New fragrance substances and their uses

Abstract

The present invention relates to novel 4-(3',8',8'-trimethyl-2', 3',4',7',8',8a'-hexahydro-1H-3a',7'-methanoazulen-6'-yl)butan-2-ones of formula (I), optionally substituted with a methoxy at positions C-1 and C-3, as defined herein, and their use as amber-scented fragrance substances. In particular, the present invention relates to the use of compounds (1), (2), and (3) as fragrance substances and fixatives, as well as their incorporation into fragrance compositions in combination with other fragrance substances. Furthermore, the present invention relates to a method for perfuming a product with the compounds according to the invention and a corresponding fragranced product.

Description

Title of the invention: New perfume substances and their uses

[0001] The present invention relates to novel 4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-l / / -3a',7'-methanoazulen-6'-yl)butan-2-ones of formula (I), optionally substituted with a methoxy at positions C1 and C3, as defined herein, and their use as amber-scented fragrance substances. In particular, the present invention relates to the use of compounds (1), (2), and (3) as fragrance substances and as fixatives, as well as their implementation in fragrance compositions in combination with other fragrance substances. Furthermore, the present invention relates to a method for perfuming a product with the compounds according to the invention and a corresponding fragranced product.

[0002] “Ambergris” was already highly sought after around a thousand years before Christ among The inhabitants of the Indian Ocean coast prized amber for its extraordinary scent, its great rarity, and its supposedly aphrodisiac properties, and it was traded for its weight in gold (G. Ohloff, Irdische Düfte - Himmlische Lust - Eine Kulturgeschichte der Duftstoffe, Birkhâuser Verlag, Basel / Boston / Berlin, 1992, pp. 137-139). The earliest evidence of amber's use in perfumery comes from Ibn Chordadhbeh (* c. 820; d. c. 912), a geographer and administrator of the Jibal Province in western Persia. From the ninth century onwards, Arab sailors brought amber from the Near and Far East, from 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, Academy Press, Orlando, 1982, pp. 535-573). The waxy substance, ranging in color from light to dark gray, is a product of the pathological metabolism of the sperm whale (Physeter macrocephalus L.).This substance forms after mechanical injury to the digestive tract from sharp objects, resembling a crust, and is subsequently detached in blocks weighing 15 to 150 kg. Through oxidative aging processes in the sea under the influence of sunlight, a characteristic marine and exotic odor develops over the years, reminiscent of dry wood and tobacco, with a high persistence and strong affinity. This highly complex odor exhibits aspects of: 1. damp forest soils and moss. 2. dry tobacco leaves. 3. velvety and balsamic sandalwood. 4. warm and animal aloe wood. 5. kelp and sea water. 6. faeces (G. Ohloff, 'Chemie der Geruchs- und Geschmackstoffe', in A. Davison, MJS Dewar, K. Hafner, E. Heilbronner, U. Hofmann, K. Niedenzu, K. Schâfer, G. Wittig (ed.), F. Boschke (author), Fortschritte der chemischen Forschung, Springer Verlag, Heidelberg, 1969, vol. 12 notebook 2, p. . Ambraxjd Amberketal Sp^rambren Karanai Okoumai Ysamber K

[0003] This specific amber profile of dry, warm and balsamic wood, tobacco and marine with a velvety animal tone and great originality which has made natural amber the most expensive perfume substance in perfumery, is found in perfect balance in ambroxide (alternative trade names: Ambrox, Amboxan, Ambrofix, Ambermore, Cétalor), the natural odoriferous active principle of ambergris, in which it is present only at < 0.3% as a trace element. Ambroxide has been available semi-synthetically since the 1950s from sclareol, an ingredient of clary sage, and since then also through biotechnology and by 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 exceptional fixing properties of natural amber are explained by its content of (+)-epicoprosterine (20-40%) and (-)-ambrein (25-45%), ambroxide also forming from the latter in its natural state. If natural amber or (-)-ambrein isolated from it is still used today, And this is only the case in a very small number of niche perfumes, where it's used solely for its fixing properties. Due to the low content of natural ambroxide, as well as hygiene concerns and price, natural amber no longer plays a role in commercial fine perfumery, since consumers are accustomed to much higher concentrations of ambroxide from semi-synthetic sources. Ambroxide has therefore lost its exclusive character, which is also reflected in the price drop from over €1200 / kg in the 1980s to less than €200 / kg today in the 2020s.

[0004] In addition to the typical amber olfactory profile of ambroxide, ketals with amber notes tending towards an amber and aloe wood scent (wood infested with fungi of the species Aquilaria malaccensis, Aquilaria crassna, Aquilaria microcarpa, or Aquilaria filaria), therefore more metallic and mineral than marine and balsamic like tobacco, and above all much drier in its woody character and with a lively animal sweetness sometimes perceived as almost heady rather than warm and mossy, have played a significant role recently. The first of these amber ketals was ambracetal, or Jeger's ketal, named after its inventor, Professor Oskar Jeger, who discovered it in 1952 during studies on the degradation of manool from Halocarpus biformis (Hook.) Quinn. While some people find it very intense, it nevertheless has a high concentration of anosmia, and is therefore odorless to many others.Other amber ketals include spirambrene (1986) with additional spicy aldehyde-like accents, karanal (1987) with candle wax nuances and hot tar notes, as well as okoumal (1982) and ysambre K (1993). With the exception of ysambre K as an ethylene glycol ketal, these highly substituted ketals are not biodegradable, and karanal was even the first fragrance substance to be classified as a Substance of Very High Concern (SVHC) by the ECHA (European Chemicals Agency) due to its high persistence and very high bioaccumulation (vPvB, Article 57e). Since August 27, 2023, karanal has been banned from use in the EU.There is therefore a great need for new amber perfume substances without ketal function but with amber odorant properties similar to these amber ketals to accompany the trend towards these mineral and metallic dry wood amber notes that has dominated men's perfumery since "1 Million" (2008) and "Invictus" (2013).

[0005] This trend was initiated by very potent amber compounds such as ambrocenide (W. Pickenhagen, D. Schatkowski, for Dragoco, Eur. Pat. Appl. EP 857,723 A1, 12 / 08 / 1998), which is itself a ketal and not biodegradable, but is so intense that its environmental impact is relatively low. Its success and subsequent synthesis from cedar led to a wave in industry New, highly intense amber ketals, such as ambrostar (E. Dilk, M. Eh, H. Surburg, US 2012 / 0077722 Al, 28 / 09 / 2011), the 2-pentanone derivative of ambrocenide which has greater body and is more binding, and belambre from camphor (JA Bajgrowicz, EP761664 Al), have been developed. These "high-impact" amber ketals have reduced environmental exposure and, in the case of ambrostar, have also provided improved binding properties in application forms. However, like previous ketals, they retain all their problematic properties, particularly bioaccumulation.

[0006] A problem to be solved by the compound of the present invention was therefore to prepare new amber perfume substances which have an amber scent as well as fixative properties and, unlike current perfume substances of this scent family, are not ketals.

[0007] Consequently, a clearly defined family of 2-butanonenes, possibly substituted by a methoxy in Cl or C-3, of general formula (I), was discovered to surprise. (I), XGX ...... \

[0008] in which X and Y = H or -OMe, and

[0009] X = H when Y = -OMe, and

[0010] Y = H when X = -OMe, or

[0011] X = Y = H,

[0012] which possess the very typical and interesting amber scents of the ambracetals mentioned above without themselves being ketals. The substituent at position C-4 is derived from the sesquiterpene of renewable cedar.

