12-oxaspiro[5,5]undec-8-ene useful in fragrance compositions

Abstract

To provide a novel organic compound, a method for preparing the compound, and its use as a fragrance component.SOLUTION: A compound according to formula (-)-(Id*), where the compound shows negative specific rotation values, is provided.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to novel organic compounds, methods for preparing the compounds, and their use as fragrance ingredients. The invention also relates to perfume compositions and to fine fragrances or consumer products scented with the compounds or to articles such as perfume compositions containing the compounds. [Background technology]

[0002] Background of the Invention Traditionally, compounds with grapefruit and cassis characteristics are sulfur-containing organic compounds, e.g., Corpus Cassis (R) , Corps Pamplemousse (R) and 1-p-menthene-8-thiol (grapefruit mercaptan), and non-sulfur-containing organic compounds such as buccoxime (R) , Theaspiran and Etaspiren (R) However, the use of known non-sulfur compounds is expensive, and sulfur-containing compounds tend to be unstable in various applications and can cause unpleasant off-flavors. [ka]

[0003] In WO2010125100A1, it is described that a group of 1-alkoxy-2-oxaspiro[5.5]undec-8-enes constitute new grapefruit and blackcurrant odorants and are therefore a valuable new group of ingredients for the flavor and fragrance industry. One example is 1-methoxy-7,9-dimethyl-2-oxaspiro[5.5]undec-8-ene, which has, among other things, a green, fruity, floral, blackcurrant, and grapefruit odor. Summary of the Invention

[0004] Description of the invention 1-Methoxy-7,9-dimethyl-2-oxaspiro[5.5]undec-8-ene (the compound represented by formula (I)) is a compound with three stereocenters, and therefore, a total of eight stereoisomers of the compound exist. [ka]

[0005] They form four different diastereoisomers, each of which is a pair of two enantiomers. [ka]

[0006] Surprisingly, it has now been found that the olfactory benefit of compounds of formula (I) depends on the stereochemistry: one of the four diastereoisomers (±)-(Id * ) are strong aroma components, while the others only exhibit very weak aroma characteristics, if any.

[0007] Formula (±)-(Id * ) is a racemate, a 1:1 mixture of two enantiomers. Further analysis revealed that only one of these two enantiomers is olfactorily active. The two enantiomers were separated by a chiral column, and the olfactorily active one exhibited a negative specific rotation value.

[0008] Thus, in the first aspect of the present invention, a compound of the formula (-)-(Id * ) compounds according to the formula (-)-(Id * ) according to the compound ((-)-(1R * ,6R * ,7R * )-1-Methoxy-7,9-dimethyl-2-oxaspiro[5.5]undec-8-ene) is provided. The absolute configuration of the compound has not been elucidated. The compound has a strong blackcurrant, grapefruit, fruity, and juicy odor. [ka]

[0009] In a further aspect of the invention, a compound of formula (-)-(Id * ) and compounds according to the formula (+)-(Id * isomeric mixtures containing compounds according to formula (I) are provided. [ka]

[0010] In some embodiments, the isomeric mixture is represented by the formula (-)-(Id * ) and compounds according to the formula (+)-(Id * ) in a 1:1 weight ratio, which is a racemic mixture of two enantiomers (±)-(Id * ) [ka]

[0011] In another embodiment, the isomeric mixture is enriched in one of the two enantiomers, preferably the enantiomer (-)-(Id * In the composition, the formula (-)-(Id * ) and compounds according to the formula (+)-(Id * The weight ratio of the compound according to formula (I) to the compound according to formula (I) may range from about 99.99:0.01 to about 1:99, for example, from about 99.9:0.1 to about 5:95.

[0012] Generally, the formula (±)-(Id * ) and other stereoisomers have the formula " * " indicates the relative configuration in the ring system, but not the absolute configuration. Diastereoisomers of the present invention are understood as mixtures of enantiomers, as indicated by the prefix "(±)-" or "rac-". Pure enantiomers are indicated by the prefix "(+)-" or "(-)-".

