WO1999021847A1

WO1999021847A1 - Novel fragrance compound

Info

Publication number: WO1999021847A1
Application number: PCT/GB1998/003129
Authority: WO
Inventors: David Munro; Charles Stanley Sell
Original assignee: Quest International BV
Current assignee: Givaudan Nederland Services BV
Priority date: 1997-10-28
Filing date: 1998-10-21
Publication date: 1999-05-06
Anticipated expiration: 2000-04-28
Also published as: AU9548398A

Abstract

The novel compound 2-methylperhydro-as-indaceno [3a,3-b] furan exhibits an intense odour of blackcurrant or cassis of high impact and substantivity and so finds use in perfumes and in perfumed products.

Description

Novel Fragrance Compound

Field of the Invention

This invention concerns a novel fragrance compound, its method of production and its use in perfumes and perfumed products.

Summary of the Invention

In one aspect the invention provides 2-methylperhydro-as-ιndaceno [3a, 3-b] furan.

For brevity and simplicity, this material will be referred to herein as "the compound", "the novel compound" or "the compound of the invention".

The novel compound as a tetracyc c furan having the structure shown in Figure 1

The compound is one of the minor products of Lewis acid-catalysed reaction of 1 ,5,9- cyclododecatπene with propylene oxide, and can be separated and purified by chromatographic techniques The reaction is preferably carried out at -70° C, using AICI₃ as the Lewis acid.

In a further aspect the invention provides a method of making the compound of the invention, comprising Lewis acid-catalysed reaction of 1 ,5,9- cyclododecatπene with propylene oxide.

The compound of the invention exhibits an intense odour of blackcurrant or cassis of high impact and substantivity, and so may be used as such to impart, strengthen or improve the odour of a wide variety of products, or it may be used as a component of a perfume (or fragrance composition) to contribute its odour character to the overall odour of such perfume. For the purposes of this invention a perfume is intended to mean a mixture of fragrance materials, if desired mixed with or dissoved in a suitable solvent or mixed with a solid substrate, which is used to impart a desired odour to the skin and/or any product for which an agreeable odour is indispensible or desirable. Examples of such products are: fabric washing powders, washing liquids, fabric softeners and other fabric care products; detergents and household cleaning, scouring and disinfection products; air fresheners, room sprays and pomanders; soaps, bath and shower gels, shampoos, hair conditioners and other personal cleansing products; cosmetics such as creams, ointments, toilet waters, preshave, aftershave, skin and other lotions, talcum powders, body deodorants and antiperspirants, etc.

Other fragrance materials which can be advantageously combined with the compound according to the invention in a perfume are, for example, natural products such as extracts, essential oils, absolutes, resinoids, resins, concretes etc., but also synthetic materials such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, ketals, nitriles, etc., including saturated and unsaturated compounds, aliphatic, carbocyclic and heterocyclic compounds.

Such fragrance materials are mentioned, for example, in S. Arctander, "Perfume and Flavor Chemicals" (Montclair, N.J., 1969), in S. Arctander, "Perfume and Flavor Materials of Natural Origin" (Elizabeth, N.J., 1960) and in "Flavor and Fragrance Materials - 1991", Allured Publishing Co. Wheaton, III. USA.

Examples of fragrance materials which can be used in combination with the compound according to the invention are: geraniol, geranyl acetate, linalol, linalyl acetate, tetrahydrolinalol, citronellol, citroneilyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tetrahydromyrcenol, terpineol, terpinyl acetate, nopol, nopyl acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate, dimethylbenzyl-carbinol, trichloromethylphenylcarbinyl acetate, p-tert-butylcyclohexyl acetate, isononyl acetate, vetiveryl acetate, vetiverol, α-hexylcinnamaldehyde, 2-methyl-3-(p-tert-butylpheπyl)propanal, 2-methyl-3-(p-isopropylphenyl)propanal, 3-(p-tert-butylphenyl)-propanal, 2,4-dimethylcyclohex-3-enyl-carboxaldehyde, tricyclodecenyl acetate, tricyclodecenyl propionate, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde, 4-(4-methyl-3-pentenyl)-3-cyclohexenecarboxaldehyde, 4-acetoxy-3-pentyl- tetrahydropyran, 3-carboxymethyl-2-pentylcyclopentane , 2-n-heptylcyclopentanone, 3-methyl-2-pentyl-2-cyclopentenone, n-decanal, n-dodecanal, 9-decenol-1 , phenoxyethyl isobutyrate, phenylacetaldehyde dimethylacetal, phenylacetaldehyde diethylacetal, geranyl nitrile, citroneilyl nitrile, cedryl acetate, 3-isocamphylcyclohexanol, cedryl methyl ether, isolongifolanone, aubepine nitrile, aubepine, heliotropin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronellal, ionones, methylionones, isomethylionones, irones, cιs-3-hexenol and esters thereof, indan musks, tetralin musks, isochroman musks, macrocyclic ketones, macrolactone musks, ethylene brassylate

