GB2394713A - Cyclopentaindene fragrance ingredients - Google Patents
Cyclopentaindene fragrance ingredients Download PDFInfo
- Publication number
- GB2394713A GB2394713A GB0225199A GB0225199A GB2394713A GB 2394713 A GB2394713 A GB 2394713A GB 0225199 A GB0225199 A GB 0225199A GB 0225199 A GB0225199 A GB 0225199A GB 2394713 A GB2394713 A GB 2394713A
- Authority
- GB
- United Kingdom
- Prior art keywords
- trimethyl
- indene
- compound
- octahydro
- cyclopenta
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
- C07D303/06—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
Abstract
3a,6,9-Trimethyl-2,3,3a,4,5,7,8,9-octahydro-1H-cyclopenta[c]indene and derivatives thereof, in particular 5a,6-epoxy-3a,6,9-trimethyl-2,3,3a,4,5,7,8,9-octahydro-1H-cyclopenta[c]indene, are useful as fragrance ingredients having woody, ambery notes.
Description
Organic Compounds The invention relates to a tricyclic hydrocarbon and to
derivatives thereof having interesting odourant properties in the woody, amber-like direction, and to methods of forming same.
Sterically complex tricyclic hydrocarbons represent an important class of compounds, not only for their interesting odour notes, but also as key starting materials for the preparation of valuable odorants for various fragrance applications. Sesquiterpenic hydrocarbons have been converted into their corresponding epoxides, acetates and ketones as these derivatives typically have stronger and more complex odors than the original hydrocarbons. However, due to their structural complexity, such tricyclic hydrocarbons are, if not abundantly occurring in natural sources, difficult to obtain by chemical synthesis...
:. Accordingly, there is a dearth of synthetic tricyclic hydrocarbons, and those that are available are expensive to synthesise and, because they are often obtained as complex mixtures, they are diffcult to isolate. .
It is an object of the present invention to provide a novel tricyclic hydrocarbon.
having the desirable properties described above.
It is another object of the invention to provide derivatives of the novel tricyclic hydrocarbon having interesting strong ambery and woody tonality.
It is another object of the invention to provide an efficient synthesis for the tricyclic hydrocarbon and its derivatives.
In yet another aspect of the invention there is provided a fragrance composition containing the hydrocarbon and/or a derivative thereof.
Description of the Finures
Figure 1 is a reaction scheme showing the synthesis of the tricyclic hydrocarbon of the present invention starting from a cyclic triene. The figure also describes the further conversion of the tricyclic hydrocarbon into an epoxide derivative.
Detailed Description of the Invention
The tricyclic hydrocarbon of the present invention is 3a,6,9-trimethyl-
2,3,3a,4,5,7,8,9-octahydro-1 H-cyclopenta[c]indene.
According to the present invention the tricyclic hydrocarbon may be formed by adding a Lewis acid to 1,5,10-trimethyl-1,5,9-cyclododecatriene to effect cyclisation thereof. Suitable lewis acids include AIX3, ZnX2, anhydrous.
magnesium chloride, wherein X is Cl, Br or l; or an alkyl-aluminumdihalide or a.:.
dialkyl-aluminium-halide. Preferably the Lewis acid is EtAIC12.....
This conversion is carried out in a solvent that is inert to the Lewis acid. Suitable solvents are selected from the group consisting of ethers such as diethyl ether, À hydrocarbons such as hexane or toluene, or halogenated hydrocarbons such as...
dichloromethylene or dichloroethylene.
The amount of Lewis acid used for the cyclization may be stoichometric, or substoichometric, for example in the range of 2-50 mol% relative to the 1,5,10-
trimethyl-1,5,9-cyclododecatriene. In a preferred embodiment, 10 mol% of a Lewis acid, most preferably EtAICI2 is used for this conversion.
The conversion may be carried out at a range of temperatures from -75 to about -
65 C, more particularly -60 to 10 C.
The tricyclic hydrocarbon 3a,6,9-trimethyl-2,3,3a,4,5,7,8,9-octahydro-1 H-
cyclopenta[c]indene has utility as a key intermediate in the preparation of strong ambery-woody compounds. Further derivatives may be formed by adding functionality across the double bond across ring carbons 5 and 6 (see Figure 1 for example). Useful derivatives may be formed by functionalising at the double bond to introduce functionality such as epoxide, acetate or keto-functionality according to techniques generally known in the art.
