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-1 / / -3a',7'-methanoazulen-6'-yl)butan-2-ones of formula (I), optionally substituted by methoxy in the C1 and C-3 positions as defined herein and their use as amber perfuming substances. In particular, the present invention relates to the use of compounds (1), (2) and (3) as perfuming substances and as fixatives as well as their use in perfuming compositions in combination with other perfuming substances. Furthermore, the present invention relates to a method for perfuming a product with the compounds according to the invention and a corresponding perfumed product.

[0002] “Ambergris” was already highly sought after around a thousand years before Jesus Christ among the inhabitants of the Indian Ocean coast for its extraordinary odor, great rarity, and supposedly aphrodisiac properties and 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 the use of amber in perfumery comes from Ibn Chordadhbeh (* c. 820; d c. 912), a geographer and administrator of the Province of Jibal in western Persia. As early as the ninth century, Arab sailors brought amber from the Near 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, Academie Press, Orlando, 1982, pp. 535-573). The light to dark gray waxy substance is a product of the pathological metabolism of the sperm whale (Physeter macrocephalus L.) which is formed after mechanical injury to the digestive tract by sharp objects as a kind of crust and is then detached in blocks of 15 to 150 kg. Through oxidative aging processes in the sea under the action of sunlight, a typical marine and exotic odor of dry wood and tobacco develops over the years with high persistence and strong fixation capacity. This very complex odor has aspects of: 1. humid 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. . Ambroxid In (-)-Amber (*)- -Copfosterin Amberketat Karanal Okoumai Spirambran Ysamber K Ambrcœrwt Am b res ta r Belambre

[0003] This specific amber profile of dry, warm, balsamic wood, tobacco and marine with a velvety animal tone and great originality that has made natural amber the most expensive perfuming 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, 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 (+)-epi-coprosterin (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 the case only in a very small number of niche perfumes, then it is solely for its fixing properties. Due to the low content of natural ambroxide and also due to hygiene and price concerns, natural amber is not . plays a greater role in commercial fine perfumery as consumers are accustomed to much higher dosages of ambroxide from semi-synthetic sources. Ambroxide has therefore lost its exclusive character, which is also identifiable by the fall in prices from > €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 that have amber notes ranging towards an amber and aloe wood odor (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 of the tobacco type and above all much drier in its woody character and with a lively animal sweetness sometimes felt almost as heady rather than warm and mossy, have played a major role in recent times. 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. Felt by some people as very intense, it nevertheless presents a high rate of anosmia, and is therefore odorless for many others.Other amber ketals are spirambrene (1986) with additional spicy aldehyde-like overtones, karanal (1987) with candle wax-like nuances and hot tar scents, 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 European Chemicals Agency (ECHA) due to its high persistence and very high bioaccumulation (vPvB, Article 57e). Since 27 August 2023, karanal must no longer be used in the EU.There is therefore a great need for new amber perfume substances without a ketal function but with amber odoriferous properties similar to these amber ketals to accompany the trend towards these mineral and metallic amber notes of dry wood which have dominated men's perfumery since "1 Million" (2008) and "Invictus" (2013).

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

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

[0007] Consequently, a clearly delimited family of 2-butanonenes optionally substituted by a methoxy in C1 or C-3, of general formula (I), has been surprisingly discovered, (I), < xp ..A ¥

[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 the C-4 position is derived from the renewable cedar sesquiterpene.

[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), \ P \ i: y x ..3Z Y x ■.

[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) constitute amber perfume substances which are also capable of fixing amber notes of other perfume substances, i.e. of prolonging as well as modifying their hold. The compounds are therefore advantageously integrated into a series of mixtures of perfume substances and are suitable for wide application in various products. In addition, the compounds are more polar thanks to oxygen substituents so that they exhibit low bioaccumulation.

[0019] Furthermore, the present invention relates to the use of a compound or mixture of compounds as defined above as a perfuming substance, in particular as an amber perfuming substance and / or for accentuating and / or modifying an amber and / or aloe wood note of other perfuming substances and / or as a fixative, in particular for prolonging the duration of an amber and / or aloe wood note of other perfuming substances.

[0020] In the context of the present invention, amber perfume substances are perfume substances which have an amber and aloe wood odor (wood infested with fungi of the species Aquilaria malaccensis, Aquilaria crassna, Aquilaria microcarpa or Aquilaria filaria). In comparison with amber, they have a woody, rather metallic and mineral character than a marine one of the tobacco and balsamic type and above all much drier and frequently a suave, lively animal character felt almost as heady rather than a warm, mossy odor in attack.

