3-methylpentanediol and esters and ethers of unsaturated derivatives thereof and their use as synthetic perfumes

Abstract

This invention relates to the use of esters and / or ethers of 3-methylpentanediol and its unsaturated derivatives as synthetic fragrances, synthetic fragrance compositions comprising at least one ester and / or at least one ether of 3-methylpentanediol and / or its unsaturated derivatives, and methods for preparing synthetic fragrance compositions, particularly scented compositions, especially ready-to-use scented compositions, comprising incorporating at least one ester and / or one or more ethers of 3-methylpentanediol and / or its unsaturated derivatives into the composition, particularly ready-to-use compositions. The invention further relates to specific ethers of 3-methylpentanediol and its unsaturated derivatives, specific esters of 3-methylpentanediol, specific mixtures of such compounds and their unsaturated derivatives, and methods for preparing them.

Description

[0001] This invention relates to the use of esters and / or ethers of 3-methylpentanediol and its unsaturated derivatives as synthetic fragrances, synthetic fragrance compositions comprising at least one ester and / or at least one ether of 3-methylpentanediol and / or its unsaturated derivatives, and methods for preparing synthetic fragrance compositions, particularly scented compositions, especially ready-to-use scented compositions, comprising incorporating at least one ester and / or at least one ether of 3-methylpentanediol and / or its unsaturated derivatives into the composition, particularly ready-to-use compositions. The invention further relates to specific ethers of 3-methylpentanediol or its unsaturated derivatives and specific esters of 3-methylpentanediol or its unsaturated derivatives, specific mixtures of such compounds, and methods for their preparation. Background of the Invention

[0003] Synthetic fragrances, especially aromatherapy agents, are particularly important in the fields of cosmetics and cleaning and laundry compositions. Most naturally derived aromatherapy agents are expensive, often limited in their availability, and subject to variations in content, purity, and other characteristics due to fluctuations in environmental conditions. To avoid these undesirable factors, it is therefore meaningful to develop synthetic substances that possess sensory properties similar to those of more expensive natural aromatherapy agents or that have novel and meaningful sensory characteristics.

[0004] Despite the large number of existing synthetic fragrances (aromatics and flavorings), new components are still needed to meet the diverse range of properties required for various applications. These primarily include sensory properties, meaning the compound should have a favorable odor (olfactory) or taste. However, in addition, synthetic fragrances should also possess other positive secondary properties, such as efficient preparation methods, the potential to provide better sensory characteristics due to synergistic effects with other aromatics, high stability under certain application conditions, high extensibility, and high persistence.

[0005] However, because even small changes in chemical structure can produce large changes in sensory properties such as odor and taste, research into substances possessing specific sensory properties, such as a specific odor, is extremely difficult. Therefore, in most cases, research into new fragrances and flavors is difficult and laborious, and it is uncertain whether substances with the desired odor and / or taste will actually be found.

[0006] EP 0908455 describes a flavor enhancer composition comprising macrocyclic compounds such as 15-17 members and a method for its preparation. Specifically, 3-methyl-1,5-pentanediol diacetate [CAS No. 40065-27-8] is used as a reactant in the preparation of 3-methyl-5-oxopentanediol acetate. However, 3-methyl-1,5-pentanediol diacetate is not mentioned as a synthetic flavoring agent.

[0007] GB 1,424,230 relates to a method for preparing (cyclic) aliphatic / aromatic diethers, which are said to be usable as insecticides. In this method, 5-isopropoxy-3-methyl-1-pentanol and 5-sec-butoxy-3-methyl-1-pentanol are used as intermediates in the synthesis of the target compound. These intermediates do not have specific properties.

[0008] CH 600761 relates to zirconia derivatives and their use as pesticides. Specifically, 5-isopropoxy-3-methyl-1-pentanol and 1-acetoxy-5-isopropoxy-3-methyl-2-pentene are used as intermediates in the synthesis of the target compound. These intermediates do not possess specific properties.

[0009] BRMoser describes the preparation of diesters and their use as fuel performance enhancers for biodiesel and petroleum diesel fuels in Energy & Fuels, 2014, 28, 3262-3270. 3-Methylbutyrate [3-methyl-5-(3-methylbutyryloxy)pentyl] ester is used. 3-Methylbutyrate (5-hydroxy-3-methylpentyl) ester is used as an intermediate in its preparation.

[0010] S. Sultana et al. described the synthesis of high-allyl alcohols catalyzed by SC(III) in Tetrahedron Letters 2013, 54, 1576-1578. In this study, 3-methylbut-3-enyl acetate reacted with paraformaldehyde to yield a stereoisomer mixture of (5-hydroxy-3-methylene-pentyl)acetate, [(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate, and [(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate. These compounds did not exhibit specific properties.

[0011] The following compounds are known:

[0012] - Compound (5-acetoxy-3-methylene-pentyl) acetate (CAS No. 40760-37-0),

[0013] - Compound [(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate (CAS No. 1262763-96-1),

[0014] - Compound [(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate (CAS No. 1262764-00-0),

[0015] - Compound (5-acetoxy-3-methyl-pentyl) acetate (CAS No. 40065-27-8, EP 0908455),

[0016] - Compound [(E)-5-formyloxy-3-methyl-pent-3-enyl]formate (CAS No. 53799-56-7),

[0017] - Compound [(Z)-5-formyloxy-3-methyl-pent-3-enyl]formate (CAS No. 53799-55-6),

[0018] - Compound (3-methyl-5-propionyloxy-pentyl)propionate (CAS No. 1438983-26-6),

[0019] - Compound [5-(2,2-dimethylpropionyloxy)-3-methyl-pentyl]2,2-dimethylpropionate (CAS No. 762268-77-9),

[0020] - Compound 1,5-dimethoxy-3-methylene-pentane (CAS No. 79437-43-7),

[0021] - Compound (E)-1,5-dimethoxy-3-methyl-pent-2-ene (CAS No. 123351-71-3),

[0022] - Compound (Z)-1,5-dimethoxy-3-methyl-pent-2-ene (CAS No. 123351-70-2),

[0023] - Compound 1,5-dimethoxy-3-methyl-pentane (CAS No. 4457-73-2),

[0024] - Compound (Z)-1,5-diethoxy-3-methyl-pent-2-ene (CAS No. 1086266-95-6),

[0025] - Compound 1,5-diethoxy-3-methyl-pentane (CAS No. 99868-13-0),

[0026] - Compound (E)-1,5-diisopropoxy-3-methyl-pent-2-ene (CAS No. 116097-01-9),

[0027] - Compound (Z)-1,5-diisopropoxy-3-methyl-pent-2-ene (CAS No. 116114-80-8),

[0028] - Compound 1,5-dibutoxy-3-methylene-pentane (CAS No. 79437-42-6),

[0029] - Compound (E)-1,5-dibutoxy-3-methyl-pent-2-ene (CAS No. 121997-62-4),

[0030] - Compound (Z)-1,5-dibutoxy-3-methyl-pent-2-ene (CAS No. 121997-61-3),

[0031] -5-Isopropoxy-3-methyl-1-pentanol,

[0032] -5-sec-butoxy-3-methyl-1-pentanol,

[0033] -1-Acetoxy-5-isopropoxy-3-methyl-2-pentene,

[0034] -(5-hydroxy-3-methyl-pentyl)3-methylbutyrate,

[0035] -[3-methyl-5-(3-methylbutyryloxy)pentyl]3-methylbutyrate,

[0036] 5-hydroxy-3-methylene-pentyl)acetic acid ester,

[0037] -[(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0038] -[(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0039] -(5-hydroxy-3-methyl-pentyl)carbamate.

[0040] The following mixtures are known:

[0041] A mixture of [(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate and [(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate (CAS No. 18273-38-6),

[0042] A mixture of [(E)-3-methyl-5-propionyloxy-pent-3-enyl]propionate and [(Z)-3-methyl-5-propionyloxy-pent-3-enyl]propionate (CAS No. 38169-71-0),

[0043] A mixture of (E)-1,5-dimethoxy-3-methyl-pent-2-ene and (Z)-1,5-dimethoxy-3-methyl-pent-2-ene (CAS No. 54284-82-1),

[0044] A mixture of (Z)-1,5-diethoxy-3-methyl-pent-2-ene and (E)-1,5-diethoxy-3-methyl-pent-2-ene (CAS No. 42173-34-2),

[0045] A mixture of (E)-3-methyl-1,5-dipropoxy-pent-2-ene and (Z)-3-methyl-1,5-dipropoxy-pent-2-ene (CAS No. 54284-83-2),

[0046] A mixture of (E)-1,5-dibutoxy-3-methyl-pent-2-ene and (Z)-1,5-dibutoxy-3-methyl-pent-2-ene (CAS No. 79437-47-1),

[0047] A mixture of (5-hydroxy-3-methylene-pentyl)acetate, [(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate and [(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate.

[0048] To date, no prior art describes the use of esters and ethers derived from 3-methylpentanediol and its unsaturated derivatives as synthetic fragrances. Invention Overview

[0050] The object of this invention is to provide substances that exhibit pleasant sensory properties and can be advantageously used as synthetic flavorings. Another object of this invention is to provide substances that can be used as synthetic flavorings in ready-to-use compositions. In particular, substances with strong odors and pleasant aromas are sought. Furthermore, these synthetic flavorings should be combinable with other synthetic flavorings, allowing for the creation of new, advantageous sensory characteristics. Additionally, these synthetic flavorings should be available from readily available raw materials, allowing for their rapid and economical production, and should be free from toxicological concerns.

[0051] Surprisingly, these and other purposes were achieved through esters and ethers derived from 3-methylpentanediol and its unsaturated derivatives.

[0052] Therefore, a first aspect of the present invention relates to the use of a compound of general formula (I) or a stereoisomer thereof or a mixture of stereoisomers thereof or a mixture of different compounds (I) as a synthetic fragrance:

[0053]

[0054] in:

[0055] Described as One of the keys is a single key, and the other is either a double key or a single key.

[0056] R 1 It is hydrogen, C1-C4 alkyl or -(C=O)-R 3,

[0057] R 2 It is hydrogen, C1-C4 alkyl or -(C=O)-R 4 ,

[0058] R 3 It is hydrogen or C1-C4 alkyl, and

[0059] R 4 It is hydrogen or C1-C4 alkyl.

[0060] The condition is if R 1 If it is hydrogen, then R 2 It is not hydrogen.

[0061] In particular, the present invention relates to the use of compounds of general formula (Ia) or (Ib) or their stereoisomers or mixtures thereof, or mixtures of different compounds (Ia) or mixtures of different compounds (Ib) as synthetic fragrances:

[0062]

[0063] in:

[0064] Described as One of the keys is a single key, and the other is either a double key or a single key.

[0065] R 1a It is hydrogen, C1-C4 alkyl or -(C=O)-R 3 ,

[0066] R 2a It is hydrogen or C1-C4 alkyl.

[0067] R 1b It is hydrogen or -(C=O)-R 3 ,

[0068] R 2b It is hydrogen or -(C=O)-R 4 ,

[0069] R 3 It is hydrogen or C1-C4 alkyl, and

[0070] R 4 It is hydrogen or C1-C4 alkyl.

[0071] The condition is if R 1a If it is hydrogen, then R 2a Not hydrogen, and if R 1b If it is hydrogen, then R 2b It is not hydrogen.

[0072] The present invention further relates to synthetic fragrance compositions comprising at least one compound of formula (I), (Ia) or (Ib) as defined above, a stereoisomer thereof or a mixture thereof, and at least one other component selected from other synthetic fragrances and non-synthetic fragrance carriers other than compounds (I), (Ia) and (Ib).

[0073] Further findings revealed that compounds of general formulas (I), (Ia), or (Ib) typically exhibit pleasant and characteristic odors and can be used to prepare flavored compositions, particularly ready-to-use flavored compositions. Additionally, they can be advantageously combined with other synthetic fragrances different from compounds (I), (Ia), and (Ib) to produce novel aroma characteristics.

[0074] Therefore, the present invention further relates to a method for preparing a flavored composition, particularly a ready-to-use flavored composition, comprising incorporating at least one compound of formula (I), (Ia) or (Ib), its stereoisomer, or a mixture of its stereoisomers into the composition to be flavored, particularly the ready-to-use composition.

[0075] The present invention also relates to the use of compounds of formula (I), (Ia) or (Ib) as defined above, their stereoisomers, mixtures of their stereoisomers, or mixtures of different compounds of formula (I), (Ia) or (Ib) in improving the aroma characteristics of flavored compositions, particularly ready-to-use flavored compositions.

[0076] In the group consisting of compounds of formula (I), compounds of formula (Ia), or esters of formula (Ib), some of the compounds of formula (I) are not described in the art.

[0077] Therefore, the present invention also relates to new compounds of general formula (I), their stereoisomers, mixtures of their stereoisomers, or mixtures of different compounds of general formula (I):

[0078]

[0079] in:

[0080] Described as One of the keys is a single key, and the other is either a double key or a single key.

[0081] R 1 It is hydrogen, C1-C4 alkyl or -(C=O)-R 3 ,

[0082] R 2 It is hydrogen, C1-C4 alkyl or -(C=O)-R 4 ,

[0083] R 3 It is hydrogen or C1-C4 alkyl, and

[0084] R 4 It is hydrogen or C1-C4 alkyl.

[0085] The condition is if R 1 If it is hydrogen, then R 2 Not hydrogen,

[0086] Exclude the following compounds and mixtures:

[0087] 5-(5-acetoxy-3-methylene-pentyl)acetate,

[0088] -[(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0089] -[(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0090] 5-(5-acetoxy-3-methyl-pentyl)acetate,

[0091] -[(E)-5-formyloxy-3-methyl-pent-3-enyl]carbamate,

[0092] -[(Z)-5-formyloxy-3-methyl-pent-3-enyl]carbamate,

[0093] -(3-methyl-5-propionyloxy-pentyl)propionate,

[0094] -[5-(2,2-dimethylpropionyloxy)-3-methyl-pentyl]2,2-dimethylpropionate,

[0095] -1,5-Dimethoxy-3-methylene-pentane,

[0096] -(E)-1,5-dimethoxy-3-methyl-pent-2-ene,

[0097] -(Z)-1,5-Dimethoxy-3-methyl-pent-2-ene,

[0098] -1,5-Dimethoxy-3-methyl-pentane,

[0099] -(Z)-1,5-diethoxy-3-methyl-pent-2-ene,

[0100] -1,5-Diethoxy-3-methyl-pentane,

[0101] -(E)-1,5-diisopropoxy-3-methyl-pent-2-ene,

[0102] -(Z)-1,5-Diisopropoxy-3-methyl-pent-2-ene,

[0103] -1,5-Dibutoxy-3-methylene-pentane,

[0104] -(E)-1,5-Dibutoxy-3-methyl-pent-2-ene,

[0105] -(Z)-1,5-Dibutoxy-3-methyl-pent-2-ene,

[0106] -5-Isopropoxy-3-methyl-1-pentanol,

[0107] -5-sec-butoxy-3-methyl-1-pentanol,

[0108] -1-Acetoxy-5-isopropoxy-3-methyl-2-pentene,

[0109] -(5-hydroxy-3-methyl-pentyl)3-methylbutyrate,

[0110] -[3-methyl-5-(3-methylbutyryloxy)pentyl]3-methylbutyrate,

[0111] 5-hydroxy-3-methylene-pentyl)acetic acid ester,

[0112] -[(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0113] -[(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0114] 5-(5-hydroxy-3-methyl-pentyl)carbamate,

[0115] A mixture of [(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate and [(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0116] A mixture of -[(E)-3-methyl-5-propionyloxy-pent-3-enyl]propionate and [(Z)-3-methyl-5-propionyloxy-pent-3-enyl]propionate,

[0117] A mixture of (E)-1,5-dimethoxy-3-methyl-pent-2-ene and (Z)-1,5-dimethoxy-3-methyl-pent-2-ene.