[0013] When compound exists in different stereoisomeric forms, it may be used as a mixture.Alternatively, it may be separated into diastereoisomeric groups or as pure stereoisomers.Separation into stereoisomers adds complexity to the preparation and purification of compound, therefore, for economic reasons, it is preferred to use compound as the mixture of its stereoisomers.However, if it is desired to prepare individual stereoisomers, it may be achieved according to methods known in the art, for example, stereoselective synthesis, preparative HPLC and GC.

[0014] In one aspect of the present invention, a compound of formula (±)-(Id * ) can be obtained in highly enriched or essentially pure form as the corresponding diastereoisomers (±)-(Ia * ), (±)-(Ib * ) and / or (±)-(Ic * ) in low amounts or essentially free of the preferred diastereoisomer (±)-(Id * ) is present in at least 90% by weight, specifically at least 95% by weight, more specifically at least 98% by weight, and even more specifically 99% by weight or greater.

[0015] In another aspect of the invention, a relatively high amount of a compound of the formula (±)-(Id * ) can be used to synthesize the preferred diastereoisomer according to the formula (Ia) with the other diastereoisomers (±)-(Ia * ), (±)-(Ib * ) and / or (±)-(Ic * ) together in low amounts. This is because the preferred diastereoisomer (±)-(Id * ) is present in at least 50% by weight, specifically at least 60% by weight, more specifically at least 70% by weight, and even more specifically 80% by weight or more.

[0016] In a further aspect of the invention, a compound of formula (-)-(Id * ) or according to the formula (±)-(Id *) is provided for use as a fragrance. In yet another aspect of the present invention, a compound of formula (-)-(Id * ) or according to the formula (±)-(Id * A fragrance composition is provided comprising a compound according to

[0017] The compounds of the present invention may be used alone or in combination with known odorant molecules selected from a wide range of currently available natural products, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and synthetic molecules, and / or in admixture with one or more ingredients or excipients conventionally used in conjunction with odorants in perfume compositions, such as carrier materials and other auxiliaries commonly used in the art.

[0018] As used herein, "carrier material" means a material that is substantially neutral from the odorant's point of view, i.e., a material that does not significantly alter the odorant's sensory properties.

[0019] The term "adjuvant" refers to an ingredient that may be used in a fragrance composition for reasons not specifically related to the olfactory performance of the fragrance composition. For example, an adjuvant may be an ingredient that serves as an aid in the processing of the fragrance ingredient(s) or ingredients, or a composition containing said ingredient(s), or may be an ingredient that improves the handling or storage of the fragrance ingredient or composition containing it. It may also be an ingredient that provides an additional benefit, such as imparting color or a tactile feel. It may also be an ingredient that confers lightfastness or chemical stability to one or more ingredients contained in the fragrance composition. A detailed description of the nature and types of adjuvants commonly used in adjuvant-containing perfume compositions cannot be exhaustive, but it should be stated that such ingredients are well known to those skilled in the art.

[0020] As used herein, "fragrance composition" refers to any composition comprising a compound represented by formula (I) and a substrate, e.g., a diluent conventionally used in conjunction with an odorant, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (IPM), pentane-1,2-diol, triethyl citrate (TEC), and alcohol (e.g., ethanol). Optionally, the composition may comprise an antioxidant adjuvant. The antioxidant may be selected from the following: Tinogard (R) TT (BASF), Tinogard (R) Q (BASF), Tocopherol (including its isomers, CAS 59-02-9; 364-49-8; 18920-62-2; 121854-78-2), 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT, CAS 128-37-0) and related phenols, hydroquinone (CAS 121-31-9).