Accordingly, in another aspect of the invention there is provided a derivative of 3a,6,9-trimethyl-2,3,3a,4,5,7,8,9-octahydro-1 Hcyclopenta[c]indene having woody, ambery aspects. In a particular embodiment there is provided 5a,6-
epoxy-3a,6,9-trimethyl-2,3,3a,4,5,7,8,9-octahydro-1 H-cyclopenta[c]indene.
À..e 5a,6-epoxy-3a,6,9-trimethyl-2,3,3a,4,5,7,8,9-octahydro-1 Hcyclopenta[c]indene.
À. may be formed by the conversion of 3a,6,9-trimethyl-2,3,3a,4,5,7,8,9octahydro-.:.
1H-cyclopenta[c]indene. The conversion may be carried out using a peracid, for.
example peracetic acid in a suitable solvent, for example, one of the solvents.
referred to herein above. The temperature of the reaction mixture is preferably held at about 10 degrees centigrade or lower.
:e À À. The tricyclic hydrocarbon of the present invention and its derivatives may be employed as fragrance ingredients in all manner of fragranced products from fine fragrances to cosmetics and detergents, e.g. in shampoos, skin-care products or soaps. However, the unique ambery, woody aspects of the compounds do not detract from the broad range of possible applications in perfumery and the compounds may find use in practically all fields of perfumery, for example in fine
perfumery, or in perfumed products of all kinds, for example luxury perfumes, cosmetic articles, consumer healthcare products or household products, e.g. washing agents, detergents and soaps.
In these applications the compounds may be used alone or in admixture with other fragrances. Preferably however, the compounds are admixed with other fragrance molecules. The use of a compound of the present invention in this regard is not limited to any particular perfume type nor to any special olfactory direction, odourant or class of substance. Thus, a compound of the present invention may be mixed with, for example, ethereal oils and extracts, e.g. castoreum, costus root oil, oak moss absolute, geranium oil, jasmin absolute, patchouli oil, rose oil, sandalwood oil or ylang-
ylang oil; - alcohols, e.g. citronellol, Ebanol@, eugenol, geraniol, Super Muguet@, linalool, phenylethyl alcohol, Sandalore@, terpineol or Timberol@; - aldehydes and ketones, e.g. a-amylcinnamaldehyde, Georgywood@, hydroxycitronellal, Iso E Supers, Isoraldeine, Hedione@, maltol, methyl cedryl À ketone, methylionone or vanillin; À - ether and acetals, e.g. Ambrox@, geranyl methyl ether, rose oxide or Spirambrene@;. - esters and lactones, e.g. benzyl acetate, cedryl acetate, y-decalactone, Helvetolide@, y-undecalactone or vetivenyl acetate; - macrocycles, e.g. ambrettolide, ethylene brassylate or Exaltolide@; and - heterocycles, e.g. isobutylchinoline.
However, due to their unique character, the compounds of the present invention are especially well suited for use as ambery, woody compositions, for example as found in dry, masculine scents.
In addition to their admixture with other fragrances, the compounds of the present invention may be admixed with one or more ingredients or excipients conventionally used in conjunction with fragrances in fragrance compositions, for example carrier materials, and other auxiliary agents commonly used in the art, such as anti-microbial agents, solvents, colourants, anti-oxidants and the like.
The proportions in which the compounds of the present invention are employed in compositions according to the present invention may vary within a large range of values and will depend upon the nature of the composition one intends to perfume, for example the nature of coingredients, and the particular effect that the perfumer seeks. Generally however, one may employ up to about 30% by weight in fine fragrances and up to about 50% by weight in other perfumed products. À Àe e. À.- There now follows a series of examples that serve to illustrate the invention.. :.
:.:e Example 1.....
