Novel performance and use thereof

Abstract

The present invention relates to novel 4-(3 ', 8', 8 '-trimethyl-2', 3 ', 4', 7 ', 8', 8a '-hexahydro-1H-3a', 7 '-methylazulen-6'-yl) butan-2-ones of formula (I), optionally substituted with methoxy groups at the C-1 and C-3 positions, as defined herein, and their use as ambergris-like fragrances. In particular, the present invention relates to the use of compounds (1), (2) and (3) as perfumes and as fixatives and their use in combination with other perfumes in perfume compositions. Furthermore, the invention relates to a method for perfuming a product with a compound according to the invention, and to a corresponding fragrance product.

Description

Technical Field

[0001] This invention relates to novel 4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1H-3a',7'-methacin-6'-yl)but-2-one of formula (I) as defined herein, optionally substituted with methoxy groups at the C-1 and C-3 positions, and its use as an ambergris-like fragrance. Specifically, this invention relates to the use of compounds (1), (2), and (3) as fragrances and as fixatives, and their use in combination with other fragrances in flavoring compositions. Furthermore, this invention relates to a method for flavoring a product with compounds according to the invention, and to a corresponding fragrance product. Background Technology

[0002] Ambergris, derived from the French word "ambre gris," was highly sought after by inhabitants of the Indian Ocean coast around 1000 BC due to its unusual scent, extreme rarity, and its perceived aphrodisiac properties, rivaling even gold (G. Ohloff, *Irdische Düfte - Himmlische Lust - EineKulturgeschichte der Duftstoffe*, Birkhäuser Verlag, Basel / Boston / Berlin, 1992, pp. 137-139). The first evidence of ambergris's use in perfumes comes from Ibn Chordadhbeh (*c. 820; †c. 912), a geographer and administrator from Djibar in western Persia. As early as the 9th century, Arab sailors brought ambergris from the Middle East and Far East, North Africa and India to Europe (G. Ohloff, *The Fragrance of Ambergris*, in E.T. 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 (Physetermacrocephalus L.). After mechanical damage to the digestive tract by sharp objects, the product forms a crust, which is then excreted in 15-150 kg lumps. Over the years, under the influence of sunlight and undergoing oxidative aging in the ocean, it develops a distinctive, exotic marine, dry woody-tobacco aroma with high substantiality and adhesiveness. This highly complex scent has the following characteristics: 1. Damp, moss-covered forest ground cover. 2. Dried tobacco leaves. 3. Balsam-cream sandalwood. 4. Warm-animal-scented alder. 5. Seaweed and seawater.6. Feces (G. Ohloff, "Chemie der Geruchs- und Geschmackstoffe", in A. Davison, MJSDewar, K. Hafner, E. Heilbronner, U. Hofmann, K. Niedenzu, K. Schäfer, G. Wittig (Hgg.), F. Boschke (Schriftl.), Fortschritte der chemischenForschung, Springer Verlag, Heidelberg, 1969, Vol. 12, No. 2, p. 185).

[0003]

[0004] This unique woody-dry, warm-balm-and-marine-tobacco-like ambergris character, with its creamy-animal notes and high originality, makes natural ambergris one of the most prized fragrances in the perfume industry. These characteristics are perfectly balanced in ambroxol (alternative trade names: Ambrox, Amboxan, Ambrofix, Ambermore, Cetalor), the natural olfactory source of ambergris, which exists as a trace component in ambergris at a concentration of <0.3%. Since the 1950s, ambroxol has been obtained semi-synthetically from sage alcohol, a component of sage, and can now also be obtained through biotechnology and cyclization via 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 can be explained by the content of (+)-epistosterol (20%-40%) and (-)-ambroxol (25%-45%), the latter of which also forms ambroxol in nature. If natural ambergris or (-)-ambroside isolated from it is still used today, and this is only the case in a very small number of niche fragrances, then this is solely due to the properties of these fixatives. Natural ambergris no longer plays a role in commercial fine fragrances due to its low content and also because of hygiene concerns and price, as consumers have become accustomed to much higher doses of ambergris from semi-synthetic sources. Consequently, ambroxol has now lost its exclusivity, which can also be seen in the price decline from over €1200 / kg in the 1980s to below €200 / kg in the 2020s.

[0005] However, in addition to the typical ambergris fragrance characteristics of ambergris ether, ketals have recently played an important role, possessing an ambergris-like character between ambergris and alder (the fungal-infected wood of species such as Aquilaria malaccensis, Aquilaria crassna, Aquilaria microcarpa, or Aquilaria filaria), namely a more metallic mineral flavor rather than a tobacco-balm-oceanic note, and most importantly, a drier woody character, and a strong animalic sweetness that is sometimes almost considered pungent rather than a mossy-warm scent. The first of these ambergris-like ketals is ambergris ketal, or Jeger ketal, named after its inventor, ETH Zurich professor Oskar Jeger, who discovered it in 1952 during his research on the degradation of manool from Halocarpus biformis (Hook.) Quinn. Some find it very strong, but it has an anosmia rate, so it is odorless to many others. Other ambergris-like ketals include Spirambren (1986) with an added spicy aldehyde note, carrageenan (1987) with a candle-waxy nuance and signs of hot tar, and octane (1992) and ambergris K (1993). Except for ambergris K as an ethylene glycol ketal, these highly substituted ketals are non-biodegradable, and carrageenan was even the first fragrance substance to be classified as a substance of extremely high concern (SVHC) by the European Chemicals Agency (ECHA) due to its high persistence and extremely high bioaccumulation (vPvB, item 57e). From 27 August 2023, carrageenan may no longer be permitted for use in the EU. Therefore, there is a great need for novel ambergris-like fragrances that do not have ketal functions but have ambergris-like aroma properties similar to these ambergris ketals in order to cater to the trend of these dry woody, mineral-metallic ambergris notes that have dominated the men's fragrance industry since "1 Million" (2008) and "Invictus" (2013).