[0021] The following list shows the formula (-)-(Id * ) or according to the formula (±)-(Id * ) include known odorant molecules that can be combined with compounds according to: - essential oils and extracts, such as bead onion, costus root oil, oakmoss absolute, geranium oil, tree moss absolute, basil oil, fruit oils such as bergamot oil and mandarin oil, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil, jasmine oil, rose oil, sandalwood oil, absinthe oil, lavender oil and / or ylang-ylang oil;

[0022] - Alcohols, such as cinnamic alcohol ((E)-3-phenylprop-2-en-1-ol); cis-3-hexenol ((Z)-hex-3-en-1-ol); citronellol (3,7-dimethyloct-6-en-1-ol); dihydromyrcenol (2,6-dimethyloct-7-en-2-ol); Ebanol TM((E)-3-Methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-ol); Eugenol (4-allyl-2-methoxyphenol); Ethyl linalool ((E)-3,7-dimethylnona-1,6-dien-3-ol); Farnesol ((2E,6Z)-3,7,11-trimethyldodeca-2,6,10-trien-1-ol); Geraniol ((E)-3,7-dimethylocta-2,6-dien-1-ol); Super Muguet TM ((E)-6-Ethyl-3-methyloct-6-en-1-ol); Linalool (3,7-dimethylocta-1,6-dien-3-ol); Menthol (2-isopropyl-5-methylcyclohexanol); Nerol (3,7-dimethyl-2,6-octadien-1-ol); Phenylethys Alcohol (2-phenylethanol); Rhodinol™ (3,7-dimethyloct-6-en-1-ol); Sandalore TM (3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol); terpineol (2-(4-methylcyclohex-3-en-1-yl)propan-2-ol); or Timberol TM (1-(2,2,6-trimethylcyclohexyl)hexan-3-ol); 2,4,7-trimethylocta-2,6-dien-1-ol, and / or [1-methyl-2(5-methylhex-4-en-2-yl)cyclopropyl]-methanol;

[0023] - Aldehydes and ketones, such as anisaldehyde (4-methoxybenzaldehyde); alpha-amyl cinnamaldehyde (2-benzylideneheptanal); Georgywood TM (1-(1,2,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone); Hydroxycitronellal (7-hydroxy-3,7-dimethyloctanal); Iso E Super (R)(1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone);Isoraldeine (R) ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one);Hedione (R) (Methyl 3-oxo-2-pentylcyclopentaneacetate); 3-(4-isobutyl-2-methylphenyl)propanal; maltol; methyl cedryl ketone; methyl ionone; verbenone; and / or vanillin;

[0024] - Ethers and acetals, e.g. Ambrox (R) (3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran); geranyl methyl ether ((2E)-1-methoxy-3,7-dimethylocta-2,6-diene); rose oxide (4-methyl-2-(2-methylprop-1-en-1-yl)tetrahydro-2H-pyran); and / or Spirambrene (R) (2',2',3,7,7-pentamethylspiro[bicyclo[4.1.0]heptane-2,5'-[1,3]dioxane]);

[0025] - esters and lactones, such as benzyl acetate; cedryl acetate ((1S,6R,8aR)-1,4,4,6-tetramethyloctahydro-1H-5,8a-methanoazulen-6-yl acetate); γ-decalactone (6-pentyltetrahydro-2H-pyran-2-one); Helvetolide (R) (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropylpropionate); γ-undecalactone (5-heptyloxolan-2-one); and / or vetivelyl acetate ((4,8-dimethyl-2-propan-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulen-6-yl)acetate);

[0026] - Macrocycles, such as Ambrettolide ((Z)-oxacycloheptadecan-10-en-2-one); ethylene brassylate (1,4-dioxacycloheptadecan-5,17-dione); and / or Exaltolide (R) (16-oxacyclohexadecan-1-one); and - Heterocycles, for example isobutylquinoline (2-isobutylquinoline).

[0027] In yet another aspect of the present invention, a compound of formula (-)-(Id * ) or according to the formula (±)-(Id * ) are provided articles, such as fine fragrances or personal or household care products, scented with compounds according to the present invention.

[0028] Expression (-)-(Id * ) or according to the formula (±)-(Id * Compounds according to the formula (Id) can be used in a wide range of scented articles, including all areas of luxury and functional fragrances, such as perfumes, air care products, household products, laundry products, body care products, and cosmetics. The compounds can be used in widely varying amounts, depending on the particular article and the nature and amount of other odorant ingredients. The proportion is typically 0.0001 to 3 weight percent of the article. In one embodiment, the compounds of the present invention can be used in fabric softeners in amounts of 0.001 to 0.3 weight percent (e.g., 0.01 to 0.1 weight percent, including 0.05 weight percent). In another embodiment, compounds according to the formula (Id) can be used in fabric softeners in amounts of 0.001 to 0.3 weight percent (e.g., 0.01 to 0.1 weight percent, including 0.05 weight percent). * ) or according to the formula (±)-(Id * ) can be used in fine perfumery in amounts of 0.001 to 30 percent by weight (for example up to about 10 percent or up to 20 percent by weight), more preferably between 0.01 and 5 percent by weight. However, these values ​​are given only as an example, since the skilled perfumer can achieve an effect or create novel accords at lower or higher concentrations.