[0118] A mixture of (E)-1,5-diethoxy-3-methyl-pent-2-ene and (Z)-1,5-diethoxy-3-methyl-pent-2-ene,

[0119] A mixture of (E)-3-methyl-1,5-dipropoxy-pent-2-ene and (Z)-3-methyl-1,5-dipropoxy-pent-2-ene.

[0120] A mixture of (E)-1,5-dibutoxy-3-methyl-pent-2-ene and (Z)-1,5-dibutoxy-3-methyl-pent-2-ene, and

[0121] A mixture of (5-hydroxy-3-methylene-pentyl)acetate, [(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate and [(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate.

[0122] Therefore, the present invention also relates to new compounds of general formula (Ia), their stereoisomers, mixtures of their stereoisomers, or mixtures of different compounds of general formula (Ia):

[0123]

[0124] in:

[0125] Described as One of the keys is a single key, and the other is either a double key or a single key.

[0126] R 1a It is hydrogen, C1-C4 alkyl or -(C=O)-R 3 ,

[0127] R 2a It is hydrogen or C1-C4 alkyl, and

[0128] R 3 It is hydrogen or C1-C4 alkyl.

[0129] The condition is if R 1a If it is hydrogen, then R 2a Not hydrogen;

[0130] Exclude the following compounds and mixtures:

[0131] -1,5-Dimethoxy-3-methylene-pentane,

[0132] -(E)-1,5-dimethoxy-3-methyl-pent-2-ene,

[0133] -(Z)-1,5-Dimethoxy-3-methyl-pent-2-ene,

[0134] -1,5-Dimethoxy-3-methyl-pentane,

[0135] -(Z)-1,5-diethoxy-3-methyl-pent-2-ene,

[0136] -1,5-Diethoxy-3-methyl-pentane,

[0137] -(E)-1,5-diisopropoxy-3-methyl-pent-2-ene,

[0138] -(Z)-1,5-Diisopropoxy-3-methyl-pent-2-ene,

[0139] -1,5-Dibutoxy-3-methylene-pentane,

[0140] -(E)-1,5-Dibutoxy-3-methyl-pent-2-ene,

[0141] -(Z)-1,5-Dibutoxy-3-methyl-pent-2-ene,

[0142] -5-Isopropoxy-3-methyl-1-pentanol,

[0143] -5-sec-butoxy-3-methyl-1-pentanol,

[0144] -1-Acetoxy-5-isopropoxy-3-methyl-2-pentene,

[0145] -(5-hydroxy-3-methyl-pentyl)3-methylbutyrate,

[0146] 5-hydroxy-3-methylene-pentyl)acetic acid ester,

[0147] -[(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0148] -[(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0149] 5-(5-hydroxy-3-methyl-pentyl)carbamate,

[0150] A mixture of (E)-1,5-dimethoxy-3-methyl-pent-2-ene and (Z)-1,5-dimethoxy-3-methyl-pent-2-ene.

[0151] A mixture of (E)-1,5-diethoxy-3-methyl-pent-2-ene and (Z)-1,5-diethoxy-3-methyl-pent-2-ene,

[0152] A mixture of (E)-3-methyl-1,5-dipropoxy-pent-2-ene and (Z)-3-methyl-1,5-dipropoxy-pent-2-ene.

[0153] A mixture of (E)-1,5-dibutoxy-3-methyl-pent-2-ene and (Z)-1,5-dibutoxy-3-methyl-pent-2-ene, and

[0154] -(5-hydroxy-3-methylene-pentyl)acetate, [(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate and

[0155] A mixture of [(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetic acid esters.

[0156] Furthermore, the present invention also relates to novel compounds of general formula (Ib), their stereoisomers, mixtures of their stereoisomers, or mixtures of different compounds of general formula (Ib):

[0157]

[0158] in:

[0159] Described as One of the keys is a single key, and the other is either a double key or a single key.

[0160] R 1b It is hydrogen or -(C=O)-R 3 ,

[0161] R 2b It is hydrogen or C1-C4 alkyl.

[0162] R 3 It is hydrogen or C1-C4 alkyl, and

[0163] R 4 It is hydrogen or C1-C4 alkyl.

[0164] The condition is if R 1b If it is hydrogen, then R 2b Not hydrogen;

[0165] Exclude the following compounds and mixtures:

[0166] 5-(5-acetoxy-3-methylene-pentyl)acetate,

[0167] -[(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0168] -[(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0169] 5-(5-acetoxy-3-methyl-pentyl)acetate,

[0170] -[(E)-5-formyloxy-3-methyl-pent-3-enyl]carbamate,

[0171] -[(Z)-5-formyloxy-3-methyl-pent-3-enyl]carbamate,

[0172] -(3-methyl-5-propionyloxy-pentyl)propionate,

[0173] -[5-(2,2-dimethylpropionyloxy)-3-methyl-pentyl]2,2-dimethylpropionate,

[0174] -(5-hydroxy-3-methyl-pentyl)3-methylbutyrate,

[0175] -[3-methyl-5-(3-methylbutyryloxy)pentyl]3-methylbutyrate,

[0176] 5-hydroxy-3-methylene-pentyl)acetic acid ester,

[0177] -[(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0178] -[(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0179] 5-(5-hydroxy-3-methyl-pentyl)carbamate,

[0180] A mixture of [(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate and [(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0181] A mixture of -[(E)-3-methyl-5-propionyloxy-pent-3-enyl]propionate and [(Z)-3-methyl-5-propionyloxy-pent-3-enyl]propionate, and

[0182] A mixture of (5-hydroxy-3-methylene-pentyl)acetate, [(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate and [(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate.

[0183] Compounds of formula (I), (Ia), or (Ib), their stereoisomers, mixtures of their stereoisomers, and mixtures of different compounds of formula (I), (Ia), or (Ib) possess advantageous sensory properties, particularly a pleasant odor. Therefore, they are advantageously used as synthetic fragrances, for example, in fragrance compositions, body care compositions (including cosmetic compositions), oral and dental hygiene products, hygiene products, cleaning compositions (including dishwashing compositions), fabric detergent compositions, perfume dispenser compositions, food products, food supplements, pharmaceutical compositions, crop protection compositions, and other ready-to-use compositions.

[0184] By virtue of their physical properties, compounds of formula (I), (Ia), or (Ib), their stereoisomers, mixtures of their stereoisomers, and mixtures of different compounds of formula (I), (Ia), or (Ib) exhibit particularly good and generally universal solvent properties for flavored ready-to-use compositions, such as other fragrances and other conventional ingredients in fragrance compositions, especially fragrance compositions. Therefore, compounds of formula (I), (Ia), or (Ib), their stereoisomers, mixtures of their stereoisomers, and mixtures of different compounds of formula (I), (Ia), or (Ib) are advantageously combined with other synthetic fragrances, particularly allowing for the creation of fragrance compositions with novel and advantageous sensory characteristics.

[0185] Furthermore, compounds of formula (I), (Ia), or (Ib), their stereoisomers, or mixtures thereof can be synthesized in a single or two-step process, starting from readily available starting materials such as inexpensive 3-methylpentanediol and / or its unsaturated derivatives, with good yields and purity. Therefore, compounds of formula (I), (Ia), or (Ib), their stereoisomers, or mixtures thereof can be prepared on a large scale in a simple and cost-effective manner. Of course, the same applies to the preparation of mixtures of different compounds of formula (I), (Ia), or (Ib). Invention Details

[0187] Depends on the use The meaning of the bonds indicated means that compound (I) can be described as having one of the following formulas (I.1) to (I.4):

[0188]

[0189] In compound (I.1), the bond between carbon atoms a and b... It is a double bond, a bond between carbon atoms b and c. It is a single bond. In compound (I.2), the bond between carbon atoms a and b is... It is a single bond, a bond between carbon atoms b and c. It's a double bond, -CH2CH2OR at carbon atoms b and c. 1 and -CH2OR 2 The arrangement of the groups causes compound (I) to exist as the E isomer (further details of the stereoisomers are provided below). In compound (I.3), the bond between carbon atoms a and b... It is a single bond, a bond between carbon atoms b and c. It's a double bond, -CH2CH2OR at carbon atoms b and c. 1 and -CH2OR 2 The arrangement of the functional groups causes compound (I) to exist as the Z isomer. In compound (I.4), the bonds between carbon atoms a and b, and between carbon atoms b and c... They are all single keys.

[0190] In the following text, the compound of formula (I.1) is also referred to as the "exo" compound (exo), the compound of formula (I.2) is also referred to as the E compound (E), the compound of formula (I.3) is also referred to as the Z compound (Z), and the compound of formula (I.4) is also referred to as the saturated compound (sat).

[0191] In the context of this invention, the term "C1-C4 alkyl" refers to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutylene, and tert-butyl. Preferably, the term "C1-C4 alkyl" refers to C1-C3 alkyl, i.e., methyl, ethyl, n-propyl, and isopropyl, and particularly C1-C2 alkyl, i.e., methyl and ethyl.

[0192] The term "synthetic fragrance" refers to substances used to produce sensory impressions, more precisely, olfactory or olfactory impressions, especially aromatic impressions. The term "olfactory" refers to an odor impression without any positive or negative judgment, while the term "aromatic" (also known as "fragrant" or "scent") relates to odor impressions that are generally pleasant. Odors evoke taste impressions.

[0193] As used herein, the term “synthetic fragrance composition” refers to a composition that evokes an olfactory or aroma impression, particularly an odor impression, especially an aromatic impression.

[0194] Similarly, as used herein, the term "fragrant ready-to-use composition" refers to a ready-to-use composition that evokes an odor impression, particularly an aroma impression.

[0195] The term "strong odor substance" refers to a substance or synthetic fragrance that exhibits a strong odor impression. A strong odor impression should be understood to mean those properties of synthetic fragrances that allow for a surprisingly strong perception, even at very low gaseous concentrations. Intensity can be determined using threshold measurements. The threshold is, although no longer necessarily defined, the concentration of a substance in the relevant gaseous space at which the odor impression can still be perceived by a representative group of test subjects. The class of known substances that may belong to the strongest odor category, i.e., substances with very low odor thresholds, is thiols, whose thresholds are typically in the range of ppb / m³. 3 Within the range.

[0196] The terms “pleasant odor,” “pleasant odor impression,” “pleasant olfactory performance,” “feeling as a pleasant odor impression,” and similar expressions of pleasure describe the pleasantness and conciseness of the odor impression conveyed by synthetic fragrances. The more general expressions of pleasure, “favorable sensory performance” or “favorable sensory performance,” describe the pleasantness and conciseness of the sensory impression conveyed by synthetic fragrances. In this invention, the terms “sensory” and “feeling” refer to olfactory or aroma properties. “Pleasant” and “concise” are terms familiar to those skilled in the art and perfumers. “Pleasant” generally refers to a spontaneously generated, positively perceived pleasant sensory impression. However, “pleasant” is not necessarily synonymous with “sweet.” “Pleasant” can also refer to the scent of musk or sandalwood. “Concise” generally refers to a spontaneously generated sensory impression that produces some specific reproduction of the same suggestion for the same experimental group. For example, a substance may have a spontaneous memory of “red berries”: the odor is concisely “red berries.” If the red berry odor is very pleasant due to the memory of, for example, sweet ripe red berries, then the odor is called “pleasant” and / or “sweet.” However, the aroma of sour red berries can also be straightforward. If two reactions occur when smelling a substance, in this example, thus a pleasant and straightforward red berry aroma is produced, then the substance has particularly advantageous sensory properties.

[0197] Preferably, a compound of formula (I) as defined in the context, or a stereoisomer or mixture of stereoisomers thereof, or a mixture of different compounds of formula (I), is used to impart an olfactory impression. In particular, a compound of formula (I) as defined above, or a mixture thereof, or a stereoisomer or mixture of stereoisomers thereof, is used as a flavoring agent.

[0198] In addition to a single compound (I), it can be in the form of an achiral compound (I) (e.g., if described as...). Both bonds are single bonds, and R 1 and R 2 They are either the same and achiral form or pure stereoisomers (see definitions below), and mixtures of different compounds (I) may be used in addition to mixtures of various stereoisomers. The distinction of the compounds in such mixtures lies, for example, whether they are saturated (i.e., described as...). The two bonds are single bonds) or unsaturated (i.e., described as...). One of the bonds is a double bond), and the position relative to the double bond is a positional isomer, that is, a double bond is present between carbon atoms a and b or between carbon atoms b and c, and / or different groups R. 1 and / or R 2 Of course, such mixtures can also contain components in various stereoisomer forms.

[0199] The term "stereoisomer" refers to isomers that have the same molecular formula and sequence of bonded atoms, but whose atoms have different three-dimensional orientations in space. It includes optical isomers, such as enantiomers or diastereomers, the latter being due to having more than one stereocenter in the molecule, as well as geometric isomers (cis / trans or Z / E isomers) as specific forms of diastereomers.

[0200] First, according to the present invention, the term "stereoisomer" refers to the E and Z isomers of unsaturated compounds of formula (I), (Ia), or (Ib), i.e., wherein carbon atoms b and c are described as follows: Compounds in which the bond is a double bond. The E / Z configuration describes the absolute stereochemistry of the double bond in organic chemistry. Each substituent on the double bond is assigned a priority. If the two higher priority groups are on opposite sides of the double bond, the bond is designated as configuration E. If the two higher priority groups are on the same side of the double bond, the bond is designated as configuration Z.

[0201] For illustrative purposes only, the E and Z isomers of [5-formyloxy-3-methyl-pent-3-enyl]formate are shown below:

[0202]

[0203] A general description of the E and Z stereoisomers of compound (I) is given in the context of formulas (I.2) (E isomer) and (I.3) (Z isomer). For a compound to be a stereoisomer, the prerequisite is, of course, R. 1 It has the same meaning as in (I.2) and (I.3), and R 2 It has the same meaning as in (I.2) and (I.3).