[0021] In the context of the present invention, the term "fixer" means a substance which is capable of prolonging the persistence of the odoriferous notes of other perfuming substances, i.e. of ensuring an odor which 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 animal, suave and balsamic in its woody character. In addition to the lively animal sweetness sometimes felt as heady, it is characterized by complementary, more bitter spicy facets.

[0025] The present invention also relates to the use of a compound as described above, compound (2) (2), O ■-s. A .OMe / V -..y”' ■ >■-A

[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), xA y

[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 amber-like dry wood and aloe wood type 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 and animal and tobacco-like accents in such a way that it harmonizes particularly well with the velvety and balsamic sandalwood perfume substances, whereas compound (2) has rather a musk-like vibration, gives an erogenous and clean effect, whereby it highlights the fresh notes of lemon and hesperides, further reinforced by the green and mossy touch. Compound (3), again, emphasizes the sweet warm and spicy odoriferous components by its transparent character of pepper and incense and harmonizes particularly well with somewhat acidic fruity odoriferous components.

[0030] According to another aspect, the present invention relates to a perfuming composition comprising or consisting of a compound or a mixture of compounds as defined above, in particular comprising compound (1), compound (2) and / or compound (3) and one or more other perfuming 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 perfume compositions, as the application examples below show. In particular, the combination with amber or aloe wood perfume substances provides advantageous effects.

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

[0034] The combination of one of 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] Even more preferred is a perfuming composition as described above, the amber perfuming substance(s) and / or the aloe wood perfuming substance(s) being selected from the group consisting of 2,2,5,8,8,9a-hexamethyloctahydro-4 / / -4a, 9-methanoazuleno[5,6-( / ][l,3]dioxole, 2,5,8,8,9a-pentamethyl-2-propyloctahydro-477-4a, 9-methanoazuleno[5,6-( / ][ 1,3]dioxole, 2,5,8,8,9a-pentamethyl-2-(prop-1-en-1-yl)octahydro-477-4a, 9-methanoazuleno[5, 6-( / ][l,3]dioxole, 2-(methoxymethyl)-2,5,8,8,9a-pentamethyloctahydro-4 / / -4a, 9-methanoazuleno[5,6-t / ][l,3]dioxole, 2,4-dimethyl-2-(5,5,8,8-tetramethyl-5,6,7,8 -tetrahydronaphthalen-2- y 1) -1,3 -dioxolane, 2', 2', 3,7,7 -pentaméthyIspiro [ bicyclo[4.1.0]heptane-2,5'-[l,3]dioxane], 2'-isopropyl-l,7,7-trimethylspiro[bi cyclo[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-l,l,2,3,3-pentamethyl-4(5 / / )-indanone, la, 3,3,4,6,6-hexamethyl-la, 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-t / ][l,3]dioxin, 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-577-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, 2,2,9,1 l-tetramethylspiro[5.5]undec-8-en-1-yl acetate, 3,8,8,1 la-tetramethyldodecahydro-5 / / -3,5a-epoxynaphth[2,lC]oxepin, . 3a, 6,6,9a-tetramethyl-1,2,3a, 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 ' ' -en-1 ' ' -yl)cyclohex-3 ' -en-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 perfuming composition as defined above, and (ii) addition of the compound or mixture of compounds or of the perfuming 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-providing amount" is an amount in which the compound and / or mixture of compounds or fragrance composition can be perceived in the fragranced product by a consumer in comparison to a product that does not contain a corresponding compound, mixture of compounds or fragrance composition.

[0039] A method 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 aloe wood note, and / or wherein compound (2) is added to the product to be perfumed to induce, accentuate, modify and / or fix a woody, amber, aloe wood, peppery and / or green note, and / or wherein, in step (ii), compound (3) is added to the product to be perfumed to induce, accentuate, modify and / or fix a woody, amber, aloe wood, 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 perfuming composition according to the invention is advantageously suitable for wide application in the most diverse products.