[0029] In one embodiment, an acceptable amount of the formula (-)-(Id * ) or according to the formula (±)-(Id * For example, the fragranced article may comprise 0.000001% to 90% by weight (including 0.00001% by weight; 0.0001%, 0.001%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 50%, 60%, 65% by weight) based on the total weight of the article.

[0030] Expression (-)-(Id * ) or according to the formula (±)-(Id * ) can be used in consumer product formulations to combine the compounds of the invention or the compounds of formula (-)-(Id * ) or according to the formula (±)-(Id * ) or mixtures thereof may be used by simply mixing it with the consumer product base, or it may be encapsulated in a previous step with an encapsulating material, such as polymers, capsules, microcapsules and nanocapsules, liposomes, film-forming agents, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the consumer product base.

[0031] Therefore, the present invention also provides a compound of the formula (-)-(Id * ) or according to the formula (±)-(Id * ) by directly incorporating the compound into a consumer product base using conventional techniques and methods, or by incorporating a compound according to the formula (-)-(Id * ) or according to the formula (±)-(Id *and then incorporating as a fragrance ingredient a perfume composition comprising a compound according to claim 1, wherein the compound is a fragrant ingredient of a consumer product base. As described herein, the odor notes of the consumer product base are improved, enhanced, or modified through the addition of an olfactorily acceptable amount of a compound of the present invention.

[0032] Thus, the present invention further provides a method of imparting, enhancing, improving or modifying the hedonic properties of a fragrance composition or consumer product, the method comprising adding to said fragrance composition or consumer product a compound of the formula (-)-(Id * ) or according to the formula (±)-(Id * ) adding a compound according to

[0033] As used herein, "consumer product base" refers to a composition for use as a consumer product to perform specific functions such as cleaning, softening, and care. Examples of such products include: luxury perfumes, such as perfumes and eau de toilette; fabric care, household products, and personal care products, such as cosmetics, laundry care detergents, rinse conditioners, personal cleansing compositions, dishwasher detergents, and surface cleaners; laundry products, such as fabric softeners, bleaches, and detergents; body care products, such as shampoos and shower gels; and air care products (preferably containing volatile, often pleasant-smelling compounds, advantageously capable of masking unpleasant odors even in very small amounts). Air fresheners for living areas contain, for example, up to 50% by weight of natural and synthetic essential oils, such as pine needle oil, citrus oil, eucalyptus oil, and lavender oil, among others. Aerosols tend to contain smaller amounts of such essential oils, for example less than 5% or less than 2% by weight, but may additionally include compounds such as acetaldehyde (especially <0.5% by weight), isopropyl alcohol (especially <5% by weight), mineral oil (especially <5% by weight), and propellants.

[0034] Cosmetic products include: (a) Cosmetic skin care products, in particular bath products, skin cleansing and cleansing products, skin care products, eye make-up, lip care products, nail care products, intimate care products and foot care products; (b) Cosmetic products with specific effects, in particular sunscreens, tanning products, anti-pigmentation products, deodorants, antiperspirants, hair removers and shaving products; (c) Cosmetic dental care products, in particular dental and oral care products, tooth care products, cleaning agents for dental prostheses, adhesives for dental prostheses; and (d) Cosmetic hair care products, in particular hair shampoos, hair care products, hair-setting products, hair-shaping products and hair-coloring products.

