New perfumes and uses thereof

Abstract

The present invention relates to new 4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1H-3a',7'-methanoazulen-6'-yl)butan-2-one, optionally methoxy-substituted at positions C-1 and C-3, of formula (I) as defined herein, and to the use thereof as ambergris-like perfumes. In particular, the present invention relates to the use of compounds (1), (2) and (3) as perfumes and as fixatives, and to the use thereof in perfume compositions in combination with other perfumes. The present invention also relates to a method for perfuming a product with the compounds according to the invention and to a corresponding perfumed product.

Description

[0001] Munich, 8 August 2023 Our reference: SM 6787-01 WO SOE / MCL

[0002] Applicant: Symrise AG

[0003] Official file number: New registration

[0004] Symrise AG

[0005] Mühlenfeldstraße 1 , 37603 Holzminden,

[0006] New fragrances and their uses

[0007] The present invention relates to novel, optionally methoxy-substituted at position C-1 and C-3, 4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1 / 7-3a',7'-methanoazulen-6'-yl)butan-2-ones of the formula (I) as defined herein, and to their use as amber-like fragrances. In particular, the present invention relates to the use of compounds (1), (2) and (3) as fragrances and as fixatives, and to their use in fragrance compositions in combination with other fragrances. Furthermore, the present invention relates to a process for perfuming a product with the compounds according to the invention and to a corresponding perfumed product.

[0008] 'Grey ambergris' or 'ambergris' from the French "ambre gris" was already highly sought after by the coastal inhabitants of the Indian Ocean around 1,000 BC due to its unusual smell, its great rarity, and its supposed aphrodisiac properties, and was weighed against its counterweight in gold (G. Ohloff, Earthly Scents - Heavenly Lust - A Cultural History of Fragrances, Birkhäuser Verlag, Basel / Boston / Berlin, 1992, pp. 137-139). The first evidence of the use of ambergris in perfumery comes from Ibn Khordadhbeh (* c. 820; f. c. 912), a geographer and administrative official from Jibal in western Persia. As early as the ninth century, Arab sailors brought ambergris from the Near and Far East, North Africa and India to Europe (G. Ohloff, 'The Fragrance of Ambergris', in ET Theimer, Fragrance Chemistry - The Science of the Sense of Smell, Academic Press, Orlando, 1982, pp. 535-573).The light to dark gray, waxy substance is a pathological metabolic product of the sperm whale (Physeter macrocephalus L.). It forms as a kind of scab after mechanical injury to the digestive tract by sharp-edged objects and is later excreted in clumps weighing 15–150 kg. Through oxidative aging processes in the sea under the influence of sunlight, it develops over the years a typical exotic-marine, dry, woody, tobacco-like odor of high substantivity and fixative adhesive power. This highly complex odor has aspects of:

[0009] 1. Wet, mossy forest floor. 2. Dried tobacco leaves. 3. Balsamic, creamy sandalwood. 4. Warm, animal-like alderwood. 5. Seaweed and seawater. 6. Feces (G. Ohloff, "Chemistry of Odorants and Flavors," in A. Davison, M.J.S. Dewar, K. Hafner, E. Heilbronner, U. Hofmann, K. Niedenzu, K. Schäfer, G. Wittig (eds.), F. Boschke (author), Advances in Chemical Research, Springer Verlag, Heidelberg, 1969, Vol. 12, No. 2, p. 185).

[0010] Ambroxide (-)-Ambrein (+)-e ÄCoprosterol

[0011] Ysamber K Ambrocenid Ambrostar Belambre This special woody-dry, warm-balsamic and marine-tobacco-like amber profile of creamy-animalistic tonality and high originality, which made natural ambergris the most precious fragrance in perfumery, is found in perfect balance in ambroxide (alternative trade names: Ambrox, Amboxan, Ambrofix, Ambermore, Cetalor), the natural olfactory principle of ambergris, in which it only occurs as a trace component at <0.3%. Ambroxide has been semisynthetically accessible from sclareol, a component of clary sage, since the 1950s, and is now also biotechnologically accessible and via cyclization using squalene-hopene cyclase (G. Ohloff, W. Pickenhagen, P. Kraft, F. Grau, Scent and Chemistry - The Molecular World of Odors, Wiley-VCH, Weinheim, 2022, p. 243).The excellent fixative properties of natural ambergris are explained by its content of (+)-ep / -coprosterol (20-40%) and (-)-ambrein (25-45%), the latter of which also forms ambroxide in nature. While natural ambergris or (-)-ambrein isolated from it is still used today, and this is only the case in a very small number of niche fragrances, it is solely due to these fixative properties. Due to the low content of natural ambroxide, as well as hygiene concerns and the price, natural ambergris no longer plays a role in commercial fine perfumery, as consumers are accustomed to much higher dosages of ambroxide from semi-synthetic sources. Ambroxide has therefore lost its exclusivity, which is also evident in the price drop from > €1,200 / kg in the 1980s to below €200 / kg today in the 2020s.

[0012] In addition to the typical ambery odor profile of ambroxide, ketals have recently played a major role. These ketals possess ambery notes that lie somewhere between amber and alderwood (fungally infected wood of the species Aquilaria malaccensis, Aquilaria crassna, Aquilaria microcarpa, or Aquilaria filariä). They are more metallic-mineral than tobacco-balsamic and marine, and above all, they are much drier in their wood character. Instead of a mossy, warm scent, they have a sharp, animalistic sweetness that is sometimes perceived as almost pungent. The first of these ambery ketals was amber ketal or Jeger's ketal, named after its inventor, ETH professor Oskar Jeger, who discovered it in 1952 during degradation studies of the manool from Halocarpus biformis (Hook.) Quinn. Although it is perceived as very intense by some people, it has a high anosmia rate, meaning it is odorless for many others.Other amber-like ketals include spirambrene (1986), with additional spicy-aldehyde accents; karanal (1987), with candle wax-like nuances and hints of hot tar; and okoumal (1992), and ysamber K (1993). With the exception of ysamber K, an ethylene glycol ketal, these highly substituted ketals are not biodegradable. Karanal was even the first fragrance to be classified as a substance of very high concern (SVHC) by ECHA (European Chemicals Agency) due to its high persistence and very high bioaccumulation potential (vPvB, Article 57e). Karanal will no longer be permitted for use in the EU as of August 27, 2023.There is therefore a great need for novel ambara-like fragrances without ketal function but with similar ambara-like odor properties to these ambraketals in order to serve the trend for these dry-woody, mineral-metallic amber-like notes that has dominated masculine perfumery since "1 Million" (2008) and "Invictus" (2013).