3a,6,9-Trimethyl-2,3,3a,4,5,7,8,9-octahydro-1 H-cyclopenta[c]indene e - :e To a cooled (-70 C) solution of 1,5,10-trimethyl-1,5,9- cyclododecatriene (20.44g, 0.1 mol) in toluene (200 ml) was added EtAICI2 (5,6 ml of a 1.8 M solution in toluene). During the addition the temperature was kept below-65 C. The mixture was stirred at -70 C for 8 h. The reaction mixture was then quenched with saturated aqueous ammonium chloride. The organic phase was separated, washed with water and brine, dried and concentrated in vacua. The residue was distilled over a 15 cm Vigreux column (bp. 66 C/0.08 Torr) to yield 11.35g (55.5%) of a colorless oil with a purity of 70% (GC).
1H-NMR (400 MHz, CDCI3): 2,26 (m, 2H); 1.99 -1.18 (m, 11H); 1.54 (s, 3H), 1.15 0.76 (m, 2H), 0.87 (s, J = 6.5 Hz, 3H), 0.86 (s, 3H) ppm. '3C-NMR (100MHz, CDCI3):141.3 (s, C-5a), 123.1 (s, C-6), 57.5 (s, C-9a), 53.9 (s, C-3a), 39.6 (t, C
3), 37.7 (t, C-4), 33.3 (d, C-9), 32.9 (t, C-1), 31.4 (t, C-7), 29.8 (t, C-8), 26.5 (t, C-
5), 23.0 (t, C-2), 20.9 (q, 3a-CH3), 19.1 (q, 6-CH3), 17.1 (q, 9-CH3) ppm. GC/MS (El):204 (M+, 43), 189 (33), 176 (8), 162 (100), 147 (80), 133 (24) , 119 (33), 105 (38), 91 (32), 79 (17), 55 (16), 41 (23), 29 (10). IR: 2917 (s), 2869 (s), 1454 (m), 1374 (m) cm1.
Example 2
5a,6-Epoxy-3a,6,9-trimethyl-2, 3, 3a,4,5, 7,8, 9-octahyd ro- 1 Hcyclopenta[c]indene To an ice-cold suspension of 3a,6,9-trimethyl-2,3,3a, 4,5,7,8,9-octahydro-1 H-
cyclopenta[c]inden (10.00g, 49 mmol) and NaHCO3 (12.35g, 147 mmol) in methylene chloride (100 ml) was slowly added peracetic acid (32%) in such a way to keep the temperature at below 10 C. After the mixture had been stirred for 1h, water was added and the organic phase was separated, washed with water, aqueous NaHCO3 and brine, dried (MgSO.) and concentrated in vacuo to yield 10.10g of a colorless oil. This was further purified by chromatography on silica. H-NMR (400 MHz, C6D6): 2.21- 2.07 (m, 1H), 1.97-1.74 (m, 4H), 1.74-1.64 (m, 3H), 1.64-1.33 (m, 4H), 1. 25-1.14 (m, 2H), 1.16 (s, 3H), 0.98-0.91 (m, 1H), 0.94 (s, 3H), 0.76 (d, J = 6.7 Hz, 3H) ppm. '3C-NMR (100 MHz, C6D6): 76.0 (s, C-5a), 61.6 (s, C6), 55.5 (s, C-9a), 53.6 (s, C-3a), 40.5 (t, C-3), 36.6 (t, C-4), 33.6 (d, C-
9), 32.2 (t, C-7), 29.6 (t, C-1), 28.9 (C-5), 26.7 (t, C-8), 22.9 (t, C-2) , 21.2 (q, 3a-
CH3), 20.6 (q, 6-CH3), 16.6 (q, 9-CH3) ppm. GC/MS (El):220 (M+, 28), 205 (33), 161 (35), 145 (44), 135 (78), 121 (100), 107 (65), 91 (79), 79 (72), 67( 41), 55
(61), 43 (79). IR (atr): 2931s, 2871 m, 1452m,1376m, 871m, 682w cm'.
Claims (9)
1. 3a,6,9-trimethyl-2,3,3a,4,5,7,8,9-octahydro-1 H-cyclopenta[c]indene.
2. Derivatives of the compound of claim 1 having woody, ambery notes.
3. A derivative according to claim 2 that is 5a,6-epoxy-3a,6,9-trimethyl 2,3,3a,4,5,7,8,9-octahydro-1 H-cyclopenta[c]indene.
