MXPA96005301A - Cyclopentylidene-cyclopentanol in perfumery - Google Patents

Abstract

The invention relates to the use of 2-cyclopentylidene-cyclopentanol as fragrance and flavour material. The compound has an indolic odour and is therefore very useful for replacing indole in perfumes and flavourings. Unlike indole it is stable to light and in alkaline media and gives no discolouration.

Description

CICLOPENTILIDENO-CICLOPENTANOL IN PERFUMERÍA Description The present invention relates to the use of 2-cyclopentylidene-cyclopentanol as fragrance and essence material. It also refers to perfumes and perfumed products as well as essential products and essences that this alcohol contains. Many components have been developed for synthetic perfumes, especially in the last decades, to replace the known perfume materials of natural origin. However, there is a constant need for new components for synthetic perfumes that are more stable than those previously developed and / or that have additional or more delicate odor to further complete the range of fragrances from which the perfume manufacturer can select in perfumes compounds that are also suitable for various aggressive environments. Thus, indole and skatole are well-known fragrance materials with a strong animal odor often described as fecal. They have been used extensively in the art of perfumery, as, for example, in various compositions of floral perfumes, in particular in jasmine perfumes and bases. However, indole and skatole have the disadvantage that they are unstable in light and under alkaline conditions, such as in soap and therefore result in severe discoloration problems. 2-cyclopentyl-cyclopentanol is known as a fragrance material under the tradename TELLUROL. This has a camphora mint smell with a slight indolite note. Therefore, it has several uses in the art of perfumery, but is totally inappropriate as a replacement for indole or skatole. The 2-cyclopentyl-cislopentanone is described as a useful fragrance material and essential in EP-A-0 016 650. It has a cold, menthol-like odor and is especially suitable for dentifrices. It has now been found that 2-cyclopentylidene-cyclopentanol of the following formula (comprising two isomers): It is a valuable fragrance and essential material with a strong smell of indole / skatole without any note of peppermint, camphor or menthol-like disturbance. It is stable to light and alkaline and does not cause discoloration problems. Therefore in perfumes it is an excellent substitute for indole or skatole and does not show any of the disadvantages of these known fragrance materials. Although the alcohol according to the invention is itself known in the literature, olfactory properties have not been described before. The compounds can be prepared as described in the literature, compare: Le Guillanton et al, Bull. Soc,. Chim. France 1963 (3) 611-17; Lamant et al, Co pt. Ren 250, 362-4 (1960): Ousseron et al, Bull. Soc. Chim, France 1947 598-605 and Mitsui et al Bull. Soc. Chim Japan 39 (4) 694-7 (1966). A particularly useful path begins with the autocondensation of aldol of cyclopentanone, followed by reduction of the 2-cyclopentylidene-cyclopentanone compound thus formed. The reduction can be carried out as, for example, with a suitable borohydride reducing agent, according to the method of Meerwein, Ponndorf and Verley. These synthetic pathways produce mixtures of the isomers and several other minor components. Apart from the usual purification steps such as distillation and / or recrystallization, these mixtures do not require further purification or separation for use as fragrance materials in the preparation of perfumes. Therefore the invention also provides a process for the preparation of a perfume comprising the steps of: reducing 2-cyclopentylidene-cyclopentanone, purifying the reaction mixture and combining the purified reaction mixture with other fragrance materials. Therefore, the alcohol according to the present invention can be used as such to give odor or essence notes such as indole / skatole to all kinds of products. More particularly, it can be used incorporated in perfumes and essences. For the purposes of this invention a perfume is defined as a mixture of various fragrance materials, if desired dissolved in a suitable solvent or mixed with a solid substrate, which is used to provide a desired odor to the skin or all kinds of products. Examples of these perfumed products are: powders and liquids for washing fabrics, fabric softeners and other products for the care of fabrics; detergents, cleaners for hard surfaces and cleaners for the home, scrubbing and disinfection products; air fresheners, space sprinklers and ointments; candles; soaps, shampoos, hair conditioners, bath and shower gelatins and other personal care products; cosmetics such as creams, ointments, toilet waters, lotions before shaving, after