Novel odorous substances for the replacement of salicylates

Abstract

Formula (I), wherein, independently of one another, R1 = -H, -Me, -Et or -nPr R2, R3 = -H or -Me; X = C or O, wherein if X = C, one of the respective dashed lines (A) represents a double bond and if X = O, then no R3 group is present; and Y can be -H, -Me, -Et, -n-Pr, i-Pr =CH2, =CHMe, =CHEt, =CMe2; and the wavy line indicates that, in the case of a double bond, there may be geometric isomers (cis / trans-configuration) included; The invention also relates to the use of said compounds as an odorous substance.

Description

New fragrances to replace salicylates AREA OF INVENTION

[0001] The present invention is in the field of fragrances and relates to new fragrances and fragrance mixtures. Furthermore, the present invention relates to the use of fragrance mixtures and a method for conveying, modifying, and / or intensifying certain odor notes. BACKGROUND OF THE INVENTION

[0002] To set trends in the perfume industry, new fragrance ingredients are constantly needed. Therefore, perfumers and fragrance chemists are continually searching for new compounds with signature effects. Furthermore, more and more traditional, long-established compounds that have proven to be toxicologically problematic over time must be replaced, especially those known or suspected to have carcinogenic, mutagenic, or reprotoxic properties.

[0003] More recently, this group has also included the class of salicylates, which historically derive from pharmaceuticals such as Aspirin®. Favored by the resulting inexpensive access to salicylic acid, a whole range of salicylic acid esters have found their way into the perfumery and fragrance industry, especially the methyl, butyl, amyl, hexyl, benzyl, and 3-hexenyl esters (F. Elterlein, N. Bugdhan, P. Kraft, Sniffing Out the Sustainable Future: The Renewability Revolution in Fragrance Chemistry, Chem. Eur. J. 2024, e202400006). These cover a wide spectrum of different scent notes, from balsamic to green-floral, and from solar-floral to other flowers such as orchid, hyacinth, rose, mignonette, and lilac. However, all salicylates share a certain white-floral ylang-ylang character and a slightly medicinal wintergun note, which is most noticeable in the most pronounced in methyl salicylate, one of the characteristic components of wintergreen oil.

[0004] To replace the salicylates, which are suspected of being toxicologically harmful, attempts have so far been made, due to a lack of suitable substitutes, to replace only the common wintergreen-ylang-ylang character and to introduce the various floral characteristics into the composition via other fragrance components. For this purpose, the IFF introduced 'Ylanganat' (methyl otoluate, CAS 89-71-4) last year (AT Levorse, RA Weiss, M. Pawlak, IFF, US Pat. Appl. US 2005 / 0170998 A1, January 29, 2004), which has a white floral scent reminiscent of orange blossoms, ylang-ylang, and gardenias.

[0005] Although ylang-ylang, like methyl salicylate, is a methyl ester, the methyl salicylate note is surprisingly more pronounced in the corresponding ethyl benzoate (ethyl 2-methyl benzoate = EMB), the ethyl ester recently introduced into perfumery (B. Holscher, M. Mansfeld, L.-J. Kleine-Benne, T. Belmas, Symrise, PCT Int. Pat. Appl. WO 2023 / 232237 A1, May 31, 2022). The effects cannot therefore be readily transferred from salicylates to carba-analogous benzoates, presumably because the electronegative phenolic hydroxyl group is absent, resulting in a different hydrogen bond geometry. It is therefore not a recipe, but the compounds are still chemically benzoates, which is reflected not only in the toxicologically beneficial properties, but also in the odor profile.

[0006] Salicylates are important for a whole range of fragrance families, and while notes in the direction of winter green and ylang-ylang can be satisfactorily represented with ylanganate and ethyl 2-methylbenzoate, this is not the case for the vast majority of salicylate notes in the fragrance families orchid, hyacinth, rose, mignonette and lilac, as well as especially green-balsamic.

[0007] Furthermore, it has been found that the various salicylates cannot simply be imitated by adding a methyl salicylate-like substitute such as 'ylanganate' and ethyl 2-methyl benzoate to form a single fragrance or fragrance complex, because methyl and ethyl 2-methyl benzoate are too harsh in character and From a medical perspective, they stand out too clearly, which severely limits their use, especially in alcoholic fine perfumery. DESCRIPTION OF THE INVENTION

[0008] Therefore, the object of the present invention is to overcome the disadvantages of the prior art.

[0009] A further object of the present invention is to provide new compounds that are useful as fragrances, in that they not only replace existing toxicologically hazardous salicylates, but also introduce entirely new, preferably floral, fragrance notes of high signature effect into fragrance compositions.

[0010] Furthermore, it is an object of the present invention to provide a new odorant capable of improving positive and advantageous odor aspects of other odorants and / or (simultaneously) reducing, inhibiting, and / or masking undesirable, unpleasant odor aspects. In particular, the new odorant should also be characterized by improving the stability, solubility, and overall performance of other odorants and reducing the required dosage. Finally, the odorant mixtures themselves should exhibit excellent biodegradability and be harmless to humans and the environment.

[0011] According to the invention, this is achieved by the subject matter of the present patent claims. A first embodiment of the invention relates to a compound of formula (I) Formula (I), where, each independently of the other, R1 = –H, –Me, –Et, –n-Pr or –i-Pr R2, R3 = -H or -Me; X = C or O, where if X = C, one of the dashed lines represents a double bond, and if X = O, then no R3 residue is present; and Y = -H, -Me, -Et, -Pr, =CH2, =CHMe, =CHEt, =CMe2 can be and the wavy line indicates that in the case of a double bond there may be geometric isomers (cis / trans configuration) which are included.

[0012] The compounds of formula (I) of this invention therefore always possess a double bond in the side chain when X=C, which, depending on the substitution, can be cis- or trans-configured (geometric isomerism). Furthermore, depending on the substitution in the side chain of compounds (I), stereocenters are also formed, leading to further so-called optical isomers. Optical and geometric isomers can be separated by chromatographic methods, for example on chiral phases, into individual enantiomerically enriched or pure stereoisomers and / or geometric double bond isomers.The splitting of isomers, stereoisomers to a greater extent than geometric isomers, increases the complexity of the preparation and purification of these compounds, as does a stereoselective or czs- / trans-selective synthetic approach. Therefore, for purely economic reasons, the compounds of general formula (I), with the exception of the hexenyl derivatives, where the (Z)-derivatives are more commercially available, are preferably used as isomer mixtures. However, if individual geometric isomers or stereoisomers are to be prepared, this can be done according to known prior art methods, such as preparative HPLC and GC or stereoselective synthesis.

[0013] Preferred compounds are those of formula (I) in which X = C and a double bond is contained in the side chain.

[0014] Also preferred are those of formula (I) where X = O.

[0015] In another preferred embodiment of the invention, compounds are selected that are described by formula (I'), where Ri, R2, R3 = –H or –Me; X = C and Y = -H, -Me, -Et, -n-Pr or i-Pr are and where the double bond between substituents R2 and R3 can be cis- or trans-configured.

[0016] In another preferred embodiment of the invention, compounds are selected that are described by formula (I"). Formula (I") where R1 = -H or -Me, R2 = Me, R3 = -H; X = C and Y = -H, -Me, -Et, -nPr or i-Pr and where the double bond between substituents R2 and R3 can be cis- or trans-configured.

[0017] Particularly favored species of formula (I) are selected from the group consisting of Compound 1.1 [(Z)-Hex-3-enyl]-2-methylbenzoate Compound 1.2 [(£)-1-Methylhex-2-enyl]-2-methylbenzoate Compound 1.3 Allyl-2-methylbenzoate Compound I.4 1-Methylallyl 2-methylbenzoate Compound 1.5 2-methylallyl-2-methylbenzoate Compound 1,6 3-Methylbut-2-enyl-2-methylbenzoate Compound I.7 [(£)-1,2-Dimethylbut-2-enyl]-2-methylbenzoate Compound I.8 [(£)-2-Methylbut-2-enyl]-2-methylbenzoate Compound I.9 [(£)-1-Propylbut-2-enyl]-2-methylbenzoate Compound 1.10 1,2-Dimethylallyl-2-methylbenzoate Compound 1.11 [(£)-2-Methylpent-2-enyl]-2-methylbenzoate Compound 1.12 [(E / Z)-But-2-enyl]-2-methylbenzoate Compound 1.13 (2-Methoxy-1-methyl-ethyl)-2-methylbenzoate Compound 1.14 2-Methoxyethyl-2-methylbenzoate Compound 1.15 [(Z)-1-Methylhex-3-enyl]-2-methylbenzoate Compound 1.16 2-Isopropoxyethyl-2-methylbenzoate

[0018] Particularly preferred are compounds selected from the group consisting of [(£)-1-methylhex-2-enyl]-2-methylbenzoate; 2-methylalyl-2-methylbenzoate; [(£)-1,2-dimethylbut-2-enyl]-2-methylbenzoate; [(£)-2-methylbut-2-enyl]-2-methylbenzoate and [(Z)-1-methylhex-3-enyl]-2-methylbenzoate. [(Z)-1-methylhex-3-enyl]-2-methylbenzoate is most preferred.

[0019] The compounds of formula (I) possess entirely unique olfactory properties that clearly distinguish them from, and even surpass, known odorants. The compounds of formula (I) and their suitability as odorants were previously unknown. It is therefore particularly surprising that odorants with valuable, interesting, and complex odor properties have been discovered in this already well-researched field. Benzoates could complement and / or replace the scent profiles of known salicylates. However, benzoates do not correspond in smell to salicylates with the analogous residue, but possess their own distinct scent profiles.

[0020] As mentioned above, the suitability of the compounds of formula (I) as fragrances is unknown. Likewise, no descriptions of their odors are available. The inventors of the present application have therefore made the surprising discovery that the compounds of formula (I) can be used as fragrances and possess a characteristic salicylate-like odor profile in the direction of green-balsamic and / or floral orchid, hyacinth, rose, mignonette, and lilac.

[0021] Furthermore, the compounds of formula (I) are toxicologically harmless as substituted benzoates. Surprisingly, it has also been shown that the compounds of formula (I) differ significantly and characteristically in their odor from other methyl benzoates, such as the perfumery-introduced ylanganate (methyl 2-methyl benzoate) and ethyl 2-methyl benzoate, by exhibiting much weaker or even completely absent medicinal and technical aspects reminiscent of wintergreen. These are replaced by green-balsamic or floral notes reminiscent of orchid, hyacinth, rose, mignonette, and lilac, thus surpassing the two known fragrances in their applicability. These notes, perceived as medicinal and technical, severely limit the use of ylanganate (methyl 2-methyl benzoate) and ethyl 2-methyl benzoate in fine perfumery.

[0022] The fact that the compounds of formula (I) to be used according to the invention can convey a very complex and diverse overall sensory impression, which can otherwise usually only be achieved by mixtures of several components (e.g. essential oils or spice mixtures), is also particularly surprising.

[0023] Beyond their primary, namely olfactory, properties, the compounds of formula (I) also possess additional positive secondary properties, in particular a high substantivity compared to odorants with similar properties. olfactory properties, as well as higher stability in certain media and preparations compared to salicylates, and are also biodegradable with few exceptions.

[0024] As already mentioned, the compounds of formula (I) can be used in a variety of products; they can be used as individual fragrances, but can also be combined particularly advantageously with other fragrances in varying proportions to form fragrance mixtures, thereby creating novel and original perfume compositions. Accordingly, one aspect of the invention also relates to a fragrance mixture and optionally further components (solvents or the like) which contain one or more compounds of formula (I).

[0025] The fragrance mixture according to the invention comprises or consists of at least one compound of formula (I) Formula (I), where, each independently of the other, R1 = –H, –Me, –Et, –n-Pr or –i-Pr R2, R3 = –H or –Me; X = C or O, where if X = C, one of the dashed lines represents a double bond, and if X = O, then no R3 residue is present; and Y = -H, -Me, -Et, -n-Pr, i-Pr =CH2, =CHMe, =CHEt, =CMe2 and the wavy line indicates that in the case of a double bond there can be geometric isomers (cis / trans configuration) which are included; and at least one fragrance ingredient that does not correspond to formula (I).

[0026] A preferred fragrance mixture comprises or consists of at least one compound of formula (I) and at least one fragrance not conforming to formula (I).

[0027] Preferably, the fragrance mixture according to the invention comprises or consists of at least one compound of formula (I) and two or more further fragrances that do not correspond to formula (I). Particularly preferably, the fragrance mixture according to the invention comprises or consists of at least one compound of formula (I) and three or more further fragrances that do not correspond to formula (I). Most preferably, the fragrance mixture according to the invention comprises or consists of at least one compound of formula (I) and four or more further fragrances that do not correspond to formula (I).

[0028] Fragrance mixtures comprising two or more compounds of formula (I) as well as other fragrances not corresponding to formula (I) are also advantageous.

[0029] The compounds of formula (I) are usually used in a sensorily effective amount, i.e., in a total amount in which they exert a sensory effect. Preferably, the weight ratio of the total amount of compounds of formula (I) to the total amount of other odorants is in the range of 1:1000 to 1:10, more preferably in the range of 1:1000 to 1:100.

[0030] In this context, it is preferred if the total amount of compounds of formula (I) is in the range of 0.0001 to 99.9 wt.%, preferably 0.001 to 99.5 wt.%, particularly preferably 0.01 to 25 wt.%, or from 0.01 to 20 wt.%, from 0.01 to 10 wt.% and particularly preferably from 0.01 to 8 wt.%. in particular amounts to 0.01 to 4% by weight, in each case based on the total weight of the composition.

[0031] Examples of fragrances that can be advantageously combined with the compounds of formula (I) within the scope of the present invention can be found, for example, in S. Arctander, Perfume and Flavor Materials, Vol. I and II, Montclair, NJ 1969, self-published, or Common Fragrance and Flavor Materials: Preparation, Properties and Uses, by H. Surburg and Johannes Panten (Ed.), 6th edition, Wiley-VCH, Weinheim, 2016.