Solvents which can be used for perfumes which contain the compound according to the invention are, for example ethanol, isopropanol, diethyleneglycol monoethyl ether, dipropylene glycol, diethyl phthalate, tπethyl citrate, isopropyl myπstate, etc

The quantities in which the compound according to the invention can be used in perfumes or in products to be perfumed may vary within wide limits and depend, inter alia, on the nature of the product, on the nature and the quantity of the other components of the perfume in which the compound is used and on the olfactive effect desired It is therefore only possible to specify wide limits which, however, provide sufficient information for the specialist in the art to be able to use the compound according to the invention for his specific purpose In perfumes an amount of 0 01 % by weight or more of the compound according to the invention will generally have a clearly perceptible olfactive effect Preferably the amount is 0 1 to 80% by weight, more preferably at least 1 % The amount of the compound according to the invention present in products will generally be at least 10 ppm by weight, preferably at least 100 ppm, more preferably at least 1000 ppm However, levels of up to about 20% by weight may be used in particular cases, depending on the product to be perfumed

In a further aspect the invention thus provides a perfume comprising the compound of the invention in an olfactively effective amount

The invention also covers a perfumed product comprising the compound of the invention

The invention will be further described, by way of illustration, in the following Example and with reference to the accompanying figures, in which

Figure 1 shows the structure of 2-methylperhydro-as-ιndaceno [3a,3-b] furan,

Figure 2 shows the major products of Lewis acid-catalysed reaction of 1 ,5,9-cyclododecatrιene with propylene oxide, and Figure 3 illustrates the possibilities of double bond rearrangement and of internal ring closure of 1 ,5,9-cyclododecatrιene and an ionic cascade reaction leading to production of the compound of the invention

Example

Lewis Acid-Catalysed Reaction of 1 ,5,9-Cyclododecatrιene with Propylene Oxide

1 ,5,9-cyclododecatπene (150 g, 0.924 mol) and propylene oxide (69 g, 1 2 mol) were mixed together, and added, with stirring, to a suspension of AICI₃ (129 g, 0.96 mol) in CH₂CI₂ (750ml) at -50° C The reaction mixture was allowed to reach ambient temperature, then added to a mixture of ice (4000 ml) and diethyl ether (2000 ml) The ether layer was separated and dried over MgS0₄ Chromatography (silica, hexane) gave recovered 1 ,5,9-cyclododecatrιene (51 2g) Further elution, using a mixture of hexane (90%) and diethyl ether (10%) as eluent gave a pale yellow oil (27.2g), which was identified as 2-(cyclododecadιenyl)propan-1-al M+220 Kovats 1755, 1773, 1775, 1781.

H NMR (CDCI₃) Siqnal Multiplicity Area Assiαnment

9.78 d 1 CHO

9 71 d

5 60 - 5 12 m 4 CH=CH

2.53 - 1 12 m 16 CH, and CH

1 10 d 3 CH₃

0.94 d

Elution was continued, giving a small amount of pale yellow oil (5.1 g) This was re-chromatographed, giving a fore-run (1 1 g) with an intense blackcurrant odour The material was extremely complex, being a mixture of at least 15 components present at >1 % glc{SE54; 100-250° C at 4° C/min] 18.692mιn(6.3%), 18.938min(6.7%), 19.287min(1.6%), 19.809(12.9%), 19.986min(18.7%), 20.159mιn(1.0%), 20.430mιn(7.0%>), 20.647mιn(7.7%), 20.914mιn(9.4%), 21 035mιn(5.9%) 21.1 18mιn(6.2%), 21 202mιn(4.8%), 21.320mιn(3.2%), 21.395mιn(1.1 %), 21.499mιn(2.4%).