[0013] The problem to be solved defined above is therefore solved by a compound or a mixture of compounds of formula (I) including all of its stereoisomers, (I), s X p

[0014] in which X and Y = H or -OMe, and

[0015] X = H when Y = -OMe, and

[0016] Y = H when X = -OMe, or

[0017] X = Y = H.

[0018] The compounds of formula (I) are amber-colored fragrance substances that are also capable of fixing amber notes from other fragrance substances, that is, of prolonging and modifying their longevity. The compounds are therefore advantageously integrated into a range of fragrance mixtures and are suitable for a wide variety of applications in different products. Furthermore, the compounds are more polar due to oxygen substituents, resulting in low bioaccumulation.

[0019] Furthermore, the present invention relates to the use of a compound or mixture of compounds as defined above as a perfumer, in particular as an amber perfumer and / or to accentuate and / or modify an amber note and / or aloe wood of other perfumers and / or as a fixative, in particular to prolong the longevity of an amber note and / or aloe wood of other perfumers.

[0020] In the context of the present invention, amber-scented perfume substances are perfume substances that tend towards an odor of amber and aloe wood (wood infested with fungi of the species Aquilaria malaccensis, Aquilaria crassna, Aquilaria microcarpa, or Aquilaria filaria). Compared to amber, they have a woody character that is more metallic and mineral than marine, tobacco, and balsamic, and above all, much drier and frequently have a lively, sweet, animal character perceived almost as heady rather than a warm, mossy scent at first.

[0021] In the context of the present invention, a fixative is understood to mean a substance that is able to prolong the life of the odor notes of other perfume substances, that is to say, to guarantee a scent that lasts longer in a product.

[0022] The present invention further relates to the use of a compound as described above, compound (1) (1),

[0023] being used to induce, accentuate, modify and / or fix an amber and / or aloe wood note.

[0024] An aloe wood note is, compared to an amber note, distinctly more animalic, sweet, and balsamic in its woody character. In addition to the lively animalic sweetness sometimes perceived as overpowering, it is characterized by complementary spicy and more bitter facets.

[0025] The present invention also relates to the use of a compound as described below. above, compound (2) (2), O

[0026] being used to induce, accentuate, modify and / or fix a woody, amber, aloe wood, peppery and / or green note.

[0027] Furthermore, the present invention also relates to the use of a compound as described above, compound (3) (3),

[0028] being used to induce, accentuate, modify and / or fix a woody, amber or aloe wood, peppery and / or green note.

[0029] In addition to the main character of dry, ambery, aloe-like wood and the fixing properties, which are common to all representatives, compounds (1) to (3) induce, accentuate, or modify further different secondary notes. Compound (1) emphasizes the dark, sweet, warm, animalic, and tobacco-like accents, such that it harmonizes particularly well with the velvety and balsamic fragrance substances of sandalwood, while compound (2) has more of a musky vibration, giving an erogenous and clean effect, thereby highlighting the fresh notes of lemon and citrus, further reinforced by the green and mossy touch. Compound (3), again, emphasizes the warm, sweet, and spicy fragrance components with its transparent pepper and incense character and harmonizes particularly well with slightly acidic, fruity fragrance components.

[0030] According to another aspect, the present invention relates to a perfume composition comprising or consisting of a compound or a mixture of compounds such as defined above, in particular including compound (1), compound (2) and / or compound (3) and one or more other perfumer substances.

[0031] A perfume composition according to the invention may contain each 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.

[0032] The presence of compounds (1), (2) and / or (3) proves advantageous in fragrance compositions, as the application examples below will show. In particular, the combination with amber or aloe wood fragrance substances provides beneficial effects.

[0033] In particular, the present invention therefore relates to a perfume composition as described above comprising or consisting of compound (1), compound (2) and / or compound (3) and at least one amber perfume substance or aloe wood.

[0034] The combination of one of the compounds (1), (2) or (3) with ambrocenide and / or ambrostar is particularly preferred.

[0035] In a preferred embodiment of the perfume composition as described above, compounds (1), (2) or (3) constitute respectively 0.001 to 10% by weight of the perfume composition, preferably 0.2 to 2% by weight.

[0036] A perfume composition such as the one described above is even more preferable, the amber perfumer(s) and / or the aloe wood perfumer(s) being chosen from the group consisting of 2,2,5,8,8,9a-hexamethyloctahydro-477-4a,9-methanoazuleno[5,6-6?] [1,3]dioxole, 2,5,8,8,9a-pentamethyl-2-propyloctahydro-4 / / -4a,9-methanoazuleno[5,6-6?] [1,3]dioxole, 2,5,8,8,9a-pentamethyl-2-(prop-l-en-l-yl)octahydro-4 / / -4a,9-methanoazuleno[5,6-6?][1,3]dioxole, 2-(methoxymethyl)-2,5,8,8,9a-pentamethyloctahydro-4 / / -4a,9-methanoazuleno[5,6-6?][l,3]dioxole, 2,4-dimethyl-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-l,3-dioxolane, 2',2',3,7,7-pentamethylspiro[bicyclo[4.1.0]heptane-2,5'-[l,3]dioxane], 2'-isopropyl-l,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4'-[l,3]dioxane], l-(2',2',6'-trimethylcyclohexyl)hexan-3-ol, 2-methyl-5-(5',5',6'-trimethylbicyclo[2.2.1hept-2'-yl)cyclohexanone, decahydro-2,2,6,6,7,8,8-heptamethyl-2 / / -indeno[4,5- / »]furan, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5 / / )-indanone, 1a, 3,3,4,6,6-hexamethyl-1a, 2,3,4,5,6,7,7a-octahydronaphtho[2,3- / »]oxirene, 7,7,8,9,9-pentamethyl-4,4a, 5,6,7,8,9,9b-octahydroindeno[4,5-6?][1,3]dioxine, 7,7,8,9,9-pentamethyl-6,6a, 7,8,9,9a-hexahydro-5 / / -cyclopenta[ / z]quinazoline, 7,7,8,9,9-pentamethyl-6,7,8,9-tetrahydro-5 / / -cyclopenta[ / z]quinazoline, 2,6,6,7,8,8-hexamethyldecahydro-2 / / -indeno[4,5- / »]furan, 2,2,6,6,7,8,8-heptamethyldecahydro-2 / / -indeno[4,5- / »]furan, 2,2,7,7,8,9,9-heptamethyldecahydroindeno[4,3a-Z?]furan, 7-methoxy-1,1,5,5-tetramethyl-1,3,4,5,6,7-hexahydro-2 / / -2,4a-methanonaphthalene, 5,5- . dimethyl-2-propylhexahydro-2 / / -2,4a-methanonaphthalen-l(5 / / )-one, 2,2,9,11-tetramethylspiro[5.5]undec-8-en-l-yl acetate, 3,8,8,11a-tetramethyldodecahydro-5 / / -3,5a-epoxynaphth[2,1-C]oxepin, 3a,6,6,9a-tetramethyl-l,2,3a,4,6,7,8,9,9a,9b-decahydronaphtho[2,lZ?]furan and 3a,6,6,9a-tetramethyldodecahydronaphtho[2,lZ?]furan stereoisomers as well as the reaction products of the acid-catalyzed cyclization of l-(l',6'-dimethyl-4'-(4”-methylpent-3' ' -èn-1 ' ' -yl)cyclohex-3 ' -èn-1 ' -yl)ethan-1 -one.

[0037] According to another aspect, the present invention also relates to a method for perfuming a product comprising the steps of: (i) preparation of a compound or mixture of compounds of formula (I) as defined above or of a fragrance composition as defined above, and (ii) addition of the compound or mixture of compounds or of the fragrance composition to the product to be perfumed, preferably in an amount giving a sensory effect, in particular in an amount sufficient to induce, accentuate and / or modify an olfactory note.

