115-95-7 Usage
Description
Linalyl acetate is a monoterpene ester that is naturally occurring in many flowers and spice plants. It is a clear, colorless liquid with a boiling point of 220°C and is the acetate ester of linalool. Linalyl acetate is a key component of essential oils from plants such as bergamot and lavender.
Uses
Used in Flavor and Fragrance Industry:
Linalyl acetate is used as a flavoring agent in the food industry and as a preservative additive in cosmetics and fragrances such as soaps, colognes, perfumes, and skin lotions. It is an approved flavoring food additive and is the most important fragrance ingredient for bergamot, lilac, lavender, linden, neroli, ylang-ylang, and fantasy notes.
Used in Perfumery:
Linalyl acetate is extensively used in perfumery as an excellent fragrance material for bergamot, lilac, lavender, linden, neroli, ylang-ylang, and fantasy notes, particularly chypre. It is also used in smaller amounts in other citrus products.
Used in Cosmetics and Toiletries:
Linalyl acetate is used in decorative cosmetics, fine fragrances, shampoos, toilet soaps, and other toiletries due to its characteristic bergamot-lavender odor and persistent sweet, acrid taste.
Used in Non-Cosmetic Products:
Linalyl acetate is also used in non-cosmetic products such as household cleaners and detergents, as it is fairly stable toward alkali.
Occurrence:
Linalyl acetate is reported to be found in the essential oils of bergamot, lavender, clary sage, and lavandin. It is also identified among the constituents of the essential oils of Salvia officinalis, petitgrain, sassafras, neroli, lemon, Italian lime, jasmine, Mentha citrata, Mentha aquatica, Thymus mastichina, and others. It is also found in abundant quantities in the essential oil from flowers, leaves, and stems of Tagetes patula, in the distillate from leaves of Citrus aurantifolia from India, and in the essential oil of Mentha arvensis. Additionally, it is reported in citrus peel oils and juices, berries, peach, celery, tomato, cinnamon, clove, nutmeg, pepper, thymus, grape wines, avocado, mushroom, marjoram, mango, cardamom, coriander, gin, origanum, lovage, laurel, myrtle leaf, rosemary, sage, and mastic gum oil.
Taste Threshold Values:
Linalyl acetate has taste characteristics at 5 ppm, which include floral, green, waxy, terpy, citrus, herbal, and spicy nuances.
Reference
https://pubchem.ncbi.nlm.nih.gov/compound/linalyl_acetate#section=Top
A. Martin, V. Silva, L. Perez, J. Garcia-Serna, M. J. Cocero, Direct Synthesis of Linalyl Acetate from Linalool in Supercritical Carbon Dioxide: A Thermodynamic Study, Chemical Engineering & Technology, 2007, vol. 30, pp. 726-731
H. Surbung, J. Panten, Common Fragrance and Flavor Materials: Preparation, Properties und Uses, 2006, ISBN 978-3-527-31315-0
C. S. Letizia, J. Cocchiara, J. Lalko, A. M. Api, Fragrance material review on linalyl acetate, Food and Chemical Toxicology, 2003, vol. 41, pp. 965-976
Preparation
Linalyl acetate is synthesized by two methods:
1) Esterification of linalool requires special reaction conditions since it tends to
undergo dehydration and cyclization as 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 the formation
of linalyl acetate without any by-products. 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.
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.
2) Dehydrolinalool, obtained by ethynylation of 6-methyl-5-hepten-2-one, can
be converted into dehydrolinalyl acetatewith acetic anhydride in the presence
of an acidic esterification catalyst. Partial hydrogenation of the triple bond
to linalyl acetate can be carried out with, for example, palladium catalysts
deactivated with lead.
Contact allergens
Structurally close to linalool, linalyl acetate is the main component of lavender oil and is commonly used in fragrances and toiletries, and in household cleaners and detergents as well. By autoxidation, it leads mainly to hydroperoxides, with a high sensitizing potent.
Synthesis
Normally prepared by direct acetylation of linalool; another method starts from myrcene hydrochloride, anhydrous
sodium acetate and acetate anhydride in the presence of a catalyst; all synthetic methods tend to avoid the simultaneous formation
(because of isomerization) of terpenyl and geranyl acetate.
Check Digit Verification of cas no
The CAS Registry Mumber 115-95-7 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,1 and 5 respectively; the second part has 2 digits, 9 and 5 respectively.
Calculate Digit Verification of CAS Registry Number 115-95:
(5*1)+(4*1)+(3*5)+(2*9)+(1*5)=47
47 % 10 = 7
So 115-95-7 is a valid CAS Registry Number.