[0006] This trend was sparked by highly potent ambergris compounds such as Imperial Ambergris (W. Pickenhagen, D. Schatkowski, for Dragoco, European Patent Application EP 857,723 A1, December 8, 1998), which is itself a ketal and non-biodegradable, yet so potent that its environmental impact is relatively small. Its success and its sustainable synthesis from cedrene have spurred a wave of new, high-strength ambergris compounds in the industry, such as Ambrostar (E. Dilk, M. Eh, H. Surburg, US 2012 / 0077722 A1, September 28, 2011), a more substantial and better-fixed 2-pentanone derivative of Imperial Ambergris, and Belambre from camphor (JA Bajgrowicz, EP761664 A1). These “high-impact” ambergris ketals reduce environmental exposure and, in the case of Ambrostar, they also improve the fixative properties of the applied form, but they are still ketals and have all their problematic properties, especially bioaccumulation. Summary of the Invention

[0007] Therefore, the object of the present invention is to provide a novel ambergris-like fragrance that has an ambergris-like odor and fixative properties and, in contrast to previous fragrances in this odor family, is not a ketal.

[0008] Surprisingly, there exists a narrow family of 2-butanones of general formula (I) with optional methoxy substitution at the C-1 or C-3 position.

[0009] (I),

[0010] Where X and Y = H or -OMe, and

[0011] When Y = -OMe, X = H, and

[0012] When X = -OMe, Y = H, or

[0013] X=Y=H,

[0014] It possesses the interesting and very typical ambergris-like odor of the aforementioned ambergris acetate and exhibits excellent fixative properties, yet it is not an acetate itself. The substituent at the C-4 position is derived from the renewable sesquiterpene cedrene.

[0015] Therefore, the problem defined above is solved by a compound or mixture of compounds of formula (I) containing all stereoisomers.

[0016]

[0017] (I),

[0018] Where X and Y = H or -OMe, and

[0019] If Y = -OMe, then X = H, and

[0020] If X = -OMe, then Y = H, or

[0021] X=Y=H.

[0022] The compounds of formula (I) are additional ambergris-like fragrances capable of immobilizing other fragrance notes, i.e., prolonging and adjusting their adhesiveness. Therefore, these compounds can be advantageously integrated into a range of fragrance blends and are suitable for a wide range of applications in various products. Furthermore, the compounds are more polar due to oxygen substituents, resulting in low bioaccumulation.

[0023] Furthermore, the present invention relates to the use of compounds or mixtures of compounds as defined above, the uses being: as fragrances, particularly as ambergris-like fragrances; and / or for enhancing and / or adjusting the ambergris-like and / or agarwood notes of other fragrances; and / or as fixatives, particularly for prolonging the adhesion of the ambergris-like and / or agarwood notes of other fragrances.

[0024] In the context of this invention, ambergris-like fragrances are fragrances whose aroma profile falls between that of ambergris and agarwood (fungi-infected wood of species such as Aquilaria malaccensis, Aquilaria crassna, Aquilaria microcarpa, or Aquilaria filaria). Compared to ambergris, they are more metallic and mineral in aroma rather than tobacco-like, balsam-marine, and most importantly, they have a drier, woody character, and they typically possess an almost pungent, strong animalic sweetness rather than a mossy, warm aroma.

[0025] In the context of this invention, fixatives should be understood as substances that can prolong the adhesion of the aroma notes of other fragrances, i.e., substances that can ensure a more lasting aroma in the product.

[0026] The present invention further relates to the use of compounds as described above, wherein compound (1)

[0027] (1)

[0029] Used to impart, enhance, adjust, and / or fix the ambergris and / or agarwood notes.

[0030] Compared to ambergris, agarwood notes are significantly more animalic and balsam-sweet in their woody character. Besides the strong, sometimes perceived pungent animalic sweetness, it is also characterized by complementary spicy and bitter notes.

[0031] The present invention also relates to the use of compounds as described above, wherein compound (2)

[0032] (2)

[0034] Used to impart, enhance, adjust, and / or fix woody, ambergris-like, agarwood, peppery, and / or green notes.

[0035] Furthermore, the present invention also relates to the use of compounds as described above, wherein compound (3)

[0036] (3)

[0038] Used to impart, enhance, adjust, and / or fix woody, ambergris-like, or agarwood, peppery, and / or green notes.