[0032] Specifically mentioned are, for example, essential oils and extracts such as field mint, amyrisol, angelica root oil, apricot seed oil, basil oil, bayol, mugwort oil, benzoin resinoid, bergamot oil, beaver holly absolute, beeswax absolute, cabreuvabl, canangal, cassia absolute, cistus oil, citronellol, copaiba balsam oil, cypress oil, cypriol oil, davanabl, dill oil, oakmoss absolute, elemi oil / resinoid, tarragon oil, eucalyptus oil, fennel oil, spruce needle oil, fucus absolute, galbanum oil, geranium oil, grapefruit oil, guaiac wood oil, gurjun balsam oil, hay absolute, hydrocarboresin B, immortelle absolute, ginger extract / oil, jasmine absolute, jasmine absolute sambac. Chamomile blossom, Blue chamomile blossom, Cardamom blossom / abs., Carrot seed blossom, Pine needle blossom, Coriander seed blossom, Spearmint blossom, Pineapple blossom, Labdanum absolute / resinoid, Lavandin blossom, Lavender blossom, Lovage root blossom, Lime blossom, Lime blossom terpenes, Litsea cubeba oil, Longoza leaf blossom, Bay leaf blossom, Magnolia leaf blossom, Magnolia blossom blossom, Mandarin blossom, Marjoram blossom, Mastic absoluteMimosa Absolute, Musk Seed Absolute, Muscat Flower Blossom, Clary Sage Blossom, Nutmeg Blossom, Myrrh Blossom, Myrtle Blossom, Daffodil Absolute, Clove Leaf Blossom, Clove Flower Blossom, Neroli Blossom, Olibanum Blossom, Opoponax Blossom / Resinoid, Orange Flower Absolute, Orange Blossom, Origanum Blossom, Osmanthus Absolute, Palmarosa Blossom, Patchouli Blossom, Parsley Leaf Blossom, Parsley Seed Blossom, Perilla Blossom, Peruvian Balsam Blossom, Petitgrain Blossom, Petitgrain Absolute, Peppermint Blossom, Pepper Blossom (Black, Green, Pink), Allspice Blossom, Rose Absolute, Rose Blossom, Rosemary Blossom, Rum CO2 Extract, Dalmatian Sage Blossom, Spanish Sage Blossom, Sandalwood Blossom, Celery Seed Blossom, Spikenard Blossom, Star Anise Blossom, Styrax Blossom, Marigold Blossom, Tea Tree Blossom, Turpentine Blossom Thujabl, thyme blossom, tonka bean absolute, tuberose absolute, vanilla, Absolute, violet leaf concrete / absolute, vetiver leaf, juniper berry leaf, wormwood leaf, ylang-ylang oil, cedarwood leaf, cedarwood leaf Atlas, cinnamon leaf leaf, cinnamon bark leaf, lemongrass leaf, lemon leaf, lemon leaf terpenes, and isolated constituents and fractions thereof;

[0027] Alkohole, wie beispielsweise 1 -(2-tert-Butylcyclohexyl)oxybutan-2-ol (139504-68-0; Ambercore); 2,6-di-tert-Butyl-p-cresol (128-37-0; BHT Ionol); (Z)-3-Methyl-5-(2,2,3-trimethyl-1-cyclopent-3-enyl)pent-4-en-2-ol (67801-20-1; Ebanol); 4-Methyl-2-(2-methylpropyl)oxan-4-ol (63500-71-0; Florosa / Pyranol); [(1 / ?*,2S*)-1-Methyl-2-[[(1 R*,3S*,5S*)-1,2,2-trimethyl-3-bicyclo[3.1.0]hexanyl]methyl]cyclopropyl]methanol (198404-98-7; Javanol); (3 / ?*)-1-[(1 / ?*,6S*)-2,2,6-Trimethylcyclohexyl]hexan-3-ol; (3S)-1-[(1 / ?,6S)-2,2,6-trimethylcyclohexyl]hexan-3-ol (70788-30-6; Norlimbanol); 3-Methyl-5-phenylpentan-1-ol (55066-48-3; Phenoxanol); (£)-3,3-Dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (107898-54-4; Polysantol); 5-(3-methylphenyl)pentan-1-ol (25634-93-9; Rosaphen); 3-Methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol (1471313-03-7; 65113-99-7; Sandalore); (2£)-2-Ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1 -yl)-buten-1 -ol + 2- Ethyl -4-(2,2,3 - Trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (106185-75-5; 28219-61-6; Sandranol); (£)-4-Methyldec-3-en-5-ol (81782-77-6; Undecavertol); 3-[5,5,6-Trimethylbicyclo[2.2.1]hept-2-yl]cyclohexan-1-ol (70955-71-4; Sandela); Hexan-1-ol; Octan-1-ol; Decan-1 -ol; Dodecan-1-ol; Borneol; Isoborneol; Citronellol; / .-Citronellol; Dihydroeugenol; Dihydromyrcenol; Dimethyl Benzyl Carbinol; Ethyllinalool; Eugenol; Geraniol; c / s-3-Hexenol; Isobornylcyclohexanol; Linalool; Nerolidol; Phenylethylalkohol; Phenylethyl Dimethyl Carbinol; Phenylpropylalkohol; Propenyl Guaethol; Sulfurol; alpha-Terpineol; Tetrahydrolinalool; Thymol;.

[0028] Aldehyde, wie beispielsweise 2,6,10-Trimethylundec-9-enal (141-13-9; Adoxal; Farenal); alpha-,3,3-Trimethyl-cyclohexanemethanolformat (25225-08-5; Aphermat); 4-(1,1 -Dimethylethyl)phenylpropanal (18127-01-0; Bourgeonal); 6-Methoxy-2,6-dimethyloctanal (929253-05-4; Calypson); 4-Methoxy-alpha-methylphenylpropanal (5462-06-6; Canthoxal); a, 2, 2, 6- tetramethylcyclohexenebutanal (65405-84-7; Cetonal); 8,8-Dimethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthaldehyd + 1,2,3,4,5,6,7,8-Octahydro-5,5-dimethyl-2-naphthalenecarboxaldehyd (68991-96-8; 68991-97-9; Cyclomyral); 4-(octahydro-4,7-methano-5H-inden-5-ylidenbutanal (30168-23-1; Dupical); 4,8-Dimethyl-4,9-decadienal (71077-31-1; Floral Super); 3-(4-Ethylphenyl)-2,2-dimethylpropanal + 3-(2-Ethylphenyl)-2,2-dimethylpropanal (67634-15-5; 67634-14-4; Florazon); beta-Methyl-3-(1 -methylethyl)benzenepropanal (12509-85-5; Florhydral); Methylenedioxyphenylmethylpropanal (1205-17-0; Helional); a, 4-Dimethylbenzenepropanal (41496-43-9; Jasmorange, Satinaldehyd); (Z,£)-2,4-Dimethylcyclohex-3-ene-1-carbaldehyd (68039-49-6; 68737-61-1; Ligustral, Tripalal, Cyclal C, Vertocitral); 3-(4'-tert-Butylphenyl)butanal (80-54-6; Lilial); (1 / ?)-p,4-Dimethyl-3-cyclohexene-1-propanal (199445-85-7; Liminal); (4R)-4-(1-Methylethyl)-1-cyclohexene-1-propanal (1378867-81-2; Lilybelle);(4S)-4-(1-Methylethyl)-1-cyclohexene-1-propanal (1378867-82-3; Lilybelle Isomer); 4-(4-Hydroxy-4-methyl-pentyl)-3-cyclohexen-1-carboxyaldehyd (130066-44-3; Lyral); 6-Methyl-1 -8-yl-methylethyl-bicyclo[2.2.2]oct-5-ene-2-carboxaldehyd (67845-30-1; Maceal); (±)-2,6-Dimethyl-5-heptenal (106-72-9; Melonal); (E)-2,6,10-Trimethylundeca-5,9-dienal (54082-68-7; Oncidal); 6,6-Dimethyl-2-norpinene-2-propionaldehyd (33885-51-7; Pinoacetaldehyd); 1 -Methyl-4-(4-methyl-3-pentenyl)cyclohex-3-ene-1 -carboxaldehyd + 6,6-Dimethyl-2-norpinene-2-propionaldehyd (119652-81-2; 52475-86-2; Precyclemon B); 3-Phenylbutanal (16251-77-7; Trifernal); Octahydro-5-methoxy-4,7-methano-1 H-indene-2-carboxaldehyd (86803-90-9; Scentenal); rel-(3a / ?,4 / ?,5 / ?,7 / ?,7a / ?)-Octahydro-4,7-methano-1 / - / -indene-5-carboxaldehyde (145374-28-3; Vertral); 4-(4'-Methylpent-3-enyl) cyclohex-3-ene-1-carbaldehyd (37677-14-8; Vertomugal); Hexanal; Heptanal; Octanal; 2-Nonen-1-al; Nonanal; Decanal; Undecenal; 2-Methyldecanal; 10-Undecenal;Undecanal; Dodecanal; 2-Methylundecanal; Anisaldehyd; Benzaldehyd; Citral; Citronellal; Cinnamaldehyd; Cuminaldehyd; Cyclamenaldehyd; Dihydrocitronellal; trans-2-Dodecanal; Ethyl Vanillin; Geranial; Heliotropin / Piperonal; trans-2-Hexenal; alpha-Hexylzimtaldehyd; Hydratropaaldehyd; Hxdroxycitronellal; Isocyclocitral; Methoxycitronellal; Neral; Phenylacetaldehyd; Tangerinal; Vanillin;

[0029] Amine, Amide und Nitrile, wie beispielsweise 3,7-Dimethyloct-6-enenitril (51566-62-2; Argunitril); (E / Z)-3-Methyl-5-phenylpent-2-enenitril (53243-59-7; 53243-60-0; 93893-89-1; Citronitril); 3,7-Dimethylnona-2,6-dienenitril (61792-11-8; Lemonil); 4-[(3£)-4,8-Dimethylnona-3,7-dienyl]pyridin (38462-23-6; Maritima); Tridec-2-enenitril (22629-49-8; Ozonil); 2-Cyclohexylidene-2-phenylacetonitril (10461-98-0; Peonile); Indol;

[0030] Ester, wie beispielsweise czs-2-tert-Butylcyclohexylacetat + (2-tert-Butylcyclohexyl)acetat (20298-69-5; 88-41-5; Argumex HC / LC); Ethyl-3-methyl-3-phenyloxirane-2-carboxylat (77-83-8; Aldehyd C16 sogenannt); Prop-2-enyl-2-cyclohexyloxyacetat (68901-15-5; Cyclogalbanat); Methyl-2,4-dihydroxy-3,6-dimethylbenzoat (4707-47-5; Evernyl); 4-Methylpentan-2-yl-(E)-but-2-enoat (35206-51-0; Frutinat); Ethyl-2-ethyl-6,6-dimethylcyclohex-2-ene-1-carboxylat (57934-97-1; 77851-07-1; Givescon); Methyl-3-oxo-2-pentylcyclopentaneacetat (24851-98-7; Hedion); 2-(1-(3',3'-Dimethyl-1'-cyclohexyl)ethoxy)-2-methyl propyl propanoat (141773-73-1; Helvetolid); 3a,4,5,6,7,7a-Hexahydro-4,7-methanoinden-6-ylacetat (5413-60-5; Herbaflorat); 3a,4,5,6,7,7a-Hexahydro-4,7-methanoinden-6-ylacetat (5413-60-5; Herbaflorat); [(Z)-Hex-3-enyl]-methylcarbonate (67633-96-9; Leafovert); Ethyl-2-methylpentanoate (39255-32-8; Manzanat); 2-[1-(3,3-Dimethylcyclohexyl)ethoxy]-2-oxoethylpropionat (236391-76-7; Romandolid);Ethyl-2-cyclopent-2-en-1-ylacetat (15848-49-4; Sultanen); (1S,2 / ?,5S)-5-Methyl-2-(1-methylethyl)-cyclohexanolacetat + [(1 / ?,2S,5 / ?)-5-methyl-2-propan-2-ylcyclohexyl]-acetat (29066-34-0; 89-48-5; Symfresh RF I Menthylacetat); 3 - Hydroxy-2, 2,4-trimethylpentyl 2-methylpropanoat (25265-77-4; Symfresh NX); (4-Methyl-4-phenylpentan-2-yl)-acetat (68083-58-9; Vetikolacetat); Allylamylglycolat; Allylcaproat; Allylcyclohexylpropionat; Allylheptoat; Benzylacetat; Benzylsalicylat; Citronellylacetat; Dimethylbenzylcarbinylacetat; Dimethylbenzylcarbinylbutyrat; Ethylbutyrat; Ethylcaproat; 2,4-Ethyldecadienoat; Ethyl-2-methylbutyrat; Ethylenbrassylat; Geranylacetat; Herbylpropionat; 3-Hexenylacetat; cis-3 Hexenylacetat; cis-3 Hexenylbutyrat; czs-3-Hexenylisobutyrat; czs-3-Hexenylsalicylat; Hexylacetat; Hexylbutyrat; Hexylisobutyrat; Hexylsalicylat; Isoamylacetat; Isobornylacetat; Isobutylacetat; Isoeugenolacetat; Linalylacetat; Methyloctincarbonat; Nerylacetat; Phenylethylbutyrat; Phenylethylcinnamat; Prenylacetat; Styralylacetat; Methylanthranilat;

[0031] Ether, wie beispielsweise Rosenoxid, (3a / ?,5aS,9aS,9b / ?)-3a,6,6,9a-Tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran (6790-58-5; Ambroxid); 5-Hexyl-4-methyloxolan-2-on (67663-01-8; Aprifloren); Cyclohexadec-2-en-1-on (2550-59-6; 3100-36-5; 88642-03-9; Aurelion); 3,4-Diethyl-2,5-dimethylcyclohex-2-en-1-on (68845-36-3; Azarbre); 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran (1222-05-5; Galaxolid); (2 / ?,4S)-2-Methyl-4-propyl-1,3-oxathian + 2-Methyl-4-propyl-1,3-oxathian (59323-76-1, 261-699-8; Oxane / Oxanthia; 3,7'-Dimethyl-3,4,4a,5,8,8a-hexahydrospiro-(1,4-methanonaphthalen- 2[1 H],2'-oxirane) (41816-03-9; Rhubofix); Anethol; Limeoxid; Nerolin Yara Yara; Orange Flower Ether;

[0032] Ketone, wie beispielsweise 7-Methyl-3,4-dihydro-2H-[1,5]-benzodioxepin-3-on (249-320-4; Calone); 1,2,3,5,6,7-Hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-on (251-649-3; Cashmeran); [3 / ?-(3a, 3a, 6a, 7p,8aa)]-Octahydro-6-methoxy-3, 6,8,8-tetramethyl-1 / - / -3a,7-methanoazulen + (3 / ?,3aS,6 / ?,7 / ?,8aS)-octahydro-6-methoxy- 3,6,8,8-tetramethyl-1 / - / -3a,7-methanoazulen (19870-74-7; 67874-81-1; Cedramber); 3a,6,6,9a-Tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran (3738-00-9; Cetalox); 1-(5,5-Dimethyl-1-cyclohexenyl)pent-4-en-1-on (56973-85-4; Dynascon, Galbascon); 1-[Bis(2-hydroxypropyl)amino]propan-2-ol; 5-Methylhept-2-en-4-on (102322-83-8; 81925-81-7; Filberton); 4-(4-Hydroxyphenyl)butan-2-on (5471-51-2; Frambinon); (8£)-Cyclohexadec-8-en-1-on (3100-36-5; Globanon); 4-(2,5,6,6-Tetramethylcyclohex-2-enyl)but-3-en-2-on (201-219-6; alpha-iron); 1-(2,3,8,8-Tetramethyl-1,3,4,5,6,7-hexahydronaphthalen-2-yl)ethanon Reaktionsgemisch (54464-57-2; Iso E Super);Cyclohexadecanone (2550-52-9; Isomuscone), Iso E Super (reaction mixture from the acidic cyclization of 1-(1',6'-dimethyl-4'-(4"-methylpent-3"-en-1"-yl)cyclohex-3'-en-1'-yl)ethan-1-one), 5,5,9,13-tetramethyl-14,16-dioxatetracyclo[11.2.1.0; 1,10 .0 4,9 ]hexadecane (57345-19-4; ketamber); 5-Hexyl-5-methyloxolan-2-one (7011-83-8; lactojasmone); (£)-3-Methyl-4-(2,6,6-trimethyl-1-cyclohex-2-enyl)but-3-en-2-one (127-51-5; Methyl Ionone Gamma Coeur); N-1 -(2,6,6- Trimethyl-1-cyclohex-2-enyl)pent-1-en-3-on (1335-46-2; Methyl Ionone Gamma Pure); (5£)-3-methylcyclopentadec-5-en-1 -on; (5£)-3-methylcyclopentadec-5-en-1 -on (63314-79-4; 82356-51-2; Muscenon); 3-Methylcyclopentadecan-1-on (541-91-3; Muscon); 2-[2-(4-Methyl-1 -cyclohex-3-enyl)propyl]cyclopentan-1 -on (95962-14-4; Nectaryl); 1-(3-Methyl-1-benzofuran-2-yl)ethan-1-on (23911-56-0; Nerolion); Octahydro-7-methyl-1,4-methanonaphthalen-6(2H)-on (41724-19-0; Plicaton); 1-(3,5,5,6,8,8-Hexamethyl-6,7-dihydronaphthalen-2-yl)ethanon + 1 -(3, 5, 5, 6, 8, 8- Hexamethyl-6,7-dihydronaphthalen-2-yl)ethanon (1506-02-1; 21145-77-7; Tonalid); 2,2,5-Trimethyl-5-pentylcyclopentan-1-on (65443-14-3; Velouton); Damascenon; a / p / ?a-Damascon; beta-Damascon; delta -Damascon; beta-Dihydroionon; Dihydrojasmon; Ethylmaltol; a / p / ?a-lonon; beta-lonon; Jasminlacton; Jasmolacton CNC; czs-Jasmon; Maltol; Methylionon;

[0033] Lactone, wie beispielsweise 5-Heptyloxolan-2-on (104-67-6; Aldehyd C14 sogenannt); gamma-Hexalacton; 5-Pentyloxolan-2-on (203-219-1; Aldehyd C18 sogenannt); (9Z)-17-Oxacycloheptadec-9-en-1-on (28645-51-4; Ambrettolid); (12£)-1-Oxacyclohexadec-12-en-2-on + (3£)-Oxacyclohexadec-3-en-2-on (111879-80-2; 34902-57-3; Globalid); 16-Oxacyclohexadecan-1-on (106-02-5; Supra Macrolid); c / e / ta-Decalacton; gamma-Decalacton; gamma-Octalacton.

