct esterification of the appropriate alcohols. However, special precautions are required for the esterification of linalool. 

Because the lower fatty acid esters of geraniol, linalool, and citronellol are important contributors to the odor of many essential oils, these esters are widely used in the reconstitution of such oils, as well as in perfume and flavor compositions. The acetates, particularly linalyl acetate, are most widely used. The use of formates is limited by their relative instability. Higher esters are not important in terms of quantity, but are indispensable for creating specific nuances. 

Esterification of linalool requires special reaction conditions since it tends to undergo dehydration and cyclization because it is an unsaturated tertiary alcohol. These reactions can be avoided as follows esterification with ketene in the presence of an acidic esterification catalyst below 30 °C results in formation of linalyl acetate without any byproducts [71]. Esterification can be achieved in good yield, with boiling acetic anhydride, whereby the acetic acid is distilled off as it is formed a large excess of acetic anhydride must be maintained by continuous addition of anhydride to the still vessel [34]. Highly pure linalyl acetate can be obtained by transesterification of tert-butyl acetate with linalool in the presence of sodium methylate and by continuous removal of the tert-butanol formed in the process [72]. 

True French lavender grows in the Flaute Provence at an altitude of 600 1500 m. The plants are grown from seeds of the wild lavender ( population lavender). Lavender oil is produced in a yield of 10 25kg/ha. It has the following typical composition (%) m-ocimene (4 10), trans-odimene (1.5-6), 1,8-cineole (<1), camphor (<0.5), linalool (25-38), linalyl acetate (25-45), 1-terpinen-4-ol (2-6), and lavandulyl acetate (>2) [574-583a]. 

Lavandin plants are sterile and can be propagated only by using cuttings. The oils from the most important varieties, abrial and grosso, contain linalool (26-38/ 24-35%) and linalyl acetate (20-29/28-38%) as major constituents as well as 1,8-cineole (6-11/4-7%) and camphor (7-11/6-8%) [594-601]. A third variety is called super because its oil contains a high concentration of linalyl acetate (35-47%), and, thus, resembles lavender oil most closely. 

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. 

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