[0039] In addition to the common dry woody ambergris and agarwood-like main characteristics and fixative properties shared by all representative compounds, compounds (1)-(3) also impart, enhance, or adjust additional, distinct secondary notes. Compound (1) highlights a heavy sweetness, warm animalic notes, and tobacco-like flavor, thus harmonizing particularly well with the balsam-cream sandalwood flavor, while compound (2) is more musky and appears sexy and clean, highlighting a fresh citrus-lemon flavor, which is further enhanced by the green-mossy influence. On the other hand, compound (3) highlights a soft, warm-spicy flavor component with its clear incense and peppery characteristics, thus harmonizing particularly well with the acidic fruity flavor component.

[0040] According to another aspect, the present invention relates to a fragrance composition comprising or consisting of: compounds or mixtures of compounds as defined above, particularly comprising compounds (1), (2) and / or compounds (3); and one or more additional fragrances.

[0041] The spice composition according to the invention may contain any one of compounds (1) to (3), two of compounds (1) to (3), or a combination of all compounds (1) to (3).

[0042] As can be seen from the application examples below, the presence of compounds (1), (2), and / or (3) has a favorable effect on the fragrance composition. In particular, the combination with ambergris or agarwood fragrances has a favorable effect.

[0043] Therefore, specifically, the present invention relates to a fragrance composition as described above, the fragrance composition comprising or consisting of: compound (1), compound (2) and / or compound (3) and at least one ambergris or agarwood fragrance.

[0044] Particularly preferred is a combination of one of compounds (1), (2) or (3) with imperial ambergris and / or Ambrostar.

[0045] In a preferred embodiment of the flavoring composition as described above, compounds (1), (2) and / or (3) each account for 0.001% to 10% by weight, preferably 0.2% to 2% by weight of the flavoring composition.

[0046] Further preferred are the fragrance compositions as described above, wherein the ambergris fragrance and / or agarwood fragrance are selected from the group consisting of: stereoisomers 2,2,5,8,8,9a-hexamethyloctahydro-4H-4a,9-methyl-azo[5,6-d][1,3]m-dioxacyclopentene, 2,5,8,8,9a-pentamethyl-2-propyloctahydro-4H-4a,9-methyl-azo[5,6-d][1,3]m-dioxacyclopentene, 2,5,8,8,9a-pentamethyl-2-(prop-1-en-1-yl)octahydro-4H-4a,9-methyl-azo[5,6-d][1,3]m-dioxacyclopentene, 2-(methoxymethyl)-2,5, 8,8,9a-pentamethyloctahydro-4H-4a,9-methyl-bridged azuron[5,6-d][1,3]m-dioxacyclopentene, 2,4-dimethyl-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthyl-2-yl)-1,3-dioxacyclopentane, 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)hex-3-ol, 2-methyl-5-(5',5',6'-trimethylbicyclo[2 2.1 Hept-2'-yl)cyclohexanone, decahydro-2,2,6,6,7,8,8-heptamethyl-2H-indeno[4,5-b]furan, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indenophenone, 1a,3,3,4,6,6-hexamethyl-1a,2,3,4,5,6,7,7a-octahydronaphtho[2,3-b]epoxyethylene, 7,7,8,9,9-pentamethyl-4,4a,5,6,7,8,9,9b-octahydroindeno[4,5-d][1,3]dioxin, 7,7,8,9,9-pentamethyl-6,6a,7,8,9,9a-hexahydro-5H-cyclopento[h]quinazolin, 7,7, 8,9,9-pentamethyl-6,7,8,9-tetrahydro-5H-cyclopentano[h]quinazoline, 2,6,6,7,8,8-hexamethyldecahydro-2H-indo[4,5-b]furan, 2,2,6,6,7,8,8-heptamethyldecahydro-2H-indo[4,5-b]furan, 2,2,7,7,8,9,9-heptamethyldecahydroindo[4,3a-b]furan, 7-methoxy-1,1,5,5-tetramethyl-1,3,4,5,6,7-hexahydro-2H-2,4a-methylnaphthalene, 5,5-dimethyl-2-propylhexahydro-2H-2,4a-methylnaphthalene-1(5H)-one, 2,2,9,11-tetramethylspiro[5].5] The acid-catalyzed cyclization products of undecano-8-en-1-yl ester, 3,8,8,11a-tetramethyldodecano-5H-3,5a-epoxynaphthyl[2,1-C]oxaheptaene, 3a,6,6,9a-tetramethyl-1,2,3a,4,6,7,8,9,9a,9b-decahydronaphtho[2,1-b]furan, and 3a,6,6,9a-tetramethyldodecanonaphtho[2,1-b]furan, and 1-(1',6'-dimethyl-4'-(4''-methylpent-3''-en-1''-yl)cyclohex-3'-en-1'-yl)ethyl-1-one.

[0047] According to another aspect, the present invention also relates to a method for adding fragrance to a product, the method comprising the following steps:

[0048] (i) Provide a compound or mixture of compounds of formula (I) as defined above, or a flavoring composition as defined above; and

[0049] (ii) The compound or mixture of the compounds or the fragrance composition is preferably added to the product to be scented in a sensory-effective amount, particularly in an amount sufficient to impart, enhance and / or adjust olfactory characteristics.

[0050] "Sensory effective amount" is the amount of the compound, compound mixture, or fragrance composition in the flavored product that is perceptible to a consumer, compared to a product that does not contain the corresponding compound, compound mixture, or fragrance composition.