[0204] For better readability, in this application, compounds (I), (Ia), or (Ib) that may exist as Z and E stereoisomers are generally shown only as E stereoisomers. However, this does not limit the compounds to E stereoisomers (unless otherwise explicitly stated, e.g., by explicitly defining the compounds as (I.2) or (I.3) or E or Z), but includes Z isomers and mixtures of E and Z isomers.

[0205] Secondly, the term "stereoisomer" also refers to the optical isomers of saturated compounds of formula (I), (Ia), or (Ib). Optical isomers are enantiomers or diastereomers that exist due to having more than one stereocenter in the molecule. It refers to all optical isomers in their pure form, for example, all enantiomers or diastereomers in their pure form. An enantiomer is one of two stereoisomers that are non-superimposable mirror images of each other. If in compounds (I), (Ia), or (Ib), described as... Both bonds are single bonds, and R1 and R 2 If they have different meanings, then the carbon atom b with the methyl group is the stereocenter. If R 1 and R 2 If there is no stereocenter, then these compounds (I), (Ia) or (Ib) can exist as pure 3R or pure 3S enantiomers.

[0206] For illustrative purposes only, the 3R- and 3S-isomers of (5-hydroxy-3-methyl-pentyl)carbamate are shown below:

[0207]

[0208] Third, the stereocenter can also exist in the group R. 1 R 2 R 3 Or R 4 For example, if these are sec-butyl.

[0209] A mixture of stereoisomers is, for example, a racemic and non-racemic mixture of enantiomers or diastereomers of compounds (I), (Ia), or (Ib). In this document, the term "diastereomer" includes diastereomers and geometric isomers existing due to having more than one stereocenter in the molecule, namely E and Z isomers.

[0210] The term "isomer" refers to compounds that have the same elemental formula but different structures. This term includes structural isomers and stereoisomers. Stereoisomers are defined above.

[0211] Structural isomers of compound (I), particularly positional isomers of the double bond position. More precisely, compound (I) in which the double bond is between carbon atoms a and b is a structural isomer of compound (I) in which the double bond is between carbon atoms b and c; therefore, compound (I.1) is a positional isomer of compound (I.2) or (I.3). For it to be an isomer, the prerequisite is, of course, that R... 1 Having the same meaning as (I.1) and (I.2) or (I.3), R 2 It has the same meaning as (I.1) and (I.2) or (I.3).

[0212] Depending on the presence and arrangement of the double bonds, compounds of formula (I) can exist as individual "exo" isomers (I.1) (exo), E-isomers (I.2) (E), or Z-isomers (I.3) (Z), or as saturated compounds (I.4) (sat), or various mixtures thereof such as exo / E / Z / sat mixtures or exo / E / Z isomer mixtures:

[0213]

[0214] Therefore, the present invention relates to the use of morphological isomers (i.e., (I.1)), the use of E-isomers (i.e., (I.2)), the use of Z-isomers (i.e., (I.3)), the use of saturated compounds (i.e., (I.4)), and various mixtures thereof such as E / Z isomer mixtures (i.e., (I.2, I.3)), exo / E isomer mixtures (i.e., (I.1, I.2)), exo / Z isomer mixtures (i.e., (I.1, I.3)), and exo / E / Z isomer mixtures (i.e., (I.1, I.3)). Use of (I.2, I.3), or mixtures thereof (i.e. (I.1, I.2, I.3, I.4)). Therefore, unless otherwise stated, as used herein, “compound I”, “compound of general formula I”, etc., refers to pure exo-isomers, pure E-isomers, pure Z-isomers, pure saturated compounds and their various mixtures as listed above, wherein the isomers / compounds are present in equal amounts or contain an excess of one isomer / compound or do not contain one or more isomers / compounds.

[0215] Of course, in a mixture of isomers, R in all isomers 1 They have the same meaning, and R in all isomers 2 They have the same meaning. Preferably, in a mixture containing a saturated compound (I.4) and one or more of (I.1), (I.2) and (I.3), similarly, R in all isomers / compounds 1 They have the same meaning, and R in all isomers / compounds 2 They have the same meaning.

[0216] The pure exomeric isomers, pure E-isomers, pure Z-isomers, pure saturated compounds, and various mixtures of (isomers) of compound (I) possess all the advantageous sensory properties. Therefore, the pure exomeric isomers, pure E-isomers, pure Z-isomers, pure saturated compounds, and various mixtures of (isomers) of compound (I) are also suitable for use as synthetic flavorings.

[0217] Also suitable for use as synthetic fragrances are those containing R 1 and / or R 2 A mixture of compounds (I) with distinct functional groups. Such mixtures can be formed during preparation, for example, if the alkylation or acylation of the starting diol is incomplete (if the target compound is a diether or diester or a mixed ether / ester); or, if a monoester or monoester is desired, a portion of the diol is dietherified or diesterified; or if a mixture of alkylating and / or acyling agents is used. Further details will become apparent in the description of the method of preparation of compound (I). R 1 and / or R 2A mixture of compounds (I) whose functional groups differ from each other and which are produced by incomplete or undesirable reactions preferably contains only a small amount of compounds produced by incomplete conversion (e.g., where R is present). 1 Or R 2 One of them is a monoether or monoester of H (if the intention is to prepare a diether or diester) or an undesirable transformation (e.g., where R is a monoether or monoester of H). 1 Or R 2 The compound obtained is a diether or diester that is not H (if it is intended to prepare a monoether or monoester), for example, based on the total weight of all compounds (I) in the mixture, up to 25% by weight, preferably up to 10% by weight, more preferably up to 5% by weight, especially up to 2% by weight, especially up to 1% by weight.

[0218] On the other hand, the basic aroma characteristics of ether compounds of general formula (I) are generally different from those of ester compounds of general formula (I).

[0219] Therefore, a first embodiment of the present invention relates to the use of ether compounds of general formula (I), wherein in formula (I):

[0220] R 1 It is a C1-C4 alkyl group, and

[0221] R 2 It is hydrogen or C1-C4 alkyl.

[0222] The compound (I) of the first embodiment comprises monoethers and diethers of 3-methylpentanediol and its unsaturated derivatives. Generally, monoethers of 3-methylpentanediol and its unsaturated derivatives possess all the advantageous sensory properties. Therefore, both monoethers and diethers of 3-methylpentanediol and its unsaturated derivatives are equally suitable for use as synthetic fragrances.

[0223] However, a diether compound is more preferred, i.e., wherein in formula (I), R 1 and R 2 Compounds of general formula (I) selected independently of each other from C1-C4 alkyl groups. In a particular embodiment, R 1 and R 2 Each is independently a C1-C3 alkyl group. In another specific embodiment, R 1 and R 2 It is independently selected from methyl, ethyl, n-propyl, isopropyl, and n-butyl. Specifically, R 1 and R 2 They are independently selected from methyl, ethyl and n-butyl.

[0224] Furthermore, the synthesis of general formula (I) ether compounds in which the substituents connected to the oxygen atom are the same is generally simpler than the synthesis of general formula (I) ether compounds with different substituents on the oxygen atom.

[0225] Therefore, it is further preferred to use R. 1 and R 2 They are all ether compounds of the same (and all are C1-C4 alkyl) general formula (I).

[0226] More preferably, ether compounds of general formula (I) are used, wherein R 1 and R 2 They are the same and are C1-C3 alkyl groups.

[0227] Even more preferred is the use of ether compounds of general formula (I), wherein R 1 and R 2 The same and selected from methyl, ethyl, n-propyl, isopropyl and n-butyl.

[0228] Particularly preferred are ether compounds of general formula (I), wherein R 1 and R 2 They are the same and are methyl, ethyl or n-butyl.

[0229] R is particularly preferred. 1 and R 2 It is an ether compound of general formula (I) for ethyl groups.

[0230] Especially preferred for use:

[0231] -1,5-Diethoxy-3-methyl-pentane,

[0232] -1,5-Diethoxy-3-methylene-pentane,

[0233] -(E)-1,5-diethoxy-3-methyl-pent-2-ene,

[0234] -(Z)-1,5-diethoxy-3-methyl-pent-2-ene,

[0235] -1,5-Dimethoxy-3-methyl-pentane,

[0236] -1,5-Dimethoxy-3-methylene-pentane,

[0237] -(E)-1,5-dimethoxy-3-methyl-pent-2-ene,

[0238] -(Z)-1,5-Dimethoxy-3-methyl-pent-2-ene,

[0239] -1,5-Dibutoxy-3-methyl-pentane,

[0240] -1,5-Dibutoxy-3-methylene-pentane,

[0241] -(E)-1,5-Dibutoxy-3-methyl-pent-2-ene,

[0242] -(Z)-1,5-dibutoxy-3-methyl-pent-2-ene, and

[0243] - Its mixture.

[0244] In another embodiment, a composition comprising a mixture of at least two compounds selected from formulas (I.1), (I.2), (I.3), and (I.4) is used:

[0245]

[0246] Where R 1 and R 2 Having one of the general or preferred meanings as defined above in the context of the first embodiment,

[0247] The mixture contains each compound present in the mixture in an amount of 1-99% by weight, provided that the total weight of the compounds of formula (I.1), (I.2), (I.3) and (I.4) in the mixture is 100%.

[0248] Preferred compositions are those comprising a mixture of at least two compounds selected from formulas (I.1), (I.2), and (I.3), wherein each compound is present in the mixture in an amount of 1-99% by weight, provided that the total weight of the compounds of formulas (I.1), (I.2), and (I.3) in the mixture is 100%.

[0249] More preferably, a composition comprising a mixture of all three compounds of formula (I.1), (I.2), and (I.3) is used, comprising each compound in an amount of 1-99% by weight, provided that the total weight of the compounds of formula (I.1), (I.2), and (I.3) in the mixture is 100%, wherein the molar ratio of (I.1):(I.2):(I.3) is 90:5:5-10:45:45, preferably 80:10:10-20:40:40, especially 55:22.5:22.5-45:27.5:27.5, and even more especially about 50:25:25. The term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0250] A second embodiment of the present invention relates to the use of ester compounds of general formula (I), wherein in formula (I):

[0251] R 1 -(C=O)-R 3 ,

[0252] R 2 For hydrogen, -(C=O)-R 4 Or C1-C4 alkyl, and

[0253] R 3 and R 4 As defined above (i.e., hydrogen or C1-C4 alkyl).

[0254] The compound (I) of the second embodiment includes monoesters, diesters, and monoester-monoethers of 3-methylpentanediol and its unsaturated derivatives. Generally, monoesters, diesters, and monoester-monoethers of 3-methylpentanediol and its unsaturated derivatives possess all the advantageous sensory properties. Therefore, monoesters and diesters of 3-methylpentanediol and its unsaturated derivatives, as well as monoester-monoethers of 3-methylpentanediol and its unsaturated derivatives, are also suitable for use as synthetic fragrances.

[0255] More preferably, diester compounds, i.e., compounds of general formula (I), wherein in formula (I):

[0256] R 1 -(C=O)-R 3 ,

[0257] R 2 -(C=O)-R 4 and

[0258] R 3 and R 4 As defined above (i.e., hydrogen or C1-C4 alkyl).

[0259] Further preferred is the use of ester compounds of general formula (I), wherein R 3 and R 4 It is selected from hydrogen and C1-C3 alkyl, more preferably from hydrogen and C1-C2 alkyl.

[0260] Similarly, the synthesis of general formula (I) esters with the same substituents attached to the oxygen atom is generally simpler than the synthesis of general formula (I) esters with different substituents attached to the oxygen atom, and of course, simpler than the synthesis of monoester-monoether compounds.

[0261] Therefore, it is further preferred to use diester compounds of general formula (I), wherein:

[0262] R 1 -(C=O)-R 3 ,

[0263] R 2 -(C=O)-R 4 and

[0264] R 3 and R 4 As defined above (i.e., hydrogen or C1-C4 alkyl),

[0265] And the group R in it 3 and R 4 They are the same.

[0266] Even more preferred is the use of ester compounds of general formula (I), wherein R 3 and R 4 They are the same and selected from hydrogen and C1-C3 alkyl groups.

[0267] Ester compounds of general formula (I) are particularly preferred, wherein R 3 and R 4 The same and selected from hydrogen, methyl and ethyl.

[0268] Especially preferred for use:

[0269] 3-(3-formyloxy-2-methyl-propyl)formate,

[0270] 2-(formyloxymethyl)allyl carbamate,

[0271] -[(E)-3-formyloxy-2-methyl-allyl]formate,

[0272] -[(Z)-3-formyloxy-2-methyl-allyl]formate,

[0273] 3-(acetoxy-2-methyl-propyl)acetate,

[0274] 2-(acetoxymethyl)allyl acetate,

[0275] -[(E)-3-acetoxy-2-methyl-allyl]acetate,

[0276] -[(Z)-3-acetoxy-2-methyl-allyl]acetate,

[0277] -(2-methyl-3-propionyloxy-propyl)propionate,

[0278] 2-(propionyloxymethyl)allyl propionate,

[0279] -[(E)-2-methyl-3-propionyloxy-allyl]propionate,

[0280] -[(Z)-2-methyl-3-propionyloxy-allyl]propionate, and

[0281] - Its mixture.

[0282] In another embodiment, the present invention relates to the use of compositions comprising mixtures of at least two compounds selected from formulas (I.1), (I.2), (I.3), and (I.4):

[0283]

[0284] Where R 1 and R 2 Having one of the general and preferred meanings as defined above in the context of the second embodiment,

[0285] The mixture contains each compound present in the mixture in an amount of 1-99% by weight, provided that the total weight of the compounds of formula (I.1), (I.2), (I.3) and (I.4) in the mixture is 100%.

[0286] Preferred compositions are those comprising a mixture of at least two compounds selected from formulas (I.1), (I.2), and (I.3), wherein each compound is present in the mixture in an amount of 1-99% by weight, provided that the total weight of the compounds of formulas (I.1), (I.2), and (I.3) in the mixture is 100%.

[0287] More preferably, a composition comprising a mixture of all three compounds of formula (I.1), (I.2), and (I.3) is used, comprising each compound in an amount of 1-99% by weight, provided that the total weight of the compounds of formula (I.1), (I.2), and (I.3) in the mixture is 100%, wherein the molar ratio of (I.1):(I.2):(I.3) is preferably 90:5:5-10:45:45, more preferably 80:10:10-20:40:40, especially 55:22.5:22.5-45:27.5:27.5, and even more particularly about 50:25:25. The term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0288] In one particular embodiment of the invention, the ether and ester compounds of general formula (I) exist essentially in their phenotypic isomers (I.1).

[0289] In another specific embodiment of the invention, the ether and ester compounds of general formula (I) are essentially present in the form of their E-isomers (I.2).