[0013] This trend was initiated by highly potent ambergris such as ambrocenide (W. Pickenhagen, D. Schatkowski, for Dragoco, Eur. Pat. Appl. EP 857,723 A1, August 12, 1998), which, although also a ketal and non-biodegradable, is so potent that its environmental impact is relatively low. Its success and sustainable synthesis from cedrene led to a wave of new, highly potent ambergris in the industry, such as Ambrostar (E. Dilk, M. Eh, H. Surburg, US 2012 / 0077722 A1, September 28, 2011), the more substantive and better-fixing 2-pentanone derivative of ambrocenide, and Belambre from camphor (J.A. Bajgrowicz, EP761664 A1). These high-impact ambraketals reduced environmental exposure and, in the case of Ambrostar, also brought improved fixative properties to the application forms, but they are still ketals with all their problematic properties, especially bioaccumulation.

[0014] It was therefore an object of the present invention to provide new amber-like odorants which have an amber-like odor and fixative properties and, in contrast to the previous odorants of this odor family, are not ketals.

[0015] Surprisingly, a narrowly defined family of 2-butanones optionally substituted at C-1 or C-3 methoxy, of general formula (I), where X and Y = H or -OMe, and

[0016] X = H if Y = -OMe, and

[0017] Y = H if X = -OMe or

[0018] X = Y = H, which possess the interesting and very typical amber-like odors of the aforementioned ambra ketals and possess very good fixative properties without being ketals themselves. The substituent at position C-4 is derived from the renewable sesquiterpene cedrene.

[0019] The above-defined problem is therefore solved by a compound or a mixture of compounds of formula (I) including all stereoisomers, where X and Y = H or -OMe, and

[0020] X = H if Y = -OMe, and

[0021] Y = H if X = -OMe or

[0022] X = Y = H.

[0023] The compounds of formula (I) are amber-like fragrances that are also capable of fixing the amber notes of other fragrances, i.e., prolonging and modifying their adhesion. The compounds can therefore be advantageously integrated into a range of fragrance mixtures and are suitable for a wide range of applications in various products. Furthermore, the oxygen substituents make the compounds more polar, thus exhibiting low bioaccumulation.

[0024] Furthermore, the present invention relates to the use of a compound or mixture of compounds as defined above as a fragrance, in particular as an amber-like fragrance and / or for enhancing and / or modifying an amber-like and / or agarwood note of other fragrances and / or as a fixative, in particular for prolonging the adhesion of an amber-like and / or agarwood note of other fragrances. In the context of the present invention, amber-like fragrances are fragrances that lie between amber and alderwood (fungally infected wood of the species Aquilaria malaccensis, Aquilaria crassna, Aquilaria microcarpa, or Aquilaria filariä). Compared to amber, they are more metallic-mineral than tobacco-like-balsamic-marine, and above all, much drier in their woody character, and instead of a mossy-warm initial scent, they often have a sharp, animalistic sweetness that is perceived as almost pungent.

[0025] In the context of the present invention, a fixative is understood to mean a substance that is capable of prolonging the adhesion of odor notes of other fragrances, i.e. ensuring a longer-lasting fragrance in a product.

[0026] The present invention further relates to the use of a compound as described above, wherein compound (1) used to convey, enhance, modify and / or fix an amber and / or agarwood note.

[0027] Compared to an amber note, an agarwood note is significantly more animalic and balsamic-sweet in its woody character. In addition to the sharp, animalic sweetness that can sometimes be perceived as pungent, it is characterized by complementary spicy-bitter facets.

[0028] The present invention also relates to the use of a compound as described above, wherein compound (2)

[0029] is used to impart, enhance, modify, and / or fix a woody, amber-like, agarwood, peppery, and / or green note. Furthermore, the present invention also relates to the use of a compound as described above, wherein compound (3) used to impart, enhance, modify and / or fix a woody, ambery or agarwood, peppery and / or green note.

[0030] In addition to the dry, woody, amber- and agarwood-like main character and the fixative properties common to all representatives, compounds (1)-(3) convey, enhance, or modify additional, distinct secondary notes. Compound (1) emphasizes dark, sweet, warm, animalic, and tobacco-like accents, harmonizing particularly well with balsamic-creamy sandalwood fragrances, while compound (2) vibrates more muskyly, has an erogenous, and clean effect, highlighting fresh, hesperidic-citric notes, which are further enhanced by the green-mossy undertone. Compound (3), in turn, underscores soft, warm, spicy fragrance components with its transparent incense and pepper character, harmonizing particularly well with acidic, fruity fragrance components.

[0031] According to a further aspect, the present invention relates to a fragrance composition comprising or consisting of a compound or mixture of compounds as defined above, in particular comprising compound (1), compound (2) and / or compound (3), and one or more further fragrance(s).

[0032] A fragrance composition according to the invention may contain any of the compounds (1) to (3) alone or two of the compounds (1) to (3) or all of the compounds (1) to (3) in combination.

[0033] The presence of compounds (1), (2), and / or (3) has a beneficial effect on fragrance compositions, as can be seen from the application examples below. In particular, the combination with amber or agarwood fragrances brings beneficial effects.

[0034] In particular, the present invention therefore relates to a fragrance composition as described above comprising or consisting of compound (1), compound (2) and / or compound (3) and at least one amber or agarwood fragrance.

[0035] Particularly preferred is the combination of one of the compounds (1), (2) or (3) with ambrocenide and / or ambrostar.

[0036] In a preferred embodiment of the fragrance composition as described above, the compounds (1), (2) and / or (3) each make up 0.001 to 10 wt.% of the fragrance composition, preferably 0.2 to 2 wt.%.

[0037] Also preferred is a fragrance composition as described above, wherein the amber fragrance(s) and / or agarwood fragrance(s) is / are selected from the group consisting of the stereoisomeric 2,2,5,8,8,9a-hexamethyloctahydro-4 / 7-4a,9-methanoazuleno[5,6-cf][1,3]dioxole, 2,5,8,8,9a-pentamethyl-2-propyloctahydro-4 / 7-4a,9-methanoazuleno[5,6-cf][1,3]dioxole, 2,5,8,8,9a-pentamethyl-2-(prop-1-en-1-yl)octahydro-4 / 7-4a,9-methanoazuleno[5,6-cf][1,3]dioxole, 2-(Methoxymethyl)-2,5,8,8,9apentamethyloctahydro-4 / 7-4a,9-methanoazuleno[5,6-cf][1,3]dioxole, 2,4-Dimethyl-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-1,3-dioxolane, 2',2',3,7,7-Penta-methylspiro[bicyclo[4.1,0]heptane-2,5'-[1,3]dioxane], 2'-isopropyl-1,7,7-trimethyl-spiro[bicyclo[2.2.1]heptane-2,4'-[1,3]dioxane], 1-(2',2',6'-trimethylcyclohexyl)hexan-3-ol, 2-Methyl-5-(5',5',6'-trimethylbicyclo[2.2.1 hept-2'-yl)cyclohexanones, decahydro-