[0042] Preferably, the perfumed product is chosen from the group consisting of detergents and cleaning products, hygiene and care products, preferably in the field of body and hair care, cosmetics and household, preferably chosen from the group consisting of perfume extracts, eau de parfum, eau de toilette, aftershave lotions, eau de Cologne, pre-shave products, perfumed wipes, acidic, alkaline or neutral detergents, textile deodorizers, ironing aids, liquid detergents, powder detergents, laundry treatment agents, fabric softeners, soaps, washing tablets, disinfectants, surface disinfectants, air deodorizers, aerosol sprays, waxes and lacquers, body care products, hand creams and lotions, foot creams and lotions, hair removal creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, deodorants, antiperspirants, cosmetic makeup products, 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 odor.

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

[0045] In the following, the invention will be described in more detail with the aid of a few examples.

[0046] Example 1: Manufacture of 1-methoxy- and 3-methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-1'H-3a',7'-methanoazulen-6'-yl)butan-2-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 dropper, 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, the temperature rising to 50 °C. Then, it was heated at reflux for 5 hours (52 °C). The heat 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. At a reflux ratio of R:D = 25:1, a column bottom temperature of 120-150°C and a top temperature of 104-108°C, 43.7g of distillate were obtained (GC purity: 88%. Composition: 41% (E)-1,2-dimethoxyprop-1-ene, 17% (Z)-1,2-dimethoxyprop-1-ene, 30% 2,3-dimethoxyprop-1-ene).

[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-methyleneoctahydro-1H-3a,7-methanoazulene

[0069] In a 25 ml three-necked spherical flask stirring apparatus 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-methanoazulene-5-ol, 8.00 g (78.4 mmol) of a mixture of 65% (£ / Z)-l,2-dimethoxyprop-l-ene, 35% 2,3-Dimethoxyprop-1-ene, and 420 mg (7.00 mmol) of acetic acid under nitrogen atmosphere for 16 hours at 90 °C. Subsequently, the heat was removed and the preparation was diluted at room temperature with stirring with 20 ml of methyl-tert-butyl ether. It was washed twice with 20 ml of 5% sodium hydroxide solution each time and then reduced. The residue was mixed with heat with 10 ml of hexane and then recrystallized for 3 hours at 5 °C. The residue thus obtained was filtered and the mother liquor was reduced, 2.00 g of crude product being obtained (GC purity: 48%, 33% crude yield). After column chromatography (Büchi PrepChrom C-700, 80 g silica gel Kieselgel 60, eluent: eluting agent hexane / acetic acid = 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 title compound (GC purity: 99%) were obtained.

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

[0071] 'H NMR (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-methylene), 5.04 (t, J= 2.5 Hz, 1 H, Ha C=C-6', exo-methylene).

[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] RMN 13C (101 MHz, CDC13) ô = 15.5 (q, 3’-Me), 21.1 (q, C-3), 25.9 (t, C-l), 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-lH-3a',7'-methanoazulèn-6-yl)butan-2-one and l-methoxy-4-(3',8',8'-trimethyl-2',3',4',7',8',8a'-hexahydro-lH-3a',7'-methanoazulèn-6'-yl)butan-2-one by Claisen rearrangement

[0079] 1.50 g (4.66 mmol) of 5-((1',2'-dimethoxypropan-2'-yl)oxy)-3,8,8-trimethyl-6-methyleneoctahydro-1 / / -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 heater was removed. 1.09 g of crude product remained in the residue (GC purity: 78%). After column chromatography (Büchi PrepChrom C-700, 80 g silica gel Kieselgel 60, eluent: eluting agent hexane / acetic acid = 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] 13C NMR (100 MHz, CDC13): ô = 15.4 / 15.4 (2 q, 3'-Me), 24.8 / 24.8 (2 t, Cl), 25.0 / 25.4 (2 q, Cl), 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 smell: amber and dry wood, with animal touches 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'- méthanoazulèn-6’-yl)butan-2-one [Composé (2)]

[0087] GC-IR (Pureté GC 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’-H a, 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: amber dry wood, amber going towards ambrocenide (2,2,5,8,8,9a-hexamethyloctahydro-4 / / -4a, 9-methanoazuleno [5,6-6?] [ 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 reaction mixture starting to boil at 107 °C. At a reflux ratio of R:D = 10:1, a column bottom temperature of 107 to 122 °C and a head temperature of 72 to 92 °C, 91.0 g (76%) of the title compound (GC purity: 55%) were 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-methyleneoctahydro-lH-3a,7-methanoazulene