[0038] A “sensory effect quantity” is a quantity in which the compound and / or mixture of compounds or the fragrance composition can be perceived in the fragranced product by a consumer in comparison with a product which does not contain a corresponding compound, mixture of compounds or fragrance composition.

[0039] A process as described above is preferred, wherein, in step (ii), compound (1) is added to the product to be perfumed to induce, accentuate, modify and / or fix an amber and / or aloeswood note, and / or where compound (2) is added to the product to be perfumed to induce, accentuate, modify and / or fix a woody, amber, aloeswood, peppery and / or green note, and / or where, in step (ii), compound (3) is added to the product to be perfumed to induce, accentuate, modify and / or fix a woody, amber, aloeswood, peppery and / or green note.

[0040] Furthermore, the present invention relates to a perfumed product comprising a compound or a mixture of compounds as defined above or a perfume composition as described above.

[0041] A perfume composition according to the invention is advantageously suitable for a wide range of applications in the most diverse products.

[0042] Preferably, the perfumed product is chosen from the group consisting of laundry and cleaning products, hygiene and care products, preferably in the field of body and hair care, cosmetics and household products, preferably chosen from the group consisting of perfume extracts, perfumed waters, toilet waters, aftershave lotions, colognes, pre-shave products, perfumed wipes, acidic, alkaline or neutral detergents, textile deodorizers, ironing aids, liquid laundry detergents, powder laundry detergents, laundry treatment agents, fabric softeners, soaps, washing tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and lacquers, 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, makeup cosmetics, candles, lamp oils, incense sticks, insecticides, repellents and propellants.

[0043] Small quantities of perfume composition according to the invention in a product are already sufficient to guarantee a pleasant and long-lasting scent.

[0044] In a preferred embodiment of the product, the total amount of the perfume composition is in the range of 0.05 to 5% by weight, preferably 0.5 to 2% by weight, respectively with respect to the total weight of the product.

[0045] In what follows, the invention will be described in more detail with the aid of some examples.

[0046] Example 1: Production of 1-methoxy- and 3-methoxy-4-(3',8',8'-trimethyl-2', 3',4',7',8',8a'-hexahydro-1'H-3a', 7'-methanoazulen-6'-yljbutan-2-one by Claisen rearrangement

[0047] Synthesis of 1,2,2-trimethoxypropoane

[0048] In a 1-liter, three-necked spherical flask stirring apparatus equipped with a magnetic stirrer, thermometer, reflux cooler, and drip feeder, 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. Within 30 minutes, 150 g (1.70 mol) of l-methoxypropan-2-one were added dropwise, raising the temperature to 50 °C. The mixture was then heated under reflux for 5 hours (52 °C). The heating was removed, the preparation was mixed at room temperature with 3.50 g (33.7 mmol) of sodium carbonate, and then fractionally distilled in a 30 cm packed column with Raschig rings and a vacuum column head. Yield: 204 g (89%) of 1,2,2-trimethoxypropane (GC purity: 96%) as a clear, colorless liquid.

[0049] GC-IR (pureté GC 96 %) : v = 2994 / 2945 / 2838 (m), 1464 (w), 1381 (w), 1255 (w), 1136 (s), 1066 (m), 850 (w).

[0050] RMN ‘H (400 MHz, CDC13) : ô = 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-H3) ppm.

[0051] RMN 13C (101 MHz, CDC13) : ô = 100.0 (s, C-2), 74.1 (t, C-1), 59.3 (q, 1-MeO), 48.2 / 48.2 (2 q, 2-MeO2), 20.1 (q, C-3) ppm.

[0052] 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).

[0053] Élimination d’un groupe méthoxy pour donner 1’ énoléther correspondant

[0054] In a 250 ml distillation apparatus equipped with a thermometer, a magnetic stirrer, a column (10 cm Raschig rings) and a column head, 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 and heated under normal pressure. The mixture began to boil at 119 °C. For a reflux ratio of R:D = 25:1, a bottom column temperature of 120 to 150 °C and a top temperature of 104 to 108 °C, 43.7 g of distillate was obtained (GC Purity: 88%. Composition: 41% of (E)-1,2-dimethoxyprop-l-ene, 17% of (Z)-1,2-dimethoxyprop-l-ene, 30% of 2,3-dimethoxyprop-l-ene).

[0055] GC-IR (GC purity 88%): v = 2998 / 2941 / 2839 (m), 1668 (w), 1625 (w), 1460 (w), 1220 (s), 1136 (s), 1082 (m).

[0056] (E)-l,2-dimethoxyprop-l-ene:

[0057] NMR of 'H (400 MHz, C6D6): ô = 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, J = 1). H 5.57 (q).

[0058] NMR 13C (101 MHz, C6D6) : ô = 14.1 (q, C-3), 54.8 (q, 2'-MeO), 59.8 (q, l'-MeO), 127.1 (d, Cl), 144.9 (s, C-2).

[0059] GC-MS (70eV): m / z (%) = 27 (8), 39 (9), 43 (48), 59 (100), 87 (84), 102 (90), 103 (5).

[0060] (Z)-l,2-dimethoxyprop-l-ène:

[0061] NMR 'H (400 MHz, C6D6) : ô = 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), 5.0, H, 1).

[0062] NMR 13C (101 MHz, C6D6) : ô = 15.9 (q, C-3), 57.5 (q, 2'-MeO), 59.5 (q, l'-MeO), 129.1 (d, Cl), 137.0 (s, C-2).

[0063] GC-MS (70eV): m / z (%) = 29 (32), 43 (53), 59 (99), 87 (95), 102 (100), 103 (5).

[0064] 2,3-dimethoxyprop-l-ene:

[0065] 'H NMR (400 MHz, C6D6): ô = 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-Ha). 13C NMR (101 MHz, C6D6): ô = 54.4 (q, 2'-MeO), 58.0 (q, 3'-MeO), 72.8 (t, C-3), 82.1 (t, Cl), 161.0 (s, C-2).

[0067] GC-MS (70eV): m / z (%) = 29 (19), 42 (38), 45 (38), 59 (13), 72 (100), 102 (9).

[0068] Manufacture of 5-((1',2'-dimethoxypropan-2'-yl)oxy )-3,8,8-trimethyl-6-methylenoctahydro-1H-3a,7-methanoazulene

[0069] In a 25 mL three-necked spherical flask shaker equipped with a magnetic stirrer, a thermometer, and a reflux cooler, 2.00 g (9.09 mmol) of 3,8,8-trimethyl-6-methyleneoctahydro-l / / -3a,7-methanoazulen-5-ol, 8.00 g (78.4 mmol) of a mixture of (E / Z)-l,2-dimethoxyprop-l-ene 65%, 2,3-dimethoxyprop-l-ene 35%, and 420 mg (7.00 mmol) of acetic acid were shaken under a nitrogen atmosphere for 16 hours at 90 °C. The heating was then removed, and the preparation was diluted at room temperature with stirring using 20 mL of methyl-tert-butyl ether. It was washed twice, each time with 20 ml of a 5% sodium hydroxide solution, and then reduced. The residue was heated and mixed with 10 ml of hexane, then recrystallized for 3 hours at 5 °C. The resulting residue was filtered, and the mother liquor was reduced, yielding 2.00 g of crude product (GC purity: 48%, 33% crude yield).After column chromatography (Büchi PrepChrom C-700, 80 g of Kieselgel 60 silica gel, eluent: hexane / acetic acid eluent = 99:1 ->->—>95:5, 71 min, 20 ml / min at 20 ml per fraction, DC: Rf = 0.44 (SiO2 60, hexane / acetic acid = 10:1), 640 mg (22%) of the compound of the title was obtained (GC purity: 99%).