[0034] Preferably, the compounds of formula (I) are combined with one or more, particularly preferably with two, three, four, five, or more, further odorants that do not correspond to formula (I). In a preferred embodiment, these further odorants have a fruity, floral-green, floral-rosy, floral-white, bloody, musky, or woody odor note. Accordingly, the present invention also relates to an odorant mixture comprising one, two, three, four, five, or more further odorants that do not correspond to formula (I) and that impart a fruity, floral-green, floral-rosy, floral-white, bloody, musky, or woody odor note. Depending on their fragrance family (orchid, hyacinth, ylang-ylang, mignonette, rose), the use of the compounds of formula (I) according to the invention preferably results (at least partially) in an intensification or unexpected alteration of the fruity, floral-green, or bloody odor note. floral-rosy, floral-white-flowered, musky or woody scent notes are achieved.

[0035] In a preferred embodiment of the invention, the at least one further fragrance ingredient, which does not correspond to formula (I), is selected from the group consisting of Agrumex LC (2-tert-butylcyclohexyl acetate), Ethylmethylbutyrate-2 (Ethyl-2-methylbutanoate), Isoamyl acetate (3-methylbutan-1-ol), Dimethylbenzylcarbinylbutyrate (1,1-dimethyl-2-phenylethylbutyrate), Hexyl acetate (hexyl acetate), Allylcyclohexylpropionate (prop-2-en-1-yl-3-cyclohexylpropionate), Dihydromyrcenol (2,6-dimethyloct-7-en-2-ol), Ethyllinalool (3,7-dimethylnona-1,6-dien-3-ol), Helional (3-(1,3-benzodioxol-5-yl)-2-methylpropanal), Cyclamenaldehyde (2-methyl-3-[4-(propan-2-yl)phenyl]propanal), czs-jasmone (czs-3-methyl-2-pent-2-enylcyclopent-2-enone), benzyl acetate, methyl dihydrojasmonate (methyl 3-oxo-2-pentylcyclopentane acetate), methyl anthranilate (methyl 2-aminobenzoate), methyl ionone 70 ((1E)-1-(2,6,6-trimethylcyclohex-2-en-1-yl)pent-1-en-3-one; (3E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one),beta-lonon (4-(2,6,6-Trimethylcyclohex-1 -en-1 -yl)but-3-en-2-on), Geraniol (3,7-Dimethylocta-2,6-dien-1 -ol, Damascenon (1 -(2,6,6-Trimethylcyclohexa-1,3-dien-1 -yl)but-2-en-1 -on)), Phenylethylalkohol (2-Phenylethanol), Benzylsalicylat, Hexylsalicylat, Ambroxid ((3a / ?,5aS,9aS,9b / ?)-3a,6,6,9a-Tetramethyl-Dodecahydronaphtho[2,1 -b]furan), Iso E Super (Reaktionsmasse aus 1-(1,2,3,4,5,6,7,8-Octahydro-2,3,8,8-Tetramethyl-2-Naphthyl)ethan-1 -on und 1 -(1,2,3,4,6,7,8,8a-Octahydro-2,3,8,8-Tetramethyl-2- Naphthyl)ethan-1 -on und 1 -(1,2,3,5,6,7,8,8a-Octahydro-2,3,8,8-Tetramethyl-2- Naphthyl)ethan-1 -on), Cedrylacetat ([3 / ?-(3a, 3a, 6a, 7|3,8aa)]-Octahydro-3, 6,8,8-tetramethyl-1 / - / -3a,7-methanoazulen-5-yl-acetat), Sandranol (2-Ethyl-4-(2,2,3-Trimethylcyclopent-3-en-1 -yl)but-2-en-1 -ol), Polysantol ((4E)-3,3-Dimethyl-5-(2,2,3-Trimethylcyclopent-3-en-1 -yl)pent-4-en-2-ol), Vetiverylacetat (4,8-Dimethyl-2-(Propan-2-ylidene)-1,2,3,3a,4,5,6,8a-octahydroazulen-6-yl-acetat),Ambrettolide (Oxacycloheptadec-10-en-2-one), Ethylene brassylate (1,4-Dioxacycloheptadecan-5,17-dione), Globalid ((12£)-1-Oxacyclohexadec-12-en-2-one; (12Z)-1-Oxacyclohexadec-12-, en-2-one; (13£)-1 -Oxacyclohexadec-13-en-2-one; (13Z)-1 -Oxacyclohexadec-13-en-2-one)), and muscenone (3-Methyl-5-cyclopentadecen-1-one) etc.

[0036] Preferably, at least one of the compounds of formula (1) or (1a) is combined with one or more, particularly preferably with two, three, four, five or more of these preferred further fragrance ingredients.

[0037] Fragrance mixtures containing at least one of the compounds of formula (I) are advantageously used for perfumery in liquid form, undiluted or diluted with a solvent. Suitable solvents for this purpose are, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerin, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate, etc.

[0038] Furthermore, fragrance mixtures according to the invention can be adsorbed onto a carrier, which ensures both a fine distribution of the fragrances in the product and a controlled release during application. Such carriers can be inorganic materials such as sulfate, silica gels, zeolites, plasters, clays, clay granules, aerated concrete, etc., or organic materials such as wood, cellulose-based materials, sugars, dextrins (e.g., maltodextrin), or plastics such as PVC, polyvinyl acetates, or polyurethanes. The resulting combination of compositions according to the invention and the carrier material is also to be understood as a fragrance mixture according to the invention.

[0039] According to the invention, fragrance mixtures can also be microencapsulated, spray-dried or extruded and in this form added, for example, to a product to be perfumed.

[0040] If required, the properties of the modified compositions can be further optimized by so-called "coating" with suitable materials with regard to a more targeted release of fragrances, for which waxy plastics such as polyvinyl alcohol are suitable and preferably used. The resulting products again represent articles according to the invention.

[0041] According to the invention, fragrance mixtures can advantageously be used in concentrated form, in solutions or in the modified form described above for the production of perfumed articles according to the invention, such as e.g.Perfume extracts, eau de parfums, eau de toilettes, aftershave, eau de cologne, pre-shave products, perfumed refreshing wipes, and for the scenting of acidic, alkaline, and neutral cleaning agents such as floor cleaners, window cleaners, dishwashing liquids, bathroom and sanitary cleaners, scouring creams, solid and liquid toilet cleaners, powder and foam carpet cleaners, fabric refreshers, ironing aids, liquid detergents, powder detergents, laundry pretreatment products such as bleaches, soaking agents, and stain removers, fabric softeners, washing soaps, washing tablets, and disinfectants, air fresheners in liquid, gel, or applied form on a solid carrier, aerosol sprays, waxes and polishes such as furniture polishes, floor waxes, shoe creams, and body care products in solid and liquid form, soaps, shower gels, shampoos, shaving soaps, shaving foams, Badedle, cosmetic emulsions of the ol-in-water, water-in-OI and water-in-OI-in-water type, such as...For example, skin creams and lotions, face creams and lotions, sunscreens and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, hair removal creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products such as hairsprays, hair gels, firming hair lotions, hair rinses, permanent and semi-permanent hair dyes, hair styling products such as cold waves and hair straighteners, hair lotions, hair creams and lotions, deodorants and antiperspirants such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, decorative cosmetic products such as eyeshadow, nail polish, lipsticks, mascara and candles, lampshades, smoking sticks, insecticides, repellents and propellants. The preceding list is only exemplary and not exhaustive; of course, other applications are also possible.

[0042] Fragrance mixtures according to the invention can also be included in cosmetic compositions or household compositions.

[0043] Another aspect of the invention is a perfumed article comprising or consisting of (i) a fragrance mixture as described above; as well as (ii) one or more further ingredients, preferably one or more excipients and / or active ingredients.

[0044] In a preferred embodiment, the perfumed article is selected from cosmetic, hygiene, and / or household articles. Other preferred embodiments listed above also apply to the perfumed article of the present invention.

[0045] Preferably, the perfumed article is selected from the group consisting of washing and cleaning agents, hygiene or care products, preferably from the area of ​​body and hair care, cosmetics and household products, preferably from the group consisting of perfume extracts, eau de parfum, eau de toilette, aftershave lotions, eau de cologne, pre-shave products, splash cologne, perfumed refreshing wipes, acidic, alkaline or neutral cleaning agents, fabric refreshers, ironing aids, liquid detergents, powder detergents, pre-wash products, fabric softeners, laundry tablets, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, body care products, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, decorative cosmetic products, candles, lampshades. incense sticks,Insecticides, repellents, and fuels. Particularly preferred is the perfumed item made from alcoholic perfume, a personal care product, or a cleaning or care product for household use.

[0046] In a preferred embodiment of the invention, the perfumed article is selected from cosmetic, hygiene and / or household articles.

[0047] Furthermore, for the perfumed article according to the invention, it is preferred that at least one of the compounds of formula (I) is in a sensorially The effective amount of the compound is sufficient for a consumer to perceive one or more olfactory properties selected from the group consisting of solar, floral (ylang-ylang, orchid, hyacinth, mignonette, rose, orange blossom, jasmine, tuberose, mimosa), powdery, fruity, green, voluminous, long-lasting, delicate, opulent, and / or narcotic. It is also preferred that the total amount of compounds of formula (I), based on the total weight of the perfumed article, is in the range of 0.00001 to 10 wt.%, preferably 0.0001 to 5 wt.%, particularly preferably 0.001 to 2 wt.%, and particularly preferably 0.005 to 1 wt.%.

[0048] The additives, excipients, and / or active ingredients described above are preferably not fragrances. These may include, for example, preservatives, antibacterial agents, chelating agents, cleaning agents, emulsifiers, fats, etc., and basically any substances used as additives, excipients, and / or active ingredients in cosmetics, particularly in fragrance mixtures, as well as in household products.

[0049] Another implementation method involves the use of a compound of where, each independently of the other, R1 = –H, –Me, –Et, –n-Pr or –i-Pr R2, R3 = –H or –Me; R4 = –H, –Me or –Et; X = C or O, where if X = C, each of the dashed lines represents a double bond; and if X = O, then no residue 3 is present; and Y can be -H, -Me, -Et, -n-Pr, -z-Pr, =CH₂, =CHMe, =CHEt, =CMe₂.

[0050] In a preferred embodiment of the invention, at least one compound of formula (I) is used in fragrance compositions to achieve at least one of the following odor notes and / or odor effects: solar, floral (ylang-ylang, orchid, hyacinth, mignonette, rose, orange blossom, jasmine, tuberose, mimosa), powdery, fruity, green, voluminous, long-lasting, fine, opulent and / or narcotic.

[0051] Furthermore, the use of the compounds of formula (I), either a compound of formula (I) or a mixture of several compounds of formula (I), is preferred for mediating, modifying and / or enhancing one or more odor notes of odorants that do not correspond to formula (I), wherein the one or more odor notes are selected from the group consisting of fruity, floral-green, floral-rosy, floral-white, musky and woody.

[0052] Consequently, the inventors made the surprising discovery that the compounds of formula (I) are suitable as fragrances and, in small doses, in combination with other fragrances, especially those with fruity, floral-green, floral-rosy, floral-white, musky, and woody notes, produce special effects. Compared to the prior art methyl benzoates, these effects are significantly better, which was not anticipated.

[0053] Furthermore, the compounds of formula (I) to be used according to the invention can enhance the intensity of an odorant mixture (fragrance composition or scent composition) and round off the overall odor of the mixture. The compounds described herein can therefore be used to give an odorant mixture more strength, purity, florality, naturalness, volume, fruitiness, freshness, spice, warmth, longevity, and complexity. To impart fineness, greenness, less sweat odor, less animal odor, less mushroom odor and / or less terpene odor, in particular the compounds according to the invention can be used to impart more aroma, spice and / or warmth to a fragrance mixture.

[0054] Furthermore, the compounds of formula (I) are suitable as means to increase the substance vitality and / or retention of a fragrance mixture.

[0055] In a preferred embodiment of the invention, an odorant mixture according to the invention is used to convey, modify, and / or enhance one or more odor notes of odorants that do not correspond to formula (I), wherein the one or more odor notes are selected from the group consisting of fruity, floral-green, floral-rosy, floral-white, musky, and woody odorants. As already described above, the odorant mixture according to the invention comprises at least one compound of formula (I) and at least one odorant that does not correspond to formula (I).

[0056] All of the above-mentioned preferred embodiments also apply to the use of the compound(s) of formula (I).

[0057] Another aspect of the invention relates to a method for imparting an odor note and / or modifying and / or enhancing an existing odor note, comprising or consisting of the following steps: a) Providing at least one compound of formula (I) Formula (I), where, each independently of the other, R₁ = –H, –Me, –Et, –n-Pr or –i-Pr R2, R3 = –H or –Me; X = C or O, where if X = C, one of the dashed lines represents a double bond; and if X = O, then no residue 3 is present; and Y can be -H, -Me, -Et, -n-Pr, -z-Pr, =CH₂, =CHMe, =CHEt, =CMe₂; b) Providing at least one fragrance substance that does not conform to formula (I); c) Addition of at least one compound of formula (I) to at least one odorant not corresponding to formula (I) in a sensorially effective quantity sufficient to impart an odor note and / or to modify and / or enhance an existing odor note.

[0058] In a preferred embodiment of the invention, the odor note is selected from the group consisting of: solar, floral (ylang-ylang, orchid, hyacinth, mignonette, rose, orange blossom, jasmine, tuberose, mimosa), powdery, fruity, green, voluminous, long-lasting, fine, opulent and / or narcotic.

[0059] All of the above-mentioned preferred embodiments also apply to the method according to the invention.

[0060] The invention will now be characterized based on the examples provided. Unless otherwise stated, all concentration values ​​are given in percent by weight. EXAMPLES Example 1 General procedure for the Steglich esterification of 2-methylbenzoic acid

[0061] In a three-necked flask stirring apparatus equipped with a magnetic stirrer, internal thermometer, reflux condenser, and a nitrogen atmosphere, 2-methylbenzoic acid, dichloromethane, 4-dimethylaminopyridine, and the corresponding alcohol were placed at room temperature. Dicyclohexylcarbodiimide was added in 3-4 equal portions. The mixture was stirred for 24 hours at room temperature. The precipitated solid was then filtered off, and the resulting mother liquor was concentrated at 50 °C and 850 to 20 mbar using a rotary evaporator. The residue was dissolved in 10 times its volume of n-hexane (e.g., 16.5 g residue = 165 ml n-hexane) at room temperature and then allowed to crystallize at 5 °C. The residue thus obtained was filtered off and the mother liquor was concentrated at 60 °C and 400->20 mbar using a rotary evaporator, yielding the crude product.After column chromatography of the crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585), the respective title compound was obtained. The yield (%) was calculated based on the amount of 2-methylbenzoic acid used. Example 2 Production and odor properties of [(£)-1-Methylhex-2-enyl] 2-methylbenzoate

[0062] By transesterification: In a 1000 mL three-necked flask heating apparatus with magnetic stirrer, contact thermometer, dropping funnel, and 10 cm column (Raschig rings) with column head, 155 g (1.03 mol) of 2-methylbenzoic acid, 116 g (1.02 mol) of (µ)-hept-3-en-2-ol, and 14.0 g (0.101 mol) of potassium carbonate were heated at 600 mbar in reflux. The resulting methanol was distilled off (bottom temp.: 160–180 °C, top temp.: 54–123 °C, reflux ratio 50:1, reaction time: 10 h). During this time The vacuum was steadily reduced to 400 mbar. After fractional destination, 121 g (51%) of the title compound were obtained as a mixture of isomers (boiling point: 110 °C, 1 mbar. GC purity: 92% [(£)-1-methylhex-2-enyl]-2-methylbenzoate, 7% [(E)-1-propylbut-2-enyl]-2-methylbenzoate). [(E)-1-Methylhex-2-enyl]-2-methylbenzoate

[0063] Odor: floral, like hyacinth, salicylate-like, tending towards benzyl salicylate.

[0064] DC: R f = 0.37 (SiO260, hexane / ethyl acetate = 20:1).

[0065] GC / MS: m / z (%): 41 (4), 55 (52), 65 (7), 81 (13), 91 (19), 119 (100), 137 (2), 145 (1), 203 (1), 217 (1), 232 (1).

[0066] GC-IR (Thermo Nicolet 6700): h = 3072 (w) / 3033 (w) / 2977 (w) / 2940 (w) / 2883 (w), 1733 (s), 1604 (w) / 1458 (w) / 1381 (w), 1289 (m), 1253 (s) / 1136 (f) / 1076 (m) / 1047 (m) / 967 (f), 736 (f).