[0038] 2,2, 6, 6,7,8, 8-heptamethyl-2 / 7-indeno[4,5-b]furane, 6,7-Dihydro-1 ,1 ,2,3,3-pentamethyl- 4(5 / - / )-indanone, 1 a,3,3,4,6,6-Hexamethyl-1 a,2,3,4,5,6,7,7a-octahydronaphtho[2,3-b]oxi- rene, 7,7,8,9,9-Pentamethyl-4,4a,5,6,7,8,9,9b-octahydroindeno[4,5-cf][1 ,3]dioxine, 7,7,8,9,9-Pentamethyl-6,6a,7,8,9,9a-hexahydro-5 / 7-cyclopenta[h]quinazoline, 7, 7, 8, 9, 9- pentamethyl-6,7,8,9-tetrahydro-5 / 7-cyclopenta[h]quinazoline, 2,6,6,7,8,8-Hexamethylde- cahydro-2 / 7-indeno[4,5-b]furane, 2,2,6,6,7,8,8-Heptamethyldecahydro-2 / 7-indeno[4,5- b]furane, 2,2,7,7,8,9,9-Heptamethyldecahydroindeno[4,3a-b]furane, 7- Meth oxy-1 ,1 ,5,5- tetramethyl-1 ,3,4,5,6,7-hexahydro-2 / 7-2,4a-methanonaphthalene, 5,5-Dimethyl-2-propyl- hexahydro-2 / 7-2,4a-methanonaphthalen-1 (5 / - / )-one, 2,2,9, 11-Tetramethylspiro[5.5]undec- 8-en-1-yl acetate, 3,8,8, 11 a-tetramethyldodecahydro-5 / 7-3,5a-epoxynapht[2,1-C]oxepines, 3a,6,6,9a-tetramethyl-1,2,3a,4,6,7,8,9,9a,9b-decahydronaphtho[2,1-b]furans and 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furans as well as the reaction products from the acid-catalyzed cyclization of 1-(1 ',6'-dimethyl-4'-(4"-methylpent-3"-en-1 ”-yl)cyclohex-3'-en-1 '-yl)ethan-1-one.

[0039] According to a further aspect, the present invention also relates to a method for perfuming a product comprising the steps:

[0040] (i) providing a compound or mixture of compounds of formula (I) as defined above or a fragrance composition as defined above, and

[0041] (ii) adding the compound or mixture of compounds or the fragrance composition to the product to be perfumed, preferably in a sensorially effective amount, in particular in an amount sufficient to impart, enhance and / or modify an olfactory note.

[0042] A “sensory effective amount” is the amount in which the compound or mixture of compounds or fragrance composition in the perfumed product can be perceived by a consumer compared to a product which does not contain the corresponding compound, mixture of compounds or fragrance composition.Preferred is a process as described above, wherein in step (ii) compound (1) is added to the product to be perfumed in order to impart, enhance, modify and / or fix an amber-like and / or agarwood note and / or wherein compound (2) is added to the product to be perfumed in order to impart, enhance, modify and / or fix a woody, amber-like, agarwood, peppery and / or green note and / or wherein in step (ii) compound (3) is added to the product to be perfumed in order to impart, enhance, modify and / or fix a woody, amber-like, agarwood, peppery and / or green note.

[0043] Furthermore, the present invention relates to a perfumed product comprising a compound or mixture of compounds as defined above or a fragrance composition as described above.

[0044] A fragrance composition according to the invention is advantageously suitable for a wide range of applications in a wide variety of products.

[0045] Preferably, the perfumed product is selected from the group consisting of detergents and cleaning agents, hygiene and care products, preferably in the field of body and hair care, cosmetics and household, preferably selected from the group consisting of perfume extracts, eau de parfums, eau de toilettes, aftershave lotions, eau de colognes, pre-shave products, perfumed wet wipes, acidic, alkaline or neutral detergents, textile fresheners, ironing aids, liquid detergents, powdered detergents, laundry treatment agents, fabric softeners, laundry soaps, detergent tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and varnishes, body care products, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, deodorants, antiperspirants, decorative cosmetic products, candles, lamp oils,Incense sticks, insecticides, repellents and propellants.

[0046] Even small amounts of the fragrance composition according to the invention in a product are sufficient to ensure a pleasant, long-lasting fragrance.

[0047] In a preferred embodiment of the product, the total amount of the fragrance composition is in a range of 0.05 to 5 wt.%, preferably 0.5 to 2 wt.%, in each case based on the total weight of the product.

[0048] The invention is described in more detail below with reference to some examples. Example 1: Preparation of 1-methoxy- and 3-methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1'H-3a',7'-methanoazulen-6'-yl)butan-2-ones by Claisen rearrangement

[0049] Synthesis of 1,2,2-trimethoxypropane

[0050] 157 g (4.91 mol) of methanol, 600 mg (6.12 mmol) of sulfuric acid, and 190 g (1.79 mol) of trimethyl orthoformate were placed at room temperature in a 1-liter three-necked flask equipped with a magnetic stirrer, thermometer, reflux condenser, and dropping funnel. 150 g (1.70 mol) of 1-methoxypropan-2-one were added dropwise over a period of 30 minutes, during which time the temperature rose to 50 °C. The mixture was then heated under reflux (52 °C) for 5 hours. The heating was removed, 3.50 g (33.7 mmol) of sodium carbonate were added to the mixture at room temperature, and the mixture was then fractionally distilled under vacuum on a 30 cm packed column equipped with Raschig rings and a column head. Yield: 204 g (89%) 1,2,2-trimethoxypropane (GC purity: 96%) as a colorless clear liquid.

[0051] GC-IR (GC purity 96%): v = 2994 / 2945 / 2838 (m), 1464 (w), 1381 (w), 1255 (w), 1136 (s), 1066 (m), 850 (w).

[0052] 1H-NMR (400 MHz, CDCh): ö = 3.41(s,6H,2-MeO2), 3.37(s,3H,1-MeO), 3.23(s,1-H2), 1.35(s,3H,3-H3) ppm.

[0053] 13 C-NMR (101 MHz, CDCh): ö = 100.0(s,C-2), 74.1(t,C-1), 59.3(q,1-MeO), 48.2 / 48.2(2q,2-MeO2), 20.1(q,C-3) ppm.

[0054] GC-MS (70eV): m / z(%) = 41(25), 43(60), 45(15), 47(12), 53(1), 57(7), 71(45), 89(100), 103(47), 119(6).

[0055] Elimination of a Methoxy group to the corresponding Enolether

[0056] 82.0 g (0.61 mol) of the previously synthesized 1,2,2-trimethoxypropane, 1.00 g (12.6 mmol) of pyridine, and 400 mg (4.08 mmol) of 85% phosphoric acid were placed in a 250 ml distillation apparatus equipped with a thermometer, magnetic stirrer, column (10 cm Raschig rings), and column head. The mixture was heated under atmospheric pressure. The mixture began to boil at 119 °C. At a reflux ratio of R:D = 25:1, a bottom temperature of 120-150 °C and a head temperature of 104-108 °C, 43.7 g of distillate were obtained (GC purity: 88%. Composition: 41% (E)-1,2-dimethoxyprop-1-ene, 17% (Z)-1,2-dimethoxyprop-1-ene, 30% 2,3-dimethoxyprop-1-ene).