[0051] Preferred is the method as described above, wherein in step (ii), compound (1) is added to the product to be scented to impart, enhance, adjust and / or fix the ambergris and / or agarwood notes, and / or wherein compound (2) is added to the product to be scented to impart, enhance, adjust and / or fix the woody, ambergris, agarwood, pepper and / or green notes, and / or wherein in step (ii), compound (3) is added to the product to be scented to impart, enhance, adjust and / or fix the woody, ambergris, agarwood, pepper and / or green notes.

[0052] Furthermore, the present invention relates to a fragrance product comprising a compound or mixture of compounds as defined above or a fragrance composition as described above.

[0053] The flavored compositions according to the present invention are advantageously suitable for wide application in a wide variety of products.

[0054] Preferably, the fragrance product is selected from the group consisting of: detergents and cleaners, hygiene and care products, preferably in the fields of body and hair care, cosmetics and household use, and preferably selected from the group consisting of: pure fragrances, perfumes, eau de toilette, aftershave lotions, colognes, preshave products, scented wipes, acidic, alkaline or neutral detergents, textile fresheners, ironing aids, liquid detergents, powder detergents, laundry treatments, fabric softeners, laundry soaps, detergent pods, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and varnishes, body care products, hand creams and hand lotions, foot creams and foot lotions, hair removal creams and hair removal lotions, aftershave creams and aftershave lotions, tanning creams and tanning lotions, hair care products, deodorants, antiperspirants, decorative cosmetics, candles, lamp oil, incense sticks, insecticides, insect repellents and sprays.

[0055] Even a small amount of the fragrance composition according to the invention in the product is sufficient to ensure a pleasant and long-lasting aroma.

[0056] In a preferred embodiment of the product, the total amount of the flavoring composition is in the range of 0.05% by weight to 5% by weight, preferably 0.5% by weight to 2% by weight, in each case based on the total weight of the product. Detailed Implementation

[0057] The invention is described in more detail below with reference to some embodiments.

[0058] Example 1: Preparation of 1-methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1'H-3a',7'-methazon-6'-yl)but-2-one and 3-methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1'H-3a',7'-methazon-6'-yl)but-2-one by Claisen rearrangement

[0059] Synthesis of 1,2,2-trimethoxypropane

[0060] 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 loaded into a 1-liter three-necked flask equipped with a magnetic stirrer, thermometer, reflux condenser, and dropping funnel at room temperature. 150 g (1.70 mol) of 1-methoxypropyl-2-one was added dropwise over 30 minutes while the temperature was raised to 50 °C. The reaction mixture was then heated under reflux for 5 h (52 °C). Heating was removed, and 3.50 g (33.7 mmol) of sodium carbonate was added to the mixture at room temperature. The mixture was then fractionally distilled under vacuum on a 30 cm packed column with a Raschig ring and column head. Yield: 204 g (89%) of 1,2,2-trimethoxypropane as a colorless, transparent liquid (GC purity: 96%).

[0061] GC-IR (GC purity 96%): ν = 2994 / 2945 / 2838 (m), 1464 (w), 1381 (w), 1255(w), 1136 (s), 1066 (m), 850 (w).

[0062] 1 H-NMR (400 MHz, CDCl 3) : δ = 3.41 (s, 6 H, 2-MeO2), 3.37 (s, 3 H, 1-MeO), 3.23 (s, 1-H2), 1.35 (s, 3 H, 3-H (3) ppm.

[0063] 13 C-NMR (101 MHz, CDCl 3) : δ = 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.

[0064] 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).

[0065] Eliminate the methoxy group of the corresponding enol ether

[0066] 82.0 g (0.61 mol) of 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 introduced into a 250 ml distillation apparatus equipped with a thermometer, magnetic stirrer, column (10 cm Raschig ring), and column head, and heated at atmospheric pressure. The mixture began to boil at 119 °C. 43.7 g of distillate (GC purity: 88%. Composition: 41% (E)-1,2-dimethoxyprop-1-ene, 17% (Z)-1,2-dimethoxyprop-1-ene, 30% 2,3-dimethoxyprop-1-ene) was obtained at a reflux ratio of R:D = 25:1, a bottom temperature of 120–150 °C, and a top temperature of 104–108 °C.

[0067] GC-IR (GC purity 88%): ν = 2998 / 2941 / 2839 (m), 1668 (w), 1625 (w), 1460 (w), 1220 (s), 1136 (s), 1082 (m).

[0068] (E)-1,2-Dimethoxypropyl-1-ene:

[0069] 1 H-NMR (400 MHz, C (6) D6 ): δ = 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).

[0070] 13 C-NMR (101 MHz, C (6) D6 ) δ = 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).

[0071] GC-MS (70eV): m / z (%) = 27 (8), 39 (9), 43 (48), 59 (100), 87 (84), 102 (90), 103 (5).

[0072] (Z)-1,2-Dimethoxypropyl-1-ene:

[0073] 1 H-NMR (400 MHz, C(6) D6 ): δ = 1.52 (d, J = 1.0 Hz, 3 H 3-H 3) , 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).

[0074] 13 C-NMR (101 MHz, C (6) D6 ) δ = 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).