5 The most intense cassis odour was associated with the peaks at 19.809min and 19.986mιn. These were isolated by capillary glc trapping, using a modified HP 5890 glc instrument, fitted with an HP5 column [SE 54 type], length 30m, internal diameter 0.53mm, surface coating 1.Oδmicrometer. The carrier gas was nitrogen, flow rate 2ml mm The temperature programme utilised was 50° C (0.5 min)/50° C mm ¹ to 100°C/10°C mm ¹ to o 280°C In excess of 400 cycles were used, giving a mixture of the two desired products, and allowing the identification of the major product as 2-methylperhydro-as-ιndaceno- [3a,3-b]furan

¹³C NMR (CDCI₃) Major isomer: 89.74(quatemary, ether), 72.89(CH, ether), 50.33(CH), 43.57(CH), 40 44(CH), 39.32(CH₂), 38.99(CH₂), 37.02(CH), 32.81 (CH₂), 32.58(CH₂), 5 30.88(CH₂), 29.73(CH₂), 29.61 (CH₂), 23 34(CH₃), 21.75(CH₂).

Minor isomer- 93 39(quaternary, ether), 72 84(CH, ether), 48 81 (CH), 48 11 (CH), 41.00(CH₂), 39.16(CH), 35.33(CH₂), 32.05(CH), 31.33(CH₂), 30.92(CH₂), 28.09(CH₂), 26.24(CH₂), 24 56(CH₂), 24 11 (CH₂), 21 13(CH₃)

The mam products of the reaction of 1 ,5,9-cyclododecatπene (1 ) are shown in Figure 2. 0 These are 2-(cyciododecadιenyl) propan-1-al (2) (15-22% conversion, based on recovered cyclododecatπene), 2-methyl-2,3,3a,4,5,8,9,12,13a-decahydrocyclododeca[b]furan (3) (5% conversion), and a complex mixture of isomeπc (M+220) and higher molecular weight alcohols (40-55% conversion), from which the tπcyclic propan-2-ol (4) was isolated.

The compound of the invention is associated with the furan fraction, and is a tetracyclic 5 furan formed in low yield (isolated in this example in < 0 1 % yield) by an ionic cascade reaction following formation of the initial carbonium ion, as shown in the reaction scheme of Figure 3. Figure 3 also shows the possibilities of double bond rearrangement and of internal ring closure of 1 ,5,9-cyclododecatrιene following formation of the initial carbonium ion, illustrated for attack to give the propan-2-ol side chain Reducing the reaction temperature to -70° C gives an increased yield of the compound of the invention, but remains only 1.6% (by glc), and extensive chromatographic purification is necessary to give a 0.5% isolated yield. Experiments using SnCI₄ as catalyst failed to give any of the novel compound.

Claims

1 The compound 2-methylperhydro-as-ιndaceno [3a,3-b] furan

2 The compound of claim 1 , prepared by Lewis acid-catalysed reaction of 1 ,5,9-cyclododecatπene with propylene oxide

3 A method of making the compound of claim 1 , comprising Lewis acid-catalysed reaction of 1 ,5,9-cyclododecatrιene with propylene oxide

4 A method according to claim 3, wherein the Lewis acid is AICI₃

5 A method according to claim 3 or 4, wherein the reaction is carried out at a temperature in the range -70° C to -50° C

6 A perfume comprising the compound of claim 1 or 2 in an olfactively effective amount

7 A perfume according to claim 6, wherein the compound is present in an amount of at least 0 01 % by weight

8 A perfume according to claim 7, wherein the compound is present in an amount in the range 0 1 to 80% by weight

9 A perfumed product comprising a compound according to claim 1 or 2 or a perfume according to claim 6, 7 or 8