[0057] GC-IR (GC purity 88%): v = 2998 / 2941 / 2839 (m), 1668 (w), 1625 (w), 1460 (w), 1220 (s), 1 136 (s), 1082 (m).

[0058] (E)-1,2-Dimethoxyprop-1-ene:

[0059] 1 H-NMR (400 MHz, C e D e): ö = 1.97 (d, J = 1.0 Hz, 3 H, 3-H3), 3.16 (s, 3 H, 2-MeO), 3.19 (s, 3 H, 1-MeO), 5.57 (q, J = 1.0 Hz, 1 H 1-H).

[0060] 13 C NMR (101 MHz, C e D e ) ö = 14.1 (q, C-3), 54.8 (q, 2’-MeO), 59.8 (q, 1 ’-MeO), 127.1 (d, C-1), 144.9 (s, C-2).

[0061] GC-MS (70eV): m / z (%) = 27 (8), 39 (9), 43 (48), 59 (100), 87 (84), 102 (90), 103 (5).

[0062] (Z)-1 ,2-Dimethoxyprop-1-en:

[0063] 1 H-NMR (400 MHz, CeDe): ö = 1.52 (d, J = 1.0 Hz, 3 H 3-H3), 3.14 (s, 3 H, 1-MeO), 3.62 (s, 3 H, 2-MeO), 5.08 (q, J = 1.0 Hz, 1 H, 1-H).

[0064] 13 C NMR (101 MHz, CeDe) ö = 15.9 (q, C-3), 57.5 (q, 2’-MeO), 59.5 (q, 1 ’-MeO), 129.1 (d, C-1), 137.0 (s, C-2).

[0065] GC-MS (70eV): m / z (%) = 29 (32), 43 (53), 59 (99), 87 (95), 102 (100), 103 (5).

[0066] 2,3-Dimethoxyprop-1-en:

[0067] 1H-NMR (400 MHz, CeDe): ö = 3.13 (s, 3 H, 3-MeO), 3.20 (s, 3 H, 2-MeO), 3.81 (d, J = 1.0 Hz, 2 H, 3-H2), 3.96 (d, J = 2.0 Hz, 1 H, 1-Hb), 4.26 (dt, J = 2.0, 1.0 Hz, 1 H, 1-H a ).

[0068] 13 C NMR (101 MHz, CeDe) ö = 54.4 (q, 2’-MeO), 58.0 (q, 3’-MeO), 72.8 (t, C-3), 82.1 (t, C- 1), 161.0 (s, C-2).

[0069] GC-MS (70eV): m / z (%) = 29 (19), 42 (38), 45 (38), 59 (13), 72 (100), 102 (9).

[0070] Herstellung von 5-((1 ’,2’-Dimethoxypropan-2’-yl)oxy)-

[0071] 3,8,8-trimethyl-6-methylenoctahydro-1H-3a,7-methanoazulen

[0072] In a 25 ml three-necked flask equipped with a magnetic stirrer, thermometer, and reflux condenser, 2.00 g (9.09 mmol) of 3,8,8-trimethyl-6-methyleneoctahydro-1 / 7-3a,7-methanoazulen-5-ol, 8.00 g (78.4 mmol) of a mixture of 65% (E / Z)-1,2-dimethoxyprop-1-ene, 35% 2,3-dimethoxyprop-1-ene, and 420 mg (7.00 mmol) of acetic acid were stirred at 90 °C for 16 h under a nitrogen atmosphere. The heating was then removed, and the reaction mixture was diluted with 20 ml of methyl tert-butyl ether while stirring at room temperature. The mixture was washed twice with 20 ml of 5% sodium carbonate solution each time and then concentrated. The residue was treated with 10 ml of hexane under warm conditions and then allowed to crystallize for 3 h at 5 °C. The resulting residue was filtered off, and the mother liquor was concentrated to yield 2.00 g of crude product (GC purity: 48%, 33% crude yield).After column chromatography (Büchi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1 — >95:5, 71 min, 20 ml / min at 20 ml per fraction, TLC: Rs = 0.44 (SiC>2 60, hexane / ethyl acetate = 10:1) 640 mg (22%) of the title compound were obtained (GC purity: 99%).

[0073] Eluting component: GC-IR (GC 34%, Thermo Nicolet 6700): v = 2949 (s) 1643 (w), 1463 (w), 1384 (w), 1131 (m), 1050 (m).

[0074] 1 H NMR (400 MHz, CDCh) ö = 0.83 - 0.88 (m, 3 H, 1 '-Me), 0.92 - 1 .00 (m, 6 H, 8'-Me2), 1 .23 - 1 .37 (m, 3 H, 2'-, 4'-, 9'-H b ), 1 .37 - 1 .50 (m, 4 H, 3-Me, 1 '-Hb), 1.51 - 1 .64 (m, 1 H, 1 '-Ha), 1 .68 - 1 .80 (m, 2 H, 3'-H, 9'-H a ), 1 .80 - 1 .91 (m, 2 H, 8a'-H, 2'-H a ), 1 .91 - 2.07 (m, 1 H, 4'-H a ), 2.34 (d, J = 4.5 Hz, 1 H, 7'-H), 3.33 (s, 3 H, 2-MeO), 3.34 - 3.39 (m, 4 H, 1- MeO, 1-Hb), 3.49 (d, J = 10.0 Hz, 1 H, 1-H a), 4.46 - 4.61 (m, 1 H, 5’-H), 4.68 - 4.77 (m, 1

[0075] H, HbC=C-6’, exo-Methylen), 5.04 (t, J = 2.5 Hz, 1 H, H a C=C-6’, exo-Methylen).

[0076] 13 C NMR (101 MHz, CDCh) ö = 15.4 (q, 3’-Me), 21 .9 (q, C-3), 25.9 (t, C-1 ’), 26.1 / 26.8 (2q, 8’-Me), 36.9 (t, C-2’), 41 .7 (d, C-3’), 42.1 (s, C-8’), 43.7 (t, C-4’), 45.0 (t, C-9’), 49.6 (q, 3-MeO), 54.7 (s, C-3a’), 57.1 (d, C-8a’), 59.3 (q, 1-MeO), 60.9 (d, C-7’), 69.7 (d, C-5’), 75.8 (t, C-1), 101.1 (s, C-2), 107.6 (t, H2C=C-6’), 152.3 (s, C-6’).