[0067] 1H NMR (400 MHz, CDCl₃): δ = 7.89 (dd, J = 7.5, 1.5 Hz, 1H), 7.37 (td, J = 7.5, 1.5 Hz, 1H), 7.23 (t, J = 7.5 Hz, 1H), 7.22 (d, J = 7.5 Hz, 1H), 5.78 (dt, J = 14.5, 6.8 Hz, 1 H), 5.60 - 5.54 (m, 1 H), 5.59 - 5.52 (m, 1 H), 2.59 (s, 3H), 2.07 - 1.99 (m, 2H), 1.42 (d, J = 6.2 Hz, 3H), 1.45 - 1.37 (m, 2H), 0.90 (t, J = 7.4 Hz, 3H).

[0068] 13 C NMR (101 MHz, CDCl₃): δ = 167.1, 139.8, 133.3, 131.7, 131.8, 130.4, 130.4, 129.8, 125.6, 71.7, 34.3, 22.1, 21.7, 20.6, 13.6. Nebenverbindung (7 %): [(E)-1-Propylbut-2-enyl]-2-methylbenzoat

[0069] Geruch: salicylatartig.

[0070] GC / MS: m / z (%): 55 (36), 65 (5), 81 (13), 91 (16), 97 (11), 119 (100), 136 (1), 161 (1), 176 (1), 189 (1), 203 (1), 232 (1).

[0071] GC-IR (GC: 95 %), Thermo Nicolet 6700): h = 3072 (w) / 3033 (w) / 2970 (m) / 2943 (w) / 2883 (w), 1733 (m), 1603 (w), 1460 (w), 1386 (w), 1289 (m) / 1252 (s), 1138 (w) / 1075 (m), 962 (w), 935 (w), 736 (w).

[0072] 1 H NMR (400 MHz, CDCl₃): δ = 7.90 (dd, J = 8.2, 1.5 Hz, 1H), 7.38 (td, J = 7.5, 1.5 Hz, 1H), 7.25 - 7.21 (m, 2H), 5.81 (dqt, J = 15.2, 6.6, 0.7 Hz, 1H), 5.52 (ddq, J = 15.1, 7.3, 1.7 Hz, 1H), 5.44 (q, J = 6.9 Hz, 1H), 2.59 (s, 3H),1.76 (ddt, J = 13.5, 9.6, 7.0 Hz, 1H), 1.71 (dd, J = 6.6, 1.7 Hz, 3H), 1.64 (ddt, J = 13.3, 9.3, 6.3 Hz, 1H), 1.47 - 1.35 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H).

[0073] 13 C NMR (101 MHz, CDCl₃): δ = 167.1, 139.0, 131.7, 131.6, 130.4, 130.4, 129.8, 129.1, 125.6, 75.2, 36.8, 21.8, 18.6, 17.8, 13.9. Beispiel 3 Herstellung von (£)-Hept-3-en-2-ol durch Grignard-Reaktion

[0074] In a 2-liter three-necked flask stirred tank equipped with a fly stirrer, contact thermometer, reflux condenser, dropping funnel, and sodium atmosphere, 400 mL (1.20 mol) of 3 M methylmagnesium chloride dissolved in THF and 400 mL of THF were placed. Then, 108 g (1.10 mol) of cis-3-hexenal dissolved in 220 mL of THF were added dropwise over 2 h, during which time the reaction temperature rose to 54 °C. The mixture was stirred for 2.5 h at 55 °C for the secondary reaction. The heater was removed, and the mixture was allowed to cool to room temperature. Then, 100 mL of water were slowly added at 10–20 °C. The precipitated solid was precipitated with 200 g of 20% sulfuric acid at 5–15 °C. After adding 200 ml of MTBE and 300 ml of water, the phases were separated, and the organic phase was washed successively with 200 ml each of a 5% sodium chloride solution and a 5% sodium carbonate solution. Concentration on a rotary evaporator at 60 °C and 150 to 50 mbar yielded 116 g (90%) of the title compound (GC purity: 97%).

[0075] DC: R f= 0,28 (SiO260, Hexan / Essigester = 5:1).

[0076] GC / MS: m / z (%): 29 (12), 43 (44), 55 (17), 57 (59), 67 (2), 71 (100), 81 (6), 85 (12), 99 (6), 114 (1).

[0077] GC-IR (Thermo Nicolet 6700): h = 3649 (w), 2976 (s) / 2939 (s) / 2883 (m), 1668 (w), 1456 (w) / 1378 (w), 1055 (w) / 968 (w).

[0078] 1 H NMR (400 MHz, CDCI3): 5 = 0.90 (t, J = 7.4 Hz, 3H), 1.26 (d, J = 6.3 Hz, 3H), 1.34 - 1.43 (m, 2H), 1.45 (d, 1 H), 1.94 - 2.06 (m, 2H), 4.26 (ddq, J = 6.4, 6.4, 6.4 Hz, 1 H), 5.52 (ddt, J = 15.4, 6.7, 1.4 Hz, 1 H), 5.63 (dtd, J = 15.5, 6.7, 1.0 Hz, 1 H).

[0079] 13 C NMR (101 MHz, CDCl₃): δ = 13.7 (q), 22.3 (t), 23.5 (q), 34.2 (t), 69.0 (d), 76.8, 77.0, 77.3, 131.0 (d), 134.3 (d). Beispiel 4 Herstellung und Geruchseigenschaften von [(3Z)-Hex-3-enyl]-2-methylbenzoat

[0080] In a 2-liter three-necked flask stirred mixture equipped with a magnetic stirrer, water separator, and reflux condenser, 330 g (2.43 mol) of 2-methylbenzoic acid, 575 ml of toluene, 12.0 g (63.2 mmol) of p-toluenesulfonic acid monohydrate, and 292 g (2.92 mol) of cis-3-hexenol were placed and then heated under reflux for 8 h in the water separator (reaction temperature: 113–128 °C), during which 44.0 ml of water were separated. The heating element was removed, and the mixture was allowed to cool to room temperature. At room temperature, the mixture was washed successively with 250 ml of 5% sodium chloride solution and then with 100 ml of 5% sodium chloride solution. The organic phase was concentrated at 40–80 °C and 80–5 mbar using a rotary evaporator. The crude yield was 519 g (94%). GC purity: 95.5%. After fractional destination (30 cm column with Wilson coils and column head), 414 g (78%) of the title compound were obtained (boiling point: 117–119 °C, 2 mbar, GC purity: 99%).

[0081] Geruch: salicylatartig, grun-floral, floral nach Hyazinthe und Orchidee, fruchtig nach Birne.

[0082] DC: R f = 0,17 (SiO260, Hexan / Essigester = 10:1)

[0083] GC / MS: m / z (%): 41 (9), 55 (9), 63 (2), 67 (64), 82 (100), 91 (39), 119 (90), 137 (7).

[0084] GC-IR (GC %, Thermo Nicolet 6700): h = 3072 (w) / 3020 (w) / 2973 (w), 1737 (m), 1604 (w), 1461 (w), 1384 (w), 1290 (m) / 1252 (s), 1139 (w) / 1083 (m), 736 (w).

[0085] 1 H NMR (400 MHz, CDCl3): δ = 1H NMR (400 MHz, CDCl₃) δ 7.90 (dd, J = 8.1, 1.5 Hz, 1 H), 7.39 (td, J = 7.5, 1.5 Hz, 1 H), 7.28 - 7.18 (m, 2H), 5.60 - 5.48 (m, 1 H), 5.46 - 5.35 (m, 1H), 4.30 (t, J = 6.8 Hz, 2H), 2.60 (s, 3H), 2.57 - 2.46 (m, 2H), 2.15 - 2.02 (m, 2H), 0.97 (t, J = 7.5 Hz, 3H).

[0086] 13C NMR (101 MHz, CDCl3): δ = 13C NMR (101 MHz, CDCl₃) δ 167.7, 140.1, 134.6, 131.9, 131.6, 130. 6, 129.9, 125.7, 123.9, 64.3, 26.9, 21.8, 20.7, 14.2. Example 5 Preparation of (£)-2-methylbut-2-en-1-ol by lithium alate reduction

[0087] In a 1-liter three-necked flask equipped with a flutter, contact thermometer, dropping funnel, and sodium atmosphere, 200 ml of THF and 11.0 g (268 mmol) of lithium aluminum hydride were placed. Then, at 20–30 °C, 75 g (892 mmol) of (E)-2-methylbut-2-enal in 100 ml of THF were added dropwise over 1 h. For the secondary reaction, the mixture was stirred for 1.2 h at 40 °C, followed by the slow addition of 17.0 g of isopropanol at 15–20 °C, then 9.0 g (281 mmol) of methanol at 15–20 °C, and finally 110 ml of water at a maximum temperature of 20 °C. Finally, at 5-10 °C, 100 ml of 20% sulfuric acid was added dropwise. After adding 200 ml of MTBE, the organic phase was separated and rinsed with 2 x 100 ml of MTBE. The organic phase was then washed successively with 150 ml each of saturated sodium chloride solution and 5% sodium carbonate solution.After concentration on a rotary evaporator at 50 °C and 500 to 120 mbar, 110 g of crude product were obtained, which were boiled dry for 6 h with 200 ml of MTBE in a water separator at 75 °C (18.8 ml water). After fractional destination (10 cm Vigreux, with distillation and water bath), 69.0 g (90%) of the title compound were obtained (GC purity: 97%).

[0088] GC / MS: m / z (%): 29 (18), 43 (49), 53 (26), 67 (19), 71 (100), 86 (50).

[0089] GC-IR (Thermo Nicolet 6700): h = 3658 (w), 2931 (s) / 2878 (s), 1453 (w), 1382 (w), 1189 (w), 1008 (s), 824 (w).

[0090] 1 H NMR (400 MHz, CDCl₃): δ = 5.56 - 5.41 (m, 1H), 4.00 (d, J = 4.6 Hz, 2H), 1.69 - 1.65 (m, 3H), 1.63 (dp, J = 6.7, 1.1 Hz, 3H), 1.37 (t, 1 H).

[0091] 13 C NMR (101 MHz, CDCl₃): δ = 135.50, 120.66, 77.35, 77.04, 76.72, 69.07, 13.36, 13.10. Example 6 Production and odor properties of allyl-2-methyl benzoate

[0092] In a 500 mL three-necked flask stirred flask apparatus equipped with a magnetic stirrer, contact thermometer, dropping funnel, and a 10 cm column (Raschig rings) with a column head, 150 g (1.10 mol) of 2-methylbenzoic acid, 70.0 g (1.21 mol) of allyl alcohol, and 14.0 g (0.101 mol) of potassium carbonate were heated by reflux. The resulting methanol was distilled off (bottom temp.: 125–159 °C, top temp.: 70–83 °C, reflux ratio 15:1, reaction time: 13 h). After fractional removal of the crude product, 93 g (48%) of the title compound were obtained (boiling point: 107 °C, 10 mbar; GC purity: 99%).

[0093] Scent: floral, reminiscent of ylang-ylang, salicylate-like towards benzyl salicylate, with fruity hints and associations of azaleas, hawthorn and tulips.

[0094] DC: R f = 0.63 (SiO260, hexane / ethyl acetate = 20:1).

[0095] GC / MS: m / z (%): 39 (15), 51 (3), 65 (23), 79 (15), 91 (59), 107 (2), 119 (84), 135 (100), 147 (31), 158 (22), 176 (12).

[0096] GC-IR (Thermo Nicolet 6700): h = 3075 (w) / 3032 (w) / 2950 (w), 1739 (m), 1455 (w) / 1361 (w), 1290 (w) / 1252 (s), 1137 (w) / 1078 (m), 975 (w) / 931(w), 736(w).

[0097] 1 H NMR (400 MHz, CDCl3): δ = 7.94 (dd, J = 8.1, 1.5 Hz, 1H), 7.40 (td, J = 7.5, 1.5 Hz, 1H), 7.29 - 7.20 (m, 2H), 6.11 - 5.97 (m, 1H), 5.46 - 5.36 (m, 1H), 5.34 - 5.24 (m, 1H), 4.83 - 4.77 (m, 2H), 2.61 (s, 3H).

[0098] 13 C NMR (101 MHz, CDCl₃): δ = 167.2, 140.3, 132.4, 132.0, 131.7, 130.6, 129.6, 125.7, 118.2, 65.4, 21.8. Example 7 Production and odor properties of 1-methylallyl 2-methylbenzoate

[0099] Analogous to the general manufacturing procedure for Steglich esterification, 9.40 g (69.0 mmol) of 2-methylbenzoic acid and 5.00 g (69.3 mmol) of 3-buten-2-ol were used. 1.70 g (13.9 mmol) of 4-dimethylamiopyridine in 150 ml of dichloromethane were reacted with 13.0 g (62.4 mmol) of dicyclohexylcarbodiimide, yielding 10.4 g (70%) of crude product after standard purification (GC purity: 89%). Column chromatography of 1.00 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585) yielded 413 mg (32%) of the title compound (GC purity: 97%). Odor: salicylate-like, floral, reminiscent of orchids, with slight medicinal notes.

[0100] DC: R f = 0.5 (SiO260, hexane / ethyl acetate = 20:1).

[0101] GC / MS: m / z (%): 39 (12), 55 (52), 65 (22), 71 (1), 79 (4), 91 (52), 105 (1), 119 (100), 135 (30), 147 (15), 157 (4), 161 (17), 172 (11), 1902 (6).

[0102] GC-IR (Thermo Nicolet 6700): h = 3075 (w) / 3030 (w) / 2988 (w) / 2943 (w), 1735 (m), 1603 (w), 1458 (w), 1380 (w), 1289 (w) / 1253 (s), 1136 (w) / 1077 (m), 736 (w).

[0103] 1 H NMR (400 MHz, CDCl3): δ = 7.92 (dd, J = 8.1, 1.5 Hz, 1H), 7.39 (td, J = 7.5, 1.5 Hz, 1 H), 7.28 - 7.20 (m, 2H), 5.97 (ddd, J = 17.3, 10.6, 5.8 Hz, 1 H), 5.59 (pt, J = 6.6, 6.0, 1.4 Hz, 1H), 5.33 (dt, J = 17.3, 1.3 Hz, 1H), 5.19 (dt, J = 10.6, 1.2 Hz, 1H), 2.60 (s, 3H), 1.45 (d, J = 6.5 Hz, 3H).

[0104] 13 C NMR (101 MHz, CDCl₃): δ = 166.9, 140.0, 137.8, 131.8, 131.6, 130.5, 130.0, 125.7, 115.9, 71.4, 21.7, 20.1. Beispiel 8 Herstellung und Geruchseigenschaften von 2-Methylallyl-2-methylbenzoat

[0105] Analogous to the general preparation procedure for the Steglich esterification, 16.0 g (118 mmol) of 2-methylbenzoic acid, 8.50 g (118 mmol) of 2-methyl-2-propen-1-ol, and 2.90 g (23.7 mmol) of 4-dimethylamiopyridine were reacted with 22.1 g (107 mmol) of dicyclohexylcarbodiimide in 240 ml of dichloromethane, yielding 18.2 g (78%) of crude product after the described purification (GC purity: 96%). Column chromatography of 1.00 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20°C) was performed. By distillation of 549 mg (45%) of the title compound (100% GC purity) in 1 ml per fraction and subsequent ball tube distillation (Biichi B-585). Odor: floral, salicylate-like, floral-rosy in the direction of citronellol, with slightly peppery accents and hints of ylang-ylang balsam and linalool.

[0106] DC: / ? f = 0.39 (SiO2 60, hexane / ethyl acetate = 20:1).

[0107] GC / MS: m / z (%): 39 (7), 55 (6), 65 (13), 79 (4), 91 (37), 105 (1), 119 (100), 135 (25), 147 (5), 157 (3), 172 (4), 190 (2).

[0108] GC-IR (Thermo Nicolet 6700): ñ = 3078 (w) / 3034 (w) / 2984 (w) / 2944 (w), 1739 (s), 1603 (w), 1458 (w), 1385 (w), 1291 (m) / 1249 (s), 1138 (w) / 1082 (m) / 1249 (m), 736 (w).