[0290] In another specific embodiment of the invention, the ether and ester compounds of general formula (I) are essentially present in the form of their Z-isomer (I.3).

[0291] In another specific embodiment of the invention, the ether and ester compounds of general formula (I) are essentially saturated compounds of (I.4) (i.e., those described as...). It exists in the form of a saturated derivative with two single bonds.

[0292] In this regard, the term "basic" means that the exo, E, Z or sat derivative of a particular compound is present in an amount of at least 90% by weight, preferably at least 95% by weight, and particularly at least 98% by weight, based on the total amount (weight) of the exo, E, Z and sat derivatives.

[0293] Typically, compound (I) is produced as exo / E / Z or as a mixture of exo / E / Z / sat. The separation of exo, E, Z and sat derivatives can be difficult and laborious, or even impossible to achieve completely with reasonable effort.

[0294] Therefore, preferred embodiments of the invention relate to the use of compounds of general formula (I) as defined above and below, wherein the compounds of general formula (I) are present in the form of a mixture of exo / E / Z isomers, which may also contain the saturated derivative sat (therefore, a mixture of exo / E / Z / sat). In particular, a mixture of exo / E / Z isomers is used.

[0295] In one embodiment, in these mixtures, the four derivatives may be present in equal or nearly equal amounts, for example, in an exo / E / Z / sat molar ratio of 25:25:25:25, 31:23:23:23, 23:31:23:23, 23:23:31:23, or 23:23:23:31, or one derivative, i.e., an exo, E, Z, or sat derivative, may be present in excess, for example, one derivative may be present in an exo / E / Z / sat molar ratio of 91:3:3:3, 3:91:3:3, 3:3:91:3, or 3:3:3:3:91. In a particular embodiment, the saturated derivative sat, if present, is present only in a small amount. In a particular embodiment, the molar ratio of exoisomer:E-isomer:Z-isomer:sat derivative is 48:25:25:2-49:25:25:1.

[0296] In another embodiment, in these mixtures, the three exo / E / Z isomers may be present in equimolar amounts of 33.3:33.3:33.3, or one isomer, i.e., the exo, E, or Z isomer, may be present in excess, for example, one isomer may be present in exo / E / Z or E / exo / Z or E / Z / exo or Z / exo / E or Z / E / exo isomer molar ratios of 90:9:1, 90:5:5, 80:10:10, 60:20:20, 50:25:25, 40:30:30, wherein the isomer ratio is preferably 75:12.5:12.5-45:27.5:27.5, especially about 50:25:25. The term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0297] A preferred embodiment of the present invention relates to the use of a composition comprising a mixture of at least two compounds (I) selected from formulas (I.1), (I.2), and (I.3), wherein...

[0298] -(I.1) is present in an amount of 0-75% by weight, preferably 10-75% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0299] -(I.2) is present in an amount of 0-50% by weight, preferably 5-45% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0300] -(I.3) is present in an amount of 0-50% by weight, preferably 0-45% by weight, based on the total weight of (I.1), (I.2) and (I.3), provided that at least two of compounds (I.1), (I.2) and (I.3) are present in an amount of >0% by weight based on the total weight of (I.1), (I.2) and (I.3), and the total weight of compounds (I.1), (I.2) and (I.3) present in the mixture is 100%.

[0301] A more preferred embodiment of the invention relates to the use of compositions comprising mixtures of all three compounds of formulas (I.1), (I.2), and (I.3), wherein

[0302] -(I.1) is present in an amount of 25-75% by weight, preferably 30-60% by weight, and especially 35-55% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0303] -(I.2) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0304] -(I.3) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0305] The condition is that the total weight of compounds (I.1), (I.2), and (I.3) is 100%.

[0306] A specific embodiment is the use of a composition comprising a mixture of all three compounds of general formulas (I.1), (I.2), and (I.3), comprising each compound in an amount of 1-99% by weight, provided that the total weight of the compounds of formulas (I.1), (I.2), and (I.3) is 100%, wherein the ratio of (I.1):(I.2):(I.3) is 90:5:5-10:45:45, preferably 80:10:10-20:40:40, especially 55:22.5:22.5-45:27.5:27.5, and more especially about 50:25:25. Similarly, the term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0307] Preferred embodiments of the present invention relate to the use of compositions comprising mixtures of at least two ether compounds selected from formulas (I.1), (I.2), and (I.3), wherein R 1 and R 2 As defined in the first embodiment above relating to ether compounds, wherein

[0308] -(I.1) is present in an amount of 0-75% by weight, preferably 10-75% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0309] -(I.2) is present in an amount of 0-50% by weight, preferably 5-45% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0310] -(I.3) is present in an amount of 0-50% by weight, preferably 0-45% by weight, based on the total weight of (I.1), (I.2) and (I.3), provided that at least two of compounds (I.1), (I.2) and (I.3) are present in an amount of >0% by weight based on the total weight of (I.1), (I.2) and (I.3), and the total weight of compounds (I.1), (I.2) and (I.3) present in the mixture is 100%.

[0311] A more preferred embodiment of the invention relates to the use of compositions comprising mixtures of all three ether compounds selected from formulas (I.1), (I.2), and (I.3), wherein R 1 and R 2 As defined in the first embodiment above relating to ether compounds, wherein

[0312] -(I.1) is present in an amount of 25-75% by weight, preferably 30-60% by weight, and especially 35-55% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0313] -(I.2) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0314] -(I.3) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0315] The condition is that the total weight of compounds (I.1), (I.2), and (I.3) is 100%.

[0316] A specific embodiment is the use of a composition comprising a mixture of all three general formulas (I.1), (I.2), and (I.3) ether compounds, wherein R 1 and R 2 As defined in the first embodiment above, it comprises each ether compound in an amount of 1-99% by weight, provided that the weight sum of the ether compounds of formulas (I.1), (I.2), and (I.3) is 100%, wherein the ratio of (I.1):(I.2):(I.3) is 90:5:5-10:45:45, preferably 80:10:10-20:40:40, especially 55:22.5:22.5-45:27.5:27.5, and even more especially about 50:25:25. Similarly, the term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0317] Preferred embodiments of the present invention relate to the use of compositions comprising mixtures of at least two ester compounds selected from formulas (I.1), (I.2), and (I.3), wherein R 1 and R 2 As defined in the second embodiment above involving ester compounds, wherein

[0318] -(I.1) is present in an amount of 0-75% by weight, preferably 10-75% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0319] -(I.2) is present in an amount of 0-50% by weight, preferably 5-45% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0320] -(I.3) is present in an amount of 0-50% by weight, preferably 0-45% by weight, based on the total weight of (I.1), (I.2) and (I.3), provided that at least two of compounds (I.1), (I.2) and (I.3) are present in an amount of >0% by weight based on the total weight of (I.1), (I.2) and (I.3), and the total weight of compounds (I.1), (I.2) and (I.3) present in the mixture is 100%.

[0321] A more preferred embodiment of the invention relates to the use of compositions comprising mixtures of all three ester compounds selected from formulas (I.1), (I.2), and (I.3), wherein R 1 and R 2 As defined in the second embodiment above involving ester compounds, wherein

[0322] -(I.1) is present in an amount of 25-75% by weight, preferably 30-60% by weight, and especially 35-55% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0323] -(I.2) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0324] -(I.3) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0325] The condition is that the total weight of compounds (I.1), (I.2), and (I.3) is 100%.

[0326] A specific embodiment is the use of a composition comprising a mixture of all three general formulas (I.1), (I.2), and (I.3) ester compounds, wherein R 1 and R 2 As defined in the second embodiment above, each compound comprises 1-99% by weight, provided that the total weight of compounds of formulas (I.1), (I.2), and (I.3) is 100%, wherein the molar ratio of (I.1):(I.2):(I.3) is 90:5:5-10:45:45, preferably 80:10:10-20:40:40, especially 55:22.5:22.5-45:27.5:27.5, and even more especially about 50:25:25. Similarly, the term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0327] Furthermore, compounds (I), (Ia), or (Ib) can be used as synthetic fragrances with a wide range of purities, provided that impurities do not have a significant detrimental effect on the aroma of compounds (I), (Ia), or (Ib). Therefore, according to the invention, the purity of compounds (I), (Ia), or (Ib) is not particularly limited for use as synthetic fragrances. Preferably, compounds (I), (Ia), or (Ib) have a purity of at least 70%, particularly at least 90%, and especially at least 95%.

[0328] Because they originate from the preparation methods of 3-methylpentanediol and / or its unsaturated derivatives, diether compounds of general formula (I) or (Ia) may contain a small amount of monoether compound (I-OH), and diester compounds of general formula (I) or (Ib) may contain a small amount of monoester compound (II-OH):

[0329]

[0330] Where R 1a and R 2b It has one of the meanings given above.

[0331] Preferably, the amount of the monosubstituted compound (I-OH) or (II-OH) that may be included in the diether and diester compounds of general formula (I) is less than 25% by weight, more preferably less than 10% by weight, even more preferably less than 5% by weight, and particularly less than 1% by weight, based on the total amount of compound (I).

[0332] In a particularly preferred embodiment of the invention, the diether and diester compounds of general formula (I) do not contain monosubstituted compounds (I-OH) or (II-OH).

[0333] Similarly, monoether and monoester compounds of general formula (I) may contain small amounts of the corresponding disubstituted compounds. Preferably, the amount of the disubstituted compound of general formula (I) contained in the monoether and monoester compounds of general formula (I) is less than 25% by weight, more preferably less than 10% by weight, even more preferably less than 5% by weight, and particularly less than 1% by weight, based on the total amount of compound (I).

[0334] In addition, the group R 1 and R 2 Different general formula (I) diether compounds and the R group therein 3 and R 4 Different general formula (I) diester compounds (hereinafter referred to as asymmetric substituted compounds) may contain a small number of symmetric substituted compounds, i.e., where the R group 1 and R 2 For the same general formula (I) diether compounds and the R group therein 3 and R 4The same general formula (I) diester compound. Preferably, the amount of the symmetrically substituted compound that may be included in the asymmetricly substituted compound of general formula (I) is less than 25% by weight, more preferably less than 10% by weight, even more preferably less than 5% by weight, and particularly less than 1% by weight, based on the total amount of compound (I).

[0335] The above preferred embodiments can be combined with each other as needed.

[0336] Therefore, in a particularly preferred embodiment, the present invention relates to the use of compounds of general formula (I) having a purity of at least 95% and / or existing in the form of the above-described mixture of exo / E / Z isomers.

[0337] Specifically, the present invention relates to the use of a compound of general formula (I) having a purity of at least 95%, and / or existing as a mixture of exo / E / Z isomers having the aforementioned weight ratio, preferably an exo:E:Z weight ratio of 55:22.5:22.5-45:27.5:27.5, more particularly an exo:E:Z weight ratio of approximately 50:25:25, wherein R in compound (I) 1 and R 2 The same, and among all isomers of the exo / E / Z mixture, R 1 and R 2 Same. The term "approximately" takes into account measurement errors that may occur when determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0338] As described above, compounds of formula (I) or their stereoisomers or mixtures thereof, or mixtures of different formula (I) compounds, as defined in the context, are used to impart an olfactory impression. In particular, compounds of formula (I) or their mixtures thereof, or their stereoisomers or mixtures thereof, as defined above, are used as flavorings.

[0339] In particular, where R in each case 1 and R 2 It is a mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of C(=O)CH3 (see definitions above) used to impart sweet, powdery, terpene, or fruity aromas; or to produce odors with sweet, powdery, terpene, or fruity aromas. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -C(=O)CH3 exist in a weight ratio of approximately 50:25:25.

[0340] Specifically, R 1 and R 2It is a compound of -C(=O)CH3 (I.1) used to impart fruity, sweet, rubbery, musty, and dusty flavors; or to produce odors with fruity, sweet, rubbery, musty, and dusty flavors.

[0341] Specifically, R 1 and R 2 It is a compound of -C(=O)CH3 (I.2) used to impart fruity, woody, and sweet aromas; or to produce aromas with fruity, woody, and sweet notes.

[0342] Specifically, R 1 and R 2 It is a compound of -C(=O)CH3 (I.4) (see definition above) used to impart sweetness and fruitiness; or to produce an aroma with sweetness and fruitiness.

[0343] In particular, using R in each case 1 and R 2 This is a mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of -C(=O)CH2CH3, used to impart a sweet, red berry aroma; or to produce an aroma with a sweet, red berry aroma. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of C(=O)CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0344] In particular, using R in each case 1 and R 2 This is a mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of -CH3, used to impart herbal, algal, green, aquatic, and fruity aromas; or to produce odors with herbal, algal, green, aquatic, and fruity aromas. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of the -CH3 group exist in a weight ratio of approximately 50:25:25.

[0345] In particular, using R in each case 1 and R 2 This is a mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of -CH2CH3, used to impart green, herbal, raw potato, or green banana aromas; or to produce an aroma having green, herbal, raw potato, or green banana aromas. Specifically, in this mixture, wherein in each case R 1 and R 2The compounds (I.1), (I.2) and (I.3) of -CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0346] In particular, using R in each case 1 and R 2 This is a mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of -CH2CH2CH2CH3, used to impart cedar, citrus, warm, and herbal notes; or to produce an aroma with cedar, citrus, warm, and herbal notes. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -CH2CH2CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0347] Specifically, R 1 and R 2 The -CH2CH3 compound (I.4) is used to impart green, banana, and apple (ripe) aroma notes; or to produce an aroma with green, banana, and apple (ripe) aroma notes.

[0348] The term “about” takes into account the measurement error that may occur when determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0349] Monoether compounds of general formula (I) can be efficiently processed by alkylating agent R, typically in the presence of a base. 1 -X is prepared by alkylation of compound (II) or mixtures thereof:

[0350]

[0351] Where R 1 It has one of the meanings given above, and X represents a leaving group selected from halogens, such as Cl, Br, I, and sulfonates, such as toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, or perfluorobutylsulfonate.

[0352] Suitable bases are usually selected from inorganic bases and organic bases.

[0353] Suitable inorganic bases that can be used in this alkylation reaction are, for example, alkali metal carbonates such as Li2CO3, Na2CO3, K2CO3 or Cs2CO3, alkali metal hydroxides such as LiOH, NaOH or KOH, and hydrogen donors such as NaH, LiAlH4 or NaBH4.

[0354] Suitable organic bases that can be used in this alkylation reaction are, for example, tertiary amines such as trimethylamine, triethylamine, tripropylamine, ethyl diisopropylamine, etc., or basic N-heterocyclic compounds such as morpholine, pyridine, rutidine, DMAP, DABCO, DBU, or DBN.

[0355] The alkylation reaction was carried out under conventional alkylation reaction conditions familiar to those skilled in the art.