[0077] GC / MS: m / z (%): 41 (21), 55 (9), 71 (51), 95 (18), 103 (100), 119 (24), 133 (14), 147 (22), 203 (34), 220 (7), 245 (4), 290 (1).

[0078] Letzteluierende Komponente: GC-IR (GC 65 %, Thermo Nicolet 6700): v = 2949 (s), 1644 (w), 1463 (w), 1384 (w), 1131 (m), 1050 (m).

[0079] 1 H NMR (400 MHz, CDCh) ö = 0.86 (m, 3H, 3’-Me), 0.92 - 1 .00 (m, 6 H, 8’-Me2), 1 .23 -

[0080] I .37 (m, 3 H, 2’-, 4’-, 9’-H b ), 1 .37 - 1 .50 (m, 4 H, 3-Me, 1 ’-Hb), 1 .51 - 1 .64 (m, 1 H, 1 ”-H a ), 1 .68 - 1 .80 (m, 2 H, 3’-H, 9’-H a ), 1 .80 - 1 .91 (m, 2 H, 2’-H a , 8a’-H), 1 .91 - 2.07 (m, 1 H, 4’-H a ), 2.34 (d, J = 4.5 Hz, 1 H, 7a’-H), 3.30 (s, 3 H, 2-MeO), 3.34 - 3.39 (m, 2 H, 1-H b ), 3.41 (s, 3 H, 1-MeO), 3.54 (d, J = 10.0 Hz, 1 H 1-Ha), 4.46 - 4.61 (m, 1 H, 5’-H), 4.68 - 4.77 (m, 1 H, HbC=C-6’), 4.95 (t, J = 2.5 Hz, 1 H, H a C=C-6’). 13C NMR (101 MHz, CDCh) Ö = 15.5 (q, 3’-Me), 21 .1 (q, C-3), 25.9 (t, C-1 ’), 26.2 / 26.8 (2 q, 8’-Me2), 36.9 (t, C-2’), 41 .7 (d, C-3’), 42.1 (s, C-8’), 43.4 (t, C-4’), 45.0 (t, C-9’), 49.2 (q, 3-MeO), 54.8 (s, C-3a’), 57.1 (d, C-8a’), 59.3 (q, 1-MeO), 60.8 (d, C-7’), 69.3 (d, C-5’), 75.1 (t, C-1), 101.1 (s, C-2), 107.6 (t, H2C=C-6’), 152.4 (s, C-6’). m / z (%) = 41 (22), 55 (9), 71 (52), 95 (23), 103 (100), 119 (29), 133 (18), 147 (28), 203 (48), 220 (4), 290 (1).

[0081] Herstellung von 3-Methoxy-4-(3’,8’,8’-trimethyl-2’,3’,4’,7’,8’,8a’-hexahydro-1 H-3a’,7’- methanoazulen-6-yl)butan-2-on und 1 -Methoxy-4-(3’,8’,8’-trimethyl-2’,3’,4’,7’,8’,8a’- hexahydro-1 H-3a’,7’-methanoazulen-6’-yl)butan-2-on durch Claisen-Umlagerung

[0082] 1.50 g (4.66 mmol) of 5-((1',2'-dimethoxypropan-2'-yl)oxy)-3,8,8-trimethyl-6-methyleneoctahydro-1 / 7-3a,7-methanoazulene was heated in a Kugelrohr distillation apparatus (Büchi Glass Oven B-585) at 160 °C and 100 mbar for 4 h, after which the heating was removed. The residue yielded 1.09 g of crude product (GC purity: 78%). After column chromatography (Büchi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / acetic ester = 98:2—>92:8, 71 min, 20 ml / min at 20 ml per fraction, TLC: Rs = 0.33 and 0.25 (SiO260, hexane / acetic ester = 10:1), 38.0 mg of 3-methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1 / 7-3a',7'-methanoazulen-6'-yl)butan-2-one (GC purity: 94%) and 513 mg of 1- Methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1 / 7-3a',7'-methanoazulen-6'-yl)butan-2-one (GC purity: 94%) was obtained.

[0083] 3-Methoxy-4-(3’,8’,8’-trimethyl-2’,3’,4’,7’,8’,8a’-hexahydro-1H-3a’,7’-methanoazulen- 6’-yl)butan-2-on (1 :1 Gemisch von zwei Diastereomeren, [Verbindung (1)])

[0084] GC-IR (GC-Reinheit 94 %, Thermo Nicolet 6700): v = 2949 / 2901 / 2835 (s), 1729 (w), 1468 (w), 1358 (w), 1109 (m).

[0085] 1 H NMR (400 MHz, CDCh): ö = 0.83 / 0.84 (d, J = 7.0 Hz, 6 H, 3’-Me2), 0.96 / 1 .01 (2s, 12

[0086] H, 8’-Me4), 1 .28 - 1 .45 m, 6 H, (1 ‘-Hb, 2’-H b , 9’-H b )2), 1 .53 - 1 .63 (m, 2 H, (1 ’-H a )2), 1 .64 -

[0087] I .80 (m, 6 H, (3‘-H, 8 a ‘-H, 9‘-H a )2), 1 .80 - 1 .88 (m, 4 H, (2‘-H a , 4‘-H b )2), 1 .89 / 1 .90 (2s, 2 H, 7-H), 2.13 / 2.17 (2s, 6 H, (1-H3)2), 2.15 - 2.38 (m, 6 H, (4-H2)2, (4’-H a)2), 3.34 / 3.35 (2s, 6 H, 3-MeO2), 3.65 (d, J = 7.0 Hz, 1 H, 3-H) / 3.62 - 3.72 (m, 1 H, 3-H), 5.29 (dd, J = 4.0, 3.0 Hz, 1 H, 5’-H) / 5.31 - 5.38 (m, 1 H, 5’-H).

[0088] 13 C NMR (100 MHz, CDCh): ö = 15.4 / 15.4 (2q, 3’-Me), 24.8 / 24.8 (2t, C-1 ’), 25.0 / 25.4 (2q, C-1), 25.6 / 25.6 / 27.6 / 27.6 (4q, 8’-Me), 36.2 / 36.2 (2t, C-2’), 38.9 / 38.9 (t, C-4’), 40.5 / 40.5 / 40.6 / 40.7 (4t, C-4), 41 .5 / 41 .5 (2d, C-3’), 48.5 / 48.5 (2s, C-8’), 52.7 / 53.5 (2s, C-7’), 53.8 / 53.9 (2s, C-3a’), 57.9 / 58.5 (2q, 3-MeO), 59.1 / 59.2 (d, C-8a’), 86.3 / 87.1 (2d, C-3), 122.5 / 122.8 (2d, 5’=CH2), 139.2 / 139.4 (2s, C-6’), 210.8 / 211 .7 (2s, C-2).