[0109] 1 H NMR (400 MHz, CDCl3): δ = 7.96 (dd, J = 8.1, 1.5 Hz, 1 H), 7.40 (td, J = 7.5, 1.5 Hz, 1H), 7.29 - 7.22 (m, 2H), 5.07 (p, J = 2.3, 1.3 Hz, 1H), 4.98 (tp, J = 2.3, 1.5, 0.8 Hz, 1H), 4.73 (s, 2H), 2.62 (s, 3H), 1.85 (t, J = 1.1 Hz, 3H).

[0110] 13 C NMR (101 MHz, CDCl3): δ = 167.4, 140.5, 140.2, 132.2, 131.9, 130.8, 129.7, 125.9, 113.2, 68.2, 21.9, 19.8. Beispiel 9 Herstellung und Geruchseigenschaften von 3-Methylbut-2-enyl-2-methylbenzoat

[0111] Analogous to the general manufacturing procedure for Steglich esterification, 10.0 g (73.4 mmol) 2-methylbenzoic acid, 6.30 g (73.4 mmol) 3-methylbut-2-en-1-ol, 1.80 g (14.7 mmol) 4-dimethylamiopyridine were reacted in 150 ml dichloromethane with 13.8 g (66.1 mmol) dicyclohexylcarbodiimide, whereby after the described purification 11.8 g (72%) crude product were obtained (GC purity: 91%). After column chromatography of 2.00 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585), 1441 mg (56%) of the title compound were obtained (GC purity: 99%). Odor: Floral, reminiscent of weld, with a distinct salicylate character towards amyl salicylate, as well as hints of myrrh and orange blossom, with fruity facets reminiscent of plum and strawberry.

[0112] DC: / ? f = 0.61 (SiO260, hexane / ethyl acetate = 20:1)

[0113] GC / MS: m / z (%): 41 (43), 53 (7), 69 (100), 77 (2), 85 (5), 91 (41), 105 (1), 119 (96), 136 (19), 148 (15), 161 (3), 186 (4), 204 (10).

[0114] GC-IR (Thermo Nicolet 6700): ñ = 3072 (w) / 3033 (w) / 2981 (w) / 2941 (w), 1735 (m), 1604 (w), 1456 (w), 1381 (w), 1288 (m) / 1252 (s), 1137 (w) / 1076 (m), 736 (w).

[0115] 1 H NMR (400 MHz, CDCl3): δ = 7.90 (dd, J = 8.1, 1.5 Hz, 1H), 7.38 (td, J = 7.5, 1.5 Hz, 1H), 7.25 - 7.22 (m, 1H), 7.25 - 7.20 (m, 1H), 5.47 (thept, J = 7.2, 1.4 Hz, 1H), 4.80 (dt, J = 7.2, 1.0 Hz, 2H), 2.60 (s, 3H), 1.79 (q, J = 1.1 Hz, 3H), 1.78 - 1.76 (m, 3H).

[0116] 13 C NMR (101 MHz, CDCl3): δ = 167.7, 140.0, 139.0, 131.8, 131.6, 130.5, 130.0, 125.6, 118.7, 61.6, 25.8, 21.7, 18.1. Beispiel 10 Herstellung und Geruchseigenschaften von [(£)-1,2-Dimethylbut-2-enyl]-2- methylbenzoat

[0117] Analogous to the general manufacturing procedure for Steglich esterification, 5.80 g (42.4 mmol) 2-methylbenzoic acid, 5.00 g (42.4 mmol) (£)-3-methylpent-3-en-2-ol, 1.00 g (8.50 mmol) 4-dimethylamiopyridine are reacted in 150 ml dichloromethane with 8.00 g (38.2 mmol) dicyclohexylcarbodiimide, whereby after the described purification 9.10 g (78%) crude product are obtained (GC purity: 77% main amount, 2% isomer). Column chromatography of 2.00 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585) yielded 1193 mg (58%) of the title compound (GC purity: 96% main product, 2% (Z)-double bond isomer). Odor: floral, reminiscent of hyacinth, salicylate-like towards amyl and hexyl salicylate, with a pronounced green character.

[0118] DC: / ? f = 0.47 (SiO260, hexane / ethyl acetate = 20:1) Main product (96%):

[0119] GC / MS: m / z (%): 41 (9), 55 (19), 67 (29), 83 (24), 91 (15), 99 (7), 119 (100), 137 (1), 189 (1), 203 (1), 218 (1).

[0120] GC-IR (Thermo Nicolet 6700): ñ = 3072 (w) / 3031 (w) / 2988 (w) / 2938 (w) / 2878 (w), 1733 (m), 1603 (w) / 1458 (w) / 1383 (w), 1288 (m) / 1252 (s), 1138 (w) / 1076 (w), 736 (w). Nebenkomponente (2%):

[0121] GC / MS: m / z (%): 41 (9), 55 (28), 67 (19), 91 (19), 99 (5), 119 (100), 136 (2), 189 (1), 203 (1), 218 (1).

[0122] GC-IR (Thermo Nicolet 6700): ñ = 3069 (w) / 3030 (w) / 2980 (w) / 2942 (w) / 2888 (w), 1733 (s), 1602 (w) / 1458 (w) / 1383 (w), 1289 (m) / 1253 (s), 1136 (w) / 1077 (m), 963 (w), 736 (w).

[0123] 1 H NMR (400 MHz, CDCl3): δ = 7.90 (dd, J = 8.2, 1.6 Hz, 1H), 7.42 - 7.32 (m, 1H), 7.27 - 7.17 (m, 2H), 5.67 - 5.58 (m, 1 H), 5.50 (q, J = 6.5 Hz, 1H), 2.60 (s, 3H), 1.72 - 1.68 (m, 3H), 1.65 - 1.61 (m, 3H), 1.42 (d, J = 6.5 Hz, 3H).

[0124] 13 C NMR (101 MHz, CDCl3): δ = 166.9, 140.0, 135.1, 131.7, 131.6, 130.5, 130.4, 125.7, 121.8, 76.1, 21.8, 19.2, 13.1, 11.7. Example 11 Production and odor properties of [(£)-2-methylbut-2-enyl]-2-methylbenzoate

[0125] Analogous to the general preparation procedure for the Steglich esterification, 7.90 g (58.0 mmol) of 2-methylbenzoic acid, 5.00 g (58.1 mmol) of (E)-2-methylbut-2-en-1-ol, and 1.40 g (11.5 mmol) of 4-dimethylamiopyridine were reacted in 115 ml of dichloromethane with 13.4 g (64.9 mmol) of dicyclohexylcarbodiimide, yielding 13.3 g (94%) of crude product after the described purification (GC purity: 84%). Column chromatography of 1.10 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20) was performed. (ml / min at 20 ml per fraction) and subsequent bulb tube distillation (Biichi B-585) yielded 545 mg (58%) of the title compound (GC purity: 99%). Odor: floral, reminiscent of orchids, salicylate-like, similar to cyclohexyl sa I icylate, with fruity-green accents pointing towards unripe banana.

[0126] DC: / ? f = 0.38 (SiO260, hexane / ethyl acetate = 20:1).

[0127] GC / MS: m / z (%): 52 (2), 69 (21), 77 (1), 91 (21), 105 (1), 119 (100), 137 (5), 147 (1), 161 (2), 171 (1), 186 (1), 204 (2).

[0128] GC-IR (Thermo Nicolet 6700): ñ = 3072 (w) / 3033 (w) / 2985 (w) / 2936 (w) / 2879 (w), 1736 (m), 1603 (w), 1457 (w), 1388 (w), 1289 (w) / 1250 (s), 1138 (f) / 1076 (m), 942 (f), 820 (f), 736 (f).

[0129] 1 H NMR (400 MHz, CDCl3): δ = 7.95 - 7.88 (m, 1H), 7.43 - 7.34 (m, 1H), 7.29 - 7.19 (m, 2H), 5.70 - 5.56 (m, 1H), 4.69 (t, J = 1.2 Hz, 2H), 2.60 (s, 3H), 1.74 (p, J = 1.2 Hz, 3H), 1.70 - 1.64 (m, 3H).

[0130] 13 C NMR (101 MHz, CDCl3): δ = 167.6, 140.1, 131.9, 131.7, 130.9, 130.6, 129.9, 125.7, 124.2, 70.6, 21.8, 13.8, 13.3. Example 12 Production and odor properties of [(£)-1-Propylbut-2-enyl]-2-methylbenzoate (containing 4% czs double bond isomer)

[0131] Analogous to the general manufacturing procedure for Steglich esterification, 180 mg (13.2 mmol) 2-methylbenzoic acid, 1.49 g (11.9 mmol) hept-2-en-4-ol, 242 mg (2.00 mmol) 4-dimethylamiopyridine were reacted in 27 ml dichloromethane with 2.20 g (10.6 mmol) dicyclohexylcarbodiimide, whereby after the described purification 2.30 g (62%) crude product were obtained (GC purity: 79% bulk, 3% cis-isomer). After column chromatography of 1.00 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585), 316 mg (24%) of the title compound were obtained (GC purity: 95%). Main component, 4% czs-lsomer). Odor: floral, delicately floral like mignonette with salicylate character.

[0132] DC: / ? f = 0.40 (SiO260, hexane / ethyl acetate = 20:1).

[0133] cis-lsomer (4 %): GC / MS: m / z (%): 55 (39), 65 (6), 81 (13), 91 (16), 97 (11), 119 (100), 136 (2), 145 (1), 161 (1), 203 (1), 232 (1).

[0134] GC-IR (GC: 4 %), Thermo Nicolet 6700): ñ = 3070 (w) / 3028 (w) / 2970 (m) / 2942 (w) / 2883 (w), 1731 (s), 1602 (w), 1461 (w), 1384 (w), 1289 (m), 1252 (s), 1128 (w) / 1113 (w) / 1075 (m), 941 (w), 736 (w).

[0135] trans-lsomer (95 %): GC / MS: m / z (%): 55 (36), 65 (5), 81 (13), 91 (16), 97 (11), 119 (100), 136 (1), 161 (1), 176 (1), 189 (1), 203 (1), 232 (1).

[0136] GC-IR (GC: 95 %), Thermo Nicolet 6700): ñ = 3072 (w) / 3033 (w) / 2970 (m) / 2943 (w) / 2883 (w), 1733 (m), 1603 (w), 1460 (w), 1386 (w), 1289 (m) / 1252 (s), 1138 (w) / 1075 (m), 962 (w), 935 (w), 736 (w).

[0137] 1H NMR (400 MHz, CDCl3): δ = 7.90 (dd, J = 8.2, 1.5 Hz, 1H), 7.38 (td, J = 7.5, 1.5 Hz, 1H), 7.25 - 7.21 (m, 2H), 5.81 (dqt, J = 15.2, 6.6, 0.7 Hz, 1 H), 5.52 (ddq, J = 15.1, 7.3, 1.7 Hz, 1 H), 5.44 (q, J = 6.9 Hz, 1 H), 2.59 (s, 3H), 1.76 (ddt, J = 13.5, 9.6, 7.0 Hz, 1 H), 1.71 (dd, J = 6.6, 1.7 Hz, 3H), 1.64 (ddt, J = 13.3, 9.3, 6.3 Hz, 1H), 1.47 - 1.35 (m, 2H), 0.95 (t, J = 7.4 Hz, 3H).

[0138] 13 C NMR (101 MHz, CDCl3): δ = 167.1, 139.0, 131.7, 131.6, 130.4, 130.4, 129.8, 129.1, 125.6, 75.2, 36.8, 21.8, 18.6, 17.8, 13.9. Example 13 Production and odor properties of 1,2-dimethylallyl-2-methylbenzoate

[0139] Analogous to the general manufacturing procedure for the Steglich esterification, 10.0 g (73.5 mmol) of 2-methylbenzoic acid, 6.00 g (69.7 mmol) of 3-methylbut-3-en-2-ol, and 1.35 g (11.1 mmol) of 4-dimethylamiopyridine were reacted in 200 ml of dichloromethane with 12.3 g (59.6 mmol) of dicyclohexylcarbodiimide, yielding 10.7 g (66%) of crude product after the described purification (GC purity: 93%). Column chromatography of 1.20 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585) yielded 593 mg (35%) of the title compound (GC purity: 99%). Odor: floral, reminiscent of orchids, with a distinct salicylate character reminiscent of root beer and spicy hints of kimmy.

[0140] DC: / ? f = 0.46 (SiO260, hexane / ethyl acetate = 20:1).

[0141] GC / MS: m / z (%): 53 (4), 69 (19), 77 (1), 91 (25), 105 (1), 119 (100), 137 (5), 147 (1), 161 (2), 171 (1), 186 (1), 204 (1).

[0142] GC-IR (Thermo Nicolet 6700): ñ = 3077 (w) / 2988 (w) / 2943 (w), 1735 (m), 1457 (w), 1380 (w), 1289 (m) / 1252 (s), 1138 (w) / 1076 (s), 736 (w).

[0143] 1 H NMR (400 MHz, CDCl3): δ = 7.93 (dd, J = 8.1, 1.5 Hz, 1H), 7.39 (td, J = 7.5, 1.5 Hz, 1 H), 7.27 - 7.22 (m, 2H), 5.52 (q, J = 6.7 Hz, 1 H), 5.07 - 5.04 (m, 1 H), 4.92 -4.88 (m, 1H), 2.61 (s, 3H), 1.83 (s, 3H), 1.45 (d, J = 6.6 Hz, 3H).

[0144] 13 C NMR (101 MHz, CDCl3): δ = 166.8, 144.7, 140.1, 131.9, 131.7, 130.5, 130.1, 125.7, 111.8, 73.9, 21.8, 19.3, 18.4. Beispiel 14 Herstellung und Geruchseigenschaften von [(£)-2-Methylpent-2-enyl]-2- methylbenzoat

[0145] Analogous to the general manufacturing procedure for Steglich esterification, 10.0 g (73.4 mmol) 2-methylbenzoic acid, 6.62 g (66.1 mmol) alcohol, 1.35 g (11.1 mmol) 4-dimethylamiopyridine were reacted in 151 ml dichloromethane with 12.3 g (59.6 mmol) dicyclohexylcarbodiimide, whereby after the described purification 12.9 g (71%) crude product were obtained (GC purity: 88%). Column chromatography of 1.20 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585) yielded 646 mg (43%) of the title compound (GC purity: 99%). Odor: floral-warm, orchid-like, salicylate-like. TLC: / ?f = 0.38 (SiO260, hexane / ethyl acetate = 20:1).

[0146] GC / MS: m / z (%): 55 (25), 67 (20), 82 (41), 91 (23), 99 (1), 119 (100), 137 (4), 147 (1), 158 (1), 175 (1), 185 (1), 218 (1).

[0147] GC-IR (Thermo Nicolet 6700): ñ = 3072 (w) / 3033 (w) / 2974 (w) / 2944 (w) / 2887 (w), 1736 (m), 1289 (m) / 1250 (s), 1138 (w) / 1078 (m), 736 (w).

[0148] 1 H NMR (400 MHz, CDCl3): δ = 7.92 (dd, J = 8.2, 1.4 Hz, 1H), 7.39 (td, J = 7.5, 1.5 Hz, 1H), 7.25 - 7.22 (m, 2H), 5.55 (tq, J = 7.2, 1.2 Hz, 1H), 4.68 (s, 2H), 2.60 (s, 3H), 2.14 - 2.04 (m, 2H), 1.74 (t, J = 1.1 Hz, 3H), 0.99 (t, J = 7.5 Hz, 3H).

[0149] 13 C NMR (101 MHz, CDCl3): δ = 167.6, 140.1, 131.9, 131.8, 131.7, 130.6, 129.9, 129.4, 125.7, 77.3, 77.0, 76.8, 70. 7, 21.8, 21.1, 14.0, 13.9. Beispiel 15 Herstellung und Geruchseigenschaften von [(E / Z)-But-2-enyl]-2-methylbenzoat

[0150] Analogous to the general manufacturing procedure for Steglich esterification, 10.0 g (73.4 mmol) 2-methylbenzoic acid, 4.77 g (66.1 mmol) (E / Z)-but-2-en-1-ol, 1.35 g (11.1 mmol) 4-dimethylamiopyridine are reacted in 200 ml dichloromethane with 12.3 g (59.6 mmol) dicyclohexylcarbodiimide, whereby after the described purification 10.5 g (71%) crude product is obtained (GC purity: 94%). Column chromatography of 1.20 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585) yielded 706 mg (44%) of the title compound (GC purity: 98%). Odor: soft and floral, reminiscent of mignonette, salicylate-like with fruity-green hints of pineapple and chocolatey nuances.