[0075] GC-MS (70eV): m / z (%) = 29 (32), 43 (53), 59 (99), 87 (95), 102(100), 103 (5).

[0076] 2,3-Dimethoxyprop-1-ene:

[0077] 1 H-NMR (400 MHz, C (6) D6 ): δ = 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-H b ), 4.26(dt, J = 2.0, 1.0 Hz, 1 H, 1-H a ).

[0078] 13 C-NMR (101 MHz, C (6) D6 ) δ = 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).

[0079] GC-MS (70eV): m / z (%) = 29 (19), 42 (38), 45 (38), 59 (13), 72 (100),102 (9).

[0080] Preparation of 5-((1',2'-dimethoxypropyl-2'-yl)oxy)-3,8,8-trimethyl-6-methyleneoctahydro-1H-3a,7-methylazine

[0081] 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-1H-3a,7-methylbenzyl-5-ol, 8.00 g (78.4 mmol) of a mixture of 65% (E / Z)-1,2-dimethoxyprop-1-ene and 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. Heating was then removed, and the mixture was diluted with 20 ml of methyl tert-butyl ether at room temperature while stirring. It was washed twice, each time with 20 ml of 5% alkali solution, and then concentrated. The residue was mixed with 10 ml of hexane under heating and then allowed to crystallize at 5°C for 3 h. The residue was filtered off and the mother liquor was concentrated to obtain 2.00 g of crude product (GC purity: 48%, crude yield: 33%). Column chromatography was then performed (Büchi PrepChrom C-700, 80 g silica gel 60, eluent: running solvent hexane / acetate = 99:1 → 95:5, 71 min, at 20 ml / min per fraction, DC:R). f After obtaining 640 mg (22%) of the title compound (GC purity: 99%), the ratio was 0.44 (SiO260, hexane / acetate = 10:1).

[0082] First elution fraction: GC-IR (GC 34%, Thermo Nicolet 6700): ν̃ = 2949 (s) 1643 (w), 1463 (w), 1384 (w), 1131 (m), 1050 (m).

[0083] 1 H-NMR (400 MHz, CDCl 3) δ = 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'-H b ), 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, 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-H b ), 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 H, H b C=C-6', exomethylene), 5.04 (t, J = 2.5 Hz, 1 H, H a C=C-6', exomethylene).

[0084] 13 C-NMR (101 MHz, CDCl 3) δ = 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, 作“3-MeO”理解), 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').

[0085] 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).

[0086] Note: In the translation of chemical-related content, some terms may need to be adjusted according to common chemical expressions and the context. Here, "3-MeO" is tentatively translated as "3 - 甲氧基" for better understanding, but it should be adjusted according to the actual chemical structure. Also, "exomethylene" is translated as "外亚甲基", which is a relatively specialized term in organic chemistry. If there are more specific requirements or corrections, please feel free to let me know.The last eluted fraction: GC-IR (GC 65%, Thermo Nicolet 6700): ν̃ = 2949 (s), 1644 (w), 1463 (w), 1384 (w), 1131 (m), 1050 (m).

[0087] 1 H NMR (400 MHz, CDCl 3) δ = 0.86 (m, 3H, 3'-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 '-H b ), 1.51 - 1.64 (m, 1H, 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, 1H 1-H a ), 4.46 - 4.61 (m, 1 H, 5'-H), 4.68 - 4.77 (m, 1 H, H b C=C-6'), 4.95 (t, J = 2.5 Hz, 1 H, H a (C=C-6').

[0088] 13 C-NMR (101 MHz, CDCl 3)δ = 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').

[0089] m / z (%) = 41 (22), 55 (9), 71 (52), 95 (23), 103 (100), 119 (29), 133(18), 147 (28), 203 (48), 220 (4), 290 (1).

[0090] 3-Methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1H-3a',7'-methazon-6'-yl)but-2-one and 1-methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1H-3a',7'-methazon-6'-yl)but-2-one were prepared by Claysen rearrangement.

[0091] 1.50 g (4.66 mmol) of 5-((1',2'-dimethoxypropyl-2'-yl)oxy)-3,8,8-trimethyl-6-methyleneoctahydro-1H-3a,7-methylazine was heated for 4 h at 160 °C and 100 mbar on a bulb distillation apparatus (Büchi glass oven B-585), after which the heating was removed. The residue contained 1.09 g of crude product (GC purity: 78%). Column chromatography was performed (Büchi PrepChrom C-700, 80 g silica gel 60, eluent: solvent hexane / acetate = 98:2 → 92:8, 71 min, at 20 ml / min per fraction, DC:R) fAfter adjusting the concentrations of 0.33 and 0.25 (SiO260, hexane / acetate = 10:1), 38.0 mg of 3-methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1H-3a',7'-methylazin-6'-yl)but-2-one (GC purity: 94%) and 513 mg of 1-methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1H-3a',7'-methylazin-6'-yl)but-2-one (GC purity: 94%) were obtained.

[0092] 3-Methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a')-hexahydro-1H-3a',7'-methylazine-6'-yl)but-2-one (a 1:1 mixture of two diastereomers, [compound (1)])

[0093] GC-IR (GC purity 94%, Thermo Nicolet 6700): ν = 2949 / 2901 / 2835 (s), 1729(w), 1468 (w), 1358 (w), 1109 (m).