[0356] Typically, compound (II) or mixtures thereof is mixed with a sub-equimolar or nearly equimolar amount, for example, 0.7, 0.8, 0.9, or 0.95 equivalents of the alkylating agent R. 1 The -X reaction yields a monosubstituted compound (I-OH), which is then subjected to purification steps to remove unwanted byproducts or impurities, such as residual feedstocks or the corresponding disubstituted compounds.

[0357] Generally, purification steps are performed using conventional purification methods, such as crystallization, distillation, or chromatography, such as column chromatography or high-performance liquid chromatography.

[0358] Wherein group R 1 and R 2 The preparation of diether compounds of the same general formula (I) is generally carried out by reacting compound (II) or mixtures thereof with at least 2 equivalents, for example 2.0, 2.1, 2.5 or 3.0 equivalents, of an alkylating agent R. 1 -X or R 2 The reaction proceeds via the -X reaction, where the group R... 1 R 2 X has one of the meanings given above, and the resulting crude product is then subjected to purification steps as defined above. If only minor amounts of impurities and byproducts are present in the crude product mixture, the purification step can also be carried out by a simple post-extraction treatment.

[0359] Wherein group R 1 and R 2 Different general formula (I) diether compounds are typically prepared by first reacting compound (II) or a mixture thereof with a sub-equimolar or nearly equimolar amount, for example, 0.7, 0.8, 0.9, or 0.95 equivalents of alkylating agent R. 1 The -X reaction yields a monosubstituted compound (I-OH), which, after purification, is further reacted with a second alkylating agent R. 2 -X reaction proceeds.

[0360] Generally, ester compounds of general formula (I) are effectively produced by reacting compound (II) or a mixture thereof with carboxylic acid R. 3 -COOH, with carboxylic acid R 4 -COOH (where R) 3 and R 4(having one of the meanings given above), or its anhydride, or formula R 3 -(C=O)X′ or R 4 Acyl halogens of -(C=O)X' (where X' is a halogen such as Cl, Br, or I, usually Cl or Br), or carboxylic acids R. 3 -COOH and / or R 4 -COOH is prepared by reacting it with its acid anhydride and / or a mixture of acyl halides. The reaction is usually carried out in the presence of an esterification catalyst or a base.

[0361] Suitable esterification catalysts for this reaction are well known to those skilled in the art. Suitable esterification catalysts are, for example, metal-based catalysts, such as metals, metal oxides, or metal salts like metal alkoxides (iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium, and tin); mineral acids, such as sulfuric acid, hydrochloric acid, or phosphoric acid; or organic sulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid.

[0362] Suitable bases are, for example, organic bases as defined above.

[0363] Alternatively, ester compounds of general formula (I) can be obtained by reacting compound (II) or a mixture thereof with formula R in the presence of an organic base. 3 -(C=O)X′ or R 4 Acyl halogen of -(C=O)X′ (where R) 3 and R 4 It has one of the meanings given above, and X′ is a halogen such as Cl, Br or I, usually prepared by the reaction of Cl or Br).

[0364] Suitable organic bases are as defined above.

[0365] The reaction conditions for preparing ester compounds of general formula (I) are well known to those skilled in the art.

[0366] To prepare a monoester compound of general formula (I), compound (II) or a mixture thereof is typically mixed with a sub-equimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9 or 0.95 equivalents of carboxylic acid R. 3 -COOH or its anhydride or its acyl halide, or the carboxylic acid with its anhydride and / or acyl halide, reacts. Alternatively, compound (II) or a mixture thereof is typically reacted with an equal amount of acyl halide R. 3 -(C=O)X′ reacts in the presence of an organic base. The resulting crude product is then subjected to purification steps as defined above.

[0367] To prepare group R 3 and R 4 For diester compounds of the same general formula (I), compound (II) or mixtures thereof are typically mixed with at least 2 equivalents, such as 2.0, 2.1, 2.5 or 3.0 equivalents of carboxylic acid R.3 -COOH or R 4 -COOH, its anhydride, or a mixture of the said carboxylic acid and its anhydride. Alternatively, compound (II) or a mixture thereof is typically reacted with at least 2 equivalents of an acyl halide R. 3 -(C=O)X′ or R 4 -(C=O)X′ reacts in the presence of an organic base. The resulting crude product is then subjected to purification steps as defined above. If only minor amounts of impurities and byproducts are present in the crude product mixture, the purification step can also be carried out by a simple post-extraction treatment.

[0368] Wherein group R 3 and R 4 Different general formula (I) diester compounds are typically prepared by first reacting compound (II) or a mixture thereof with a sub-equimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9, or 0.95 equivalents of carboxylic acid R. 3 -COOH or its anhydride reacts to give a monosubstituted compound (II-OH), which, after purification, is further reacted with a second carboxylic acid R. 4 The reaction proceeds via a reaction between -COOH or its anhydride.

[0369] Alternatively, group R 3 and R 4 Different compounds (I) can also be prepared by first mixing compound (II) or a mixture thereof with a sub-equimolar or nearly equimolar amount, for example, 0.7, 0.8, 0.9, or 0.95 equivalents of the acyl halide R. 3 -(C=O)X′ reacts in the presence of an organic base to give a monosubstituted compound (II-OH), which, after purification, is further reacted with a second acidic halide R. 4 It is achieved through the reaction -(C=O)X′.

[0370] The starting compound (II) or mixture thereof is a diol structural unit of a monomer commonly used in the synthesis of polymer materials. Therefore, compound (II) or mixture thereof is readily available from commercial sources. Alternatively, compound (II) or mixture thereof can also be synthesized in large quantities using methods skillfully described in the art, such as by dimerization of dimethyl ketene.

[0371] Composition:

[0372] The following description applies both to the synthetic fragrance compositions according to the invention and to the applications according to the invention.

[0373] Compounds of formula (I), mixtures thereof, stereoisomers thereof, or mixtures thereof may be used in a variety of compositions, such as ready-to-use compositions. The olfactory properties, physical properties (e.g., solubility in common solvents and compatibility with other common components of such compositions) and toxicological acceptability of compounds of formula (I) highlight their particular suitability for the stated purpose and composition.

[0374] In addition, compounds of general formula (I) exhibit advantageous secondary properties.

[0375] For example, compounds of general formula (I) can provide a better sensory character due to synergistic effects with other fragrances, meaning they can provide a promoting effect on other fragrances. Therefore, they are suitable as promoters of other fragrances.

[0376] The enhancing effect refers to the enhancement and strengthening of the overall impression of a mixture in aromatic formulations. Within the peppermint range, for example, menthol is known to enhance the aroma or flavor mixture of peppermint oil, particularly in the top notes, producing a considerably stronger and more complex perception, even though the ether itself, as a pure substance, does not exhibit a strong odor at all. In fragrance applications, as a pure substance, (Methyl dihydrojasmonate) exhibits only a slight jasmine scent and acts as a scent enhancer to improve the diffusion, freshness, and volume of a fragrance composition. This enhancing effect is particularly desirable when the application requires a top note characteristic that needs to be conveyed particularly quickly and strongly, such as in deodorants, air fresheners, or in the taste zones of chewing gum.

[0377] To achieve this promoting effect, the compound of general formula (I), its stereoisomers or mixtures thereof are generally used in an amount of 0.1-20% by weight based on the total weight of the fragrance mixture, preferably in an amount of 0.5-5% by weight, and particularly in an amount of 0.6-3% by weight.

[0378] Furthermore, compounds of general formula (I), their stereoisomers, or mixtures thereof can have other positive effects on the compositions in which they are used. For example, compounds of general formula (I), their stereoisomers, or mixtures thereof can enhance the overall properties of the composition, such as stability, formulation stability, extensibility, or durability.

[0379] Therefore, another embodiment of the present invention relates to the use of a compound of general formula (I), its stereoisomers, mixtures of its stereoisomers, or mixtures of different compounds (I) as a synthetic flavoring in ready-to-use compositions.

[0380] As used herein, the term "ready-to-use composition" refers to a composition intended for direct application or use by the end user.

[0381] Generally speaking, the synthetic fragrances of the present invention, i.e., compounds of general formula (I) as defined above, can be used in ready-to-use compositions that are flavored ready-to-use compositions.

[0382] The synthetic fragrances of the present invention, namely compounds of general formula (I) as defined above, can be used in ready-to-use fragrance compositions, for example, compositions for personal care, compositions for home care, compositions for industrial applications, and compositions for other applications, such as pharmaceutical compositions or crop protection compositions.

[0383] Preferably, the ready-to-use composition is selected from fragrance compositions, body care compositions (including cosmetic compositions), oral and dental hygiene products, hygiene products, cleaning compositions (including dishwashing compositions), fabric detergent compositions, perfume dispenser compositions, food, food supplements, pharmaceutical compositions, and crop protection compositions.

[0384] In the above composition, compound (I), its stereoisomers, mixtures of its stereoisomers or their double bond isomers are used as synthetic fragrances, preferably as flavoring agents.

[0385] In particular, where R in each case 1 and R 2 It is a mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of C(=O)CH3 (see definitions below) used to impart sweet, powdery, terpene, or fruity flavors to the compositions listed above. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -C(=O)CH3 exist in a weight ratio of approximately 50:25:25.

[0386] Specifically, R 1 and R 2 It is a compound (I.1) of -C(=O)CH3 used to impart fruity, sweet, rubbery, musty, and dusty flavors to the compositions listed above.

[0387] Specifically, R 1 and R 2 The compound (I.2) of -C(=O)CH3 is used to impart fruity, woody, and sweet flavors to the compositions listed above.

[0388] Specifically, R 1 and R 2 It is a compound (I.4) of -C(=O)CH3 (see definition below) used to impart a sweet, fruity flavor to the compositions listed above.

[0389] In particular, using R in each case 1 and R2 A mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of -C(=O)CH2CH3 (as defined below) is used to impart a sweet, red berry aroma to the compositions listed above. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of C(=O)CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0390] In particular, using R in each case 1 and R 2 A mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of -CH3 (as defined below) is used to impart herbaceous, algae-like, green, aquatic, and fruity aromas to the compositions listed above. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of the -CH3 group exist in a weight ratio of approximately 50:25:25.

[0391] In particular, using R in each case 1 and R 2 A mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of -CH2CH3 (as defined below) is used to impart green, herbal, raw potato, and green banana aromas to the compositions listed above. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0392] In particular, using R in each case 1 and R 2 A mixture of isomers of compounds of formulas (I.1), (I.2), and (I.3) of -CH2CH2CH2CH3 (as defined below) is used to impart cedar, citrus, warm, and herbal fragrances to the compositions listed above. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -CH2CH2CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0393] Specifically, R 1 and R 2 The -CH2CH3 compound (I.4) (see definition below) is used to impart green, banana, and apple (ripe) aromas to the compositions listed above.

[0394] The term “about” takes into account the measurement error that may occur when determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0395] The fragrance composition may be selected from fine fragrances, air fresheners, aerosol sprays, scented cleaners, candles, and aromatic oils such as lamp oil or massage oil, in liquid, gel, or solid carrier forms.

[0396] Examples of fine fragrances include fragrance extracts, eau de parfums, eau de toilettes, colognes, solid perfumes, and extrait parfums.

[0397] Body care compositions include cosmetic compositions and may be selected from aftershave, preshave products, spray cologne, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, water-in-oil, oil-in-water and water-in-oil-in-water cosmetic emulsions, such as 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, aftershave creams and lotions, and tanning creams and lotions; powders, hydrogels, hair care products, such as hair sprays, hair gels, hair styling lotions, conditioners, shampoos, and permanent and semi-permanent hair dyes; hair styling compositions, such as cold perms, and hair smoothing compositions, hair conditioners, shampoos and lotions; deodorants and antiperspirants, such as underarm sprays, roll-ons, deodorant sticks, and deodorant creams; decorative cosmetics, such as eyeliners, eyeshadows, nail polishes, foundations, lipsticks, and eyebrow dyes.

[0398] Oral and dental hygiene products can be selected from toothpaste, dental floss, mouthwash, breath freshener, dental foam, dental gel and dental strips.

[0399] Hygiene products may include fragrances, insecticides, repellents, propellants, rust removers, scented wipes, armpit pads, baby diapers, sanitary napkins, toilet paper, cosmetic wipes, handkerchiefs, dishwashing liquids, and deodorants.

[0400] Cleaning compositions, such as solid surface cleaners, optionally flavored acidic, alkaline, and neutral cleaners, such as floor cleaners, window cleaners, bathroom and sanitary cleaners, flushing lotions, solid and liquid toilet cleaners, powder and foam carpet cleaners, dishwashing detergents for manual and machine washing, waxes and polishes such as furniture polish, floor wax, shoe polish, disinfectants, surface disinfectants and sanitary cleaners, brake cleaners, pipe cleaners, limescale cleaners, grill and oven cleaners, algae and moss removers, mold release agents, and facade cleaners.

[0401] Fabric detergent compositions may be selected from liquid detergents, powder detergents, garment pretreatment agents such as bleach, soaking agents and stain removers, fabric softeners, detergent soaps, and detergent sheets.

[0402] Food means unprocessed, cooked or processed edible substances, ice, beverages or ingredients intended for or intended to be used wholly or in part for human consumption, or chewing gum, gum, jelly and candy.

[0403] Food supplements are products intended to be ingested that contain dietary ingredients intended to add additional nutritional value to food. Dietary ingredients can be one or any combination of the following substances: vitamins, minerals, herbs or other botanical ingredients, amino acids, dietary substances used to supplement the diet by increasing dietary intake, concentrates, metabolites, components, or extracts. Food supplements can be found in many forms, such as tablets, capsules, softgels, gel capsules, liquids, or powders.

[0404] Pharmaceutical compositions include compositions intended for the diagnosis, care, relief, treatment or prevention of disease, and articles (different from food) intended to affect the structure or any function of the body of a human or other animal.

[0405] Crop protection compositions comprise compositions intended to manage plant diseases, weeds, and other pests (vertebrates and invertebrates) that harm crops and forests.

[0406] The compositions of this invention may further comprise one or more substances, such as preservatives, abrasives, anti-acne agents, agents against skin aging, antibacterial agents, weight-loss agents, anti-dandruff agents, anti-inflammatory agents, anti-irritant agents, soothing agents, antimicrobial agents, antioxidants, astringents, antiperspirants, antibacterial agents, antistatic agents, adhesives, buffers, carrier materials, chelating agents, cell stimulants, cleansers, conditioning agents, depilatory agents, surfactants, deodorants, antiperspirants, emulsifiers, enzymes, essential oils, fibers, film-forming agents, color fixatives, foam forming agents, foam stabilizers, substances for preventing foaming, foam promoters, fungicides, gelling agents, gelling agents, hair conditioning agents, hair styling agents, hair softeners, moisturizers, moisturizing substances, wetting substances, bleaching agents, strengthening agents, and detergents. Fluorescent whitening agents, impregnating agents, antifouling agents, friction reducing agents, lubricants, moisturizing creams, ointments, sunscreens, plasticizers, covering agents, polishing agents, glitter agents, polymers, powders, proteins, fatliquoring agents, exfoliating agents, siloxanes, skin soothing agents, skin cleansers, skin care agents, skin healing agents, skin brightening agents, skin protectants, skin softeners, coolants, skin coolants, warming agents, skin warming agents, stabilizers, UV absorbers, UV filters, fabric softeners, suspending agents, skin tanning agents, thickeners, vitamins, oils, waxes, fats, phospholipids, saturated fatty acids, monounsaturated or polyunsaturated fatty acids, α-hydroxy acids, polyhydroxy fatty acids, liquefying agents, dyes, color protectants, pigments, preservatives, polyols, surfactants, electrolytes, organic solvents, or siloxane derivatives.

[0407] As described above, it has been further found that compounds of general formula (I) generally exhibit pleasant and characteristic odors and can be used to prepare flavored ready-to-use compositions, and / or they can be advantageously combined with other synthetic fragrances different from compound (I) to produce new fragrance characteristics.

[0408] Therefore, specific embodiments of the present invention relate to the use of compounds of formula (I), their stereoisomers, or mixtures thereof in improving the aroma characteristics of flavored ready-to-use compositions.

[0409] The present invention further relates to synthetic fragrance compositions comprising at least one compound of formula (I) as defined above, a stereoisomer thereof or a mixture thereof, and at least one other component selected from other synthetic fragrances and non-synthetic fragrance carriers other than compound (I).

[0410] This includes synthetic fragrance compositions comprising at least one compound of formula (I) as defined above, a stereoisomer thereof or a mixture thereof, and at least one other synthetic fragrance different from compound (I).

[0411] Further comprising a synthetic fragrance composition comprising at least one compound of formula (I) as defined above, a stereoisomer thereof or a mixture thereof and at least one non-synthetic fragrance carrier.

[0412] It also includes synthetic fragrance compositions comprising at least one compound of formula (I) as defined above, a stereoisomer thereof or a mixture thereof, at least one other synthetic fragrance different from compound (I) and at least one non-synthetic fragrance carrier.

[0413] Preferably, the synthetic fragrance composition comprises at least one compound of formula (I) as defined above, a stereoisomer thereof or a mixture thereof, at least one other synthetic fragrance different from compound (I) and at least one non-synthetic fragrance carrier.

[0414] Other synthetic fragrances different from compound (I) may be, for example, one, preferably two, three, four, five, six, seven, or eight other synthetic fragrances selected from: geranium acetate (3,7-dimethyl-2,6-octadien-1-yl) ester, α-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate (Phenirat) 1 Hedione (2,6-dimethyl-7-octen-2-ol), dihydromyrcenol (preferably with a cis isomer content of greater than 60% by weight) 9 Hedione HC 9 ), 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydro-cyclopentane[g]benzopyran (Galaxolid) 3 ), tetrahydrolinalool (3,7-dimethyloctyl-3-ol), ethyllinalool, benzyl salicylate, 2-methyl-3-(4-tert-butylphenyl)propionaldehyde (Lysmeral) 2a ), cinnamyl alcohol, 4,7-bridged methylene-3a,4,5,6,7,7a-hexahydro-5-indanyl acetate and / or 4,7-bridged methylene-3a,4,5,6,7,7a-hexahydro-6-indanyl acetate (Herbaflorat 1 Citronellol, citronellol acetate, tetrahydrogeraniol, vanillin, linalool acetate, phenethyl acetate (1-phenylethyl acetate), octahydro-2,3,8,8-tetramethyl-2-naphthyl ethyl ketone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (Iso E Super) 3 ), ethyl salicylate, 4-tert-butylcyclohexyl acetate (Oryclone) 1 ), 2-tert-butylcyclohexyl acetate (Agrumex HC) 1), α-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one), n-α-methylionone, α-isomethylionone, coumarin, terpineol acetate, 2-phenylethanol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde (Lyral) 3 ), α-pentylcinnamaldehyde, ethylene brassinate, (E)- and / or (Z)-3-methylcyclopentadecano-5-enone (Muscenon) 9 ), 15-pentadecano-11-enolactone and / or 15-pentadecano-12-enolactone (Globalide) 1 ), 15-cyclopentadecanolactone (Macrolide) 1 ), 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl) ethyl ketone (Tonalid) 10 ), 2-Isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol) 9 ), 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (Sandolen) 1 ), cis-hexenyl acetate, trans-hexenyl acetate, trans-2 / cis-6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral) 1 ), 2,4,4,7-Tetramethyloct-6-en-3-one (Claritone) 1 ), 2,6-dimethyl-5-hepten-1-aldehyde (Melonal 2 ), borneol, 3-(3-isopropylphenyl)butyraldehyde (Florhydral 2 ), 2-methyl-3-(3,4-methylenedioxyphenyl)propionaldehyde (Helional) 3 ), 3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon) 1 ), 7-methyl-2H-1,5-benzodioxane -3(4H)-one (Calone), 3,3,5-trimethylcyclohexyl acetate (preferably with 70% by weight or more of the cis isomer content), and 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalene-2-ol (Ambrinol S) 1 ).

[0415] If product names are given above, then these refer to the following sources:

[0416] 1 Symrise GmbH, a German brand name;

[0417] 2a BASF SE, a German brand name;

[0418] 2 Givaudan AG, a Swiss brand name;

[0419] 3 International Flavors & Fragrances Inc., a US brand name;

[0420] 5 Danisco Seillans SA, a French brand name;

[0421] 9 Firmenich SA, a Swiss brand name;

[0422] 10 PFW Aroma Chemicals BV is the Dutch trade name.

[0423] Compounds of formula (I) as defined above, their stereoisomers, or mixtures thereof, which can be combined with, for example, to obtain the compositions of the present invention, other synthetic fragrances can be found, for example, in S. Arctander's own publication, Perfume and Flavor Chemicals, Volumes I and II, Montclair, NJ, 1969, or in K. Bauer, D. Garbe, and H. Surburg, Common Fragrance and Flavor Materials, 4th edition, Wiley-VCH, Weinheim 2001. Specifically, it may be mentioned that:

[0424] Naturally derived extracts, such as essential oils, gels, absolutes, resins, resin-like substances, fragrances, tinctures, etc.

[0425] Ambergris tincture; sandalwood oil; angelica seed oil; angelica root oil; fennel oil; valerian oil; clove basil oil; tree moss absolute oil; laurel oil; artemisia oil; benzoin resin; bergamot oil; beeswax absolute oil; birch oil; bitter almond oil; celery oil; thorn leaf oil; balsam soybean oil; juniper oil; calamus oil; camphor oil; cannam oil; cardamom oil; calamus oil; cinnamon oil; cinnamon absolute oil; castoreum absolute oil; cedar leaf oil; cedarwood oil; rock rose oil; lemongrass oil; citronella oil; basil balsam; coriander oil; costus root oil; cumin oil; cypress oil; artemisia oil; dill fruit oil; dill seed oil; oak moss absolute oil; oak moss absolute oil (Absolute); Elemi oil; Tarragon oil; Lemon eucalyptus oil; Eucalyptus oil; Fennel oil; Pine needle oil; Geffen oil; Geffen resin; Geranium oil; Grapefruit oil; Guaiac oil; Guvin balsam; Guvin balsam oil; Immortelle absolute; Immortelle oil; Ginger oil; Orris root absolute; Orris root oil; Jasmine absolute; Acorus oil; Chamomile essential oil; Roman chamomile oil; Carrot seed oil; Carrageenan oil; Pine needle oil; Spearmint oil; Coriander oil Rockrose oil; Rockrose absolute; Rockrose resin; Mixed lavender absolute; Mixed lavender oil; Lavender absolute; Lavender oil; Lemongrass oil; Angelica pubescens oil; Distilled white lemon oil; Pressed white lemon oil; Lina oil; Litsea cubeba oil; Bay leaf oil; Nutmeg oil; Marjoram oil; Orange oil; Cinnamon bark oil; Mimosa absolute; Musk seed oil; Musk tincture; Sage oil; Nutmeg oil; Myrrh absolute; Myrrh oil; Peach bark oil Clove oil; clove leaf oil; clove flower oil; neroli oil; frankincense absolute; frankincense oil; parsnip root oil; neroli absolute; orange oil; oregano oil; palmarosa oil; patchouli oil; perilla seed oil; Peruvian balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; pepper oil; chili oil; pine oil; peppermint oil; rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil Sandalwood oil; celery seed oil; lavender oil; star anise oil; styrax oil; marigold oil; fir needle oil; tea tree oil; turpentine oil; thyme oil; turmeric balsam; tonka bean absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; wine lees oil; wormwood oil; wintergreen oil; hyssop oil; civet absolute; laurel leaf oil; cinnamon oil and its fractions or components separated therefrom;

[0426] Various aromatics from the hydrocarbon group, such as 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longleafene; myrcene; ocimene; Valencia citriene; (E,Z)-1,3,5-undecanetriene; styrene; diphenylmethane;

[0427] Aliphatic alcohols, such as hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixtures of 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methylenehepten-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoct-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;

[0428] Aliphatic aldehydes and their acetals, such as hexanal; heptanal; octanal; nonanal; decanal; undecanoal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal Heptanal diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronelloloxyacetaldehyde; (E / Z)-1-(1-methoxypropoxy)-hex-3-ene; aliphatic ketones and their oximes, such as 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one;

[0429] Aliphatic sulfur-containing compounds, such as 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylhexyl acetate; 1-menthol-8-thiol;

[0430] Aliphatic nitriles, such as 2-nonenonitrile; 2-undecenonitrile; 2-tridecenonitrile; 3,12-tridecadienonitrile; 3,7-dimethyl-2,6-octadienonitrile; 3,7-dimethyl-6-octenonitrile;

[0431] Esters of aliphatic carboxylic acids, such as (E)- and (Z)-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-matrix acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate Esters; (E)- and (Z)-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylvalerate; ethyl hexanoate; allyl hexanoate; ethyl heptaate; allyl heptaate; ethyl octanoate; (E,Z)-ethyl 2,4-decadienoate; methyl 2-octanoate; methyl 2-nonanoate; allyl 2-isopentoxyacetate; methyl 3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate;

[0432] Acyclic terpenoid alcohols, such as geraniol; nerol; linalool; lavenderol; nerolidol; farnesol; tetrahydrolinalool; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloct-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octadien-3-ol; 2,6-dimethyl-2,5,7-octadien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, terpenoid esters, and 3-methyl-2-butenoates; acyclic terpenoids. Terpenoids and ketones, such as geranialdehyde; neraldehyde; citronellol; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geraniol; and dimethyl- and diethyl acetals of geranialdehyde, neraldehyde, and 7-hydroxy-3,7-dimethyloctanal; cyclic terpenoid alcohols, such as menthol; isopreneol; α-terpenoid alcohol; terpen-4-ol; menthol-8-ol; menthol-1-ol; menthol-7-ol; borneol; isoborneol; oxylinalool; noprol; cedrol; ambroxol; vetiverol; guaiacol; and their formate, acetate, propionate, isobutyrate, butyrate, isovalerate, valerate, hexanoate, crotonate, terpenoid ester and 3-methyl-2-butenoate;

[0433] Cyclic terpenoid aldehydes and ketones, such as menthone; isomenthone; 8-mercaptoisomenth-3-one; carvone; camphor; frankincense; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irisone; α-trakone; β-trakone; β-trakone; δ-trakone; γ-trakone; 1-(2,4,4-trimethyl-2-cyclohexene- 1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-bridged methylenenaphthalene-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; nocacolone; dihydronocacolone; 4,6,8-megalotrien-3-one; α-sweet orange aldehyde; β-sweet orange aldehyde; acetylated cedarwood oil (methyl cedarone);

[0434] Cyclic alcohols, such as 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isoborneolcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecanetrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0435] Alicyclic alcohols, such as α-3,3-trimethylcyclohexylethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopentan-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopentan-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopentan-1-yl)-2-buten-1-ol; 3-methyl-5- -(2,2,3-trimethyl-3-cyclopentan-1-yl)pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopentan-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopentan-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexyl-3-ol;

[0436] Cyclic and alicyclic ethers, such as eucalyptol; methyl cedarwood ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclododecane; α-epoxycedarwood; 3a,6,6,9a-tetramethyldodecanonaphthalene[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecanonaphthalene[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo-[10.1.0]tetane-4,8-diene; rose ether; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-di alkyl;

[0437] Cyclic and macrocyclic ketones, such as 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentenone; 3-methyl-5-cyclopentenone; 3-methyl Cyclopentadecanone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-amylcyclohexanone; 5-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecene-1-one; 7-cyclohexadecene-1-one; (7 / 8)-cyclohexadecene-1-one; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclohexadecone;

[0438] Alicyclic aldehydes, such as 2,4-dimethyl-3-cyclohexenaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenaldehyde; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenaldehyde;

[0439] Alicyclic ketones, such as 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecanetrienone; tert-butyl(2,4-dimethyl-3-cyclohexen-1-yl)one;

[0440] Esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; octahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; octahydro-2,5,5,8a-tetramethyl-2-acetate. - Naphthyl ester; 4,7-bridged methylene-3a,4,5,6,7,7a-hexahydro-5 or 6-indanyl acetate; 4,7-bridged methylene-3a,4,5,6,7,7a-hexahydro-5 or 6-indanyl propionate; 4,7-bridged methylene-3a,4,5,6,7,7a-hexahydro-5 or 6-indanyl isobutyrate; 4,7-bridged methylene octahydro-5 or 6-indanyl acetate;

[0441] Esters of alicyclic alcohols, such as 1-cyclohexylethyl crotonate;

[0442] Esters of alicyclic carboxylic acids, such as allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; methyl ketoacetate of cis- and trans-dihydrojasmonic acid; methyl ketoacetate of cis- and trans-jasmonic acid; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxacyclopentane-2-ethyl acetate;

[0443] Aromatic aliphatic alcohols, such as benzyl alcohol; 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;

[0444] Esters of aliphatic alcohols and aliphatic carboxylic acids, such as benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; α-trichloromethyl benzyl acetate; α,α-dimethylphenylethyl acetate; α,α-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;

[0445] Aromatic aliphatic ethers, such as 2-phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; solanal dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-diphenylacetaldehyde. Alkane; 4,4a,5,9b-tetrahydroindenyl[1,2-d]-me-di 4,4a,5,9b-Tetrahydro-2,4-dimethylindenyl[1,2-d]-me-di Britain.