[0151] DC: / ? f = 0.45 (SiO260, hexane / ethyl acetate = 20:1).

[0152] HM (89 %): GC / MS: m / z (%): 55 (59), 65 (19), 79 (4), 91 (57), 105 (1), 119 (100), 135 (27), 147 (14), 161 (14), 172 (10), 190 (5).

[0153] GC-IR (Thermo Nicolet 6700): ñ = 3072 (w) / 3033 (w) / 2952 (w), 1737 (m), 1290 (w) / 1252 (s), 1138 (w) / 1084 (m), 965 (w), 736 (w).

[0154] NV (7 %): GC / MS: m / z (%): 55 (52), 65 (18), 79 (4), 91 (50), 105 (1), 119 (100), 135 (23), 147 (12), 161 (13), 172 (9), 190 (3)

[0155] 1 H NMR (400 MHz, CDCl3): δ = 1.75 (dq, J = 6.5, 1.3 Hz, 3H), 2.60 (s, 3H), 4.73 (dp, J = 6.5, 1.2 Hz, 2H), 5.71 (dddd, J = 15.2, 8.1, 4.8, 1.7 Hz, 1H), 5.87 (dqt, J = 15.4, 6.5, 1.2 Hz, 1 H), 7.20 - 7.28 (m, 2H), 7.38 (td, J = 7.5, 1.5 Hz, 1 H), 7.88 - 7.94 (m, 1H).

[0156] 13 C NMR (101 MHz, CDCl3): δ = 17.8 (q), 21.7 (q), 65.5 (t), 76.8, 77.0, 77.3, 125.3 (d), 125.7 (d), 129.8 (s), 130.6 (d), 131.3 (d), 131.7 (d), 131.9 (d), 140.1 (s), 167.5 (s). Beispiel 1 Production and odor properties of (2-methoxy-1-methylethyl)-2-methylbenzoate

[0157] Analogous to the general manufacturing procedure for Steglich esterification, 10.0 g (73.5 mmol) 2-methylbenzoic acid, 7.43 g (80.8 mmol) 1-methoxypropan-2-ol, 1.35 g (11.0 mmol) 4-dimethylamiopyridine are reacted in 151 ml dichloromethane with 12.3 g (59.6 mmol) dicyclohexylcarbodiimide, whereby after the described purification 10.7 g (68%) crude product is obtained (GC purity: 97%). Column chromatography of 1.10 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585) yielded 605 mg (39%) of the title compound (GC purity: 100%). Odor: floral-green, reminiscent of hyacinth, salicylate-like, with a creamy-woody aftertaste reminiscent of Iso E Super.

[0158] DC: / ? f = 0.21 (SiO260, hexane / ethyl acetate = 20:1)

[0159] GC / MS: m / z (%): 45 (7), 65 (12), 72 (37), 91 (31), 119 (100), 164 (1), 176 (1), 191 (1), 208 (5).

[0160] GC-IR (Thermo Nicolet 6700): ñ = 3073 (w) / 2989 (w), 2941 (w) / 2887 (w), 1735 (s), 1604 (w), 1460 (w), 1289 (m) / 1254 (s), 1124 (m) / 1080 (s), 961 (w), 854 (w), 736 (w).

[0161] 1 H NMR (400 MHz, CDCl3): δ = 7.92 - 7.88 (m, 1H), 7.41 - 7.35 (m, 1H), 7.28 - 7.19 (m, 2H), 5.32 (pd, J = 6.4, 4.1 Hz, 1H), 3.59 (dd, J = 10.5, 6.2 Hz, 1H), 3.51 (dd, J = 10.5, 4.2 Hz, 1H), 3.40 (s, 3H), 2.60 (s, 3H), 1.36 (d, J = 6.5 Hz, 3H).

[0162] 13 C NMR (101 MHz, CDCl3): δ = 167.3, 140.0, 131.8, 131.6, 130.5, 130.1, 125.7, 75.2, 69.6, 59.2, 21.7, 16.8. Beispiel 17 Herstellung und Geruchseigenschaften von 2-Methoxyethyl-2-methylbenzoat

[0163] Analogous to the general manufacturing procedure for Steglich esterification, 10.0 g (73.4 mmol) 2-methylbenzoic acid, 6.15 g (80.8 mmol) 2-methoxyethanol, 1.35 g (11.1 mmol) 4-dimethylamiopyridine are reacted in 150 ml dichloromethane with 12.3 g (59.6 mmol) dicyclohexylcarbodiimide, whereby after the described purification 10.0 g (69%) crude product is obtained (GC purity: 98%). Column chromatography of 1.10 g of crude product (Biichi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Biichi B-585) yielded 730 mg (47%) of the title compound (GC purity: 100%). Odor: floral, orchid-like, salicylate-like with spicy aspects of clove and cinnamon.

[0164] DC: / ? f = 0.31 (SiO260, hexane / ethyl acetate = 10:1).

[0165] GC / MS: m / z (%): 45 (5), 51 (2), 58 (42), 65 (17), 77 (1), 91 (56), 105 (1), 119 (100), 136 (2), 162 (1), 179 (1), 194 (12).

[0166] GC-IR (Thermo Nicolet 6700): ñ = 3073 (w) / 2953 (w) / 2889 (w) / 2831 (w), 1739 (m), 1604 (w) / 1459 (w) / 1396 (w), 1290 (m) / 1254 (s), 1134 (m), 1085 (s), 764 (w).

[0167] 1 H NMR (400 MHz, CDCl3): δ = 7.96 - 7.91 (m, 1H), 7.41 - 7.36 (m, 1H), 7.25 - 7.21 (m, 2H), 4.49 - 4.41 (m, 2H), 3.74 - 3.68 (m, 2H), 3.46 - 3.37 (m, 3H), 2.60 (s, 3H).

[0168] 13 C NMR (101 MHz, CDCl3): δ = 167.6, 140.2, 132.0, 131.6, 130.7, 129.5, 125.7, 77.3, 77.1, 76.8, 70.6, 63.7, 59.0, 21.7. Beispiel 18 Herstellung von (4Z)-Hept-4-en-2-ol (als Hauptprodukt im Isomerengemisch)

[0169] Analogous to R. Naef, A. Velluz, A. Jaquier, J. Agr. Food Chem. 2008, 56, 517-527, and A.D. Jones, D.W. Knight, Chem. Common. 1996, 915-916, 1.06 g (9.46 mmol) of hept-4-yn-2-ol were hydrogenated in 30 mL of ethanol with 50.0 mg of palladium catalyst (NanoSelect™ LF 100, 0.6% Pd on carbon, BASF) at 25-30 °C in a 50 mL three-necked flask equipped with a magnetic stirrer. The catalyst was filtered off and the filtrate concentrated, yielding 1.04 g of crude product. After bulb tube distillation (Buchi B-585, 100-130 °C and 60->30 mbar) 831 mg (77%) of the title compound were obtained as an isomer mixture with (4Z)-Hept-4-en-2-ol as the main product, with the spectroscopic data corresponding to literature values.

[0170] GC-IR (Thermo Nicolet 6700): ñ = 2975 (br s), 1381 (w), 1243 (w), 1218 (w), 1204 (w), 1062 (m).

[0171] GC / MS: m / z (%>): 45 (99), 55 (86), 65 (2), 70 (100), 81 (17), 96 (15), 99 (1), 114 (1). Example 19 Production and odor properties of (Z)-1-methylhex-3-enyl-2-methylbenzoate (as the main product in the isomer mixture)

[0172] Analogous to the preparation procedure for the Steglich esterification in Example 1, 954 mg (7.01 mmol) 2-methylbenzoic acid, 800 mg (7.02 mmol) (Z)-hept-4-en-2-ol from Example 17a, and 100 mg (0.82 mmol) 4-dimethylamiopyridine are reacted in 15 ml of dichloromethane with 1.45 g (6.25 mmol) of dicyclohexylcarbodiimide, whereby, after the purification described, 1.90 g (100%) of crude product are obtained (GC purity: 86% sum of isomers). Column chromatography of 1.40 g of this crude product (Buchi PrepChrom C-700, 80 g silica gel 60, eluent: hexane / ethyl acetate = 99:1, 20 ml / min at 20 ml per fraction) and subsequent bulb distillation (Buchi B-585) yielded 729 mg (60%) of the title compound (GC purity: 100% sum of isomers). Odor: solar, floral, salicylate-like in the direction of amyl and cyclohexyl sa I icylate, green-fruity with subtle hints of pineapple and allylamyl glycolate.

[0173] 1 H NMR (400 MHz, CDCI3): δ = 0.96 (t, J = 7.5 Hz, 3H), 1.35 (d, J = 6.4 Hz, 3H), 2.05 - 2.12 (m, 2H), 2.44 - 2.54 (m, 2H), 2.59 (s, 3H), 5.10 - 5.23 (m, 1H), 5.34 - 5.47 (m, 1H), 5.48 - 5.63 (m, 1H), 7.19 - 7.25 (m, 2H), 7.33 - 7.43 (m, 1H), 7.83 - 7.93 (m, 1H).

[0174] 13 C NMR (101 MHz, CDCl3): 14.1 (q), 19.6 (q), 20.7 (t), 21.7 (q), 33.6 (t), 71.1 (d), 123.6 (d), 125.6 (d), 130.4 (s), 130.4 (d), 131.6 (d), 131.7 (d), 134.5 (d), 139.9 (s), 167.3 (s).

[0175] GC / MS: m / z (%>): 65 (8), 81 (16), 91 (25), 96 (31), 105 (1), 119 (100), 135 (1), 163 (2), 188 (1), 232 (1). Applications of the compounds of formula (I) according to the invention in perfumed articles Example 20 Demo Formula, Hyacinth and Marshmallow Fluff with Compound 1.2 Evaluation with 3% dosage in candle, stearin material Trial 1 Trial 2 Trial 3 ALDEHYDE C18 SOG. 15,000 15,000 15,000 GERANYL FORMIATE 4,000 4,000 4,000 ORANGE OIL ITAL. SWEET DEL. 18,000 18,000 18,000 ETHYLMALTOL 12,000 12,000 12,000 PENTANANDIONE-2,3 6,000 6,000 6,000 ANISAL DEHYDE PURE 30,000 30,000 30,000 ETHYLVANILLINE 46,000 46,000 46,000 CU MARIN 1,000 1,000 1,000 OCTAHYDROCU MARIN 7,000 7,000 7,000 PHENYLETHYL ALCOHOL 150,000 150,000 150,000 VANILLIN 27,000 27,000 27,000 HEDION 50,000 50,000 50,000 HYDRATROPAALDEHYDDIMETHYLACETAL 17,000 17,000 17,000 VERATRUMALDEHYD 25,000 25,000 25,000 BUTYLBUTYRYLLACTAT 12,000 12,000 12,000 STYRAX RESIN CLAIR 2,500 2,500 2,500 OCTALACTON GAMMA 10% BB 6,000 6,000 6,000 SKATOL 10% BB 2,500 2,500 2,500 ACETYLPYRAZIN-2 1% BB 6,000 6,000 6,000 ACETYLMETHYLANTHRANILAT 10% BB 2,500 2,500 2,500 TERRANOL® 2,500 2,500 2,500 VERTOPRENAL 3,500 3,500 3,500 EUGENOL NAT. 4,000 4,000 4,000 ETHYLBUTYRAT 6,000 6,000 6,000 BENZYLACETAT 36,000 36,000 36,000 ZIMTALKOHOL 18,000 18,000 18,000 PHENYLETHYLSALICYLAT 73,000 73,000 73,000 ACETANISOL KRIST. 3,500 3,500 3,500 PHENYLPROPYLALKOHOL 5,000 5,000 5,000 PHENYLACETALDEHYD DIMETHYLACETAL 7,500 7,500 7,500 PHENYLACETALDEHYD 18,000 18,000 18,000 MACROLIDE® SUPRA 18,000 18,000 18,000 EMB 0,000 30,000 0,000 I.2 0,000 0,000 30,000 BENZYLBENZOAT M 365,500 335,500 335,500 1.000,000 1.000,000 1.000,000 Kombination mit: Evaluierungsergebnisse EMB intensifies the sweet vanilla-marshmallow aspect of the fragrance, while the hyacinth facet recedes into the background. Compound 1.2 supports the floral-hyacinth and green character of the fragrance and reduces the sweetness of the vanillin. This reduces the marshmallow effect and the base It harmonizes perfectly with the floral heart note. Example 21 Demo formula, Ylamingo' with compound 1.3

[0176] Evaluation with a 10% dosage in air freshener (with ethylene-vinyl acetate beads) Material Experiment 1 Experiment 2 Experiment 3 1 ORANGENOEL 55,000 55,000 55,000 ALDEHYD C18 SOG. 10,000 10,000 10,000 GERANIOL 15,000 15,000 15,000 YLANG YLANGOEL COMPLETE 1.500 1,500 1,500 ISOEUGENOL 7.500 7,500 7,500 GERANYLACETAT 7.500 7,500 7,500 ISOAMYLACETAT 6,000 6,000 6,000 PINEN BETA NAT. 40,000 40,000 40,000 LINALOOL 12,000 12,000 12,000 PHENYLETHYLALKOHOL 30,000 30,000 30,000 KRESOLPHENYLACETAT PARA 1.500 1,500 1,500 HEDION 40,000 40,000 40,000 DECALACTON GAMMA 27,000 27,000 27,000 HEXENOL CIS-3 12,000 12,000 12,000 PINEN ALPHA LAEVO NAT. 30,000 30,000 30,000 AURANTIOL 7,000 7,000 7,000 PASSIONSFRUCHT RECOVERY AROMA 60 8,000 8,000 8,000 10% DPG BENZALDEHYD DD 10% IPM 10,000 10,000 10,000 ETHYLMALTOL 1% IPM 11,500 11,500 11,500 THIOMENTHANON-8,3 1% IPM 11,500 11,500 11,500 ESTRAGOL NAT. 1% DPG 1,000 1,000 1,000 CYCLOGALBANAT® 10% IPM 2,000 2,000 2,000 OCTALACTON GAMMA 10% IPM 11,000 11,000 11,000 OXANTHIA 50% IN TEC 1% IPM 9.500 9,500 9,500 UNDECAVERTOL 10% IPM 11,000 11,000 11,000 PRENYLACETAT 7.500 7,500 7,500 ALDEHYD C14 SOG. 45,000 45,000 45,000 ETHYLBUTYRAT 2,000 2,000 2,000 ETHYLCAPRONAT 4,000 4,000 4,000 ETHYLHEPTYLAT 6,000 6,000 6,000 HEXYLACETAT 2,000 2,000 2,000 ETHYLMETHYLBUTYRAT-2 8,000 8,000 8,000 METHYLBENZOAT 5,000 5,000 5,000 BENZYLACETAT 40,000 40,000 40,000 PHENYLPROPYLALKOHOL 9,000 9,000 9,000 KRESOLMETHYLETHER PARA 1,000 1,000 1,000 BENZYLSALICYLAT 25,000 25,000 25,000 2,6,6-TRIMETHYLBICYCLO[3.1.1]HEPTAN- 20,000 20,000 20,000 2-OL MAGNOLAN® 40,000 40,000 40,000 ALLYLCYCLOHEXYL PROPIONATE 12,000 12,000 12,000 EMB 0.000 4,000 0.000 I.3 PUR 0.000 0.000 4.000 ISOPROPYL MYRISTATE 396,000 392,000 392,000 1,000,000 1,000,000 1,000,000 Combination with evaluation results EMB intensifies the sulfurous notes in the fruity part of the mango with a technical winter green note to enhance the fragrance's effect. The winter green effect further supports the ylang-ylang character. Compound 1.3 The juiciness of the mango is enhanced by this compound. and the floral ylang-ylang / jasmine accord becomes more harmonious. Example 22 Demo formula, 'Orchid Bouquet' with the combination of formula 1.8. Evaluation with 10% dosage in Eau de Toilette. Material: Test 1, Test 2, Test 3 HYDROXYCITRONELLAL 10,000 10,000 10,000 PHENYLETHYLDIMETHYLCARBINOL 5,000 5,000 5,000 FLOROSA 25,000 25,000 25,000 ALDEHYD C18 SOG. 10,000 10,000 10,000 BERGAMOTTOEL 5,000 5,000 5,000 GERANIOL 15,000 15,000 15,000 AMBROXIDE 5,000 5,000 5,000 AMYLZIMTALDEHYD ALPHA 20,000 20,000 20,000 CITRONELLOL 10,000 10,000 10,000 CITRONELLYLACETAT 1,000 1,000 1,000 GERANYLACETAT 2,000 2,000 2,000 ETHYLMALTOL 5,000 5,000 5,000 JAVANOL 5,000 5,000 5,000 ETHYLVANILLIN 10,000 10,000 10,000 CUMARIN 3,000 3,000 3,000 LINALOOL 50,000 50,000 50,000 LINALYLACETAT 30,000 30,000 30,000 NEROLIDOL 5,000 5,000 5,000 PHENYLETHYLALKOHOL 20,000 20,000 20,000 VANILLIN 30,000 30,000 30,000 CYCLAMENALDEHYD 4,000 4,000 4,000 ETHYLENBRASSYLAT 30,000 30,000 30,000 HEDION 100,000 100,000 100,000 JASMON CIS 1,000 1,000 1,000 HEXENOL CIS-3 1,000 1,000 1,000 ETHYLLINALOOL 40,000 40,000 40,000 ISO E SUPER 70,000 70,000 70,000 DAMASCENON 1,000 1,000 1,000 IONON BETA 5,000 5,000 5,000 INDOL FF 1,000 1,000 1,000 MUSCENONE 2,000 2,000 2,000 FLORALOZONE 1,000 1,000 1,000 CASHMERAN 2,000 2,000 2,000 LILYBELLE® 1% DPG 5,000 5,000 5,000 DUPICAL 1% DPG 5,000 5,000 5,000 MANZANATE 10% DPG 5,000 5,000 5,000 FLORHYDRAL 10% DPG 1,000 1,000 1,000 HEXENYLACETAT CIS-3 10% DPG 5,000 5,000 5,000 ETHYLHEPTYLAT 10% DPG 5,000 5,000 5,000 METHYLANTHRANILAT 10% DPG 5,000 5,000 5,000 PRENYLACETAT 10% DPG 5,000 5,000 5,000 ALLYLCYCLOHEXYLPROPIONAT 10% 5,000 5,000 5,000 DPG KRESOLMETHYLETHER PARA 10% DPG 2,000 2,000 2,000 CINNAMYL ACETATE 10% DPG 5,000 5,000 5,000 SANDRANOL® 50,000 50,000 50,000 AGRUMEX LC 5,000 5,000 5,000, BENZYL ACETATE 5.000 5.000 5.000 EMB 0.000 0.000 50.000 Compound I.8 0.000 50.000 0.000 DIPROPYLENE GLYCOL 368.000 318.000 318.000 1,000,000 1,000,000 1,000,000 Combination of evaluation results with: EMB The fragrance is evolving into a technical, medical one. Wintergreen direction and loses the delicate floral and complex Orchid profile. Compound 1.8 The green top note is enhanced by the compound, It supports the opulent floral character through solar effects and balances the floral body in the heart note with the creamy- sandalwood base note. Example 23 Demo formula 'Springwash' with compound 1.12 Evaluation in 0.6% dosage in softgels Material Versuch 1 Versuch 2 Versuch 3 DIHYDROMYRCENOL 30,000 30,000 30,000 HERBAFLORAT 40,000 40,000 40,000 PHENYLETHYLDIMETHYLCARBINOL 8,000 8,000 8,000 FLOROSA 42,000 42,000 42,000 NECTARYL 1,000 1,000 1,000 GERANIOL 20,000 20,000 20,000 UNDECAVERTOL 20,000 20,000 20,000 MANZANATE 3,000 3,000 3,000 MAJANTOL® 20,000 20,000 20,000 GLOBALIDE® 50,000 50,000 50,000 CITRONELLOL 40,000 40,000 40,000 GERANYLACETAT 2,000 2,000 2,000 NERYLACETAT 2,000 2,000 2,000 HEXYLZIMTALDEHYD ALPHA 50,000 50,000 50,000 DIMETHYLBENZYLCARBINYLACETAT 3,000 3,000 3,000 LINALOOL 30,000 30,000 30,000 OCTAHYDROCUMARIN 1,000 1,000 1,000 TERPINEOL REIN 20,000 20,000 20,000 ALDEHYD C11 UNDECYLENIC 2,000 2,000 2,000 CYCLAMENALDEHYD 15,000 15,000 15,000 TETRAHYDROLINALOOL 20,000 20,000 20,000 HEDION 40,000 40,000 40,000 HEXENYLACETAT CIS-3 1,000 1,000 1,000 VERATRUMALDEHYD 3,500 3,500 3,500 METHYL IONONE 10,000 10,000 10,000 HERBYLPROPIONAT 60,000 60,000 60,000 LEAFOVERT® 1,000 1,000 1,000 ISO E SUPER 60,000 60,000 60,000 DAMASCONE DELTA 4,000 4,000 4,000 LILYBELLE® 1% DPG 7,000 7,000 7,000 DUPICAL 1% DPG 7,000 7,000 7,000 FLORHYDRAL 10% DPG 3,000 3,000 3,000 ACETANISOL CRIST. 10% DPG 5,000 5,000 5,000 VERTOCITRAL 5,000 5,000 5,000 MENTHON L / ISOMENTHONE D 1,000 1,000 1,000 AGRUMEX LC 50,000 50,000 50,000 ALDEHYDE C14 SO-G. 10,000 10,000 10,000 ETHYL CAPRONATE 1,000 1,000 1,000 ETHYL HEPTYLATE 2,000 2,000 2,000 HEXYL ACETATE 5,000 5,000 5,000 BENZYL ACETATE 5,000 5,000 5,000 CINNAMED DEHYDE 1,000 1,000 1,000 ORYCLON SPECIAL 50,000 50,000 50,000 MACROLIDE® SUPRA 5,000 5,000 5,000 CYCLOGALBANAT® 10,000 10,000 10,000 RESEDAFOL 5,000 5,000 5,000 CYCLODUMOL ACETATE 10,000 10,000 10,000 EMB 0.000 0.000 50,000 1.12 0.000 50,000 0.000 DIPROPYLENE GLYCOL 219,500 169,500 169,500 1,000,000 1,000,000 1,000,000 Combination of evaluation results with: EMB creates a technical winter green note that overshadows the floral-green and fruity-apple character of the composition. 1.12 The combination supports the green-floral note of the composition and thus improves the reseda effect. Example applications of the compounds of formula (I) according to the invention in fragrance mixtures Example 24 Combination experiments of [(E)-1-Methylhex-2-enyl]-2-methylbenzoate (compound I.2) with fruity, floral-green, floral-rosy, floral-white-flowered, musky and woody odorants Crowd Name CAS I.2 Description of the fragrance effect The mixture containing the compound [(E)-1-methylhex-2-enyl]-2-methylbenzoate smells like aldehyde C14 Sog. 104-67-6 5% It becomes fruitier and peach-like, milkier, and the fatty note is reduced. The conifer content is reduced, while the fruity-apple and earthy notes of Agrumex LC 88-41-5 6% are improved. Ethyl methyl - The olfactory profile changes from 7452-79-1 8% butyrate-2 butyrate-like apple to a green kiwi. The fruity banana profile is greener, less isoamyl acetate 123-92-2 10% pungent and retains a natural character. The mixture acquires a more natural note from unripe plums with facets of carbinyl butyrate 5%. Peach. The fruity pear profile is less pungent (hexyl acetate 142-92-7 6%) and therefore retains a more natural and juicy character. Allylcyclohexyl The fruity pineapple note is enveloped by a propionate 2705-87-5 7% maltoglycine cocoon and appears less juicy. Crowd Name CAS I.2 Description of the fragrance effect The scent in the mixture of 18479-58-Dihydromyrcenol 15% shifts towards rosewood and is less 8 aromatic. The fruitiness is reduced, while the 10339-55- Ethyllinalool 10% aromatic-bergamot-like character 6 is amplified. The mixture with [(E)-1-methylhex-2-enyl]-2-methylbenzoate shifts to a cyclamenaldehyde 103-95-7 4% A more natural cyclamen character with a reduced ozonic note. The technical solvent character disappears upon mixing with [(£)-1- benzyl acetate 140-11-4 8% Methylhex-2-enyl]-2-methylbenzoate and goes in a more natural jasmine direction. The radiance and volume of the 24851-98- Hedione 2% mixture are significantly improved, and it is effective in the 7th solar The technical-medical anthranilate note Methylanthranilate 134-20-3 20% is reduced and the mixture acquires a fruitiness in the direction of pineapple. The smell of the mixture shifts in a more fruity-violet direction with a reduced leather note when Methyl Ionone 1335-46-2 8% is added. The fruity-raspberry note and the woody Ionone Beta 79-77-6 3% The proportions increase in the mixture. Crowd Name CAS 1.2 Description of the fragrance effect The mixture acquires a significantly stronger natural rose character, due to the geraniol 106-24-1 7%. It resembles rose petals and reduces the geranium effect. 23696-85- The tobacco-honey note is intensified and the Damascenone 9% Seven rosy notes are pushed into the background. The leatheriness is intensified in the mixture of phenylethyl 60-12-8 15%, resulting in a rose absolute character. generated. Benzyl salicylate 118-58-1 30% The green hyacinth note is intensified. The material is significantly improved by the addition of 10% ambroxide. 6790-58-5 2% softer and creamier, making the amber IPM The grade is reduced. 54464-57- The floral violet note is intensified and the Iso E Super 3% 2. Reduced woody-ambery note. The powderiness and floral notes are achieved with cedryl acetate 77-54-3 2% emphasized. 28219-61-6 Sandranol® 6% The mixture becomes milkier and more floral. 6 Crowd Name CAS I.2 Description of the fragrance effect Vetiveryl acetate 68917-34- 5% The tobacco and vetiver notes are intensified. Extra 0 The musky character is softened with a 28645-51- Ambrettolide 18% fur effect and thus is less reminiscent of vegetable 4. Musk seeds. The reduced woodiness results in an ethylene brassylate 105-95-3 12% Stronger powderiness with a pronounced conditioning effect. The musk is given a warm, animalic note, enveloped in a powerful and 80-2 typical metallic note. 63314-79- The powderiness is improved by the new compound Muscenone 20% 4 supported. Example 25 Combination experiments of compound 1.3 with fruity, floral-green, floral-rosy, floral-white-flowered, musky and woody odorants. Quantity Name CAS I.3 Fragrance description The compound gives the mixture an aldehyde C14 Sog. 104-67-6 1% floral note reminiscent of peach blossom and reduces the greasy character. Crowd Name CAS I.3 Fragrance description The freshness of the conifer facet is reduced by 2% in Agrumex LC 88-41-5, which makes the fruity apple note appear more earthy. The technically effective kiwi note is reduced by 3% with ethyl methyl-7452-79-1 and the fruity apple and butyrate-2. Strawberry-like facet highlighted. The food-like character is reduced, isoamyl acetate 123-92-2 3%, which makes the fruity banana character greener and more candy-like. Due to the reduced fat content, the Dimethylbenzyl- 10094-34-5 1% plum note gains a hint of fig carbinyl butyrate in naturalness. The fruity pear character is enhanced by Hexyl acetate 142-92-7 2% and gains in naturalness. Allylcyclohexyl The pineapple note seems less artificial. propionate 2705-87-5 2% and takes on a greener character. The floral notes are intensified, which gives the Dihydromyrcenol 18479-58-8 4% material more volume and reduces aromatic aspects. Due to the reduced bergamot character, the mixture contains ethyl linalool 10339-55-6 4%. a more natural character Freesias. Crowd Name CAS I.3 Fragrance description The watery and ozone note is reduced by cyclamenaldehyde 103-95-7 1%, resulting in a stronger cyclamen effect. The technical solvent note is reduced, thereby enhancing the floral jasmine effect. Benzyl acetate 140-11-4 4% and the fruity banana note appears more harmonious. The strength of the material increases enormously with Hedione 24851-98-7 0.5%, making it appear more floral and citrusy. The technical-medical anthranilate note is reduced and the material contains methyl anthranilate 134-20-3 6%. a much stronger orange blossom character. The dryness of the iris increases, and Methyl Ionone 1335-46-2 4% The material becomes softer. The tea effect and woodiness (Ionone Beta 79-77-6 2%) decrease, and the floral violet note is intensified. The floral rose note takes on a pink character, which is due to the palmarosa effect. Geraniol 106-24-1 5% This is caused by a reduction in the geranium facet. The fruity dried fruit note gains 3% in freshness with Damascenone 23696-85-7 and reduces the hay and Tobacco facets. Crowd Name CAS I.3 Fragrance description The leatheriness and honey-like aspects of phenylethyl- 60-12-8 6% are reduced, thereby diminishing the effect of alcohol. red flower petals are increased. The solar character is masked by a predominantly floral note in the direction of ylang-ylang and tuberose. The ambergris note is achieved through an increased ambroxide content of 10%. 6790-58-5 2% Powderiness intensifies and reduces the effect of IPM dry and woody. The woody-ambery note predominates and Iso E Super 54464-57-2 0.5% The floral violet character fades. The cedarwoodiness is reduced by cedryl acetate 77-54-3 1% Dryness and becomes creamier. The sandalwood note gains creaminess. Sandranol® 28219-61-6 1% and florality. Vetiveryl acetate. The vetiver note decreases and the material 68917-34-0 3% The Extra version becomes creamier and nuttier. The musk note takes on a velvety effect, making the material softer, and Ambrettolide 28645-51-4 6% It gets warmer. The musk seed effect is reduced. Crowd Name CAS I.3 Fragrance description The material loses its woodiness. Due to the presence of the white-blossom note Ethylene Brassylate 105-95-3 1% The soft, nourishing aspects are greatly enhanced. The typical metallic note is reduced, making the musk body Globalide® 111879-80-2 4% It appears softer, warmer, drier, and earthier. The animalic facets are significantly enhanced by Muscenon 63314-79-4 2%, and the musky body is enveloped by a white-blooded note. Example 26 Combination experiments of compound 1.8 with fruity, floral-green, floral-rosy, floral-white-flowered, musky and woody fragrances Crowd Name CAS I.8 Fragrance description The peach note gets a velvety effect, aldehyde C14 Sog. 104-67-6 5% which enhances the naturalness and makes the material appear less greasy. The earthy-coniferous note becomes weaker, Agrumex LC 88-41-5 6%, which intensifies the fruity apple note and transforms it into a red apple. The butyrate note is reduced, whereby ethyl methyl- 7452-79-1 8% intensifies the fruity apple note and siiBer butyrate-2 becomes. Crowd Name CAS I.8 Fragrance description The fruity banana note seems less artificial and the naturalness is enhanced. The fruitiness is intensified, so that the plum note is enhanced by a cake effect (carbinyl butyrate 5). is circumnavigated. The green note is intensified, giving the hexyl acetate 142-92-7 6% fruity pear note a peel effect. Allylcyclohexyl The pineapple note loses its juiciness and the propionate 2705-87-5 7% The green note is amplified. The floral freesia note will 18479-58- Dihydromyrcenol 15% highlighted, as the aromatic facet 8 is reduced. The intensified bergamot note, 10339-55- Ethyllinalool 10%, makes the material reminiscent of rosewood. The 6 Fruitiness is reduced. Due to the increased water content and the 4% reduced ozone content of cyclamenaldehyde 103-95-7, the material acquires a floral lily of the valley effect. The technical solvent note is reduced, and the green facet gives the benzyl acetate 140-11-4 8% The material has a floral jasmine sambac effect. Crowd Name CAS I.8 Fragrance description The solar effect is intensified, causing the 24851-98- Hedione 2% material to radiate more intensely and a 7 gains more pronounced volume. The orange blossom facet is achieved through the reduced technical-medical methyl anthranilate 134-20-3 20% The anthranilate note is highlighted, which enhances the material. The leatheriness is reduced and the floral Methyl Ionone 1335-46-2 8% and thereby intensified the dry iris note. The floral violet note transforms into a drier, powderier, iris-like Ionone Beta 79-77-6 3% Floral notes surrounded by a hint of hay. Due to the reduced metallic effect of Geraniol 106-24-1 7%, the material gains a powdery and natural quality reminiscent of palmarosa. 23696-85- The dried fruit note is intensified, which Damascenone 9% 7 supports the floral-rosy facet. The floral rose note becomes much more natural with the addition of phenylethyl compound. 60-12-8 15% The alcoholic, honey-like, blood-leaf character is perceptible. The floral-green hyacinth character is reduced by benzyl salicylate 118-58-1 by 30% and the floweriness transforms into that of an orchid. Crowd Name CAS I.8 Fragrance description The addition of the compound increases ambroxide by 10% 6790-58-5 2% also the amber character, which is associated with an IPM is surrounded by a dry tobacco note. The woody-ambery character of the 54464-57- Iso E Super 3% material is complemented by a floral iris effect 2 dominates. The compound evaluates the cedarwoodiness Cedrylacetate 77-54-3 2% on. The sandalwood note loses its creaminess (28219-61-6 Sandranol® 6%) and becomes drier. This increases the 6 also the strength of the material. Vetiveryl acetate 68917-34 - The smokiness increases, thereby increasing the 5% Extra dry, woody vetiver notes predominate. 28645-51- The musk note becomes more animalic and the ambrettolide 18% Four musk grain facets are amplified. The creaminess and the metallic ethylene brassylate 105-95-3 12% elements are enhanced, thereby reducing the woodiness of the musk. 111879- The musk becomes greener and the typical- Globalide® 15% 80-2 metallic note additionally amplified. Crowd Name CAS I.8 Fragrance description The musk note gets a warm 63314-79- Muscenone 20% effect, which additionally enhances the animalic-velvety 4 Grades promote. Example 27 Combination experiments of compound 1.12 with fruity, floral-green, floral-rosy, floral-white-flowered, musky and woody odorants. Quantity Name CAS 1.12 Fragrance description The juiciness of the peach note is improved by adding aldehyde C14 Sog. 104-67-6 3% and the lactonic content is reduced. The earthy component is enhanced by the compound Agrumex LC 88-41-5 4%, which creates an apple peel effect. The apple note is enhanced by a more natural ethyl methyl- 7452-79-1 5% character, which is the technical butyrate-2 Kiwi flavor dominates. The fruity-banana note is rather unripe. Isoamyl acetate 123-92-2 5% and resembles a green banana. Dimethylbenzyl - A dried fruit effect harmonizes the 10094-34-5 3% carbinyl butyrate butyrate-like plum note. Crowd Name CAS 1.12 Fragrance description The fruity, pear-like note is enhanced by Hexyl acetate 142-92-7 4%, resulting in a more natural and juicy effect. Allylcyclohexyl The fruity pineapple note transitions into a rather propionate 2705-87-5 5% A sweet, sugary, and green pineapple note. The aromatic facet is enhanced by a floral freesia effect with an ozonic note, thanks to Dihydromyrcenol 18479-58-8 8%. The bergamot effect is reduced (Ethyllinalool 10339-55-6 7%) and the aromatic-coriander-like character is intensified. The ozonic facet is increased and the cyclamenaldehyde 103-95-7 3% The material feels softer. The floral-jasmine note is achieved through a benzyl acetate 140-11-4 6% A green-fruity effect is added. The olfactory profile is determined by a Hedione 24851-98-7 1% The green-fruity effect is intensified. The olfactory profile is rather gentle and methyl anthranilate 134-20-3 12% is white, tending towards orange blossom. Crowd Name CAS 1.12 Fragrance description The effect of the material is enhanced by Methyl Ionone 1335-46-2 6% and the floral notes are supported by a honey note. The combination intensifies the dry iris and wood character. The compound gives the material a more natural and greener palmarosa effect. The rosy tobacco component is intensified, and the Damascene 23696-85-7 6% Improved effect. Phenylethyl - The green-pink effect is stronger and 60-12-8 10% The alcohol is reminiscent of geranium. The solar facet is reduced and the benzyl salicylate 118-58-1 15% The material has a floral-green appearance. Ambroxide 10% The effect of dry cedar wood is 6790-58-5 2% IPM intensifies and reduces the amber note. The woody-ambery character is reduced by 2% with Iso E Super 54464-57-2 and the floral violet effect is intensified. Crowd Name CAS 1.12 Fragrance description The cedarwood character is drier and contains cedryl acetate 77-54-3 2% less round. The creaminess of the sandalwood character is Sandranol® 28219-61-6 4% reduced and significantly drier. Vetiveryl acetate reduces the rhubarb note and the 68917-34-0 4% Extra Material becomes nuttier, leaning towards vetiver. The olfactory profile of the musk is enhanced with the compound Ambrettolide 28645-51-4 9% combined with a floral-metallic note. The nourishing-cosmetic effect of ethylene brassylate 105-95-3 8% is supported by a fruity effect and the woody note is reduced. The enhanced metallic effect increases Globalid® 111879-80-2 by 8% the effect of the musk material. The animal note is supported by the Muscenon 63314-79-4 10% compound, enhancing the strength and dry earthiness. Example 28 Overview of the odor effects achieved by using the compounds of formula (I) according to the invention