[0094] 1 H-NMR (400 MHz, CDCl 3) : δ = 0.83 / 0.84 (d, J = 7.0 Hz, 6 H, 3'-Me2), 0.96 / 1.01 (2s, 12 H, 8'-Me4), 1.28 - 1.45 m, 6 H, (1'-H b , 2'-H b , 9'-H b) 2 ),1.53 - 1.63 (m, 2 H, (1'-H a) 2 ), 1.64 - 1.80 (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-H 3) 2 ), 2.15 - 2.38 (m, 6 H, (4-H 2) 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).

[0095] 13 C-NMR (100 MHz, CDCl 3) : δ = 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'=CH 2) , 139.2 / 139.4 (2s, C-6'), 210.8 / 211.7 (2s, C-2).

[0096] MS (EI): m / z (%): 43 (33), 55 (16), 69 (21), 79 (18), 91 (42), 105(33), 119 (33), 131 (24), 147 (26), 159 (32), 173 (15), 187 (7), 203(8), 215(100), 247(68), 258(68), 275(1), 290(1).

[0097] Scent description: Ambergris-like and dry woody-amber scent with an animalic note tending toward agarwood and cashmere (1,1,2,3,3-pentamethyl-1,2,3,5,6,7-hexahydro-4H-indanone).

[0098] 1-Methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1H-3a',7'-methylazine-6'-yl)but-2-one [Compound (2)]

[0099] GC-IR (GC purity 94%, Thermo Nicolet 6700): ν = 2948 (s), 1732 (w), 1464 (w), 1110 (w).

[0100] 1 H-NMR (600 MHz, CDCl 3) : δ = 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'-H b ), 1.65 - 1.71 (m, 2 H, 8 (a) ' -H, 9'-H b ), 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'-H b , 4-H a ),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).

[0101] 13 C-NMR (151 MHz, CDCl 3): δ = 15.4 (q, 3'-Me), 24.8 (t, C-1'), 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).

[0102] MS (EI): 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).

[0103] Scent description: Dry woody notes - amber, with an ambergris-like quality reminiscent of imperial ambergris (2,2,5,8,8,9a-hexamethyloctahydro-4H-4a,9-methyl-azuro[5,6-d][1,3]-dioxane), with a peppery note, reminiscent of the influence of sedge acetone ((3S,5R,8S)-3,4,5,6,7,8-hexahydro-3α,8α-dimethyl-5α-(1-methylvinyl)azuro-1(2H)-one) and subtle green notes.

[0104] Example 2: Preparation of 4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1'H-3a',7'-methylazine-6'-yl)but-2-one by Claysen rearrangement

[0105] Synthesis of 2-ethoxyprop-1-ene

[0106] In a 250-ml distillation apparatus equipped with a thermometer, magnetic stirrer, column (10 cm, Raschig ring), 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 at atmospheric pressure, and the reaction mixture began to boil at 107 °C. 91.0 g (76%) of the title compound (GC purity: 55%) was separated by distillation at a reflux ratio of R:D = 10:1, a bottom temperature of 107–122 °C, and a top temperature of 72–92 °C.

[0107] GC-IR (Thermo Nicolet 6700): ν = 3121 / 2990 / 2941 (m), 1657 (m), 1599(w), 1449 / 1376 (m), 1283 / 1277 (s), 1098 / 1085 (s), 798 (m).

[0108] 1 H-NMR (400 MHz, C (6) D6 ) δ = 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,1H, 3-H b ), 3.89 (dq, J = 2.0, 1.0 Hz, 1H, 3-H a ).

[0109] 13 C-NMR (101 MHz, C (6) D6 ) δ = 14.6 (q, C-2'), 21.2 (q, C-3), 62.7 (t, C-1'), 81.3 (t, C-1), 160.1 (s, C-2).

[0110] GC-MS (70eV): m / z (%) = 29 (32), 39 (20), 43 (100), 58 (89), 86 (94).

[0111] 5-((2'-ethoxypropyl-2'-yl)oxy)-3,8,8-trimethyl-6-methyleneoctahydro-1H-3a,7-methylazine

[0112] In a 10-ml one-necked flask equipped with a magnetic stirrer, thermometer, and reflux condenser, 1.00 g (4.55 mmol) of 3,8,8-trimethyl-6-methyleneoctahydro-1H-3a,7-methylbenzyl-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 under a nitrogen atmosphere. The heater was removed, and the mixture was diluted with 50 ml of methyl tert-butyl ether with stirring at room temperature, washed once with 20 ml of 5% sodium carbonate solution, and then concentrated to dryness on a rotary evaporator to separate 1.10 g (79%) of the product (GC purity: 80%).

[0113] GC-IR (Thermo Nicolet 6700): ν = 2949 / 2919 / 2882 (s), 1645 (w), 1464(w), 1384 (w), 1278 (w), 1204 (w), 1164 (w), 1050 (m).

[0114] 1 H-NMR (400 MHz, C (6) D6 ): δ = 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-H b ), 1.32 - 1.39 (m, 2 H, 1-H b, 9-H b ), 1.41 / 1.45 (2s, 6 H, 1'-H3, 3'-H3), 1.46 - 1.53 (m, 2 H, 1-H a , 4-H b ), 1.57 - 1.67 (m, 1 H, 3-H), 1.65 - 1.74 (m, 1H, 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''-H b ), 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).