[0446] Aromatic and aliphatic aldehydes, such as benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; solanal; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; meat Cinnamaldehyde; α-Butylcinnamaldehyde; α-Pentylcinnamaldehyde; α-Hexylcinnamaldehyde; 3-Methyl-5-phenylpentanal; 4-Methoxybenzaldehyde; 4-Hydroxy-3-Methoxybenzaldehyde; 4-Hydroxy-3-Ethoxybenzaldehyde; 3,4-Methylenedioxybenzaldehyde; 3,4-Dimethoxybenzaldehyde; 2-Methyl-3-(4-Methoxyphenyl)propanal; 2-Methyl-3-(4-Methylenedioxyphenyl)propanal;

[0447] Aromatic and arylita-ketones, such as acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)-acetophenone; 2-benzofuranyl-acetophenone; (3-methyl-2-benzofuranyl)acetophenone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indanyl]acetophenone; 5′,6′,7′,8′-tetrahydro-3′,5′,5′,6′,8′,8′-hexamethyl-2-naphthyl ketone;

[0448] Aromatic and aryl aliphatic carboxylic acids and their esters; for example, benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geraniyl phenylacetate; phenyl ethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenyl cinnamate; cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-hexenyl salicylate; benzyl salicylate; phenyl ethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; triethyl 3-phenylglycerol; ethyl 3-methyl-3-phenylglyceroate;

[0449] Nitrogen-containing aromatic compounds, such as 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenonitrile; 3-methyl-5-phenylpentenonitrile; methyl anthranilate; N-methyl anthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[0450] Phenols, phenyl ethers, and phenyl esters, such as artemisia argyi; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenol acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-tolyl phenylacetic acid;

[0451] Heterocyclic compounds, such as 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0452] Lactones, such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-lactone; 1,4-undecanelide; 1,4-dodecanelide; 1,5-decanelide; 1,5-dodecanelide; 4-methyl-1,4-decanelide; 1,15-pentadecanolide; cis- and trans-11-pentadecane-1,15-lactone; cis- and trans- -12-Pentadecene-1,15-lactone; 1,16-Hexadecanelactone; 9-Hexadecene-1,16-lactone; 10-oxa-1,16-hexadecanelactone; 11-oxa-1,16-hexadecanelactone; 12-oxa-1,16-hexadecanelactone; ethylene 1,12-dodecanoic acid; ethylene 1,13-tridecanoic acid; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin.

[0453] Typically, at least one non-synthetic fragrance carrier is a compound, mixture of compounds, or other additive that does not have or does not have significant sensory properties. The non-synthetic fragrance carrier is used to dilute and / or immobilize the synthetic fragrance contained in the synthetic fragrance composition, namely the compound of formula (I), and optionally one or more other synthetic fragrances different from compound (I).

[0454] Suitable carrier materials can be liquid or oily carrier materials, as well as waxy or solid carrier materials.

[0455] Suitable liquid or oily carrier materials are selected from water, alcohols such as methanol or ethanol, aliphatic diols and polyols having a melting temperature below 20°C, such as ethylene glycol, glycerol, diglycerol, propylene glycol or dipropylene glycol and 1,2-butanediol, cyclic siloxanes such as hexamethylcyclotrisiloxane or decamethylcyclopentasiloxane, diethylene glycol monoethyl ether, diethyl phthalate, isopropyl myristate, triethyl citrate, benzyl benzoate, vegetable oils such as fractionated coconut oil, or fatty alcohol esters having a melting temperature below 20°C, such as tetradecyl acetate or tetradecyl lactate, glycerides having a melting temperature below 20°C, and fatty acid alkyl esters having a melting temperature below 20°C, such as isopropyl myristate.

[0456] Suitable waxy or solid carrier materials include, for example, fatty alcohols with a melting temperature below 20°C, such as myristol, stearyl alcohol, or cetyl alcohol; polyols with a melting temperature above 20°C; esters of fatty acids and fatty alcohols with a melting temperature above 20°C, such as lanolin, beeswax, carnauba wax, candelilla wax, or Japanese wax; waxes prepared from petroleum, such as anhydrite; water-insoluble porous minerals, such as silica gel; silicates, such as talc; microporous crystalline aluminosilicates (zeolites); clay minerals, such as bentonite; or phosphates, such as sodium tripolyphosphate; paper, paperboard, wood, fabric composites made from natural and / or synthetic fibers, or nonwoven materials.

[0457] Suitable carrier materials are also selected from water-soluble polymers, such as polyacrylates or quaternized polyvinylpyrrolidone, or water- and alcohol-soluble polymers, such as special thermoplastic polyesters and polyamides. Polymer carrier materials can exist in various forms, such as gels, pastes, solid particles like microcapsules, or fragile coatings.

[0458] Preferably, the synthetic fragrance composition is selected from the ready-to-use fragrance compositions as defined above.

[0459] Generally, the total amount of at least one compound of formula (I), its stereoisomers, or mixtures thereof in the synthetic fragrance compositions of the present invention is usually suitable for a particular intended use or application, and therefore can be varied over a wide range. Typically, standard commercial amounts commonly used in perfumes are employed.

[0460] Therefore, the total amount of at least one compound of formula (I), its stereoisomer or mixture thereof in the composition is 0.001-99.9% by weight, preferably 0.01-90% by weight, more preferably 0.05-80% by weight, even more preferably 0.1-60% by weight, particularly 0.1-40% by weight, based on the total weight of the composition.

[0461] In one embodiment of the invention, the total amount of at least one compound of formula (I), its stereoisomers or mixtures thereof in the composition is 0.001-5% by weight, preferably 0.01-2% by weight, based on the total weight of the composition.

[0462] Another embodiment of the present invention relates to a composition comprising at least one compound of formula (I), a stereoisomer thereof or a mixture thereof, and at least one component selected from surfactants, modifiers and solvents.

[0463] One embodiment of the present invention relates to a composition comprising at least one compound of formula (I), a stereoisomer thereof, or a mixture thereof, and at least one solvent.

[0464] In the context of this invention, "solvent" is used to dilute compounds of formula (I) as defined above, their stereoisomers, or mixtures thereof. Some solvents also have immobilizing properties.

[0465] One or more solvents may be present in the composition at a concentration of 0.01-99% by weight based on the composition. In one embodiment of the invention, the composition comprises 0.1-90% by weight, preferably 0.5-80% by weight, of solvent based on the composition. The amount of solvent may depend on the choice of composition. In one embodiment of the invention, the composition comprises 0.05-10% by weight, preferably 0.1-5% by weight, more preferably 0.2-3% by weight based on the composition. In one embodiment of the invention, the composition comprises 20-70% by weight, preferably 25-50% by weight, of solvent based on the composition.

[0466] Preferred solvents include ethanol, dipropylene glycol (DPG), propylene glycol, 1,2-butanediol, glycerol, diethylene glycol monoethyl ether, diethyl phthalate (DEP), isopropyl myristate (IPM), triethyl citrate (TEC), and benzyl benzoate (BB).

[0467] Particularly preferred solvents are selected from ethanol, propylene glycol, dipropylene glycol, triethyl citrate, benzyl benzoate, and isopropyl myristate.

[0468] In a preferred embodiment of the present invention, the solvent is selected from ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butanediol, dipropylene glycol, triethyl citrate, and isopropyl myristate.

[0469] According to another aspect, compounds of formula (I), their stereoisomers, or mixtures thereof are suitable for use in compounds containing surfactants. Based on their characteristic fragrance properties, compounds of formula (I), their stereoisomers, or mixtures thereof are particularly suitable for adding fragrance to compositions containing surfactants, such as detergents (especially laundry detergents and multi-purpose detergents).

[0470] Therefore, one embodiment of the present invention relates to a composition comprising at least one compound of formula (I), a stereoisomer thereof or a mixture thereof and at least one surfactant.

[0471] The surfactant can be selected from anionic, nonionic, cationic, and / or amphiphilic or amphoteric surfactants. Compositions containing surfactants, such as shower gels, bubble baths, shampoos, etc., preferably contain at least one anionic surfactant.

[0472] The compositions of the present invention typically contain a surfactant in an amount of 0-40% by weight, preferably 0-20% by weight, more preferably 0.1-15% by weight, and particularly 0.1-10% by weight, based on the total weight of the composition. Typical examples of nonionic surfactants are fatty alcohol polyethylene glycol ethers, alkylphenol polyethylene glycol ethers, fatty acid polyethylene glycol esters, fatty acid amide polyethylene glycol ethers, fatty amine polyethylene glycol ethers, alkoxylated triglycerides, mixed ethers and mixed formaldehydes, optionally partially oxidized alkyl (alkenyl) oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkyl glucamides, hydrolyzed proteins (especially wheat-based plant products), polyol fatty acid esters, glycol esters, dehydrated sorbitan esters, polysorbates, and amine oxides. If the nonionic surfactants contain polyethylene glycol ether chains, they may have a conventional homologue distribution, although they preferably have a narrow range of homologue distributions.

[0473] Amphoteric surfactants are surfactants whose molecules contain at least one quaternary ammonium group and at least one –COO group. (-) Or –SO3 (-) Surfactant compounds with specific functional groups. Particularly suitable amphoteric surfactants are so-called betaines, such as N-alkyl-N,N-dimethylglycinine ammonium, such as cocoalkyldimethylglycinine ammonium, N-acylaminopropyl-N,N-dimethylglycinine ammonium, such as cocoylaminopropyldimethylglycinine ammonium, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline and cocoylaminoethylhydroxyethylcarboxymethylglycinate salts containing 8-18 carbon atoms in the alkyl or acyl groups. Fatty acid amides known by the CTFA name Cocamidopropyl Betaine are particularly preferred.

[0474] Amphoteric surfactants are also particularly suitable as co-surfactants. Amphoteric surfactants are those that remove C8-C... 18In addition to alkyl or acyl groups, the molecule contains at least one free amino group and at least one -COOH- or –SO3H- group, and is capable of forming an internal salt. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylacylaminopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid, and alkylaminoacetic acid, all containing about 8-18 carbon atoms in their alkyl groups. Particularly preferred amphoteric surfactants are N-cocoalkylaminopropionate, cocoylaminoethylaminopropionate, and acylsarcosine.

[0475] Anionic surfactants are characterized by water-soluble anionic groups, such as carboxylic acid esters, sulfate esters, sulfonates, or phosphate esters, and lipophilic groups. A large number of skin-safe anionic surfactants are known to practitioners from relevant textbooks and are commercially available. These are particularly alkyl sulfates, alkyl ether sulfates, alkyl ether carboxylates, acyl thiocyanates, acyl sarcosinates, and those containing linear C4 groups, in the form of alkali metal, ammonium, or alkanol ammonium salts. 12 -C 18 Alkyl or acyl taurine, and sulfosuccinate and acyl glutamate in alkali metal or ammonium salt form.

[0476] Particularly suitable cationic surfactants are quaternary ammonium compounds, preferably ammonium halides, and especially chlorides and bromides, such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, and trialkylmethylammonium chloride, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride. Additionally, readily biodegradable quaternary ester compounds, such as dialkylammonium methyl sulfate and methylhydroxyalkyldialkyloxyalkylammonium methyl sulfate sold under the name Stepantexe, are also suitable. The corresponding products in this series can be used as cationic surfactants. "Esterquats" should generally be understood as quaternized triethanolamine esters of fatty acids. They can provide a specific softness to compositions. They are known substances prepared by relevant organic chemical methods. Other cationic surfactants suitable for use according to the invention are quaternized hydrolyzed proteins.

[0477] One embodiment of the present invention relates to a composition comprising at least one compound of formula (I), a stereoisomer thereof, or a mixture thereof, and at least one oil component.

[0478] The oil component is typically present in total amounts of 0.1-80, preferably 0.5-70, more preferably 1-60, even more preferably 1-50% by weight, particularly 1-40% by weight, more particularly 5-25% by weight, especially 5-15% by weight, based on the composition.

[0479] The oil component may be selected, for example, from guerbert alcohols based on fatty alcohols containing 6-18, preferably 8-10 carbon atoms, and other esters, such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl benzyl ester, myristyl erucic acid, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl benzyl ester, cetyl erucic acid, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl benzyl ester, stearyl erucic acid, isostearyl myristate. Esters, isostearyl palmitate, isostearyl stearate, isostearyl isostearyl oleate, isostearyl benzyl ester, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearyl oleate, oleyl benzyl ester, oleyl erucic acid ester, benzyl myristate, benzyl palmitate, benzyl stearate, benzyl isostearyl oleate, benzyl benzyl ester, benzyl benzyl ester, benzyl erucic acid ester, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearyl oleate, oleyl benzyl ester, and oleyl erucic acid ester; suitable also includes C. 18 -C 38 Alkyl-hydroxycarboxylic acids and linear or branched C6-C 22 Esters of fatty alcohols, especially dioctyl malate, are esters of linear and / or branched fatty acids with polyols (e.g., propylene glycol, glycol, or trimerol), based on C6-C. 10 fatty acid triglycerides, based on C6-C 18 A liquid mixture of mono-, di-, and triglycerides of fatty acids, C6-C 22 Esters of fatty alcohols and / or guerbert alcohols with aromatic carboxylic acids, especially benzoic acid; esters of dicarboxylic acids with polyols containing 2-10 carbon atoms and 2-6 hydroxyl groups; vegetable oils; branched primary alcohols; substituted cyclohexanes; and linear and branched C6-C alcohols. 22 Fatty alcohol carbonates, such as dioctyl carbonate (Cetiol@CC), are based on guerbert carbonates of fatty alcohols containing 6-18, preferably 8-10 carbon atoms, with benzoic acid and linear and / or branched C6-C... 22 Esters of alcohols (e.g.) TN), linear or branched, symmetrical or asymmetrical dialkyl ethers, each containing 6-22 carbon atoms, such as dioctyl ether (TN). OE), epoxidized fatty acid esters with ring-opening products of polyols and hydrocarbons, or mixtures thereof.

[0480] Preparation method:

[0481] Another embodiment of the present invention relates to a method for preparing a flavored ready-to-use composition, comprising incorporating at least one compound of formula (I) as defined above, a stereoisomer thereof, or a mixture thereof into the ready-to-use composition.

[0482] The method includes incorporating at least one compound of formula (I), its stereoisomers, or mixtures thereof into a ready-to-use composition that has no or insignificant sensory properties to provide the ready-to-use composition with a distinctive odor and / or aroma. Additionally, the method includes improving the odor and / or aroma of a ready-to-use composition that already possesses significant sensory properties by incorporating at least one compound of formula (I), its stereoisomers, or mixtures thereof into the ready-to-use composition.

[0483] The preferred ready-to-use compositions are those described above.

[0484] The total amount of at least one compound of formula (I), its stereoisomers, or mixtures thereof incorporated into a ready-to-use composition is highly dependent on the intended use or application and can therefore vary over a wide range. Typical amounts of at least one compound of formula (I), its stereoisomers, or mixtures thereof incorporated into a ready-to-use composition are those as defined above with respect to the composition.