[0177] In a demo formula (Butterfly Flower) of the composition given below, each of the listed 6 substances was added at 50 parts by weight to 1000 parts by weight. The odor tests were conducted using a 1% concentration in a transparent shower gel. Fragrance quantity DIHYDROMYRCENOL 35,000 HYDROXYCITRONELLAL 15,000 PHENYLETHYLDIMETHYLCARBINOL 5,000 FLOROSA 40,000 ORANGE OIL 13,000 ALDEHYDE C18 SO-CALLED 2,000 PHENYLETHYLPHENYL ACETATE 4,000 UNDECAVERTOL 13,000 YLANG YLANGOEL COMPLETE 0.500 MAJANTOL® 6,000 PHENIRAT® 20,000 GLOBALIDE® 20,000 CITRONELLOL 6,000 CITRONELLYLACETAT 5,000 FLORHYDRAL 4,000 PEONILE 7,000 ANISALDEHYD REIN 4,000 DIMETHYLBENZYLCARBINYLACETAT 18,000 LINALOOL 80,000 PHENYLETHYLALKOHOL 50,000 TERPINEOL ALPHA 2,000 VANILLIN 3,000 CYCLAMENALDEHYD 8,000 ETHYLENBRASSYLAT 40,000 HEDION 140,000 HEXENYLACETAT CIS-3 4,000 BOURGEONAL 5,000 ETHYLLINALOOL 50,000 DAMASCON ALPHA 1,000 ISO E SUPER 50,000 IONON BETA 5,000 IONON ALPHA 8,000 SANDALORE 7,000 VETIKOLACETAT® 2,000 CASHMERAN 2,000 ROSENOXID HIGH CIS 10% DPG 5,000 JASMIN ABS. SAMBAC 10% DPG 2,000 CUMINALDEHYD 10% DPG 2,000 CALONE 10% DPG 4,000 JASMON CIS 10% DPG 4,500 METHYLHEPTENONE-6,5,2 10% DPG 4,000 ALDEHYDE C12 LAURIN 10% DPG 3,000 HEXENOL CIS-3 10% DPG 6,000 AMBROXIDE 10% IPM 4,000 AURELIONE® 10,000 VERTOCITRAL 6,000 AMBERWOOD® F 2,000 Hexenyl salicylate CIS-3 20,000 PRENYL ACETATE 2,000 ALDEHYDE C14 SOG. 6,000 HEXYL ACETATE 8,000 STYROLYL ACETATE 15,000 ETHYLMETHYLBUTYRATE-2 2,000 Benzyl acetate 15,000 Phenylacetaldehyde 2,000 DIMETHYLACETAL CYCLOGALBANAT® 4,000 AGRUMEX HC 15,000 PEARADISE 3,000 ALLYLCYCLOHEXYL PROPIONATE 3,000 JASMAPRUNAT 6,000 CITRON OIL TERPENES 20,000 Each of the 6 components 50,000 DIPROPYLENE GLYCOL _ 102,000 1,000,000

[0178] The following results were achieved: Combination with: Evaluation results in the Blooming shower gel tests in water 2-Methyl- The pleasant fruity-floral technical, ethyl benzoate note is complemented by an anthranilate-like note (state of the art). The technical, anthranilate-like note is less noticeable in the room. (EMB) Wintergreen note masked and strongly perceived in the Dominates. Compared to the shower gel sample, the floral ylang-ylang note appears significantly spicier. Combination 1.3 The white-flowered ylang-ylang and jasmine note of the perfume oil are supported and intensified by the stronger floral-ylang note and bring out a nuance of a fruity pear note in the room. Combination 1.2 By intensifying the floral-green and fruity notes, a creamy, long-lasting note develops in the room and gives the hyacinth effect. The shower gel radiates and the jasmine note of the perfume oil are supported and intensified by the stronger floral-green note and brings out a nuance of a fruity pear note in the room. Combination 1.2 By intensifying the floral-green and fruity notes, a creamy, long-lasting note develops in the room and gives the fragrance a strong pear character. Compound 1.5 The floral notes transform into a powdery and green rose note. Only a slight effect on the overall fragrance can be observed. The scent appears somewhat fruitier and rosier. Combination 1.8 The white-flowered facets of the solar, white-flowered ylang-ylang and jasmine radiation increase enormously in the room and have a very fine, top-notch effect. Connection 1.12 The composition appears fuller, the creaminess of the green and creamier, and the freesia effect is noticeable, creating a siiben perceptible in the room, a freesia effect. and creates a strong, floral radiance. Example 29 Combination experiments of compound 1.5 with fruity, floral-green, floral-rosy, floral-white-flowered, musky and woody fragrances Crowd Name CAS 1.5 Fragrance description Crowd Name CAS I.5 Fragrance description The fruitiness fades and a powdery aldehyde C14 Sog. 104-67-6 5% appears. The note is perceptible. The fruity apple note becomes more harmonious. Agrumex LC 88-41-5 6% and more natural. Ethyl methyl - The butyrate note is reduced and the 7452-79-1 8% Butyrate-2 makes the fruity apple note juicier. The banana fruit note becomes more mature and Isoamyl acetate 123-92-2 10% It resembles a natural banana peel. A stronger plum liqueur note is perceptible with Dimethyl benzyl 10094-34-5%, and the apricot note is carbinyl butyrate 5. reduced. The fruity pear note is achieved through the hexyl acetate 142-92-7 6% Subtlety even juicier. Allylcyclohexyl propionate 2705-87-5 7% further enhances the juicy effect of the pineapple note and reduces the green facet. 18479-58- The aromatic bergamot and tea note Dihydromyrcenol 15% 8 becomes more intense. Crowd Name CAS I.5 Fragrance description 10339-55- The floral notes become more harmonious and Ethyllinalool 10% 6 is more reminiscent of Freesia. The powderiness increases and the technical cyclamenaldehyde 103-95-7 4% The cyclamen note becomes more harmonious. The floral jasmine note is given a benzyl acetate 140-11-4 8% stronger ylang-ylang facet. The powderiness and floral notes are increased by 24851-98- Hedione 2%, giving the material fullness and 7 Harmony. The technical anthranilate note is reduced by 20% with methyl anthranilate 134-20-3, resulting in a more natural orange blossom note. The dry and powdery iris note is highlighted by the Methyl Ionone 1335-46-2 8% molecule, and the material loses its leathery quality. The dry facet of the material contains Ionone Beta 79-77-6 3% rounded, which creates more fullness. The geranium note is reduced and the geraniol content is 106-24-1 7%. Florality gains in fullness and volume. Crowd Name CAS I.5 Fragrance description The tobacco note is reduced and the fruity, dried fruit character of the 23696-85- Damascenone 9% increases. and becomes more harmonious. The leatheriness and the green facets of the phenylethyl rose note are enhanced by the increased 60-12-8 15% Alcohol reduces the powdery appearance. This makes the rose look softer. The typical solar note becomes greener and Benzyl salicylate 118-58-1 30% fruitier due to the addition of the compound. Ambroxide 10% The dry woodiness is enhanced by the 6790-58-5 2% IPM reduced powderiness, increased. The material retains its strength and a 54464-57- Iso E Super 3% more dominant violet facet, which the 2 The woodiness fades into the background. The material gains in volume. However, cedryl acetate 77-54-3 2% It also loses its dry, woody texture. The milky and creamy note is greatly enhanced by Sandranol® 6% (28219-61-6) and gives the material a 6 pronounced nourishing effect. Vetiveryl acetate 68917-34 - The material is made by the balanced 5% Extra 0 grapefruit and wood notes are softer. Crowd Name CAS 1.5 Fragrance description 28645-51- The musk seed note is reduced and ambrettolide 18% 4. The material becomes softer. The woodiness of the musk is intensified. Ethylene brassylate 105-95-3 12% and gives the material more intensity. 111879 - The musk has a softer and cleaner effect in Globalid® 15% 80-2 combination with the connection. 63314-79- The musk note is complemented by a floral muscenone 20% 4. Lily of the valley note added.

Claims

PATENT CLAIMS 1. Combination of formula (I) Formula (I), where, each independently of the other, R1 = –H, –Me, –Et, –n-Pr or –i-Pr R2, R3 = –H or –Me; X = C or O, where if X = C, one of the dashed lines represents a double bond, and if X = O, then no R3 residue is present; and Y = -H, -Me, -Et, -n-Pr, i-Pr =CH2, =CHMe, =CHEt, =CMe2 and the wavy line indicates that in the case of a double bond there may be geometric isomers (cis / trans configuration) which are included.

2. Compound according to claim 1 in which X = C in formula (I) and a double bond is contained in the side chain.

3. Combination according to claim 1, in which each independently of the others, R1, R2, R3 = –H or –Me; X = C and each of the dashed lines represents a double bond; and Y can be -H, -Me, -Et, -n-Pr, -z-Pr, =CH₂, =CHMe, =CHEt, =CMe₂.

4. Compound according to claim 1 with Ri, R2, R3 = -H or -Me; X = C and Y = -H, -Me, -Et, -nPr or iPr according to the general formula (I'), the double bond between substituents R2 and R3 can be cis- or trans- configured.

5. Compound according to claim 1 with R1 = -H or -Me, R2 = Me, R3 = -H; X = C and Y = -H, -Me, -Et, -Pr according to the general formula (I"), Formula (I"), where the double bond between substituents R2 and R3 can be cis- or trans-configured.

6. [(E)-1-Methylhex-2-enyl]-2-methylbenzoate.

7. 2-Methylallyl-2-methylbenzoate.

8. [(E)-1,2-Dimethylbut-2-enyl]-2-methylbenzoate.

9. [(E)-2-Methylbut-2-enyl]-2-methylbenzoate.

10. Fragrance mixture comprising or consisting of at least one compound of claims 1-9 and at least one fragrance not conforming to formula (I).

11. Use of one or more of the compounds listed in points 1-9 as a fragrance.

12. Use according to claim 11 in fragrance compositions to achieve at least one of the following fragrance notes: solar, floral (ylang-ylang, orchid, hyacinth, mignonette, rose, orange blossom, jasmine, tuberose, mimosa), powdery, fruity, green, voluminous, long-lasting, fine, opulent and / or narcotic.

13. Use according to claim 11 and / or 12 for conveying, modifying and / or enhancing one or more odor notes selected from the group consisting of the notes fruity, floral-grim, floral-rosy, floral-white-blooded, musky or woody.

14. Use of an odorant mixture according to claim 10 for conveying, modifying and / or enhancing one or more odor notes selected from the group consisting of the notes: fruity, floral-green, floral-rosy, floral-white, musky or woody.

15. Method for imparting an odor note and / or modifying and / or enhancing an existing odor note, comprising or consisting of the following steps: a) Providing at least one compound of formula (I) Formula (I), where, each independently of the other, Ri = -H, -Me, — Et, -n-Pr or - z-Pr R2, R3 = –H or –Me; X = C or O, where if X = C, one of the dashed lines represents a double bond, and if X = O, then no R3 residue is present; and and Y can be -H, -Me, -Et, -n-Pr, -z-Pr, =CH₂, =CHMe, =CHEt, =CMe₂; b) Providing at least one fragrance substance that does not conform to formula (I); c) Addition of at least one compound of formula (I) to at least one odorant not corresponding to formula (I) in a sensorially effective quantity sufficient to impart an odor note and / or to modify and / or enhance an existing odor note.

16. The method according to claim 15, wherein the odor note is selected from the group consisting of: solar, floral (ylang-ylang, orchid, hyacinth, mignonette, rose, orange blossom, jasmine, tuberose, mimosa), powdery, fruity, green, voluminous, long-lasting, fine, opulent and / or narcotic.

17. Perfumed article, comprising or consisting of (i) at least one compound of claims 1-9; and (ii) one or more further components, preferably one or more excipients and / or active ingredients.

18. Perfumed article according to claim 17, wherein the article is selected from cosmetic, hygiene and / or household articles.

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