4. Use of a compound according to any of the preceding claims as a fragrance ingredient.
5. A fragranced composition containing a compound as defined in any of the claims 1 to 3. À À Àe
6. A method of forming the compound of claim 1 comprising the step of...
cyclising 1,5,10-trimethyl-1,5,9-cyclododecatriene with a Lewis acid...
À -
7. A method according to claim 6 wherein the Lewis acid is EtAIC12..
À.
8. A method of forming the compound of claim 3 comprising the step of reacting the compound of claim 1 with a peracid.
9. A method according to claim 8 wherein the peracid is peracetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0225199A GB2394713A (en) | 2002-10-30 | 2002-10-30 | Cyclopentaindene fragrance ingredients |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0225199A GB2394713A (en) | 2002-10-30 | 2002-10-30 | Cyclopentaindene fragrance ingredients |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0225199D0 GB0225199D0 (en) | 2002-12-11 |
| GB2394713A true GB2394713A (en) | 2004-05-05 |
Family
ID=9946827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0225199A Withdrawn GB2394713A (en) | 2002-10-30 | 2002-10-30 | Cyclopentaindene fragrance ingredients |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2394713A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0172376A1 (en) * | 1984-07-26 | 1986-02-26 | Firmenich Sa | Tricyclic epoxide and its use as perfuming ingredient |
-
2002
- 2002-10-30 GB GB0225199A patent/GB2394713A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0172376A1 (en) * | 1984-07-26 | 1986-02-26 | Firmenich Sa | Tricyclic epoxide and its use as perfuming ingredient |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0225199D0 (en) | 2002-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU748249B2 (en) | Macrocycles | |
| US20070027060A1 (en) | 2-methyl-4-pheny1-1,3-dioxolane | |
| EP0746552B1 (en) | Tetrahydrofurans and tetrahydropyrans | |
| AU726079B2 (en) | Dioxacycloalkan-8-one | |
| US5792740A (en) | Fragrant macrocyclic lactones | |
| US4302363A (en) | Perfume compositions containing 4(5)-acetyl-7,7,9(7,9,9)-trimethylbicyclo[4.]non-1-ene | |
| EP1523542B1 (en) | Fragrance composition | |
| ES2320207T3 (en) | ORGANIC COMPOUNDS. | |
| US5679634A (en) | Use of dihydrobenzofuranones as perfuming ingredients | |
| GB2394713A (en) | Cyclopentaindene fragrance ingredients | |
| US6235926B1 (en) | Perfuming ingredients of woody, fruity odor | |
| JPH05262757A (en) | Cyclic isolongifolanone-ketals, their production and their use | |
| US4251398A (en) | Cyclohexyl-pentanolides and their use in perfume | |
| US4392993A (en) | Alicyclic unsaturated compounds, their preparation and use of same as perfume ingredients | |
| US3929894A (en) | Process for the preparation of isopropenyl-bicyclo{8 4,4,0{9 dec-1-en-3-ones | |
| CA1117021A (en) | Perfumery compositions with trimethyl-tetrahydropyran-2-ones | |
| US5441930A (en) | Isomeric 11-oxatricyclo[7.3.02,6]dodecene derivatives, their production and their use as fragrances and fragrance compositions containing them | |
| US4661286A (en) | Oxaspirododecane derivatives and perfume compositions containing them | |
| US3978089A (en) | Caryophyllane epoxide | |
| WO1981000204A1 (en) | Novel norbornyl-substituted pyrans,method for their synthesis and use thereof in perfumery | |
| WO1980000839A1 (en) | Novel norcamphanyl-substituted pyrans,method for their synthesis and use thereof in perfumery | |
| US4322318A (en) | Novel prenyl 4-caranones | |
| CH685390A5 (en) | New poly:alkyl-tetra:hydro-furan derivs | |
| WO2024023169A1 (en) | Chromen-5-one derivatives for use as fragrances | |
| KR20070097481A (en) | Spiro[bornyl-2,4'-(1,3-dioxanes)] and their uses as fragrance ingredients |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |