(S,Z)-3,7-dimethylnonona-6-en-1-ol and its use as a fragrance

Abstract

A compound according to formula IIa, which is (S,Z)-3,7-dimethylnon-6-en-1-ol, and its use as a fragrance. [Formula 1] JPEG2023520023000014.jpg23163

Description

Technical Field

[0001] The present invention relates to novel organic compounds, methods for preparing said compounds, and their use as fragrance components. The present invention also relates to fine fragrances or consumer product compositions perfumed with said compounds, or fragrance compositions containing said compounds, and to articles in fragrance compositions.

Background Art

[0002] Background of the Invention Citronellol (dihydrogeraniol, 3,7-dimethyloct-6-en-1-ol, the compound represented by formula (I)) is widely used as a fragrance and food ingredient. It has a floral, rose-citrus odor and flavor. Although it is safe to use in foods, some concerns have been raised for its use in perfumes as it can cause allergic reactions in some people. Citronellol is listed in the list of 26 fragrance allergens designated by the European Union. Consequently, fragrances containing citronellol must be labeled.

Chem.

Summary of the Invention

[0003] Description of the Invention 3,7-dimethylnonano-6-en-1-ol (ethylcitronellol, the compound represented by formula (II)) corresponds to citronellol morphologically elongated by one methyl group. It is a compound with one stereocenter and a double bond, and can exist in a total of four stereoisomers. [ka] In the compound represented by formula (II), the stars indicate the stereocenter of the C atom, and the wavy lines indicate the unspecified stereoconfiguration of adjacent double bonds. 3,7-Dimethylnona-6-en-1-ol has been previously reported. It was identified by GC-MS as a compound in raspberry juice (Shipin Kexue 2013, 34, 199-203) and in fungi (Junwu Xuebao 2012, 31, 92-101). It can be obtained from citronellol in a four-step synthesis (Biosci. Biotechnol. Biochem. 2002, 66, 582-587). It can also be prepared from methyl ethyl ketone in a seven-step synthesis according to Dragoco's report (1978 11 / 12, 235). However, its fragrance properties have not yet been reported. Surprisingly, it has been found today that ethyl citronellol possesses floral rose, citronellol, peony, and lychee aromas, and has a gas chromatography (GC) threshold of 0.22 ng. Therefore, in a first aspect of the present invention, the compound represented by formula (II) can be used as a fragrance material, for example, as a substitute for citronellol. It is not listed in the list of 26 fragrance allergens designated by the European Union.

[0004] Surprisingly, it was further discovered that the aromatic effect of the compound represented by formula (II) depends on its stereochemistry: only one of the four stereoisomers is a strong aromatic, while the others exhibit aromatic properties that are very weak, if any. Furthermore, none of the isomers of 3,7-dimethylnona-6-en-1-ol are on the list of 26 aromatic allergens designated by the European Union. Therefore, in a further aspect of the present invention, (S,Z)-3,7-dimethylnonano-6-en-1-ol(IIa) is provided. [ka] The compound has a remarkably low gas chromatography (GC) threshold of 0.032 ng compared to the GC threshold of 1.8 ng for citronellol. Such a high-performance molecule, with a GC threshold 1 / 100th that of citronellol, can be used at lower doses, resulting in less exposure to humans and the environment. It has floral, rose-like, fruity, and lychee-like aromas. It can be used as a fragrance material and as a substitute for citronellol.

[0005] In a further aspect of the present invention, (S,Z)-3,7-dimethylnona-6-en-1-ol(IIa) (as shown in the following text as an isomer mixture) and at least one other compound selected from the group consisting of: (R,E)-3,7-dimethylnonano-6-en-1-ol(IIb), (S,E)-3,7-dimethylnonano-6-en-1-ol(IIc), and (R,Z)-3,7-dimethylnonano-6-en-1-ol(IId) [ka] A mixture of isomers containing the above is provided.

[0006] (R,E)-3,7-dimethylnonano-6-en-1-ol (IIb) has a GC threshold of 0.75 ng, which is even lower than the value for citronellol. It has a technically harsh aroma that is dusty, waxy, rosy, tetrahydrogeranol, and pelargol-like. It blends well with IIa, adding volume and complementing the overall aromatic impression. (S,E)-3,7-dimethylnonona-6-en-1-ol(IIc) and (R,Z)-3,7-dimethylnonona-6-en-1-ol(IId) are both weak aromas with GC thresholds of 2.2 ng and 3.4 ng, respectively. Their aromas are described as oily and oily floral. They do not significantly contribute to the overall aroma of the isomer mixture.

[0007] If a compound exists in the form of different stereoisomers, it may be used as a mixture. Alternatively, it may be separated into a group of diastereoisomers or as pure stereoisomers. Separating stereoisomers adds complexity to the preparation and purification of the compound; therefore, it is preferable, simply for economic reasons, to use a compound as a mixture of its stereoisomers. However, if it is desired to prepare individual stereoisomers, this may be achieved by methods known in the art, such as stereoselective synthesis, preparative HPLC, and GC. In one aspect of the present invention, the compound represented by formula (IIa) is provided in a highly enriched or essentially pure form, free from small amounts or substantially no compounds (IIb), (IIc), and / or (IId). This means that the compound represented by formula (IIa) is present in at least 90% by weight, particularly at least 95% by weight, more particularly at least 98% by weight, and even more particularly at 99% by weight or more.

[0008] In another aspect of the present invention, an isomer mixture is provided comprising a substantial amount of the compound represented by formula (IIa) together with compounds (IIb), (IIc), and / or (IId). This means that the compound of formula (IIa) is present in an amount of at least 20% by weight, particularly at least 30% by weight, more particularly at least 40% by weight, and even more particularly at least 50% by weight. The weight ratio of the compound represented by formula (IIa) to the compound represented by formula (IIb) in the isomer mixture may range from about 4:6 to about 99:1. In another aspect of the present invention, a mixture of (S)-isomers (IIa) and (IIc) is provided in a pure form or an enantio-enriched form. A racemic mixture of (S)-isomers (IIa) and (IIc) has a GC threshold of 0.93 ng.

[0009] In a further aspect of the present invention, a compound according to formula (IIa), or (S,Z)-3,7-dimethylnonano-6-en-1-ol (IIa) and at least one other compound selected from the group consisting of: (R,E)-3,7-dimethylnonano-6-en-1-ol(IIb), (S,E)-3,7-dimethylnonano-6-en-1-ol(IIc), and (R,Z)-3,7-dimethylnonano-6-en-1-ol(IId) The use of an isomer mixture containing the above as a fragrance is provided.

[0010] In a further aspect of the present invention, a compound according to formula (IIa), or (S,Z)-3,7-dimethylnonano-6-en-1-ol (IIa) and at least one other compound selected from the group consisting of: (R,E)-3,7-dimethylnonano-6-en-1-ol(IIb), (S,E)-3,7-dimethylnonano-6-en-1-ol(IIc), and (R,Z)-3,7-dimethylnonano-6-en-1-ol(IId) A fragrance composition is provided which includes an isomer mixture containing and .

[0011] The compounds or mixtures of isomers of the present invention, alone or in combination with known fragrance molecules selected from a wide range of natural products and currently available synthetic molecules such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocycles and heterocycles, and / or in combination with one or more components or excipients conventionally used in conjunction with the fragrance substances in a fragrance composition, such as a carrier material and other auxiliaries commonly used in the art, may be used in admixture.

[0012] As used herein, "carrier material" means a substance that is substantially neutral from the perspective of the fragrance substance, i.e., a material that does not significantly change the sensory properties of the fragrance substance. The term "auxiliary" refers to a component that can be employed in the fragrance composition for reasons not particularly related to the olfactory performance of the fragrance composition. For example, the auxiliary may be a component that acts as an adjuvant for processing the fragrance component(s) or the composition containing said component(s), or it may improve the handling or storage of the fragrance component or the composition containing it. It may also be a component that provides additional advantages such as imparting color or texture. It may also be a component that imparts light resistance or chemical stability to one or more components contained in the fragrance composition. A detailed description of the nature and type of adjuvants commonly used in the fragrance composition containing it cannot be exhaustive, but it must be mentioned that such components are well known to those skilled in the art.

[0013] As used herein, "perfume composition" means any composition comprising a compound according to formula (IIa), or a mixture of isomers, and a base material, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (IPM), pentane-1,2-diol, triethyl citrate (TEC) and an alcohol (such as ethanol), and a conventionally used diluent in combination with a fragrance substance. Optionally, the composition may contain an antioxidant adjuvant. Said antioxidant may be selected from Tinogard® TT (BASF), Tinogard® Q (BASF), tocopherol (containing 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).

[0014] The following list includes examples of known fragrance molecules that can be combined with a compound according to formula (IIa) or a mixture of isomers. - Essential oils and extracts, such as castoreum, costus root oil, oakmoss absolute, geranium oil, woodmoss absolute, basil oil, bergamot oil and fruit oils such as 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,

[0015] - Alcohols, for example, cinnamon alcohol ((E)-3-phenylpropa-2-en-1-ol); cis-3-hexenol ((Z)-hexa-3-en-1-ol); citronellol (3,7-dimethylocta-6-en-1-ol); dihydromyrcenol (2,6-dimethylocta-7-en-2-ol); Ebanol (registered trademark) ((E)-3-methyl-5-(2,2,3-trimethylcyclopene) (T-3-en-1-yl)penta-4-en-2-ol); eugenol (4-allyl-2-methoxyphenol); ethyllinalool ((E)-3,7-dimethylnonano-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 (registered trademark) ((E)-6-ethyl-3-methylocta-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); Phenylethyl alcohol (2-phenylethanol); Rhodinol (registered trademark) (3,7-dimethylocta-6-en-1-ol); Sandalore (registered trademark) (3- Methyl-5-(2,2,3-trimethylcyclopenta-3-en-1-yl)pentan-2-ol); terpineol (2-(4-methylcyclohexa-3-en-1-yl)propane-2-ol); or Timberol® (1-(2,2,6-trimethylcyclohexyl)hexane-3-ol); 2,4,7-trimethylocta-2,6-dien-1-ol, and / or [1-methyl-2(5-methylhexa-4-en-2-yl)cyclopropyl]methanol;

[0016] - Aldehydes and ketones, e.g., anisaldehyde (4-methoxybenzaldehyde); alpha-amylcinnamaldehyde (2-benzylideneheptanal); Georgywood® (1-(1,2,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalene-2-yl)ethanone); hydroxycitronellal (7-hydroxy-3,7-dimethyloctanal); Iso E Super(trademark)(1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalene-2-yl)ethanone); Isoraldeine(trademark)((E)-3-methyl-4-(2,6,6-trimethylcyclohexa-2-en-1-yl)buta-3-en-2-one); Hedione(trademark)(methyl 3-oxo-2-pentylcyclopentane acetate); 3-(4-isobutyl-2-methylphenyl)propanal; maltol; methylcedyl ketone; methyl ionone; verbenone; and / or vanillin;

[0017] - Ethers and acetals, e.g., Ambrox® (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-methylpropa-1-en-1-yl)tetrahydro-2H-pyran); and / or Spirambrene® (2',2',3,7,7-pentamethylspiro[bicyclo[4.1.0]heptane-2,5'-[1,3]dioxane]);

[0018] - Esters and lactones, e.g., benzyl acetate; cedyl acetate ((1S,6R,8aR)-1,4,4,6-tetramethyloctahydro-1H-5,8a-methanoazulene-6-yl acetate); γ-decalactone (6-pentyltetrahydro-2H-pyran-2-one); Helvetolide® (2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropylpropionate); γ-undecalactone (5-heptyloxolan-2-one); and / or vetiveryl acetate ((4,8-dimethyl-2-propane-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-azulene-6-yl) acetate);

[0019] - Macrocycles, e.g., ambretlide ((Z)-oxacycloheptadeca-10-en-2-one); ethylene brassylate (1,4-dioxacycloheptadecan-5,17-dione); and / or Exaltolide® (16-oxacyclohexadecan-1-one); and - Heterocycles, for example, isobutylquinoline (2-isobutylquinoline).

[0020] In yet another aspect of the present invention, a fragrance article such as a fine fragrance or personal care product or household care product is provided, which is scented with a compound according to formula (IIa) or an isomer mixture containing (S,Z)-3,7-dimethylnona-6-en-1-ol (IIa).

[0021] Compounds according to formula (IIa) or isomer mixtures containing (S,Z)-3,7-dimethylnonona-6-en-1-ol(IIa) can be used in a wide range of aromatic articles, for example, in any area of ​​fine and functional perfumes such as fragrances, air care products, household products, laundry products, body care products, and cosmetics. The compound can be used in a wide range of amounts depending on the properties and quantities of the particular article and other aromatic components. The proportion is typically from 0.0001 to 5% by weight of the article. In one embodiment, the compound of the present invention or isomer mixtures containing (S,Z)-3,7-dimethylnonona-6-en-1-ol(IIa) can be used in fabric softeners in amounts from 0.001 to 0.3% by weight (for example, 0.01 to 0.1% by weight, including 0.05). In another embodiment, compounds according to formula (IIa) or isomer mixtures containing (S,Z)-3,7-dimethylnona-6-en-1-ol (IIa) may be used in consumer products such as shampoos, fabric softeners or fabric cleaners, as well as fine perfumes, in amounts between 0.001 and 30% by weight (for example, up to about 10 or up to 20% by weight), more preferably between 0.01 and 5% by weight. However, these values ​​are given only as examples, as a skilled perfumer may also achieve the desired effect at lower or higher concentrations, or create new accords.

[0022] In one embodiment, a fragrance article is provided comprising an acceptable amount of a compound according to formula (IIa) or an isomer mixture containing (S,Z)-3,7-dimethylnona-6-en-1-ol (IIa). For example, the fragrance article may contain, based on the total amount of the article, 0.000001% to 90% by weight of the compound or isomer mixture (including 0.00001% by weight; 0.0001% by weight, 0.001% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.5% by weight, 1% by weight, 5% by weight, 8% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 50% by weight, 60% by weight, and 65% by weight).

[0023] Compounds according to formula (IIa) or isomer mixtures containing (S,Z)-3,7-dimethylnonona-6-en-1-ol(IIa) may be employed in a consumer product base by simply mixing a fragrance composition or mixture thereof containing the compound of the present invention or an isomer mixture containing the compound according to formula (IIa) or (S,Z)-3,7-dimethylnonona-6-en-1-ol(IIa) with the consumer product base, or it may be encapsulated in a capture material, such as polymers, capsules, microcapsules and nanocapsules, liposomes, film-forming agents, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, in an earlier step, and then mixed with the consumer product base.

[0024] Accordingly, the present invention also provides a method for producing a fragrance article, comprising introducing a compound according to formula (IIa) or an isomer mixture containing (S,Z)-3,7-dimethylnona-6-en-1-ol (IIa) as a fragrance component by directly mixing the compound into a consumer product base, or by mixing a fragrance composition containing a compound according to formula (IIa) or an isomer mixture containing (S,Z)-3,7-dimethylnona-6-en-1-ol (IIa) and then mixing it with a consumer product base using conventional techniques and methods. By adding an olfactory-acceptable amount of the compound of the present invention as described above, the fragrance note of the consumer product base will be improved, enhanced, or modified.

[0025] Therefore, the present invention further provides a method for imparting, enhancing, improving, or modifying the pleasure properties of a fragrance composition or consumer product, the method comprising adding to the fragrance composition or consumer product a compound according to formula (IIa) or an isomer mixture containing (S,Z)-3,7-dimethylnona-6-en-1-ol (IIa).

[0026] As used herein, “consumer product base” means a composition intended for use as a consumer product that fulfills a specific action such as cleaning, softening, and care. Examples of such products include fine perfumes, e.g., fragrances and eau de toilettes; fabric care, household and personal care products such as cosmetics, laundry care detergents, rinse conditioners, personal cleansing compositions, dishwasher detergents, and surface cleaners; laundry products, e.g., fabric softeners, bleaches, and detergents; body care products, e.g., shampoos and shower gels; and air care products (including products that preferably contain volatile and mostly pleasant-smelling compounds and can advantageously mask unpleasant odors even in very small amounts). Air fresheners for living areas contain, among other things, natural and synthetic essential oils such as pine needle oil, citrus oil, eucalyptus oil, and lavender oil, in amounts up to, for example, 50% by weight. As aerosols, they tend to contain smaller amounts of such essential oils, for example, less than 5% or less than 2% by weight, but further contain compounds such as acetaldehyde (in particular, <0.5% by weight), isopropyl alcohol (in particular, <5% by weight), mineral oil (in particular, <5% by weight), and propellants.

[0027] Cosmetic products: (a) Cosmetic skincare products, especially bath products, skin cleansing and makeup removal products, skincare products, eye makeup, lip care products, nail care products, intimate care products, and foot care products; (b) Cosmetic products having specific effects, in particular sunscreens, sunscreens, depigmentation products, deodorants, antiperspirants, depilators, and shaving products; (c) Cosmetic dental care products, especially dental and oral care products, tooth care products, cleaners for dental prostheses, adhesives for dental prostheses; and (d) Cosmetic hair care products, especially hair shampoos, hair care products, hair styling products, hair shaping products, and hair coloring products. It includes.

[0028] Ethyl citronellol(II) can be prepared in various processes, for example, in two steps starting with ethyl linalool(III), as described in Example 1 below. Alternatively, it can be obtained in four steps starting with citronellol (Biosci. Biotechnol. Biochem. 2002, 66, 582-587), or in seven steps from methyl ethyl ketone, as reported by Dragoco (1978 11 / 12, 235).

[0029] In one embodiment, the starting material for a process to prepare ethylcitronellol(II) is obtained from a renewable source. Such starting material also allows access to the final product from a renewable source.

[0030] The present invention is further illustrated hereby by the following non-limiting examples. example: Example 1. Preparation of 3,7-dimethylnonona-6-en-1-ol(II) Ethyl citronellol (II) is prepared in a two-step process, starting with ethyl linalool (III) and proceeding through ethyl geraniol / ethylnerol (IV). a) 3,7-dimethylnonano-2,6-dien-1-ol(IV) [ka] Under N2 conditions, ethyl linalool (III, 637.8 g, 3.79 mol), VO(OSiPh3)3 (20.1 g, 0.022 mol), and PhMe (139 g) were placed in a 1000 mL three-necked round-bottom flask equipped with a condenser. The solution was refluxed (heating plate set to 110°C). The reaction was tracked by GC until an equilibrium mixture of 70:30 ethyl linalool:ethyl geraniol / ethylnerol (3,7-dimethylnona-2,6-dien-1-ol) was observed. After a total reaction time of 3 hours, the reaction mixture was cooled to room temperature. After removal of PhMe, a pale brown crude liquid (667 g) was obtained. The reaction mixture was passed through a wiped film evaporator (length = 16 cm, outer diameter 5.5 cm, 80°C, 0.04 mbar) to obtain recovered VO(OSiPh3)3 (17 g) and crude material (ethyl linalool + ethyl geraniol / ethyl nerol mixture) (562.8 g). The crude material was filtered and fractional distillation (Sulzer-packed column (length = 50 cm, inner diameter 30 mm)) yielded ethyl linalool (250.1 g), followed by ethyl geraniol / ethyl nerol (IV, 92 g, 100% purity, 48%) separated as a mixture of four isomers in the ratios of 1:3.36:3.51:5.59).

[0031] E / E, E / Z, Z / E, and Z / Z mixture isomers: 1 H-NMR (CDCl3, 400 MHz): δ = 5.47 - 5.37 (m, 4 x 1H), 5.14 - 5.03 (m, 4 x 1H), 4.14 (d, J=6.8 Hz, 2 x 2H), 4.11 - 4.07 (m, 2 x 2H), 2.16 - 1.94 (m, 4 x 6H), 1.89 (br s, 4 x 1H), 1.75 (m, 2 x 3H), 1.67 (m, 4 x 3H), 1.60 (s, 2 x 3H), 1.00 - 0.94 (m, 4 x 3H) ppm. 1313C-NMR (CDCl3, 100 MHz): δ = 139.6 (s), 139.5 (s), 139.34 (s), 139.28 (s), 137.9 (s), 137.7 (s), 137.3 (s), 137.1 (s), 124.43 (d), 124.37 (d), 123.42 (d), 123.35 (d), 122.3 (d), 122.1 (d), 59.1 (t), 58.78 (t), 58.76 (t), 39.8 (t), 39.5 (t), 32.22 (t), 32.19 (t), 31.9 (t), 26.3 (t), 26.2 (t), 26.1 (t), 25.9 (t), 24.7 (t), 24.6 (t), 23.3 (q), 22.72 (q), 22.68 (q), 16.1 (q), 15.8 (q), 12.73 (q), 12.69 (q), 12.67 (q), 12.6 (q) ppm.

[0032] E / E isomer (major): 13 13C-NMR (CDCl3, 100 MHz): δ = 139.3 (s), 137.1 (s), 123.4 (d), 122.3 (d), 59.1 (t), 39.5 (t), 32.2 (t), 26.2 (t), 16.1 (q), 15.8 (q), 12.7 (q) ppm. Peak 1. MS (EI, Rt 6.43 min., 70 eV): 168 (1, [M]+·), 121 (9), 93 (17), 84 (14), 83 (33), 67 (15), 55 (100), 53 (10), 41 (39), 39 (15), 29 (11). Peak 2. MS (EI, Rt 6.51 min., 70 eV): 168 (1, [M]+·), 121 (9), 93 (18), 84 (14), 83 (35), 67 (15), 55 (100), 53 (10), 41 (38), 39 (14), 29 (10). Peak 3. MS (EI, Rt 6.62 min., 70 eV): 168 (0, [M]+·), 137 (9), 93 (9), 84 (8), 83 (37), 67 (13), 55 (100), 53 (9), 41 (36), 39 (12), 29 (10). Peak 4. MS (EI, Rt 6.67 min., 70 eV): 168 (1, [M]+·), 93 (9), 84 (8), 83 (39), 67 (13), 55 (100), 53 (9), 43 (8), 41 (35), 39 (12), 29 (9).

[0033] b) 3,7-dimethylnonano-6-en-1-ol(II) [ka] Under an air atmosphere, 3,7-dimethylnonano-6-en-1-ol (IV, 92 g, 0.547 mol, 100% purity) and MeOH (108 g), followed by Raney nickel (0.92 g, added all at once in pellet form), were added to a 500 mL autoclave container, and the container was sealed. While stirring (600 rpm), the autoclave was flushed three times with N2 (1.8 bar), then three times with H2 (2.0 bar). After adjusting the H2 pressure to 10 bar, the autoclave was heated to 50°C while increasing the stirring speed to 1500 rpm. Sampling was performed following the progress of the reaction. At t=6h39min, heating of the autoclave and H2 flow were stopped. After cooling, the pressure was released, and the autoclave was flushed three times with N2 (1.8 bar). The reaction mixture was filtered to remove the heterogeneous catalyst, and MeOH was removed to obtain 3,7-dimethylnona-6-en-1-ol (II, 78.6 g, purity 86.9%, yield 79.8%) as a colorless liquid containing two double-bonded isomers in a 2:1 ratio.

[0034] 1H-NMR (CDCl3、400 MHz): δ = 5.14 - 5.03 (m、2 x 1H、E+Z)、3.74 - 3.60 (m、2 x 2H、E+Z)、2.09 - 1.89 (m、2 x 4H、E+Z)、1.67 (q、J=1.2 Hz、3H、Z)、1.60 (sb、3H、E)、1.66 -1.13 (m、2 x 5H、E+Z)、0.98 (t、J=7.5 Hz、3H、E)、0.96 (t、J=7.5 Hz、3H、Z)、0.91 (d、J=6.7 Hz、3H、E)、0.91 (d、J=6.6 Hz、3H、Z) ppm. 13 C-NMR (CDCl3、100 MHz): δ = 137.0 (s、Z)、136.7 (s、E)、124.3 (d、Z)、123.1 (d、E)、61.1 (2t、E+Z)、39.8 (2t、E+Z)、37.5 (t、Z)、37.2 (t、E)、32.3 (t、E)、29.2 (2d、E+Z)、25.3 (t、E)、25.0 (t、Z)、24.7 (t、Z)、22.8 (q、Z)、19.5 (2q、E+Z)、15.8 (q、E)、12.8 (q、Z)、12.7 (q、E) ppm. ピーク 1。MS (EI、Rt = 6.43 min.、70 eV): 170 (3、[M]+·)、123 (39)、95 (18)、83 (18)、81 (42)、71 (18)、70 (19)、69 (21)、67 (26)、55 (100)、41 (45). ピーク 2。MS (EI、Rt = 6.43 min.、70 eV): 170 (3、[M]+·)、123 (39)、95 (18)、83 (19)、81 (41)、71 (18)、70 (18)、69 (21)、67 (26)、55 (100)、41 (45).

[0035] Example 2. Stereoisomer separation 3,7-dimethylnonano-6-en-1-ol(II) was converted to the corresponding 3,7-dimethylnonano-6-en-1-yl-4-nitrobenzoate(V) to enable separation into individual isomers by supercritical fluid chromatography (SFC), and subsequently esterified to the individual compounds (IIa), (IIb), (IIc), and (IId). [ka] a) 3,7-dimethylnonal-6-en-1-yl-4-nitrobenzoate(V): To a stirred solution of compound 1 (5 g, 29 mmol, 1 equivalent) in 100 mL of DCM at 0°C, p-nitrobenzoic acid (2) (7.35 g, 44 mmol, 1.5 equivalents), DCC (11.3 g, 55 mmol, 1.9 equivalents), and DMAP (1.41 g, 11.6 mmol, 0.4 equivalents) were added. The mixture was stirred at room temperature for 16 hours. The reaction mixture was filtered, and the filtered solid was washed with 50 mL of DCM. The filtrate was washed with 200 mL of water, dried over sodium sulfate, and concentrated under reduced pressure. The crude product (V) was purified by HPLC to obtain compound 3 (6 g, 64%) as a colorless liquid.

[0036] b) SFC separation: Compound (V) (6g) was subjected to SFC purification (15% cosolvent: 0.5% isopropylamine in methanol, column: Lux A1 (250×30mm, 5μ), flow rate: 3ml / min) to obtain four fractions (Vc), (Va), (Vb), and (Vd).

[0037] c) Ester hydrolysis: To a stirred solution of compound Va in THF-MeOH&H2O (7:2:1 volume), LiOH·H2O (2 equivalents) was added at room temperature. The mixture was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure, diluted with water, and extracted with butyl. The combined organic layer was dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified by flash column chromatography using 6-7% butyl in petroleum ether as the eluent to obtain IIa as a colorless liquid. Compounds (Vb), (Vc), and (Vd) were hydrolyzed to produce compounds (IIb), (IIc), and (IId), respectively. The configurations of the individual isomers were assigned by chiral GC and NMR analysis.

[0038] Example 3. Perfume example In the following accords, compound (IIa), a mixture of (s)-isomers (IIa) and (IIc), and citronellol are compared. This shower gel accord should be applied at a concentration of 1-1.5% of the final use base.

[0039] [Table 1]

[0040] The typical accord provides a fresh, juicy, fruity citrus accord, primarily combining fresh citrus lemon top notes with rosy raspberry lychee heart notes. Citronellol (used in accord A) supports the neat, overall rosy freshness and bloom in use. (S)-ethylcitronellol (IIa+IIc, used in Accord B) provides a neat and additional pleasurable freshness and naturalness to the Accord in use. Furthermore, it brings a significant advantage of clearly improved bloom and diffusion during the shower experience. (S,Z)-ethylcitronellol (IIa, used in Accord C) brings both an intense floral rose-like character and a pleasant juicy fruity lychee feel to the composition, and compared to citronellol, it brings a neat and preferred intensity, and excellent bloom and room filling in use, with a clear pleasurable advantage even when added at 1 / 5. Compared to the racemic (S)-ethylcitronellol, this particular isomer brings bloom and pleasant pleasurable characteristics without the more technical and rough aspects of the (S,E)-isomer.

[0041] Example 4. Comparison of GC thresholds In the table below, the GC thresholds of citronellol, linalool, and geraniol-nerol mixtures are compared to their corresponding so-called ethyl analogues, which are morphologically elongated by a single methyl group.

[0042] [Table 2]

[0043] Linalool: 3,7-dimethyl-1,6-octadien-3-ol; Ethyllinalool: 3,7-dimethylnonona-1,6-dien-3-ol; Geraniol / Nerol: E / Z-3,7-dimethyl-2,6-octadien-1-ol; Ethyl-geraniol / Nerol: E / Z-3,7-dimethylnonona-2,6-dien-1-ol. Typically, substitution of a methyl group with an ethyl group is observed to not significantly alter the GC threshold related to the compound's effect or performance. In the case of ethyl citronellol, it is surprising that this compound exhibits significantly higher performance than its methyl analogue, citronellol.

Claims

1. (S,Z)-3,7-dimethylnonano-6-en-1-ol, formula IIa 【Chemistry 1】 The use of the compound represented by as a substitute for citronellol.

2. (S,Z)-3,7-dimethylnonano-6-en-1-ol, formula IIa 【Chemistry 2】 Compounds represented by, Compounds represented by formula IIb, compounds represented by formula IIc, and compounds represented by formula IId 【Transformation 3】 At least one further compound selected from the group consisting of, Use of an isomer mixture containing as a substitute for citronellol.

3. (S,Z)-3,7-dimethylnonano-6-en-1-ol, formula IIa 【Chemistry 4】 A compound represented by, or Formula IIa is (S,Z)-3,7-dimethylnonano-6-en-1-ol. 【Transformation 5】 Compounds represented by, Compounds represented by formula IIb, compounds represented by formula IIc, and compounds represented by formula IId 【Transformation 6】 at least one further compound selected from the group consisting of A method for improving, enhancing, or modifying a consumer product base by adding an isomer mixture containing as a substitute for citronellol to the consumer product base, The method wherein the consumer product base is a composition for use in consumer products selected from high-quality fragrances, household products, laundry products, body care products, cosmetic products, and air care products.

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