[0070] First eluted component: GC-IR (GC 34%, Thermo Nicolet 6700): v = 2949 (s) 1643 (w), 1463 (w), 1384 (w), 1131 (m), 1050 (m).

[0071] RMN ‘H (400 MHz, CDC13) ô = 0.83 - 0.88 (m, 3 H, l’-Me), 0.92 - 1.00 (m, 6 H, 8’-Me2), 1.23 - 1.37 (m, 3 H, 2’-, 4’-, 9’-Hb), 1.37 - 1.50 (m, 4 H, 3-Me, l’-Hb), 1.51 -1.64 (m, 1 H, l’-Ha), 1.68 - 1.80 (m, 2 H, 3’-H, 9’-Ha), 1.80 - 1.91 (m, 2 H, 8a’-H, 2’-Ha), 1.91 - 2.07 (m, 1 H, 4’-Ha), 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-Ha), 4.46 - 4.61 (m, 1 H, 5’-H), 4.68 - 4.77 (m, 1 H, HbC=C-6’, exo-méthylène), 5.04 (t, J= 2,5 Hz, 1 H, HaC=C-6’, exo-méthylène).

[0072] RMN 13C (101 MHz, CDC13) ô = 15.4 (q, 3’-Me), 21.9 (q, C-3), 25.9 (t, C-l), 26.1 / 26.8 (2 q, 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-l), 101.1 (s, C-2), 107.6 (t, H2C=C-6’), 152.3 (s, C-6’).

[0073] 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).

[0074] Composant élué en dernier : GC-IR (GC 65 %, Thermo Nicolet 6700) : v = 2949 (s), 1644 (w), 1463 (w), 1384 (w), 1131 (m), 1050 (m).

[0075] RMN ‘H (400 MHz, CDC13) ô = 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’-Hb), 1.37 - 1.50 (m, 4 H, 3-Me, l’-Hb), 1.51-1.64 (m, 1H, 1”-Ha), 1.68- 1.80 (m, 2H, 3’-H, 9’-Ha), 1.80-1.91 (m, 2 H, 2’-Ha, 8a’-H), 1.91 - 2.07 (m, 1 H, 4’-Ha), 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-Hb), 3.41 (s, 3 H, 1-MeO), 3.54 (d, J = 10,0 Hz, 1H 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, HaC=C-6’).

[0076] 13C NMR (101 MHz, CDC13) ô = 15.5 (q, 3'-Me), 21.1 (q, C-3), 25.9 (t, Cl), 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, Cl), 101.1 (s, C-2), 107.6 (t, H2C=C-6'), 152.4 (s, C-6').

[0077] m / z (%) = 41 (22), 55 (9), 71 (52), 95 (23), 103 (100), 119 (29), 133 (18), 147 (28), 203 (48), 220 (4), 290 (1).

[0078] Manufacture of 3-methoxy-4-(3',8',8'-trimethyl-2', 3',4',7',8',8a'- hexahydro-1H-3a', 7'-methanoazulen-6-yl)butan-2-one and 1-methoxy-4-(3',8',8'-trimethyl-2', 3',4',7',8',8a'-hexahydro-1H-3a', 7'-methanoazulen-6'-yl)butan-2-one by Claisen rearrangement

[0079] 1.50 g (4.66 mmol) of 5-((l',2'-dhnethoxypropan-2'-yl)oxy)-3,8,8-trimethyl-6-methylenoctahydro-l / / -3a,7-methanoazulene was heated on a Kugelrohr distillation apparatus (Büchi Glass Oven B-585) at 160 °C and 100 mbar for 4 hours, after which the heating was removed. 1.09 g of crude product remained in the residue (GC purity: 78%). After column chromatography (Büchi PrepChrom C-700, 80 g of Kieselgel 60 silica gel, eluent: hexane / acetic acid eluent = 98:2–92:8, 71 min, 20 mL / min at 20 mL per fraction, DC: Rf = 0.33 and 0.25 (SiO2 60, hexane / acetic acid = 10:1), 38.0 mg of 3-methoxy-4-(3',8',8'-trimethyl-2', 3',4',7',8',8a'-hexahydro-l / / -3a', 7'-methanoazulen-6'-yl)butan-2-one (GC purity: 94%) and 513 mg of l-methoxy-4-(3',8',8'-trimethyl-2', 3',4',7',8',8a'-hexahydro-lH-3a', 7'-methanoazulen-6'-yl)butan-2-one (GC purity: 94%).

[0080] 3-methoxy-4-(3',8',8'-trimethyl-2', 3',4',7',8',8a'-hexahydro-lH-3a', 7'- méthanoazulèn-6’- yl)butan -2-one (mélange de deux diastéréomères à 1:1, [Composé (1)])

[0081] GC-IR (Pureté GC 94 %, Thermo Nicolet 6700) : v = 2949 / 2901 / 2835 (s), 1729 (w), 1468 (w), 1358 (w), 1109 (m).

[0082] RMN ‘H (400 MHz, CDC13) : ô = 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, (l‘-Hb, 2’-Hb, 9’- Hb)2), 1.53 - 1.63 (m, 2 H, (l’-Ha)2), 1.64 - 1.80 (m, 6 H, (3‘-H, 8a‘-H, 9‘-Ha)2), 1.80 - 1.88 (m, 4 H, (2‘-Ha, 4‘-Hb)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’- Ha)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).

[0083] RMN 13C (100 MHz, CDC13) : ô = 15.4 / 15.4 (2 q, 3’-Me), 24.8 / 24.8 (2 t, C-l), 25.0 / 25.4 (2 q, C-l), 25.6 / 25.6 / 27.6 / 27.6 (4q, 8’-Me), 36.2 / 36.2 (2 t, 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 (2 q, 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).

[0084] MS (El): 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).

[0085] Description of the odor: amber and dry wood, with animal notes tending towards aloe wood and Cashmeran (l,l,2,3,3-pentamethyl-l,2,3,5,6,7-hexahydro-4 / / -inden-4-one).

[0086] l-methoxy-4-(3',8',8'-trimethyl-2', 3',4',7',8',8a'-hexahydro-lH-3a', 7'- methanoazulèn-6'-yl)butan-2-one [Compound (2)]

[0087] GC-IR (GC purity 94%, Thermo Nicolet 6700): v = 2948 (s), 1732 (w), 1464 (w), 1110 (w).

[0088] RMN ‘H (600 MHz, CDC13) : ô = 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’-Ha), 1.53 - 1.62 (m, 1 H, l’-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’-Hb, 4’-Ha, 7’-H), 2.12 - 2.21 (m, 2 H, 4’-Hb, 4-Ha), 2.27 - 2.36 (m, 1 H, 4-Hb), 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).

[0089] RMN 13C (151 MHz, CDC13) : ô = 15.4 (q, 3’-Me), 24.8 (t, C-l), 25.6 / 27.6 (2 q, (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-l), 119.1 (d, 5’=CH2), 142.8 (s, C-6’), 208.6 (s, C-2).

[0090] 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).

[0091] Description of the odor: dry amber wood, amber going towards ambrocenide (2,2,5,8,8,9a-hexamethyloctahydro-4 / / -4a,9-methanoazuleno[5,6-d\ [1,3]dioxol) with a peppery touch reminiscent of rotundone ((35,5R,85)-3,4,5,6,7,8-hexahydro-3a,8a-dimethyl-5a-(l-methylethenyl)azulen-l(2 / / )-one) and green nuances.