[0115] 13 C-NMR (101 MHz, C (6) D6 ): δ = 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).

[0116] 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).

[0117] 4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1'H-3a',7'-methylazine-6'-yl)but-2-one [compound (3)]

[0118] 1.10 g (2.88 mmol) of 5-((2-ethoxypropyl-2-yl)oxy)-3,8,8-trimethyl-6-methyleneoctahydro-1H-3a,7-methylazine (GC purity 80%) was heated at 160 °C and 100 mbar for 4 h on a bulb distillation apparatus (Büchi glass oven B-585). The heater was removed and the product was allowed to cool to room temperature, retaining 800 mg of crude product (GC purity 33%, crude yield 35%) in the residue. Column chromatography was performed (Büchi PrepChrom C-700, 80 g silica gel 60, eluent: running solvent hexane / acetate = 97:3 → 92:8, 71 min, at 20 ml / min per fraction, DC:R) f After obtaining 240 mg (32%) of the title compound (GC purity 99%), the compound was obtained by using 0.20 (SiO260, hexane / acetate = 20:1).

[0119] Scent description: Dry pepper, woody ambergris-like, with distinct cedarwood and black pepper notes, and a tangy apple note in the initial scent.

[0120] GC-IR (Thermo Nicolet 6700): ν = 2950 / 2908 / 2838 (s), 1732 (m), 1467(w), 1363 (w), 1273 (w), 1221 (w), 1157 (w).

[0121] 1 H NMR (600 MHz, CDCl 3) : δ = 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'-H a ), 1.68 (ddd, J = 11.0, 4.5, 1.5 Hz, 2 H, 8a'-H, 9'-H a ), 1.71 -1.78 (m, 1 H, 3'-H), 1.78 - 1.84 (m, 2 H, 4a'-H b , 7'-H), 1.84 - 1.90 (m, 1 H,2'-H a ), 2.10 - 2.21 (m, 5 H, 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, 1 H, 3-H b ), 2.57 (ddd, J = 16.5, 10.0, 5.5Hz, 1H, 3-H a ), 5.18 (dt, J = 4.0, 2.0 Hz, 1 H, 5'-H). 13 C NMR (151 MHz, CDCl 3) δ = 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).

[0122] 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).

[0123] Example 3: Application of the compound in a multifaceted dried woody ambergris composition with a fresh citrus contrast.

[0124] Fragrance composition 3.1

[0125]

[0126]

[0127] Compound (2) imparts more properties, character, and typical features to the composition through a heavy woody ambergris-like contrast. It introduces amber dynamics, thereby enhancing the woody base characteristics of the fragrance. In addition, compound (2) harmonizes with and adds brilliance to the fresh citrus top notes. Compound (2) also makes the overall fragrance long-lasting and well-fixed.

[0128] Fragrance composition 3.2

[0129]

[0130]

[0131] Compound (1) makes the overall olfactory impression stronger and longer-lasting. In addition, compound (1) gives the composition an unambiguous masculine character and harmonizes very well with the sweet and powdery aspects of the fragrance, thus highlighting them.

[0132] Fragrance composition 3.3

[0133]

[0134]

[0135] Compound (3) brings an interesting new aspect to the spice composition: it makes the overall composition more complex, stronger, longer-lasting, and more modern. The spice smells warmer and softer amber. The citrus notes are now more multifaceted and pronounced. In addition, compound (3) improves the composition, giving it a fresh peppery aspect and even luxurious smoky notes.

[0136] Fragrance composition 3.4

[0137]

[0138]

[0139] The combination of compound (2) with Imperial Ambergris® creates a clean musky note with a warm amber base.

[0140] Fragrance composition 3.5:

[0141]

[0142]

[0143]

[0144] The combination of compound (1) with Ambergris® enhances the stimulating notes of Ambergris® and makes the amber complex appear softer and more pleasing to the senses.

[0145] Fragrance composition 3.6

[0146]

[0147]

[0148]

[0149] In the combination of compound (3) and Imperial Ambergris®, the composition appears more authentic, noble and pleasing to the senses, as the combined effect creates a warm, inviting peppery, incense and agarwood note.

Claims

1. A compound or mixture of compounds of formula (I) comprising all stereoisomers. （I）， Where X and Y = H or -OMe, and When Y = -OMe, X = H, and When X = -OMe, Y = H, or X=Y=H.

2. Use of the compound or compound mixture according to claim 1, wherein the use is as: as a fragrance, particularly as an ambergris-like fragrance; and / or for enhancing and / or adjusting the ambergris-like and / or agarwood notes of other fragrances; and / or as a fixative, particularly for prolonging the adhesion of the ambergris-like and / or agarwood notes of other fragrances.

3. Use of the compound according to claim 2, wherein compound (1) （1） Used to impart, enhance, adjust, and / or fix the ambergris and / or agarwood notes.

4. Use of the compound according to claim 2, wherein compound (2) （2） Used to impart, enhance, adjust, and / or fix woody, ambergris-like, agarwood, peppery, and / or green notes.