[0035] As shown in Scheme 1 below, compounds of formula (I) can be prepared by cleaving the corresponding alcohol R of the corresponding hemiacetate of formula (II) in the presence of a catalytic amount of an acid catalyst under conditions known to those skilled in the art. 1 The preparation of hemiacetals of formula (II) can be prepared by reaction with OH. The preparation of hemiacetals of formula (II) is described, for example, by Yue Zou et al. (Chem. Eur. J. 2008, 14, 5335-5345).

[0036] Scheme 1: [ka]

[0037] By varying the conditions for acetalization of the hemiacetal of formula (II) to the compound of formula (I) (second step), the ratio of diastereoisomers can be controlled. Relatively higher amounts of acid and longer reaction times result in the formation of the diastereoisomers (±)-(Id * )-enriched (up to 75%) mixtures. On the other hand, shorter reaction times lead to the formation of the diastereoisomers (±)-(Ic * ) leading to a higher proportion of

[0038] Separation of stereoisomers can be achieved by a variety of chromatographic techniques using chiral and / or achiral stationary phases. The present invention is further illustrated by the following non-limiting examples.

[0039] example Example 1: Preparation of stereoisomers of compounds of formula (I) The hemiacetal 7,9-dimethyl-2-oxaspiro[5.5]undec-8-en-1-ol was obtained according to Yue Zou et al. (Chem. Eur. J. 2008, 14, 5335-5345). The crude product, 7,9-dimethyl-2-oxaspiro[5.5]undec-8-en-1-ol (233 g, ≦0.969 mol, 81.8% purity), was combined with methanol (156 g, 4.865 mol, 5 eq., Fluka), toluene (30 ml, Honeywell), and aq. sulfuric acid (11.81 g, 0.117 mol, 97%, 0.12 eq.). The resulting mixture was immersed in an oil bath preheated to 85 °C and refluxed (65 °C) for 1 h, cooled to RT, transferred to a separatory funnel, diluted with MTBE (100 ml, technical) and treated with aq. saturated sodium carbonate solution (200 ml, resulting in pH 8). The separated aqueous phase was extracted three times with MTBE (100 ml). The combined organic phases were neutralized by washing with aq. saturated NaCl (100 ml), dried over MgSO4, filtered and the filtrate was concentrated on a rotavapor (55 °C, 80 mbar) and under HV (20 °C, 0.08 mbar) to give 195.6 g of a brown oil (GC-purity: 99%).

[0040] The resulting product (I) is a diastereomeric product of four diastereomers ((±)-(Ia * ), (±)-(Ib * ), (±)-(Ic * ), (±)-(Id * )), and each diastereomer is a 50:50 mixture of enantiomers (e.g., (±)-(Ia * )About: (-)-(Ia * ) / (+)-(Ia *)) exists as the diastereoisomeric ratio (±)-(Ia * ):(±)-(Ib * ):(±)-(Ic * ):(±)-(Id * ) is 3:8:15:74 (for the ratio of anomeric signals at C1, 1 (determined by H-NMR).

[0041] Example 2: Separation of stereoisomers of compounds of formula (I) GC-sniffing of the resulting product (I) showed that only one of the diastereomers was olfactorily active. More specifically, only one of the eight optically active diastereomers was found to be olfactorily active, as the best separation was obtained using a chiral GC column.

[0042] Minor isomer (±)-(Ia * ) and (±)-(Ib * ) was obtained by using a chiral column (ZB-wax) to obtain the major isomer (±)-(Ic * ) and (±)-(Id * ), and (±)-(Ia * ) and (±)-(Ib * ) was found to be odorless. Good separation was obtained using chiral GC column Hydrodex-beta-3-P: (±)-(Ia * ) and one enantiomer of (±)-(Ic * Only one enantiomer of (Ia) coeluted. The elution order is as follows: * )(I C * )), (Ib * ),(I C * )', (Ib * )', (Ia * )', (Id * ), (Id * )', and the slowest eluting (Id * ) enantiomers are olfactorily active.