[0092] Example 2: Production 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

[0093] Synthesis of 2-ethoxyprop-l-ene

[0094] In a 250 ml distillation apparatus equipped with a magnetic stirrer, a thermometer, a column (10 cm, Raschig rings) and a 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 normal pressure, the mixture reaction starting to boil at 107 °C. At a reflux ratio of R : D = 10:1, a bottom column temperature of 107 to 122 °C and a top temperature of 72 to 92 °C, 91.0 g (76%) of the compound of the title (GC purity: 55%) was isolated by distillation.

[0095] 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).

[0096] NMR 'H (400 MHz, C6D6) ô = 1.08 (t, J= 7.0 Hz, 3H, l'-Me), 1.79 (d, J= 1.0 Hz, 3H C-3), 3.48 (q, J = 7.0 Hz, 2H, l'-H2), 3.83 (d, J= 1.0 Hz, 1H, 3-HZ?), 3.89 (dq, J = 2.0, 1.0 Hz, 1H, 3-Ha).

[0097] 13C NMR (101 MHz, C6D6) ô = 14.6 (q, C-2'), 21.2 (q, C-3), 62.7 (t, Cl), 81.3 (t, Cl), 160.1 (s, C-2).

[0098] GC-MS (70eV): m / z (%) = 29 (32), 39 (20), 43 (100), 58 (89), 86 (94).

[0099] 5-((2'-ethoxypropan-2'-yl)oxy )-3,8,8-trimethyl-6-methylenoctahydro-1H-3a,7-methanoazulene

[0100] In a 10 mL single-neck spherical flask stirring apparatus equipped with a magnetic stirrer, thermometer, and reflux cooler, 1.00 g (4.55 mmol) of 3,8,8-trimethyl-6-methyleneoctahydro-l / / -3a,7-methanoazulen-5-ol, 5.00 g (58.1 mmol) of 2-ethoxyprop-l-ene, and 200 mg (3.33 mmol) of acetic acid were stirred under a nitrogen atmosphere at 75 °C for 6 hours. The heating was removed, the preparation was diluted at room temperature with stirring using 50 mL of methyl-tert-butyl ether, washed once with 20 mL of 5% sodium hydroxide solution, and then reduced on a rotary evaporator until dry, 1.10 g (79%) of the product being isolated. (GC purity: 80%).

[0101] GC-IR (Thermo Nicolet 6700): v = 2949 / 2919 / 2882 (s), 1645 (w), 1464 (w), 1384 (w), 1278 (w), 1204 (w), 1164 (w), 1050 (m).

[0102] RMN ‘H (400 MHz, C6D6) : ô = 0.87 (d, J = 7,0 Hz, 3 H, 3-Me), 0.90 / 1.06 (s, 6 H, 8-Me2), 1.16 (t, 7=7,0 Hz, 3 H, 2”-H3), 1.22-1.31 (m, 1 H, 2-Hb), 1.32- 1.39 (m, 2 H, 1-Hb, 9-Hb), 1.41 / 1.45 (2s, 6 H, l’-H3, 3’-H3), 1.46 - 1.53 (m, 2 H, 1-Ha, 4-Hb), 1.57 - 1.67 (m, 1 H, 3-H), 1.65 - 1.74 (m, 1 H, 9-Ha), 1.74 - 1.80 (m, 1 H, 2-Ha), 1.80 - 1.89 (m, 1 H, 8a-H), 2.06 (ddd, J= 12.0, 7.5, 3,0 Hz, 1 H, 4-Ha), 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”-Ha), 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).

[0103] RMN 13C (101 MHz, C6D6) : ô = 15.8 (q, 3-Me), 15.8 (q, C-2”), 25.8 / 26.3 (2 q, C-l, -3’), 26.2 (t, C-l), 26.4 / 27.0 (2 q, 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-l”), 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).

[0104] 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).

[0105] 4-(3',8',8'-trimethyl-2', 3',4',7',8',8a'-hexahydro-1'H-3a', 7'-methanoazulen-6'- yl)butan-2-one [Compound (3)]

[0106] 1.10 g (2.88 mmol) of 5-((2-ethoxypropan-2-yl)oxy)-3,8,8-trimethyl-6- Methyleneocta-hydro-l / / -3a,7-methanoazulene (GC purity 80%) was heated in a Kugelrohr distillation apparatus (Büchi Glass Oven B-585) for 4 hours at 160 °C and 100 mbar. The heating was removed and the product was allowed to cool to room temperature, with 800 mg of crude product remaining in the residue (GC purity: 33%, 35% crude yield). After column chromatography (Büchi PrepChrom C-700, 80 g of Kieselgel 60 silica gel, eluent: hexane / acetic acid eluent = 97:3—> 92:8, 71 min, 20 ml / min to 20 ml per fraction, DC: Rf = 0.20 (SiO2 60, hexane / acetic acid = 20:1)), 240 mg (32%) of the compound of the title was obtained (GC purity 99%).

[0107] Description of the odor: dry and peppery, woody-amber, with clear aspects of cedarwood and black pepper, as well as a sour spicy apple note in the initial odor.

[0108] GC-IR (Thermo Nicolet 6700) : v = 2950 / 2908 / 2838 (s), 1732 (m), 1467 (w), 1363 (w), 1273 (w), 1221 (w), 1157 (w).

[0109] RMN ‘H (600 MHz, CDC13) : ô = 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’-Hb,), 1.53 - 1.61 (m, 1 H, l’-Ha), 1.68 (ddd, 7=11.0, 4.5, 1,5 Hz, 2 H, 8a’-H, 9’-Ha), 1.71-1.78 (m, 1 H, 3’-H), 1.78-1.84 (m, 2H, 4a’-Hb, 7’-H), 1.84- 1.90 (m, 1 H, 2’-Ha), 2.10-2.21 (m, 5 H, 1-H3, 4-, 4’-Hb), 2.24 - 2.35 (m, 1 H, 4-Ha), 2.48 (ddd, J= 16.0, 9.5, 6,0 Hz, 1 H, 3-Hb), 2.57 (ddd, J= 16.5, 10.0, 5,5 Hz, 1 H, 3-Ha), 5.18 (dt, J= 4.0, 2,0 Hz, 1 H, 5’-H). RMN 13C (151 MHz, CDC13) ô = 15.4 (q, 3’-Me), 24.8 (t, C-l), 25.6 / 27.6 (2 q, Me-2C-8’), 29.9 (q, C-l), 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).

[0110] 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).

[0111] Example 3: Application of the compounds in a rich, nuanced dry wood amber composition with a fresh lemon contrast