[0089] MS (El): m / z (%): 43 (33), 55 (16), 69 (21), 79 (18), 91 (42), 105 (33), 1 19 (33), 131 (24), 147 (26), 159 (32), 173 (15), 187 (7), 203 (8), 215 (100), 247 (68), 258 (68), 275 (1), 290 (1).

[0090] Odor description: amber-like and dry woody-ambery, with animalic accents towards agarwood and cashmeran (1,1,2,3,3-pentamethyl-1,2,3,5,6,7-hexahydro-4 / 7-inden-4-one).

[0091] 1-Methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1H-3a',7'-methanoazulen-6'-yl)butan-2-one [Compound (2)]

[0092] GC-IR (GC purity 94%, Thermo Nicolet 6700): v = 2948 (s), 1732 (w), 1464 (w), 1110 (w).

[0093] 1 H NMR (600 MHz, CDCh): ö = 0.84 (d, J = 7.0 Hz, 3 H, 3'-Me), 0.95 / 1 .00 (2s, 6 H, (8'- Me)2), 1.31 - 1 .43 (m, 3 H, 1 '-,2'-,9'-H a ), 1 .53 - 1 .62 (m, 1 H, 1 '-Hb), 1 .65 - 1 .71 (m, 2 H, 8a'-H, 9'-Hb), 1.71 - 1 .77 (m, 1 H 3'-H), 1 .78 - 1 .90 (m, 3 H, 2'-H b , 4'-H a , 7'-H), 2.12 - 2.21 (m, 2 H, 4'-Hb, 4-Ha), 2.27 - 2.36 (m, 1 H, 4-H b ), 2.45 - 2.61 (m, 1 H, 3-H2), 3.42 (s, 3 H, 1-MeO), 4.02 (s, 2 H, 1-H2), 5.17 - 5.22 (m, 1 H, 5'-H).

[0094] 13 C NMR (151 MHz, CDCh): ö = 15.4 (q, 3'-Me), 24.8 (t, CT), 25.6 / 27.6 (2q, (8'-Me)2), 31 .3 (t, C-4), 36.1 (t, C-2'), 37.2 (t, C-3), 38.8 (t, C-4'), 40.7 (t, C-9'), 41 .4 (d, C-3'), 48.4 (s, C-8'), 53.5 (d, C-7'), 54.0 (s, C-3a'), 59.0 (d, C-8a'), 59.3 (q, 1-MeO), 77.7 (t, C-1), 119.1 (d, 5'=CH2), 142.8 (s, C-6'), 208.6 (s, C-2).

[0095] MS (El): m / z (%) = 41 (44), 55 (32), 69 (100), 81 (24), 91 (28), 109 (34), 118 (32), 135 (39), 149 (15), 162 (30, 177 (25), 187 (13), 205 (10), 220 (10).

[0096] Odour description: dry, woody-ambery, amber-like in the direction of ambrocenide (2,2,5,8,8,9a-hexamethyloctahydro-4 / 7-4a,9-methanoazuleno[5,6-c(][1,3]dioxole), with a peppery touch reminiscent of rotundone ((3S,5R,8S)-3,4,5,6,7,8-hexahydro-3cr,8cr-dimethyl-5cr-(1-methyl-ethenyl)azulen-1(2 / 7)-one) and green nuances.

[0097] Example 2: Preparation of 4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1 'H-3a',7'-methanoazulen-6'-yl)butan-2-one by Claisen rearrangement Synthesis of 2-ethoxyprop-1-ene

[0098] In a 250 ml distillation apparatus equipped with a thermometer, magnetic stirrer, column (10 cm, Raschig rings), and column head, 100 g (758 mmol) of 2,2-diethoxypropane, 1.20 g (15.2 mmol) of pyridine, and 500 mg (4.34 mmol) of 85% phosphoric acid were heated under atmospheric pressure, with the reaction mixture beginning to boil at 107 °C. At a reflux ratio of R:D = 10:1, a bottom temperature of 107-122 °C, and a head temperature of 72-92 °C, 91.0 g (76%) of the title compound were isolated by distillation (GC purity: 55%).

[0099] GC-IR (Thermo Nicolet 6700): v = 3121 / 2990 / 2941 (m), 1657 (m), 1599 (w), 1449 / 1376 (m), 1283 / 1277 (s), 1098 / 1085 (s), 798 (m).

[0100] 1 H NMR (400 MHz, C e D e) ö = 1 .08 (t, J = 7.0 Hz, 3H, 1 '-Me), 1 .79 (d, J = 1 .0 Hz, 3H C-3), 3.48 (q, J = 7.0 Hz, 2H, 1 '-H2), 3.83 (d, J = 1 .0 Hz, 1 H, 3-Hb), 3.89 (dq, J = 2.0, 1 .0 Hz, 1 H, 3-Ha).

[0101] 13 C NMR (101 MHz, C e D e ) ö = 14.6 (q, C-2'), 21.2 (q, C-3), 62.7 (t, CT), 81 .3 (t, C-1), 160.1 (s, C-2).

[0102] GC-MS (70eV): m / z (%) = 29 (32), 39 (20), 43 (100), 58 (89), 86 (94).

[0103] 5-((2'-Ethoxypropan-2'-yl)oxy)-3,8,8-trimethyl-6-methyleneoctahydro-1H-3a,7-methanoazulene

[0104] In a 10 ml single-neck flask equipped with a magnetic stirrer, thermometer and reflux condenser, 1.00 g (4.55 mmol) of 3,8,8-trimethyl-

[0105] 6-methyleneoctahydro-1 / 7-3a,7-methanoazulen-5-ol, 5.00 g (58.1 mmol) of 2-ethoxyprop-1-ene, and 200 mg (3.33 mmol) of acetic acid were stirred at 75 °C for 6 h. The heating was removed, and the reaction mixture was diluted with 50 ml of methyl tert-butyl ether while stirring at room temperature, washed once with 20 ml of 5% sodium carbonate solution, and then evaporated to dryness on a rotary evaporator, yielding 1.10 g (79%) of product (GC purity: 80%).

[0106] GC-IR (Thermo Nicolet 6700): v = 2949 / 2919 / 2882 (s), 1645 (w), 1464 (w), 1384 (w), 1278 (w), 1204 (w), 1164 (w), 1050 (m).