[0043] Separation details: Chiral GC method (Thermo Scientific Trace 1310 GC & TriPlus 100LS Autosampler): Split ratio 1:1 between FID (Front Detector) & sniffing port (A2D), 1 μl (10,000 ng / μl in MtBE), split 20:1, hot needle injection technique, injector 210°C, carrier gas H2, constant flow 1.5 ml / min, column 25 m x 0.25 mm Hydrodex-beta-3P (Macherey-Nagel, P / N 723358.25, S / N 20114 / 61), temperature program 2 min @ 50°C - 2°C / min - 2 min @ 190°C, FID base 230°C, air 350 ml / min, H2 35 ml / min, N2 makeup 40 ml / min, Chromeleon 7.2.

[0044] On a preparative scale, the major stereoisomer (+)-(Id * ) and (-)-(Id * ) was achieved by supercritical fluid chromatography (SFC): Approximately 19 g of (I) was dissolved in 190 mL of methanol (Merck, HPLC grade) and subjected to SFC (230 injections, 1 ml injection volume) using a PIC10-150 equipped with a Phenomenex Lux A1 (30 × 250 mm, 5 μm) column maintained at 35°C with a UV detector at 210 nm, applying a flow rate of 3 ml / min. Elution (mobile phase: A: 90% SFC grade carbon dioxide, B: methanol (Merck HPLC grade); isocratic, flow rate 100 ml / min) and collection of fractions at room temperature yielded two fractions: F1 (~2.0 L) and F2 (~2.2 L), which were concentrated (35°C, 560 mbar) to give approximately 4.0 g of separated fractions. F2 was (+)-(Id * ), (I), while F1 consists of the olfactorily inactive enantiomer of the main diastereomeric pair (+)-(Id * ) consisted of a mixture of the remaining stereoisomers.

[0045] Semi-prep. HPLC separation: Fraction F1 obtained by SFC and diluted to 200 mg / ml in MeOH (Fisher Scientific, M / 4000 / 15) was subjected to a Thermo Scientific Ultimate 3000 HPLC equipped with Chromeleon 7.2 CDS software and a DAD detector (UV detection at 210 nm, 1.6 μl injection volume, 110 injections) equipped with a Merck LichroCART-ChiraDex column (4 × 250 mm, 5 μm) cooled to 6°C, and purified water / MeOH 25:75% v / v, isocratic elution was applied at a flow rate of 0.6 ml / min.

[0046] Solid phase extraction (SPE): A cartridge (Waters Oasis HLB 6 cc cartridge, 186000115) was conditioned with 5 mL of MtBE (VWR, 2.2105.320), 5 mL of MeOH, and 5 mL of purified water:MeOH 90:10% v / v. Pooled fractions obtained by LC prep were diluted with 900 mL of purified water and applied to the cartridge at a flow rate of approximately 5.5 h / L. After washing with 50 mL of purified water, the cartridge was flushed with a syringe piston and dried under vacuum for 15 min. Elution was performed four times with 2 mL of MtBE. The eluate was pooled and the phases were separated. The MtBE phase was dried onto two NaSO syringe cartridges (Chromafix Dry / NaSO, 250 mg, 731852), flushed twice with 0.5 ml of MtBE, and the solvent was evaporated under a stream of N at room temperature to give 13 mg of (-)-(Id * ) (GC: 94% purity).

[0047] (±)-(Ia * ): (±)-(1S * ,6R * ,7S * )-1-Methoxy-7,9-dimethyl-2-oxaspiro[5.5]undec-8-ene 1H-NMR (600 MHz, C6D6): δ (selected signals) 5.33–5.30 (m, 1 H), 4.55 (s, 1 H), 3.72–3.67 (m, 1 H), 3.48–3.43 (m, 1 H), 3.25 (s, 3 H), 2.72–2.66 (m, 1). H), 1.59 (s, 3 H), 0.86 (dd, J = 7.2, 3 H). 13 C-NMR (150 MHz, C6D6): δ 132.4(s), 126.9(d), 101.5(d), 59.4(h), 54.9(q), 37.2(s), 32.3(d), 27.5(h), 27.1(h), 26.9(h), 23.5(q), 21.6 (t), 15.8 (q).

[0048] (±)-(Ib * ): (±)-(1R * ,6R * ,7S * )-1-dip-7,9-dip-2-dip[5.5]dip-8-p 1 H-NMR (600 MHz, C6D6): δ (selected signals) 5.33–5.30 (m, 1 H), 4.49 (s, 1 H), 3.71–3.66 (m, 1 H), 3.50–3.46 (m, 1 H), 3.23 (s, 3 H), 2.50–2.44 (m, 1). H), 1.57 (s, 3 H), 0.93 (dd, J = 7.2, 3 H). 13 C-NMR (150 MHz, C6D6): δ 131.3(s), 127.2(d), 101.9(d), 58.4(h), 54.7(q), 36.9(s), 34.7(d), 27.0(h), 25.9(h), 24.4(h), 23.4(q), 21.4 (t), 16.9 (q).

[0049] (±)-(Ia * )および(±)-(Ib * ): GC-MS (EI): 210 (8), 195 (2), 179 (9), 178 (26), 163 (18), 150 (15), 135 (14), 122 (19), 121 (23), 108 (21), 107 (100), 105 (17), 97 (24), 94 (20), 93 (37), 91 (34), 79 (21), 77 (16), 61 (10), 67 (18), 41 (23), 39 (11).

[0050] (±)-(Ic * ):(±)-(1S * ,6R * ,7R * )-1-Methoxy-7,9-dimethyl-2-oxaspiro[5.5]undec-8-ene 1 H-NMR (600 MHz, C6D6): δ selected signals 5.30-5.25 (m, 1 H), 4.38 (s, 1 H), 3.74-3.68 (m, 1 H), 3.47-3.41 (m, 1 H), 3.23 (s, 3 H), 2.54-2.48 (m, 1 H), 1.57 (s, 3 H), 1.07 (dd, J = 0.8, 7.2, 3 H). 13 C-NMR (150 MHz, C6D6): δ 130.9 (s), 126.7 (d), 102.9 (d), 58.6 (t), 54.4 (q), 36.7 (s), 32.7 (d), 26.6 (t), 25.2 (t), 25.2 (t), 23.3 (q), 20.9 (t), 17.0 (q). GC-MS (EI): 210 (2), 195 (1), 179 (10), 178 (34), 163 (10), 150 (7), 135 (15), 122 (19), 121 (23), 108 (19), 107 (100), 105 (14), 97 (26), 94 (23), 93 (35), 91 (29), 79 (21), 77 (15), 61 (8), 67 (17), 41 (23), 39 (10).

[0051] (±)-(Id * ): (±)-(1R * ,6R * ,7R * )-1-Methoxy-7,9-dimethyl-2-oxaspiro[5.5]undec-8-ene 1 H-NMR (600 MHz, C6D6): δ (selected signals) 5.30-5.27 (m, 1 H), 4.16 (s, 1 H), 3.72-3.66 (m, 1 H), 3.53-3.47 (m, 1 H), 3.23 (s, 3 H), 2.09-2.01 (m, 2 H,), 1.57 (s, 3 H), 0.93 (dd, J = 7.2, 3 H). 13 C-NMR (150 MHz, C6D6): δ 130.6 (s), 126.9 (d), 103.8 (d), 59.2 (t), 54.2 (q), 38.2 (d), 36.9 (s), 26.8 (t), 25.6 (t), 21.9 (t), 21.9 (t), 23.3 (q), 15.9 (q). GC-MS (EI): 210 (1), 195 (1), 179 (10), 178 (33), 163 (7), 150 (9), 135 (16), 122 (23), 121 (24), 108 (20), 107 (100), 105 (13), 97 (27), 94 (19), 93 (33), 91 (26), 79 (18), 77 (13), 61 (6), 67 (13), 41 (16), 39 (7).

[0052] (+)-(Id * ): The main diastereomeric pair (±)-(Id * ) olfactorily inactive enantiomer 1 H-NMR (400 MHz, CDCl3): δ 5.27-5.23 (m, 1 H, HC(8)=), 4.10 (s, 1 H, HC(1)), 3.71 (ddd, 1 H, J = 2.9, 10.8, 13.2, HC(3)), 3.55 (ddt, 1 H, J = 1.5, 5.4, 11.0, HC(3)), 3.36 (s, 3 H, MeO), 1.97-1.71 (m, 5 H), 1.68-1.61 (dm, J = 14.2, 1 H), 1.61 (s, 3 H, MeC(9)=), 1.46-1.28 (m, 3 H), 0.85 (d, J = 7.1, 3 H, Me-C(7)). 13 C-NMR (100 MHz, CDCl3): δ 130.74 (s), 126.29 (d), 103.88 (d), 59.24 (t), 54.52 (q), 37.77 (d), 36.60 (s), 26.53 (t), 25.24 (t), 23.21 (q), 21.65 (t), 21.58 (t), 15.62 (q).

[0053] ORD: (25°C, c = 1.010 in EtOH): [α] D : +180.3; [α] 578 : +213.6 (Hg); [α] 405 : +435 (Hg); [α] 365 : +570.5 (Hg). GC-threshold estimate: >250ng (technical limit of this method) Scent description: Odorless.

[0054] (-)-(Id * ): The main diastereomeric pair (±)-(Id * ) olfactorily active enantiomer 1 H-NMR (400 MHz, CDCl3): δ 5.28-5.24 (br. m, 1 H, HC(8)=), 4.11 (s, 1 H, HC(1)), 3.72 (ddd, 1 H, J = 2.9, 10.8, 13.2, HC(3)), 3.56 (ddt, 1 H, J = 1.4, 5.3, 10.9, HC(3)), 3.37 (s, 3 H, MeO), 1.98-1.72 (m, 5 H), 1.69-1.62 (dm, J = 13.8, 1 H), 1.62 (s, 3 H, MeC(9)=), 1.47-1.29 (m, 3 H), 0.86 (d, J = 6.9, 3 H, Me-C(7)). 13 C-NMR (100 MHz, CDCl3): δ 130.79 (s), 126.29 (d), 103.90 (d), 59.26 (t), 54.56 (q), 37.78 (d), 36.62 (s), 26.55 (t), 25.25 (t), 23.24 (q), 21.67 (t), 21.59 (t), 15.64 (q). GC-MS (EI): 210 (1), 179 (12), 178 (38), 163 (9), 150 (10), 135 (18), 122 (24), 121 (25), 108 (19), 107 (100), 105 (13), 97 (29), 94 (18), 93 (32), 91 (27), 79 (17), 77 (13), 61 (9), 67 (14), 41 (21), 39 (10).

[0055] ORD (25°C, c = 0.491 in EtOH): [α] D : -174; [α] 546 : -202 (Hg), [α] 405 : -409 (Hg), [α] 365 : -535 (Hg). GC-threshold: 7.2ng Scent description: Fruity, cassis, grapefruit, juicy

Claims

1. Formula (-)-(Id ＊ ) Compounds according to 【Chemical 1】 wherein the compound exhibits a negative specific rotation value.

2. and the formula (+)-(Id ＊ ) Compounds according to 【Chemistry 2】 A mixture of isomers comprising:

3. Formula (-)-(Id ＊ ) and compounds according to the formula (+)-(Id ＊ 3. The isomeric mixture according to claim 2, wherein the weight ratio of compounds according to (Id) is 1:1, ＊ ) 【Chemistry 3】 The isomeric mixture,

4. The formula (-)-(Id ＊ 10. Use of a compound of formula (I) or an isomer mixture as defined in claim 2 or 3 as a fragrance.

5. an olfactory acceptable amount of a compound of the formula (-)-(Id ＊ 10. A method of improving, enhancing or modifying a consumer product base using the addition of a compound of the formula:

6. The odorant of formula (-)-(Id ＊ 10. A fragrance application comprising a compound of formula (I) or an isomeric mixture as defined in claim 2 or 3, and a consumer product base.

7. 7. The fragrance application of claim 6, wherein the consumer product base is selected from fine fragrances, household products, laundry products, body care products, cosmetic products and air care products.

8. The formula (-)-(Id ＊ 4. A fragrance composition comprising a compound represented by the formula (I) or an isomer mixture defined in claim 2 or 3, and a base material.

9. 10. The composition of claim 1, wherein the formula (-)-(Id ＊ 4. A fragrance composition comprising a compound represented by the formula:

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