[0112] Perfume composition 3.1 CAS No. Name of material Dose 56973-85-4 DYNASCONE 1 67635-15-5 FLORAZON 1.5 18479-58-8 DIHYDROMYRCENOL 100 107-75-5 HYDROXYCITRONELLAL 12 93-29-8 DTSOEUGENYL ACETATE 2 1205-17-0 HELIONAL 20 8007-75-8 ESSENCE OF TRUE BERGAMOT IE 40 106-24-1 GERANIOL SUPRA 10 127-51-5 METHYL IONONE 95 10 6790-58-5 AMBROXIDE 15 81782-77-6 UNDECAVERTOL 2 39255-32-8 MANZANATE 2 2050-08-0 AMYL SALICYLATE 8 8016-20-4 GRAPEFRUIT ESSENCE 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDI GROS SO NAT. ESSENCE CENSO 6 4940-11-0 ETHYL-MALTOL 0.5 134-20-3 METHYL ANTHRANILATE 4 91-64-5 COUMARIN 18 5471-51-2 FRAMBINON® 0.5 121-33-5 VANILLIN 5 24851-98-7 HEDIONE 60 4707-47-5 EVERNYL 3 18127-01-0 BOURGEONAL 2 19870-74-7 CEDRAMBER 10 10339-55-6 ETHYL LINALOOL 35 24720-09-0 DAMASCONE ALPHA 1 67634-00-8 ALLYL AMYL GLYCOLATE 5 13828-37-0 MAYOL 2 54464-57-2 ISO E SUPER 150 23726-93-4 DAMASCENONE 1 28940-11-6 CALONE 8 25265-71-8 DIPROPYLENE GLYCOL 96 949495-68-5 ESSENCE OF PINK PEPPER LEAF MAD AG. 5 63314-79-4 MUSCENONE 2.5 67674-46-8 AMAROCIT® 8 70788-30-6 TIMBEROL® 6 33704-61-9 CASHMERAN 25 91770-14-8 JASMINE ABS. SAMBAC 10% DPG 5 28219-61-6 SANDRANOL® 15 20298-69-5 AGRUMEX LC 55 65405-77-8 CIS-3 HEXENYL SALICYLATE 30 130169-57-2 C12-C15 ALDEHYDE 2 141773-73-1 HELVETOLIDE 20 142-92-7 HEXYL ACETATE 10 106-72-9 MELONAL 2 236391-76-7 ECOMUSK R 10 118-58-1 BENZYL SALICYLATE 75 68901-15-5 CYCLOGALBANAT® 6 2245967-74-0 PEARADISE 6 84238-39-1, 8014-09-3 Patchouli Essence 4 Compound (2) 10% DPG 20 1000

[0113] Compound (2) gives the composition more performance, character, and a distinctive signature thanks to the contrast between amber and dark wood. It brings an amber tendency that accentuates the woody base character of the fragrance. In addition, compound (2) harmonizes with the fresh citrus top note and gives it greater radiance. Compound (2) also contributes to the entire fragrance's longevity and lasting power.

[0114] Perfume composition 3.2 CAS No. Name of material Dose 56973-85-4 DYNASCONE 1 67635-15-5 FLORAZON 1.5 18479-58-8 DIHYDROMYRCENOL 100 107-75-5 HYDROXYCITRONELLAL 12 93-29-8 ISOEUGENYL ACETATE 2 1205-17-0 HELIONAL 20 8007-75-8 TRUE BERGAMOT ESSENCE IE 40 106-24-1 GERANIOL SUPRA 10 127-51-5 METHYL IONONE 95 10 6790-58-5 AMBROXIDE 15 81782-77-6 UNDECAVERTOL 2 39255-32-8 MANZANATE 2 2050-08-0 AMYL SALICYLATE 8 8016-20-4 GRAPEFRUIT ESSENCE 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDI GROS SO NAT. ESSENCE CENSO 6 4940-11-0 ETHYL-MALTOL 0.5 134-20-3 METHYL ANTHRANILATE 4 91-64-5 COUMARIN 18 5471-51-2 FRAMBINON® 0.5 121-33-5 VANILLIN 5 24851-98-7 HEDIONE 60 4707-47-5 EVERNYL 3 18127-01-0 BOURGEONAL 2 19870-74-7 CEDRAMBER 10 10339-55-6 ETHYL LINALOOL 35 24720-09-0 DAMASCONE ALPHA 1 67634-00-8 ALLYL AMYL GLYCOLATE 5 13828-37-0 MAYOL 2 54464-57-2 ISO E SUPER 150 23726-93-4 DAMASCENONE 1 28940-11-6 CALONE 8 25265-71-8 DIPROPYLENE GLYCOL 96 949495-68-5 ESSENCE OF PINK PEPPER LEAF MAD AG. 5 63314-79-4 MUSCENONE 2.5 67674-46-8 AMAROCIT® 8 70788-30-6 TIMBEROL® 6 33704-61-9 CASHMERAN 25 91770-14-8 JASMINE ABS. SAMBAC 10% DPG 5 28219-61-6 SANDRANOL® 15 20298-69-5 AGRUMEX LC 55 65405-77-8 CIS-HEXENYL SALICYLATE 3 30 130169-57-2 C12-C15 ALDEHYDE 2 141773-73-1 HELVETOLIDE 20 142-92-7 HEXYL ACETATE 10 106-72-9 MELONAL 2 236391-76-7 ECOMUSK R 10 118-58-1 BENZYL SALICYLATE 75 68901-15-5 CYCLOGALBANAT® 6 2245967-74-0 PEARADISE 6 84238-39-1, 8014-09-3 Patchouli Essence Grade 4 Compound (1) 10% DPG 20 1000

[0115] Compound (1) gives a stronger and longer-lasting overall fragrance impression. In addition, compound (1) of the composition imparts a unique masculine character and harmonizes well with and enhances the sweet and powdery nuances of the fragrance.

[0116] Fragrance composition 3.3 CAS No. Name of material Dose 56973-85-4 DYNASCONE 1 67635-15-5 FLORAZON 1.5 18479-58-8 DIHYDROMYRCENOL 100 107-75-5 HYDROXYCITRONELLAL 12 93-29-8 DTSOEUGENYL ACETATE 2 1205-17-0 HELIONAL 20 8007-75-8 ESSENCE OF TRUE BERGAMOT IE 40 106-24-1 GERANIOL SUPRA 10 127-51-5 METHYL IONONE 95 10 6790-58-5 AMBROXIDE 15 81782-77-6 UNDECAVERTOL 2 39255-32-8 MANZANATE 2 2050-08-0 AMYL SALICYLATE 8 8016-20-4 GRAPEFRUIT ESSENCE 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDI GROS SO NAT. ESSENCE CENSO 6 4940-11-0 ETHYL-MALTOL 0.5 134-20-3 METHYL ANTHRANILATE 4 91-64-5 COUMARIN 18 5471-51-2 FRAMBINON® 0.5 121-33-5 VANILLIN 5 24851-98-7 HEDIONE 60 4707-47-5 EVERNYL 3 18127-01-0 BOURGEONAL 2 19870-74-7 CEDRAMBER 10 10339-55-6 ETHYL LINALOOL 35 24720-09-0 DAMASCONE ALPHA 1 67634-00-8 ALLYL AMYL GLYCOLATE 5 13828-37-0 MAYOL 2 54464-57-2 ISO E SUPER 150 23726-93-4 DAMASCENONE 1 28940-11-6 CALONE 8 25265-71-8 DIPROPYLENE GLYCOL 96 949495-68-5 ESSENCE OF PINK PEPPER LEAF MAD AG. 5 63314-79-4 MUSCENONE 2.5 67674-46-8 AMAROCIT® 8 70788-30-6 TIMBEROL® 6 33704-61-9 CASHMERAN 25 91770-14-8 JASMINE ABS. SAMBAC 10% DPG 5 28219-61-6 SANDRANOL® 15 20298-69-5 AGRUMEX LC 55 65405-77-8 HEXENYL SALICYLATE CI S-3 30 130169-57-2 C12-C15 ALDEHYDE 2 141773-73-1 HELVETOLIDE 20 142-92-7 HEXYL ACETATE 10 106-72-9 MELONAL 2 236391-76-7 ECOMUSK R 10 118-58-1 BENZYL SALICYLATE 75 68901-15-5 CYCLOGALBANAT® 6 2245967-74-0 PEARADISE 6 84238-39-1, 8014-09-3 Patchouli Essence 4 Compound (3) 10% DPG 20 1000

[0117] Compound (3) introduces interesting new nuances to the perfume composition: it makes the overall composition more complex, more intense, longer-lasting, and more modern. The perfume has a warmer, slightly amber scent. The citrus notes appear more nuanced and clear. In addition, compound (3) enhances the composition with a fresh, peppery nuance and even luxurious accents of incense.