[0107] 1 H NMR (400 MHz, C e D e ): ö = 0.87 (d, J = 7.0 Hz, 3 H, 3-Me), 0.90 / 1 .06 (s, 6 H, 8-Me2), 1.16 (t, J = 7.0 Hz, 3 H, 2”-H3), 1.22 - 1.31 (m, 1 H, 2-Hb), 1.32 - 1.39 (m, 2H, 1-H b , 9-Hb), 1 .41 / 1 .45 (2s, 6 H, 1 '-H3, 3'-H3), 1 .46 - 1 .53 (m, 2 H, 1-H a , 4-Hb), 1 .57 - 1 .67 (m, 1 H, 3-H), 1 .65 - 1 .74 (m, 1 H, 9-H a), 1 .74 - 1 .80 (m, 1 H, 2-H a ), 1 .80 - 1 .89 (m, 1 H, 8a-H), 2.06 (ddd, J = 12.0, 7.5, 3.0 Hz, 1 H, 4-H a ), 2.37 (d, J = 4.5 Hz, 1 H, 7-H), 3.46 (dq, J = 9.0, 7.0 Hz, 1 H, 1 ”-Hb), 3.60 (dq, J = 9.0, 7.0 Hz, 1 H, 1 ”-H a ), 4.62 (ddt, J = 10.0, 7.5, 2.5 Hz, 1 H, 5-H), 4.88 / 5.29 (t, J = 3.0 Hz, 2 H, H2C=C-6).

[0108] 13 C NMR (101 MHz, C e D e ): ö = 15.8 (q, 3-Me), 15.8 (q, C-2”), 25.8 / 26.3 (2q, C-1 ’, -3’), 26.2 (t, C-1), 26.4 / 27.0 (2q, 8-Me2), 37.2 (t, C-2), 42.0 (d, C-3), 42.3 (s, C-8), 44.0 (t, C- 4), 45.6 (t, C-9), 55.2 (s, C-3a), 56.7 (t, C-1 ”), 57.4 (d, C-8a), 61.3 (d, C-7), 69.7 (d, C-5), 100.7 (s, C-2’), 108.0 (t, 5=CH2), 153.1 (s, C-6).

[0109] GC-MS (70eV): m / z (%) = 59 (39), 69 (4), 79 (2), 87 (100), 91 (5), 105 (3), 119 (4), 147 (3), 161 (2), 176 (3), 203 (3), 217 (2), 248 (2), 260 (2).

[0110] 4-(3',8',8'-Trimethyl-2',3',4',7',8',8a'-hexahydro-1 'H-3a',7'-methanoazulen-6'-yl)butan-2-one [Compound (3)]

[0111] 1.10 g (2.88 mmol) of 5-((2-ethoxypropan-2-yl)oxy)-3,8,8-trimethyl-6-methyleneocta-hydro-1 / 7-3a,7-methanoazulene (GC purity 80%) was heated for 4 h at 160 °C and 100 mbar in a Kugelrohr distillation apparatus (Büchi Glass Oven B-585). The heating was removed, and the product was allowed to cool to room temperature, leaving 800 mg of crude product in the residue (GC purity 33%, 35% crude yield). After column chromatography (Büchi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 97:3—>92:8, 71 min, 20 ml / min at 20 ml per fraction, TLC: Rs = 0.20 (SiO260, hexane / ethyl acetate = 20:1)) 240 mg (32%) of the title compound were obtained (GC purity 99%).

[0112] Odor description: dry-peppery, woody-ambery, with distinct aspects of cedarwood and black pepper, as well as a sour-spicy apple note on the nose.

[0113] GC-IR (Thermo Nicolet 6700): v = 2950 / 2908 / 2838 (s), 1732 (m), 1467 (w), 1363 (w), 1273 (w), 1221 (w), 1157 (w).

[0114] 1 H NMR (600 MHz, CDCh): ö = 0.84 (d, J = 7.0 Hz, 3 H, 3'-Me), 0.95 / 1 .00 (2s, 6 H, Me2C- 8'), 1 .32 - 1 .42 (m, 3 H, 1 '-, 2'-, 9'-H b ,), 1 .53 - 1 .61 (m, 1 H, 1 '-Ha), 1 .68 (ddd, J = 11 .0, 4.5, 1.5 Hz, 2 H, 8a'-H, 9'-H a ), 1.71 - 1.78 (m, 1H, 3'-H), 1.78 - 1.84 (m, 2H, 4a'-H b , 7'-H), 1 .84 - 1 .90 (m, 1 H, 2'-H a ), 2.10 - 2.21 (m, 5H, 1-H3, 4-, 4'-H b ), 2.24 - 2.35 (m, 1 H, 4-H a ), 2.48 (ddd, J = 16.0, 9.5, 6.0 Hz, 1H, 3-H b ), 2.57 (ddd, J = 16.5, 10.0, 5.5 Hz, 1H, 3-H a ), 5.18 (dt, J = 4.0, 2.0 Hz, 1 H, 5'-H). 13C NMR (151 MHz, CDCh) ö = 15.4 (q, 3'-Me), 24.8 (t, C-1 '), 25.6 / 27.6 (2q, Me2C-8'), 29.9 (q, C-1), 31.7 (t, C-4), 36.1 (t, C-2'), 38.7 (t, C-4'), 40.7 (t, C-9'), 41.4 (d, C-3'), 42.0 (t, C-3), 48.3 (s, C-8'), 53.5 (d, C-7'), 54.0 (s, C-3a'), 59.0 (d, C-8a'), 118.8 (d, C-5'), 143.0 (s, C-6'), 208.9 (s, C-2). GC-MS (70eV): m / z (%): 43 (44), 55 (17), 69 (26), 79 (15), 91 (98), 105 (28), 118 (25), 131 (18), 147 (12), 159 (34), 175 (100), 187 (9), 202 (46), 217 (24), 245 (3), 260 (16).

[0115] Example 3: Application of the compounds in a multifaceted dry-woody amber composition with fresh-citric contrast

[0116] Perfume composition 3.1

[0117] Compound (2) lends the composition more performance, character, and a distinctive signature through its dark, woody, amber-like contrast. It introduces an ambery dynamic that reinforces the fragrance's woody character. Furthermore, Compound (2) harmonizes with the fresh citrus top note, lending it more radiance. Compound (2) also makes the entire fragrance long-lasting and lingering.

[0118] Perfume composition 3.2

[0119] Compound (1) makes the overall olfactory impression stronger and more lasting. Furthermore, compound (1) lends the composition a distinctive masculine character and harmonizes excellently with and highlights the sweet and powdery facets of the perfume.

[0120] Perfume composition 3.3

[0121]

[0122] Compound (3) introduces interesting new facets to the fragrance composition: It makes the overall composition more complex, stronger, longer-lasting, and more modern. The fragrance smells warmer and softly ambery. The citrus notes now appear more multifaceted and clearer. Furthermore, compound (3) refines the composition with a fresh, peppery facet and even luxurious hints of incense. Perfume Composition 3.4

[0123]

[0124] The combination of compound (2) and Ambrocenide® creates a clean musk note with a warm amber undertone.

[0125] Perfume composition 3.5:

[0126] The combination of compound (1) and Ambrocenide® rounds off the harsh notes of Ambrocenide® and makes the ambery complex appear softer and more sensual. Perfume composition 3.6

[0127] In combination between compound (3) and Ambrocenide®, the composition appears more authentic, noble and sensual, as the combination effect creates warm, attractive pepper, incense and agarwood notes.