[0100] In a 10 ml single-necked spherical flask stirring apparatus equipped with a magnetic stirrer, a thermometer and a reflux cooler, 1.00 g (4.55 mmol) of 3,8,8-trimethyl-6-methyleneoctahydr o-177-3a,7-methanoazulene-5-ol, 5.00 g (58.1 mmol) of 2-ethoxyprop-1-ene and 200 mg (3.33 mmol) of acetic acid were stirred under a nitrogen atmosphere at 75 °C for 6 hours. The heat was removed, the preparation was diluted at room temperature with stirring with 50 ml of methyl-tert .-butyl ether, washed once with 20 ml of 5% sodium hydroxide solution and then reduced on a rotary evaporator to dryness, 1.10 g (79%) of product having been 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, 7 =9.0, 7,0 Hz, 1 H, 1”-Hb), 3.60 (dq, 7 = 9.0, 7,0 Hz, 1 H, 1”-Ha ), 4.62 (ddt, 7= 10.0, 7.5, 2,5 Hz, 1 H, 5-H), 4.88 / 5.29 (t, 7= 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-l'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 on a Kugelrohr distillation apparatus (Büchi Glass Oven B-585) for 4 hours at 160 °C and 100 mbar. The heater 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 silica gel Kieselgel 60, eluent: eluting agent hexane / acetic acid = 97:3—> 92:8, 71 min, 20 ml / min at 20 ml per fraction, DC: Rf = 0.20 (SiO2 60, hexane / acetic acid = 20:1)), 240 mg (32%) of the title compound (GC purity 99%) were obtained.

[0107] Odor Description: Dry and peppery, woody - amber, with distinct aspects of cedar wood and black pepper, as well as a sour spicy apple note in the opening 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’-H b), 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 an amber composition of dry wood rich in nuances with a contrast of fresh lemon

[0112] Perfume composition 3.1 CAS No. Matt. name 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 Bergamot Oil True E 40 106-24-1 Geraniol Supra 10 127-51-5 Methylionone 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 Oil 15 111879-80-2 Globalide® 30 107898-54-4 Polysantol 3 106-22-9 CITRONELLOL 950 15 8022-15-9 ESSENCE OF LAVENDER GROSS O NAT. 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 DEG. 4 COMPOUND (2) 10% DPG 20 1000

[0113] Compound (2) gives the composition more performance, character and a typical signature thanks to the contrast between amber and dark wood. It brings an amber tendency which accentuates the woody base character of the perfume. In addition, compound (2) harmonizes with the fresh lemony top note and gives it more radiant strength. Compound (2) also gives the whole perfume a long-lasting and good duration.

[0114] Perfume composition 3.2 CAS No. Mat. name 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 BERGAMOT OIL TRUE 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 OIL 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDIN OIL GROSS O NAT. 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 PINK PEPPER LEAF OIL 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, 8014-0 9-3 PATCHOULI ESSENCE DEG. 4 COMPOUND (1) 10% DPG 20 1000

[0115] Compound (1) gives a stronger and longer-lasting overall odor impression. In addition, compound (1) of the composition gives a unique masculine character and harmonizes well with the sweet and powdery nuances of the perfume and brings them to the forefront.

[0116] Perfume composition 3.3 CAS No. Mat. name 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 DE BERGAMOT VRA 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 OIL 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDIN OIL GROS SO NAT. 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% DP G 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 DEG. 4 COMPOUND (3) 10% DPG 20 1000

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

[0118] Perfume composition 3.4 CAS No. Mat. name 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 BERGAMOT TRUE OIL 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 OIL 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDIN OIL GROSSO NA T. 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 PEPPER LEAF ESSENCE RO SE 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, 8014-0 9-3 PATCHOULI OIL DEG. 4 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] Perfume composition 3.5: CAS No. Mat. name 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 BERGAMOT TRUE OIL 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 OIL 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 ESSENCE OF LAVENDER GROSSO NAT. 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 PINK PEPPER LEAF OIL 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 CIS-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, 8014-0 9-3 PATCHOULI OIL DEG. 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] Perfume composition 3.6 CAS No. Mat. name 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 DE BERGAMOT VRA 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 OIL 15 111879-80-2 GLOBALIDE® 30 107898-54-4 POLYSANTOL 3 106-22-9 CITRONELLOL 950 15 8022-15-9 LAVANDIN OIL GROSS O NAT. 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 JASMIN 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 DEG. 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, noble and sensual, the effect of the combination creating warm and attractive notes of pepper, incense and aloe wood.