shaving and others, powders for talc, deodorants for the body and antiperspirants. The known fragrances and the essential materials which can be advantageously combined with the alcohol according to the invention can be natural products and such as extracts, essential oils, absolutes, resinoids, resins, concretes, etc. , although also synthetic materials such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, carbocyclic and etherocyclic compounds. These materials are mentioned, for example, in S: Arctander, Perfume and Flavor Chemicals (Montclair, NJ, 1969, in S: Arctander, Perfume and Flavor Materials of Natural Origin (Eliz'abeth, NJ, 1960), in "Flavor and Fragrance Materials - 1991, "Allured Publishing Co. Wheaton, 111. USA and Fenaroli's Handbook of Flavor Ingredients, Vol. I and II, CRC Press, Boca Raton 1995. Examples of fragrance materials that can be used in combination with esters according to the invention are: geranyl, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalol, citronellol, citronellyl acetate, dihydromyrcenol, dihydromircenyl acetate, tetrahydromircenol, tertineol, tertinyl acetate, nopol, nopyl actetate, 2- phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl silicicate, acetate, styrallyl, benzyl benzoate, amyl salicylate, dimethylbenzylcarbinol, trichloromethylphenylcarbinyl acetate, acetate of p-tert-butylcyclohexyl, isonolyl actetate, vetiviril acetate, vetyverol, alpha-hexylcinnamaldehyde, 2-methyl-3- (p-tert-butyl-phenyl) propanal, 2-methyl-3-3 (p-isopropylphenyl) propanal, 3- (p-tert-butylphenyl) propanal, cylindrical tricyclic acetate, cyclo-tricyclic propionate, 4- (4-hydroxy-4-methyl-pentyl) -3-cyclohexenecarbaldehyde, 4- (4-methyl- 3-pentenyl) -3-cyclohexenecarbaldehyde, 4-acetoxyl-3-pentyl-tetrahydropyran, 3-carboxymethyl-2-pentylcyclopentane, 2-n-heptyl-cyclopentanone, 3-methyl-2-pentyl-2-cyclopentenone, n-decanal , n-dodecanal, 9-decenol-l, phenoxyethyl isobutyrate, phenyl-acetaldehyde dimethylacetal, phenyl-acetaldehyde diethyl acetal, geranyl nitrile, citronyl nitrile, cedril acetate, 3-isocanfilcyclohexanol, cedrilmethylether, isolongifolanone, aubepin ityl, aubepin, heliotropin, coumarin, eugenol , vanillin, diphenyloxide, hydroxycitronellal, ionones, methylionones, isomethylionones, irons, cis-3-hexenol, and the esters of the same compounds, musks of damage, tetralin musks, isochroman musks, ketones, macrocyclics, macrolactone musks, ethylene brasilate, aromatic nitroalmixes. The solvents that can be used in perfumery compositions containing compounds according to the invention are, for example: ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc. The amounts in which the alcohol according to the invention can be effectively used in perfumes or essences, or in products to be perfumed, can vary within wide limits and depends, among other things, on the nature of the product, the nature and quantity of the other components of the perfume in which the compound is used and the desired olfactory effect. Therefore it is only possible to specify broad limits which, however, provide sufficient information to a person skilled in the art to be able to use the alcohol according to the present invention for its specific purpose. In perfumes, an amount of 0.01% by weight or more of the alcohol, according to the invention in general will have a clearly noticeable olfactory effect. Preferably the amount is 0.05% by weight, although due to the odorous nature of the compound it may be rarely greater than 10% by weight. The amount of alcohol according to the present invention in the products will generally be at least 1 ppm by weight. The following examples are only intended to illustrate the preparation and use of alcohol according to the invention, but the invention is not limited in any way to these examples. Example 1 Preparation of 2-cyclopentylidene-cyclopentanol a) 2-cyclopentylidene-cyclopentanone. A 2 liter round bottom flask, mounted with a mechanical stirrer, a reflux condenser and a thermometer, was charged with 951 g (11.3 mole) of cyclopentanone and a solution of 38.2 g of potassium hydroxide in 250 ml of water. The mixture was heated with application at approximately 100 ° C for 5 hours. After cooling to room temperature, 200 ml of diethyl ether was added and the aqueous and organic phases were separated. The organic phase was washed twice with 200 ml of water, once with 200 ml of a 10% aqueous solution of hydrochloric acid and twice with 200 ml of a saturated saline solution. The organic phase is dried over anhydrous magnesium sulfate. After filtration of the organic liquid the solvent was removed using a rotary evaporator and 813.5 g of crude product was obtained. This was fractionated under reduced pressure (0.2-0.3kPa). The desired product was distilled at 105-108 ° C and obtained in a yield of 73% (623 g). b) 2-cyclopentylidene-cyclopentanol.