[0118] Perfume composition 3.4 CAS No. Name of material Dose 56973-85-4 DYNASCONE 1 67635-15-5 FLORAZON 1.5 18479-58-8 DIHYDROMYRCENOL 100 107-75-5 HYDROXYCITRONELLAL 12 93-29-8 ISOEUGENYL ACETATE 2 1205-17-0 HELIONAL 20 8007-75-8 TRUE BERGAMOT ESSENCE 40 106-24-1 GERANIOL SUPRA 10 127-51-5 METHYL IONONE 95 10 6790-58-5 AMBROXIDE 15 81782-77-6 UNDECAVERTOL 2 39255-32-8 MANZANATE 2 2050-08-0 AMYL SALICYLATE 8 8016-20-4 GRAPEFRUIT ESSENCE 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDI GROSSO NAT. ESSENCE CENSO 6 4940-11-0 ETHYL MALTOL 0.5 134-20-3 METHYL ANTHRANILATE 4 91-64-5 COUMARIN 18 5471-51-2 FRAMBINON® 0.5 121-33-5 VANILLIN 5 24851-98-7 HEDIONE 60 4707-47-5 EVENYL 3 18127-01-0 BOURGEONAL 2 19870-74-7 CEDRAMBER 10 10339-55-6 ETHYL LINALOOL 35 24720-09-0 DAMASCONE ALPHA 1 67634-00-8 ALLYL AMYL GLYCOLATE 5 13828-37-0 MAYOL 2 54464-57-2 ISO E SUPER 150 23726-93-4 DAMASCENONE 1 28940-11-6 CALONE 8 25265-71-8 DIPROPYLENE GLYCOL 96 949495-68-5 ESSENCE OF PINK PEPPER LEAF MAD AG. 5 63314-79-4 MUSCENONE 2.5 67674-46-8 AMAROCIT® 8 70788-30-6 TIMBEROL® 6 33704-61-9 CASHMERAN 25 91770-14-8 JASMINE ABS. SAMBAC 10% DPG 5 28219-61-6 SANDRANOL® 15 20298-69-5 AGRUMEX LC 55 65405-77-8 CIS-3 HEXENYL SALICYLATE 30 130169-57-2 C12-C15 ALDEHYDE 2 141773-73-1 HELVETOLIDE 20 142-92-7 HEXYL ACETATE 10 106-72-9 MELONAL 2 236391-76-7 ECOMUSK R 10 118-58-1 BENZYL SALICYLATE 75 68901-15-5 CYCLOGALBANAT® 6 2245967-74-0 PEARADISE 6 84238-39-1, 8014-09-3 Patchouli Oil 4 Grade Compound (2) 10% DPG 10 211299-54-6 427-580-1 Ambrocenide® 10 DPG 10 1000

[0119] The combination of compound (2) and ambrocenide® creates a clean musk note with a warm, amber undertone.

[0120] Fragrance composition 3.5: CAS No. Name of material Dose 56973-85-4 DYNASCONE 1 67635-15-5 FLORAZON 1.5 18479-58-8 DIHYDROMYRCENOL 100 107-75-5 HYDROXYCITRONELLAL 12 93-29-8 ISOEUGENYL ACETATE 2 1205-17-0 HELIONAL 20 8007-75-8 TRUE BERGAMOT ESSENCE 40 106-24-1 GERANIOL SUPRA 10 127-51-5 METHYL IONONE 95 10 6790-58-5 AMBROXIDE 15 81782-77-6 UNDECAVERTOL 2 39255-32-8 MANZANATE 2 2050-08-0 AMYL SALICYLATE 8 8016-20-4 GRAPEFRUIT ESSENCE 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDI GROSSO NAT. ESSENCE CENSO 6 4940-11-0 ETHYL MALTOL 0.5 134-20-3 METHYL ANTHRANILATE 4 91-64-5 COUMARIN 18 5471-51-2 FRAMBINON® 0.5 121-33-5 VANILLIN 5 24851-98-7 HEDIONE 60 4707-47-5 EVENYL 3 18127-01-0 BOURGEONAL 2 19870-74-7 CEDRAMBER 10 10339-55-6 ETHYL LINALOOL 35 24720-09-0 DAMASCONE ALPHA 1 67634-00-8 ALLYL AMYL GLYCOLATE 5 13828-37-0 MAYOL 2 54464-57-2 ISO E SUPER 150 23726-93-4 DAMASCENONE 1 28940-11-6 CALONE 8 25265-71-8 DIPROPYLENE GLYCOL 96 949495-68-5 PINK PEPPER LEAF ESSENCE MAD AG. 5 63314-79-4 MUSCENONE 2.5 67674-46-8 AMAROCIT® 8 70788-30-6 TIMBEROL® 6 33704-61-9 CASHMERAN 25 91770-14-8 JASMINE ABS. SAMBAC 10% DPG 5 28219-61-6 SANDRANOL® 15 20298-69-5 AGRUMEX LC 55 65405-77-8 CIS-3 HEXENYL SALICYLATE 30 130169-57-2 C12-C15 ALDEHYDE 2 141773-73-1 HELVETOLIDE 20 142-92-7 HEXYL ACETATE 10 106-72-9 MELONAL 2 236391-76-7 ECOMUSK R 10 118-58-1 BENZYL SALICYLATE 75 68901-15-5 CYCLOGALBANAT® 6 2245967-74-0 PEARADISE 6 84238-39-1, 8014-09-3 Patchouli Essence 4 Compound (1) 10% DPG 10 211299-54-6 427-580-1 Ambrocenide® 10 DPG 10 1000

[0121] The combination of compound (1) and ambrocenide® rounds out the harsh note of ambrocenide® and makes the amber complex appear softer and more sensual.

[0122] Fragrance composition 3.6 CAS No. Name of material Dose 56973-85-4 DYNASCONE 1 67635-15-5 FLORAZON 1.5 18479-58-8 DIHYDROMYRCENOL 100 107-75-5 HYDROXYCITRONELLAL 12 93-29-8 DTSOEUGENYL ACETATE 2 1205-17-0 HELIONAL 20 8007-75-8 ESSENCE OF TRUE BERGAMOT IE 40 106-24-1 GERANIOL SUPRA 10 127-51-5 METHYL IONONE 95 10 6790-58-5 AMBROXIDE 15 81782-77-6 UNDECAVERTOL 2 39255-32-8 MANZANATE 2 2050-08-0 AMYL SALICYLATE 8 8016-20-4 GRAPEFRUIT ESSENCE 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDI GROS SO NAT. ESSENCE CENSO 6 4940-11-0 ETHYL-MALTOL 0.5 134-20-3 METHYL ANTHRANILATE 4 91-64-5 COUMARIN 18 5471-51-2 FRAMBINON® 0.5 121-33-5 VANILLIN 5 24851-98-7 HEDIONE 60 4707-47-5 EVERNYL 3 18127-01-0 BOURGEONAL 2 19870-74-7 CEDRAMBER 10 10339-55-6 ETHYL LINALOOL 35 24720-09-0 DAMASCONE ALPHA 1 67634-00-8 ALLYL AMYL GLYCOLATE 5 13828-37-0 MAYOL 2 54464-57-2 ISO E SUPER 150 23726-93-4 DAMASCENONE 1 28940-11-6 CALONE 8 25265-71-8 DIPROPYLENE GLYCOL 96 949495-68-5 ESSENCE OF PINK PEPPER LEAF MAD AG. 5 63314-79-4 MUSCENONE 2.5 67674-46-8 AMAROCIT® 8 70788-30-6 TIMBEROL® 6 33704-61-9 CASHMERAN 25 91770-14-8 JASMINE ABS. SAMBAC 10% DPG 5 28219-61-6 SANDRANOL® 15 20298-69-5 AGRUMEX LC 55 65405-77-8 CIS-HEXENYL SALICYLATE 3 30 130169-57-2 C12-C15 ALDEHYDE 2 141773-73-1 HELVETOLIDE 20 142-92-7 HEXYL ACETATE 10 106-72-9 MELONAL 2 236391-76-7 ECOMUSK R 10 118-58-1 BENZYL SALICYLATE 75 68901-15-5 CYCLOGALBANAT® 6 2245967-74-0 PEARADISE 6 84238-39-1, 8014-09-3 Patchouli Essence 4 Compound (3) 10% DPG 10 211299-54-6 427-580-1 Ambrocenide® 10 DPG 10 1000

[0123] In combination with compound (3) and ambrocenide®, the composition appears more authentic, more noble and sensual, the effect of the combination creating warm and attractive notes of pepper, incense and aloeswood.

Claims

Demands

1. Compound or mixture of compounds of formula (I) including all its stereoisomers, (I), \ \ 0 Y ,X \ in which X and Y = H or -OMe, and X = H when Y = -OMe, and Y = H when X = -OMe, or X = Y = H.

2. Use of a compound or mixture of compounds according to claim 1 as a perfumer substance in particular as an amber perfumer substance and / or to enhance and / or modify an amber note and / or aloe wood of other perfumers and / or as a fixative in particular to prolong the longevity of an amber note and / or aloe wood of other perfumers.

3. Use of a compound according to claim 2, wherein compound (1) (1)MeO p is used to induce, enhance, modify and / or fix an amber and / or aloe wood note.

4. Use of a compound according to claim 2, wherein the compound (2)

5. (2) is used to induce, enhance, modify and / or fix a woody, amber, aloe wood, peppery and / or green note. Use of a compound according to claim 2, wherein the compound (3) (3) is used to induce, enhance, modify and / or fix a woody, amber, aloe wood, peppery and / or green note.

6. Perfume composition comprising or consisting of a compound or mixture of compounds as defined in claim 1, comprising in particular compound (1) as defined in claim 3, compound (2) as defined in claim 4 and / or compound (3) as defined in claim 5, and one or more other perfume substances.

7. Perfume composition according to claim 6, comprising or consisting of compound (1) as defined in claim 3, compound (2) as defined in claim 4 and / or compound (3) as defined in claim 5, and at least one amber or aloe wood perfume substance.

8. Perfume composition according to claim 6 or 7, wherein compounds (1), (2) and / or (3) constitute respectively 0.001 to 10% by weight of the perfume composition, preferably 0.2 to 2% by weight.

9. A fragrance composition according to claim 7 or 8, wherein the amber fragrance substance(s) and / or the

10. perfume substances of aloe wood is and / or are selected from the group consisting of 2,2,5,8,8,9a-hexamethyloctahydro-4 / / -4a, 9-methanoazuleno[5,6-d][1,3]dioxole, 2,5,8,8,9a-pentamethyl-2-propyloctahydro-4 / / -4a, 9-methanoazuleno[5,6-( / ][1,3]dioxole, 2,5,8,8,9a-pentamethyl-2-(prop-l-en-l-yl)octahydro-4 / / -4a, 9-methanoazuleno[5,6-( / ][1,3]dioxole, 2-(methoxymethyl)-2,5,8,8,9a-pentamethyloctahydro-4 / / -4a, 9-mcthanoazulcno|5,6-d] [l,3]dioxole, 2,4-dimethyl-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-l,3-dioxolane, 2',2',3,7,7-pentamethylspiro[bicyclo[4.1.0]heptane-2,5'-[l,3]dioxane], 2'-isopropyl-l,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,4'-[l,3]dioxane], l-(2',2',6'-trimethylcyclohexyl)hexan-3-ol, 2-methyl-5-(5',5',6'-trimethylbicyclo[2.2.1hept-2'-yl)cyclohexanone, decahydro-2,2,6,6,7,8,8-heptamethyl-2 / / -indeno[4,5-b]furan, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5 / / )-indanone, 1a, 3,3,4,6,6-hexamethyl-1a, 2,3,4,5,6,7,7a-octahydronaphtho[2,3- / »]oxirene, 7,7,8,9,9-pentamethyl-4,4a, 5,6,7,8,9,9b-octahydroindeno[4,5-( / ] [1,3]dioxine, 7,7,8,9,9-pentamethyl-6,6a, 7,8,9,9a-hexahydro-5 / / -cyclopenta[ / z]quinazoline, 7,7,8,9,9-pentamethyl-6,7,8,9-tetrahydro-5 / / -cyclopenta[ / z]quinazoline, 2,6,6,7,8,8-hexamethyldecahydro-2 / / -indeno[4,5- / »]furan, 2,2,6,6,7,8,8-heptamethyldecahydro-2 / / -indeno[4,5- / »]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 / / -2,4a-methanonaphthalene, 5,5-dimethyl-2-propylhexahydro-2 / / -2,4a-methanonaphthalen-1(5 / / )-one, 2,2,9,1 l-tetramethylspiro[5.5]undec-8-en-l-yl. acetate, 3,8,8,1 la-tetramethyldodecahydro-5 / / -3,5a-epoxynapht[2,lC]oxepin, 3a,6,6,9a-tetramethyl-l,2,3a,4,6,7,8,9,9a,9b-decahydronaphtho[2,l- / >]furan and 3a,6,6,9a-tetramethyldodecahydronaphtho[2,l- / >]furan stereoisomers as well as the reaction products of the acid-catalyzed cyclization of 1-(1',6'-dimethyl-4'-(4''-methylpent-3''-en-1''-yl)cyclohex-3'-en-1'-yl)ethan-1-one. A process for perfuming a product comprising the steps of: (i) preparation of a compound or mixture of compounds according to claim 1 or of a perfume composition according to any one of claims 6 to 9, and (ii) addition of the compound or mixture of compounds or of the perfume composition to the product to be perfumed, preferably in an amount giving a sensory effect, in particular in an amount sufficient to induce, accentuate and / or modify an olfactory note.

11. A process according to claim 10, wherein, in step (ii), compound (1) as defined in claim 3 is added to the product to be perfumed to induce, accentuate, modify and / or fix an amber and / or aloeswood note, and / or wherein compound (2) as defined in claim 4 is added to the product to be perfumed to induce, accentuate, modify and / or fix a woody, amber, aloeswood, peppery and / or green note, and / or wherein, in step (ii), compound (3) as defined in claim 5 is added to the product to be perfumed to induce, accentuate, modify and / or fix a woody, amber, aloeswood, peppery and / or green note.

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

13. Perfumed product according to claim 12, the product being selected from the group consisting of laundry and cleaning products, hygiene and care products, preferably in the field of body and hair care, cosmetic and household products, preferably selected from the group consisting of perfume extracts, perfumed waters, toilet waters, aftershave lotions, colognes, pre-shave products, perfumed wipes, acidic, alkaline or neutral detergents, textile deodorizers, ironing aids, liquid laundry detergents, powdered laundry detergents, laundry treatment agents, fabric softeners, soaps, washing tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and lacquers, 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, makeup cosmetics, candles, lamp oils, incense sticks, insecticides, repellents and propellants.

14. A perfumed product according to claim 12 or 13, wherein the total quantity of the perfume composition is within a range ranging from 0.05 to 5% by weight, preferably 0.5 to 2% by weight, respectively in relation to the total weight of the product.