Claims

Claims

1. A 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 fragrance substance, in particular as an amber fragrance substance and / or for strengthening and / or modifying an amber and / or aloe wood note of other fragrance substances and / or as a fixative, in particular for prolonging the durability of an amber and / or aloe wood note of other fragrance substances.

3. Use of a compound according to claim 2, wherein compound (1) (1) MeP 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 compound (2)

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

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

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

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

9. A fragrance composition according to either of claims 7 and 8, wherein the amber fragrance substance(s) and / or the aloe wood fragrance substance(s) is / are selected from the group consisting of 2,2,5,8,8,9a-hexamethyloctahydro-4 / / -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-1-en-1-yl)octahydro-4 / / -4a,9- methanoazuleno[5,6-( / ][l,3]dioxole, 2-(methoxymethyl)-2,5,8,8,9a-pentamethyloctahydro-4 / / -4a, 9-methanoazuleno[5,6-d][ 1,3]dioxole, 2,4-dimethyl 1-2- (5,5,8,8 -tetramethyl 1-5,6,7,8 -tetrahy dronaphthalen-2-yl)-l,3-dioxolane, 2', 2',3,7,7-pentamethylspiro[bicyclo[4.1.0]hep tane-2,5'-[l,3]dioxane], 2'-isopropyl-l,7,7-trimethylspiro[bi cyclo[2.2.1]heptane-2,4'-[l,3]dioxane], l-(2',2',6'-trimethylcyclohex yl)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-l,l,2,3,3-pentamethyl-4(5H)-indanone, la, 3,3,4,6,6-hexamethyl-la, 2,3,4,5,6,7,7a-octahydronaphtho[2,3-b]oxirene, 7,7,8,9,9-pentamethyl-4,4a, 5,6,7,8,9,9b-octahydroindeno[4,5-( / ][l,3]dioxin, 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-Z?]furan, 2,2,6,6,7,8,8-heptamethyldecahydro-2 / / -indeno[4,5- / ? ] furanc, 2,2,7,7,8,9,9-heptamethyldecahydroindeno[4,3 ab]furan, 7-methoxy-l,l,5,5-tetramethyl-l,3,4,5,6,7-hexahydro-2H-2,4a-methanonaphthalene, 5,5-dimethyl-2-propylhexahydro-2 7 / -2,4a-methanonaphthalen-l(5 / / )-one, 2,2,9,1 l-tetramethylspiro[ 5.5]undec-8-en-l-yl acetate, 3,8,8,1 la-tetramethyldodecahydro-5 77-3,5a-epoxynaphth[2,lC]oxepin, 3a, 6,6,9a-tetramethyl-1,2,3a, 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 1 -( 1 ' ,6' -dimethyl-4' -(4” -methylpent-3 ' ' -en-1 ' ' -yl)cyclohex-3 ' -en-l'-yl)ethan-l-one.

10. A method for perfuming a product comprising the steps of: (i) preparing a compound or mixture of compounds according to claim 1 or a perfuming composition according to one of claims 6 to 9, and (ii) adding the compound or mixture of compounds or the perfuming 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 method according to claim 10, 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 aloe wood note, and / or

12.

13.

14. wherein compound (2) is added to the product to be perfumed to induce, accentuate, modify and / or fix a woody, amber, aloe wood, peppery and / or green note, and / or wherein, in step (ii), compound (3) is added to the product to be perfumed to induce, accentuate, modify and / or fix a woody, amber, aloe wood, peppery and / or green note. Perfumed product comprising a compound or a mixture of compounds according to claim 1 or a perfume composition according to one of claims 6 to 9. Perfumed product according to claim 12, the product being selected from the group consisting of detergents and cleaning products, hygiene and care products, preferably in the field of body and hair care, cosmetics and household, preferably selected from the group consisting of perfume extracts, eau de parfum, eau de toilette, aftershave lotions, eau de Cologne, pre-shave products, perfumed wipes, acidic, alkaline or neutral detergents, fabric deodorizers, ironing aids, liquid detergents, powder 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, hair removal creams and lotions,aftershave creams and lotions, tanning creams and lotions, hair care products, deodorants, antiperspirants, cosmetic makeup products, candles, lamp oils, incense sticks, insecticides, repellents and propellants., Perfumed product according to claim 12 or 13, wherein the total amount of the perfume composition is in a range from 0.05 to 5% by weight, preferably 0.5 to 2% by weight, respectively relative to the total weight of the product.