InChI:InChI=1/C12H20O2/c1-6-12(5,14-11(4)13)9-7-8-10(2)3/h6,8H,1,7,9H2,2-5H3/t12-/m1/s1
115-95-7Relevant articles and documents
Acylation of linalool in the presence of polymeric pyrrolidinopyridines
Alieva,Truhmanova,Plate
, p. 1226 - 1229 (1996)
The effect of a number of factors on the efficiency of polymers containing immobilized pyrrolidinopyridine groups as polymeric activating reagents for the acylation of weakly reactive sterically hindered alcohols was studied. The conditions of the acylation of linalool with acetic anhydride in the presence of polymeric pyrrolidinopyridines were selected in such a way that the activity of polymeric systems under study was close to that of their low-molecular-weight analog, pyrrolidinopyridine (in a homogeneous medium).
Synthesis of dimeric terpenoyl glycoside side chains from cytotoxic saponins
Reicheneder, Sabine,Unverzagt, Carlo
, p. 4353 - 4357 (2004)
A bottleneck in the synthesis of the model compound 1, which bears a dimeric terpenoyl glycoside side chain from cytotoxic saponins, was overcome by the stepwise construction of the terpene part by regioselective acylation of the sugar with a functionalized phosphonate followed by a Horner-Wadsworth-Emmons olefination.
Kogami,Kumanotani
, p. 226 (1974)
Scalable green approach toward fragrant acetates
Puchl'Ová, Eva,Szolcsányi, Peter
, (2020/08/07)
The advantageous properties of ethylene glycol diacetate (EGDA) qualify it as a useful substitute for glycerol triacetate (GTA) for various green applications. We scrutinised the lipase-mediated acetylation of structurally diverse alcohols in neat EGDA furnishing the range of naturally occurring fragrant acetates. We found that such enzymatic system exhibits high reactivity and selectivity towards activated (homo) allylic and non-activated primary/secondary alcohols. This feature was utilised in the scalable multigram synthesis of fragrant (Z)-hex-3-en-1-yl acetate in 70percent yield. In addition, the Lipozyme 435/EGDA system was also found to be applicable for the chemo-selective acetylation of (hydroxyalkyl) phenols as well as for the kinetic resolution of chiral secondary alcohols. Lastly, its discrimination power was demonstrated in competitive experiments of equimolar mixtures of two isomeric alcohols. This enabled the practical synthesis of 1-pentyl acetate isolated as a single product in 68percent yield from the equimolar mixture of 1-pentanol and 3-pentanol.
Unravelling transition metal-catalyzed terpenic alcohol esterification: A straightforward process for the synthesis of fragrances
Da Silva,Ayala
, p. 3197 - 3207 (2016/05/24)
Iron nitrate is a simple and commercially available Lewis acid and is demonstrated to be able to catalyze β-citronellol esterification with acetic acid, achieving high conversion and ester selectivity (ca. 80 and 70%, respectively), within shorter reaction times than those reported in the literature. To the best of our knowledge, this is the first report of a terpenic alcohol esterification reaction catalyzed by Fe(NO3)3. This process is an attractive alternative to the slow and expensive enzymatic processes commonly used in terpenic alcohol esterification. Moreover, it avoids the undesirable steps of neutralizing the products, which are always required in mineral acid-catalyzed reactions. We have performed a study of the activity of different metal Lewis acid catalysts, and found that their efficiency is directly linked to the ability of the metal cation to generate H+ ions from acetic acid ionization. The measurement of pH as well as the conversions achieved in the reactions allowed us to obtain the following trend: Fe(NO3)3 > Al(NO3)3 > Cu(NO3)2 > Ni(NO3)2 > Zn(NO3)2 > Mn(NO3)2 > Co(NO3)2 > LiNO3. The first three are recognized as stronger Lewis acids and they generate more acidic solutions. When we carried out reactions with different iron salts, it was possible to conclude that the type of anion affects the solubility of the catalyst, as well as the conversion and selectivity of the process. Fe2(SO4)3 and FeSO4 were insoluble and less active. Conversely, though they were equally soluble, Fe(NO3)3 was more selective for the formation of β-citronellyl acetate than FeCl3. We assessed the effects of the main reaction variables such as reactant stoichiometry, temperature, and catalyst concentration. In addition to citronellol, we investigated the efficiency of the iron(iii) catalyst in the solvent free esterification of several terpenic alcohols (geraniol, nerol, linalool, α-terpineol) as well as other carboxylic acids.