Claims

Patent claims 1 . A compound or a mixture of compounds of formula (I) including all stereoisomers, where X and Y = H or -OMe, and X = H if Y = -OMe, and Y = H if X = -OMe or X = Y = H.

2. Use of a compound or mixture of compounds according to claim 1 as a fragrance, in particular as an amber-like fragrance and / or for enhancing and / or modifying an amber-like and / or agarwood note of other fragrances and / or as a fixative, in particular for prolonging the adhesion of an amber-like and / or agarwood note of other fragrances.

3. Use of a compound according to claim 2, wherein compound (1) used to convey, enhance, modify and / or fix an amber and / or agarwood note.

4. Use of a compound according to claim 2, wherein compound (2) used to impart, enhance, modify and / or fix a woody, ambery, agarwood, peppery and / or green note.

5. Use of a compound according to claim 2, wherein compound (3) used to impart, enhance, modify and / or fix a woody, ambery, agarwood, peppery and / or green note.

6. A fragrance composition comprising or consisting of a compound or mixture of compounds as defined in claim 1, in particular comprising compound (1), compound (2) and / or compound (3), and one or more further fragrance(s).

7. A fragrance composition according to claim 6, comprising or consisting of compound (1), compound (2) and / or compound (3) and at least one amber or agarwood fragrance.

8. Fragrance composition according to claim 6 or 7, wherein the compounds (1), (2) and / or (3) each make up 0.001 to 10 wt.% of the fragrance composition, preferably 0.2 to 2 wt.%.

9. Fragrance composition according to one of claims 7 or 8, wherein the amber fragrance(s) and / or agarwood fragrance(s) is / are selected from the group consisting of the stereoisomeric 2,2,5,8,8,9a-hexamethyl-octahydro-4 / 7-4a,9-methanoazuleno[5,6-c / ][1,3]dioxole, 2,5,8,8,9a-pentamethyl-2-propyloctahydro-4 / 7-4a,9-methanoazuleno[5,6-cf][1,3]dioxole, 2,5,8,8,9a-pentamethyl-2-(prop-1-en-1-yl)octahydro-4H-4a,9-methanoazuleno[5,6-d][1,3]dioxole, 2-(Methoxymethyl)-2, 5,8,8, 9a-pentamethyloctahydro-4 / 7-4a,9-methanoazuleno[5,6-d][1,3]dioxole, 2,4-Dimethyl-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)-1,3-dioxolane, 2',2',3,7,7-Pentamethylspiro[bicyclo[4.1,0]heptane-2,5'-[1,3]dioxane], 2'-isopropyl-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane- 2,4'-[1 ,3]dioxane], 1-(2',2',6'-Trimethylcyclohexyl)hexan-3-ol, 2-Methyl-5-(5',5',6'- trimethylbicyclo[2.2.1 hept-2'-yl)cyclohexanon, Decahydro-2,2,6,6,7,8,8-heptame- thyl-2 / 7-indeno[4,5-b]furan,6,7-Dihydro-1 ,1 ,2,3,3-pentamethyl-4(5 / - / )-indanon, 1 a,3,3,4,6,6-Hexamethyl-1 a,2,3,4,5,6,7,7a-octahydronaphtho[2,3-b]oxirene, 7.7.8.9.9-Pentamethyl-4,4a,5,6,7,8,9,9b-octahydroindeno[4,5-cf][1 ,3]dioxin, 7.7.8.9.9-Pentamethyl-6,6a,7,8,9,9a-hexahydro-5 / 7-cyclopenta[h]quinazolin, 7.7.8.9.9-pentamethyl-6,7,8,9-tetrahydro-5 / 7-cyclopenta[h]quinazoline, 2, 6, 6, 7,8,8-hexamethyldecahydro-2 / 7-indeno[4,5-b]furan, 2,2,6,6,7,8,8-heptamethylde- cahydro-2 / 7-indeno[4,5-b]furan, 2,2,7,7,8,9,9-heptamethyldecahydroindeno[4,3a-b]furan, 7-methoxy-1,1,5,5-tetramethyl-1,3,4,5,6,7-hexahydro-2 / 7-2,4a-methonaphthalene, 5,5-Dimethyl-2-propylhexahydro-2 / 7-2,4a-methanonaphthalene-1 (5 / - / )-one, 2,2,9,11-Tetramethylspiro[5.5]undec-8-en-1-yl acetate, 3,8,8,11 a-Tetramethyldodecahydro-5H-3,5a-epoxynapht[2,1-C]oxepin, 3a,6,6,9a-Tetramethyl-1,2,3a,4,6,7,8,9,9a,9b-decahydronaphtho[2,1-b]furanes and 3a,6,6,9a-Tetramethyldodecahydronaphtho[2,1-b]furanes as well as the reaction products from the acid-catalyzed cyclization of 1-(1',6'-Dimethyl-4'-(4"-methylpent-3"-en-1"-yl)cyclohex-3'-en-1 '-yl)ethan-1-one.

10. A method for perfuming a product comprising the steps: (i) providing a compound or mixture of compounds according to claim 1 or a fragrance composition according to any one of claims 6 to 9, and (ii) adding the compound or mixture of compounds or the fragrance composition to the product to be perfumed, preferably in a sensorially effective amount, in particular in an amount sufficient to impart, enhance and / or modify an olfactory note.

11. The method according to claim 10, wherein in step (ii) compound (1) is added to the product to be perfumed in order to impart, enhance, modify and / or fix an amber-like and / or agarwood note and / or wherein compound (2) is added to the product to be perfumed in order to impart, enhance, modify and / or fix a woody, amber-like, agarwood, peppery and / or green note and / or wherein in step (ii) compound (3) is added to the product to be perfumed in order to impart, enhance, modify and / or fix a woody, amber-like, agarwood, peppery and / or green note.

12. A perfumed product comprising a compound or mixture of compounds according to claim 1 or a fragrance composition according to any one of claims 6 to 9.

13. Perfumed product according to claim 12, wherein the product is selected from the group consisting of detergents and cleaning agents, hygiene and care products, preferably in the field of body and hair care, cosmetics and household, preferably selected from the group consisting of perfume extracts, eau de parfums, eau de toilettes, aftershave lotions, eau de colognes, pre-shave products, perfumed wet wipes, acidic, alkaline or neutral detergents, textile fresheners, ironing aids, liquid detergents, powdered detergents, laundry treatment agents, fabric softeners, laundry soaps, detergent tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and varnishes, body care products, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, deodorants, antiperspirants, decorative cosmetic products,Candles, lamp oils, incense sticks, insecticides, repellents and propellants.

14. Perfumed product according to claim 12 or 13, wherein the total amount of the fragrance composition is in a range of 0.05 to 5 wt.%, preferably 0.5 to 2 wt.%, in each case based on the total weight of the product.

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