A 2 liter round bottom flask, mounted with a mechanical stirrer, a reflux condenser and a thermometer, was charged with 412.4 g (2.75 moles) of 2-cyclopentylidene-cyclopentanone and 500 ml of methanol. The mixture was stirred until homogeneous at room temperature and then 40 g of sodium borohydride was added in small portions over a period of 1.5 hours. The reaction mixture was stirred after this for another 4 hours. During the addition as well as after the temperature was maintained below 40 ° C by cooling with a cold water bath, if necessary. The reaction mixture is further stirred overnight. It is then added by dropwise addition, with stirring, of 250 ml of water. The aqueous and organic layers were separated and the aqueous layer was extracted twice with 200 ml of diethyl ether. The combined organic layers were washed with 200 ml of water and dried over magnesium sulfate. After filtration the solvent was removed using a rotary evaporator and 440 g of crude product were obtained. This was fractionated under reduced pressure (0.4kPa) through a 0.5 meter packed Sulzer column. The fractions were collected at 90-100 ° C and the odor was assayed. The total fractions with an acceptable odor was 182.9 ml. The product could be further purified by recrystallization from methanol.

Example 2 A perfume composition of the "white lilac" type was prepared according to the following recipe: Phenylethylalcohol 35.2% w / w hydroxy citronellal 32.0 Cinnamic alcohol 17.5 Resinoid stirax 7.0 Anisic aldehyde 4.4 Absolute jasmine 3.5 2-cyclopentylidene-cyclopentanol 0.4 Total 100% Example 3 A perfume composition of the type "Orange blossom" was prepared according to the following recipe : Phenylethylalcohol 21.0% w / w Linalool 21.0 Small grain oil 17.0 Methyl anthranilate 13.0 Nerve 97% 12.0 Benzyl acetate 8.0 'Aurantion (Q) 4.0 Absolute orange flower 2.0 CIO aldehyde (10% in diethyl phthalate) 0.8 Geranyl formate 0.6 Aldehyde C8 (10% in diethyl phthalate) 0.4 2-cyclopenti1ideno-cyclopentanol 0.2 Total 100% (Q) marketed by Quest International

Claims (7)

1. R E I V I N D I C A C I O N S 1.- Perfumes and essences comprising fragrance or known essential materials, characterized in that they contain an effective amount of 2-cyclopentylidene-cyclopentanol.
2. 2. Perfumes and essences according to clause 1, characterized in that they contain at least 0.01% by weight of 2-cyclopentylidene-cyclopentanol.
3. 3. - Perfume products or essential products characterized in that they contain an effective amount of 2-cyclopentylidene-cyclopentanol.
4. 4. Scented products according to clause 4, characterized in that they contain at least 1 ppm by weight of 2-cyclopentylidene-cyclopentanol.
5. 5. Process for preparing a perfume comprising the steps of reducing 2-cyclopentylidene-cyclopentanone, purifying the reaction mixture and combining the purified reaction mixture with other fragrance materials.
6. 6. Process according to clause 5, characterized in that the reduction is carried out using a borohydride reducing agent.
7. 7. Procedure according to clause 5, characterized in that the reaction is carried out according to Meerwein, Ponndorf and Verley. R E S U M E N The invention relates to the use of 2-cyclopentylidene-cyclopentanol as a fragrance and essential material. The compound has an indole smell and therefore is very useful to replace indole in perfumes and essences. Unlike indole it is stable to light and in alkaline media and does not discolour.