5. Use of the compound according to claim 2, wherein compound (3) （3） Used to impart, enhance, adjust, and / or fix woody, ambergris-like, agarwood, peppery, and / or green notes.

6. A flavoring composition comprising or consisting of the following: The compound or mixture of compounds as defined in claim 1 particularly comprises compound (1), compound (2) and / or compound (3); and one or more additional flavorings.

7. The flavoring composition according to claim 6, wherein the flavoring composition comprises or is composed of the following: Compound (1), compound (2) and / or compound (3) and at least one ambergris or agarwood fragrance.

8. The fragrance composition according to claim 6 or 7, wherein each of compounds (1), (2) and / or (3) comprises 0.001% to 10% by weight, preferably 0.2% to 2% by weight, of the fragrance composition.

9. The fragrance composition according to any one of claims 7 or 8, wherein the ambergris fragrance and / or agarwood fragrance is selected from the group consisting of: stereoisomers 2,2,5,8,8,9a-hexamethyloctahydro-4H-4a,9-methyl-azo[5,6-d][1,3]m-dioxacyclopentene, 2,5,8,8,9a-pentamethyl-2-propyloctahydro-4H-4a,9-methyl-azo[5,6-d][1,3]m-dioxacyclopentene, 2,5,8,8,9a-pentamethyl-2-(prop-1-en-1-yl)octahydro-4H-4a,9-methyl-azo[5,6-d][1,3]m-dioxacyclopentene, 2-(methoxymethyl)- 2,5,8,8,9a-pentamethyloctahydro-4H-4a,9-methyl-azo[5,6-d][1,3]m-dioxacyclopentene, 2,4-dimethyl-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthyl-2-yl)-1,3-dioxacyclopentane, 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)hex-3-ol, 2-methyl-5-(5',5',6'-trimethylbis) Cyclo[2.2.1-hepta-2'-yl]cyclohexanone, decahydro-2,2,6,6,7,8,8-heptamethyl-2H-indeno[4,5-b]furan, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indenophenone, 1a,3,3,4,6,6-hexamethyl-1a,2,3,4,5,6,7,7a-octahydronaphtho[2,3-b]epoxyethylene, 7,7,8,9,9-pentamethyl-4,4a,5,6,7,8,9,9b-octahydroindeno[4,5-d][1,3]dioxin, 7,7,8,9,9-pentamethyl-6,6a,7,8,9,9a-hexahydro-5H-cyclopenta[h]quinazolin, 7, 7,8,9,9-Pentamethyl-6,7,8,9-Tetrahydro-5H-cyclopentano[h]quinazoline, 2,6,6,7,8,8-Hexamethyldecahydro-2H-indeno[4,5-b]furan, 2,2,6,6,7,8,8-Heptamethyldecahydro-2H-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-2H-2,4a-methylnaphthalene, 5,5-Dimethyl-2-propylhexahydro-2H-2,4a-methylnaphthalene-1(5H)-one, 2,2,9,11-Tetramethylspiro[5].5] The acid-catalyzed cyclization products of undecano-8-en-1-yl ester, 3,8,8,11a-tetramethyldodecano-5H-3,5a-epoxynaphthyl[2,1-C]oxaheptaene, 3a,6,6,9a-tetramethyl-1,2,3a,4,6,7,8,9,9a,9b-decahydronaphtho[2,1-b]furan, and 3a,6,6,9a-tetramethyldodecanonaphtho[2,1-b]furan, and 1-(1',6'-dimethyl-4'-(4''-methylpent-3''-en-1''-yl)cyclohex-3'-en-1'-yl)ethyl-1-one.

10. A method for adding fragrance to a product, the method comprising the following steps: (i) Providing a compound or mixture of compounds according to claim 1 or a flavoring composition according to any one of claims 6 to 9; and (ii) The compound or mixture of the compounds or the fragrance composition is preferably added to the product to be scented in a sensory-effective amount, particularly in an amount sufficient to impart, enhance and / or adjust olfactory characteristics.

11. The method according to claim 10, wherein in step (ii), compound (1) is added to the product to be scented in order to impart, enhance, adjust and / or fix the ambergris-like and / or agarwood notes, and / or wherein compound (2) is added to the product to be scented in order to impart, enhance, adjust and / or fix the woody, ambergris-like, agarwood, peppery and / or green notes, and / or wherein in step (ii), compound (3) is added to the product to be scented in order to impart, enhance, adjust and / or fix the woody, ambergris-like, agarwood, peppery and / or green notes.

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

13. The fragrance product according to claim 12, wherein the product is selected from the group consisting of: preferably detergents and cleaners, hygiene and care products in the fields of body and hair care, cosmetics and household use, preferably selected from the group consisting of: pure fragrances, perfumes, eau de toilette, aftershave lotions, colognes, preshave products, scented wipes, acidic, alkaline or neutral detergents, textile fresheners, ironing aids, liquid detergents, powder detergents, laundry treatment products, fabric softeners, laundry soaps, laundry pods, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and varnishes, body care products, hand creams and hand lotions, foot creams and foot lotions, hair removal creams and hair removal lotions, aftershave creams and aftershave lotions, tanning creams and tanning lotions, hair care products, deodorants, antiperspirants, decorative cosmetics, candles, lamp oil, incense sticks, insecticides, insect repellents and sprays.

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

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