[0485] The compounds of formula (I) used according to the present invention, their stereoisomers or mixtures thereof, compositions obtainable by the methods of the present invention described above, and synthetic fragrance compositions of the present invention comprising them may also be in microencapsulated form, spray-dried form, inclusion complex form, or extruded product form. Performance can be further optimized by so-called “coating” with a suitable material for more targeted release of fragrance, for which waxy synthetic substances, such as polyvinyl alcohol, are preferred.

[0486] Microencapsulation can be carried out, for example, by a so-called coagulation method using capsule materials made of, for example, polyurethane-based substances or soft gelatin. Spray-dried aromatic oils can be prepared, for example, by spray-drying an emulsion or dispersion containing a compound of formula (I), its stereoisomers, or mixtures thereof, wherein the carrier material may be modified starch, protein, cyclodextrin, or plant gum. Inclusion compounds can be prepared, for example, by introducing an aromatic composition and a dispersion of cyclodextrin or urea derivatives into a suitable solvent such as water. Compounds of formula (I), its stereoisomers, or mixtures thereof can be prepared by melting with a suitable waxy substance and then curing, optionally extruding in a suitable solvent such as isopropanol.

[0487] Another embodiment of the present invention relates to a method for preparing a synthetic fragrance composition, particularly a flavored composition, especially a flavored ready-to-use composition, comprising incorporating at least one compound of general formula (I), a stereoisomer thereof, or a mixture thereof into the synthetic fragrance composition, particularly a flavored composition, especially a flavored ready-to-use composition.

[0488] For example, the method can be carried out by mixing at least one compound of formula (I) as defined above, its stereoisomers or mixtures thereof, and at least one other compound selected from other synthetic fragrances and non-synthetic fragrance carriers different from compound (I).

[0489] The present invention also relates to a method for improving the aroma characteristics of synthetic fragrance compositions, particularly flavored compositions, especially flavored ready-to-use compositions, comprising incorporating at least one compound of general formula (I), its stereoisomers or mixtures thereof into the synthetic fragrance composition, particularly flavored compositions, especially flavored ready-to-use compositions.

[0490] In particular, the present invention relates to a method for preparing fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food, food supplements, pharmaceutical compositions, or crop protection compositions, comprising incorporating one or more compounds of general formula (I) as defined above, their stereoisomers, or mixtures thereof into the fragrance composition, body care composition, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food, food supplements, pharmaceutical compositions, or crop protection compositions.

[0491] In one embodiment, the present invention relates to a method of imparting a sweet, powdery, terpene-flavored, or fruity aroma to a fragrance composition, body care composition, oral and dental hygiene product, hygiene product, cleaning composition, fabric detergent composition, perfume dispenser composition, food, food supplement, pharmaceutical composition, or crop protection composition, comprising, in each case, R 1 and R 2 Compounds of type -C(=O)CH3 (I.1), (I.2), and (I.3) are incorporated into fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food products, food supplements, pharmaceutical compositions, or crop protection compositions. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -C(=O)CH3 exist in a weight ratio of approximately 50:25:25.

[0492] In another embodiment, the present invention relates to a method of imparting a fruity, sweet, rubbery, musty, or dusty flavoring to a fragrance composition, body care composition, oral and dental hygiene product, hygiene product, cleaning composition, fabric detergent composition, perfume dispenser composition, food, food supplement, pharmaceutical composition, or crop protection composition, comprising, in each case, R 1 and R 2 It is a compound of -C(=O)CH3 (I.1) incorporated into fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food, food supplements, pharmaceutical compositions or crop protection compositions.

[0493] In another embodiment, the present invention relates to a method of imparting a fruity, woody, or sweet flavoring to a fragrance composition, body care composition, oral and dental hygiene product, hygiene product, cleaning composition, fabric detergent composition, perfume dispenser composition, food, food supplement, pharmaceutical composition, or crop protection composition, comprising, in each case, R 1 and R 2 It is a compound of -C(=O)CH3 (I.2) incorporated into fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food, food supplements, pharmaceutical compositions or crop protection compositions.

[0494] In another embodiment, the present invention relates to a method of imparting a sweet or fruity flavoring to a fragrance composition, body care composition, oral and dental hygiene product, hygiene product, cleaning composition, fabric detergent composition, perfume dispenser composition, food, food supplement, pharmaceutical composition, or crop protection composition, comprising, in each case, R 1 and R 2 It is a compound of -C(=O)CH3 (I.4) incorporated into fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food, food supplements, pharmaceutical compositions or crop protection compositions.

[0495] In another embodiment, the present invention relates to a method of imparting a sweet, red berry aroma to a fragrance composition, body care composition, oral and dental hygiene product, hygiene product, cleaning composition, fabric detergent composition, perfume dispenser composition, food, food supplement, pharmaceutical composition, or crop protection composition, comprising, in each case, R 1 and R2 Compounds of type -C(=O)CH2CH3 (I.1), (I.2), and (I.3) are incorporated into fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food products, food supplements, pharmaceutical compositions, or crop protection compositions. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -C(=O)CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0496] In another embodiment, the present invention relates to a method of imparting herbal, algae-based, green, aquatic, or fruity fragrances to fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food products, food supplements, pharmaceutical compositions, or crop protection compositions, comprising, in each case, R 1 and R 2 Compounds (I.1), (I.2), and (I.3) of the -CH3 group are incorporated into fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food products, food supplements, pharmaceutical compositions, or crop protection compositions. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of the -CH3 group exist in a weight ratio of approximately 50:25:25.

[0497] In another embodiment, the present invention relates to a method of imparting a green, herbal, raw potato, or green banana fragrance to a fragrance composition, body care composition, oral and dental hygiene product, hygiene product, cleaning composition, fabric detergent composition, perfume dispenser composition, food, food supplement, pharmaceutical composition, or crop protection composition, comprising, in each case, R 1 and R 2 Compounds of type -CH2CH3 (I.1), (I.2), and (I.3) are incorporated into fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food products, food supplements, pharmaceutical compositions, or crop protection compositions. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0498] In another embodiment, the present invention relates to a method of imparting cedar, citrus, mild, herbal fragrance notes to a fragrance composition, body care composition, oral and dental hygiene product, hygiene product, cleaning composition, fabric detergent composition, perfume dispenser composition, food, food supplement, pharmaceutical composition, or crop protection composition, comprising, in each case, R 1 and R 2 Compounds of type -CH2CH2CH2CH3 (I.1), (I.2), and (I.3) are incorporated into fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food products, food supplements, pharmaceutical compositions, or crop protection compositions. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -CH2CH2CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0499] In another embodiment, the present invention relates to a method of imparting a green, banana, or apple (ripe) fragrance to a fragrance composition, body care composition, oral and dental hygiene product, hygiene product, cleaning composition, fabric detergent composition, perfume dispenser composition, food, food supplement, pharmaceutical composition, or crop protection composition, comprising, in each case, R 1 and R 2 Compounds of type -CH2CH3 (I.1), (I.2), and (I.3) are incorporated into fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food products, food supplements, pharmaceutical compositions, or crop protection compositions. Specifically, in this mixture, wherein in each case R 1 and R 2 The compounds (I.1), (I.2) and (I.3) of -CH2CH3 exist in a weight ratio of approximately 50:25:25.

[0500] The term “about” takes into account the measurement error that may occur when determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0501] As stated above, some compounds (I) and specific mixtures are novel. Therefore, the present invention also relates to compounds of general formula (I), their stereoisomers, mixtures of their stereoisomers, or mixtures of different compounds of general formula (I):

[0502]

[0503] in:

[0504] Described as One of the keys is a single key, and the other is either a double key or a single key.

[0505] R 1 It is hydrogen, C1-C4 alkyl or -(C=O)-R 3 ,

[0506] R 2 It is hydrogen, C1-C4 alkyl or -(C=O)-R 4 ,

[0507] R 3 It is hydrogen or C1-C4 alkyl, and

[0508] R 4 It is hydrogen or C1-C4 alkyl.

[0509] The condition is if R 1 If it is hydrogen, then R 2 Not hydrogen,

[0510] Exclude the following compounds and mixtures:

[0511] 5-(5-acetoxy-3-methylene-pentyl)acetate,

[0512] -[(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0513] -[(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0514] 5-(5-acetoxy-3-methyl-pentyl)acetate,

[0515] -[(E)-5-formyloxy-3-methyl-pent-3-enyl]carbamate,

[0516] -[(Z)-5-formyloxy-3-methyl-pent-3-enyl]carbamate,

[0517] -(3-methyl-5-propionyloxy-pentyl)propionate,

[0518] -[5-(2,2-dimethylpropionyloxy)-3-methyl-pentyl]2,2-dimethylpropionate,

[0519] -1,5-Dimethoxy-3-methylene-pentane,

[0520] -(E)-1,5-dimethoxy-3-methyl-pent-2-ene,

[0521] -(Z)-1,5-Dimethoxy-3-methyl-pent-2-ene,

[0522] -1,5-Dimethoxy-3-methyl-pentane,

[0523] -(Z)-1,5-diethoxy-3-methyl-pent-2-ene,

[0524] -1,5-Diethoxy-3-methyl-pentane,

[0525] -(E)-1,5-diisopropoxy-3-methyl-pent-2-ene,

[0526] -(Z)-1,5-Diisopropoxy-3-methyl-pent-2-ene,

[0527] -1,5-Dibutoxy-3-methylene-pentane,

[0528] -(E)-1,5-Dibutoxy-3-methyl-pent-2-ene,

[0529] -(Z)-1,5-Dibutoxy-3-methyl-pent-2-ene,

[0530] -5-Isopropoxy-3-methyl-1-pentanol,

[0531] -5-sec-butoxy-3-methyl-1-pentanol,

[0532] -1-Acetoxy-5-isopropoxy-3-methyl-2-pentene,

[0533] -(5-hydroxy-3-methyl-pentyl)3-methylbutyrate,

[0534] -[3-methyl-5-(3-methylbutyryloxy)pentyl]3-methylbutyrate,

[0535] 5-hydroxy-3-methylene-pentyl)acetic acid ester,

[0536] -[(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0537] -[(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0538] 5-(5-hydroxy-3-methyl-pentyl)carbamate,

[0539] A mixture of [(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate and [(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0540] A mixture of -[(E)-3-methyl-5-propionyloxy-pent-3-enyl]propionate and [(Z)-3-methyl-5-propionyloxy-pent-3-enyl]propionate,

[0541] A mixture of (E)-1,5-dimethoxy-3-methyl-pent-2-ene and (Z)-1,5-dimethoxy-3-methyl-pent-2-ene.

[0542] A mixture of (E)-1,5-diethoxy-3-methyl-pent-2-ene and (Z)-1,5-diethoxy-3-methyl-pent-2-ene,

[0543] A mixture of (E)-3-methyl-1,5-dipropoxy-pent-2-ene and (Z)-3-methyl-1,5-dipropoxy-pent-2-ene.

[0544] A mixture of (E)-1,5-dibutoxy-3-methyl-pent-2-ene and (Z)-1,5-dibutoxy-3-methyl-pent-2-ene, and

[0545] A mixture of (5-hydroxy-3-methylene-pentyl)acetate, [(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate and [(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate.

[0546] Preferably, in compound (I), R 1 and R 2 Neither of them are hydrogen.

[0547] More preferably, in compound (I), R 1 and R 2 They are all the same and are all C1-C4 alkyl, or R 1 -(C=O)-R 3 And R 2 -(C=O)-R 4 , where R 3 and R 4 They are identical and are hydrogen or C1-C4 alkyl, preferably hydrogen, methyl or ethyl.

[0548] Another embodiment of the invention relates to a compound of general formula (Ia), its stereoisomers, or mixtures of stereoisomers thereof, or mixtures of different compounds (Ia):

[0549]

[0550] in:

[0551] Described as One of the keys is a single key, and the other is either a double key or a single key, where R 1a and R2a It has one of the meanings defined above;

[0552] Exclude the following compounds and mixtures:

[0553] -1,5-Dimethoxy-3-methylene-pentane,

[0554] -(E)-1,5-dimethoxy-3-methyl-pent-2-ene,

[0555] -(Z)-1,5-Dimethoxy-3-methyl-pent-2-ene,

[0556] -1,5-Dimethoxy-3-methyl-pentane,

[0557] -(Z)-1,5-diethoxy-3-methyl-pent-2-ene,

[0558] -1,5-Diethoxy-3-methyl-pentane,

[0559] -(E)-1,5-diisopropoxy-3-methyl-pent-2-ene,

[0560] -(Z)-1,5-Diisopropoxy-3-methyl-pent-2-ene,

[0561] -1,5-Dibutoxy-3-methylene-pentane,

[0562] -(E)-1,5-Dibutoxy-3-methyl-pent-2-ene,

[0563] -(Z)-1,5-Dibutoxy-3-methyl-pent-2-ene,

[0564] -5-Isopropoxy-3-methyl-1-pentanol,

[0565] -5-sec-butoxy-3-methyl-1-pentanol,

[0566] -1-Acetoxy-5-isopropoxy-3-methyl-2-pentene,

[0567] -(5-hydroxy-3-methyl-pentyl)3-methylbutyrate,

[0568] 5-hydroxy-3-methylene-pentyl)acetic acid ester,

[0569] -[(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0570] -[(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0571] 5-(5-hydroxy-3-methyl-pentyl)carbamate,

[0572] A mixture of (E)-1,5-dimethoxy-3-methyl-pent-2-ene and (Z)-1,5-dimethoxy-3-methyl-pent-2-ene.

[0573] A mixture of (E)-1,5-diethoxy-3-methyl-pent-2-ene and (Z)-1,5-diethoxy-3-methyl-pent-2-ene,

[0574] A mixture of (E)-3-methyl-1,5-dipropoxy-pent-2-ene and (Z)-3-methyl-1,5-dipropoxy-pent-2-ene.

[0575] A mixture of (E)-1,5-dibutoxy-3-methyl-pent-2-ene and (Z)-1,5-dibutoxy-3-methyl-pent-2-ene, and

[0576] A mixture of (5-hydroxy-3-methylene-pentyl)acetate, [(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate and [(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate.

[0577] Preferably, in compound (Ia), R 1 and R 2 Neither of them are hydrogen.

[0578] Preferred embodiments of the present invention relate to diether compounds of general formula (Ia), i.e., compounds of general formula (Ia), wherein R 1a and R 2a They are independently selected from C1-C4 alkyl groups.

[0579] Further preferred are diether compounds of general formula (Ia), wherein the group R 1a and R 2a They are the same.

[0580] More preferably, compounds of general formula (Ia) are used, wherein the group R 1a and R 2a It is the same and is selected from methyl, ethyl, n-propyl, isopropyl and n-butyl.

[0581] Even more preferred are compounds of general formula (Ia), wherein the group R 1a and R 2a They are the same and are selected from methyl and ethyl.

[0582] The particularly preferred compound (Ia) is:

[0583] -1,5-Diethoxy-3-methylene-pentane,

[0584] -(E)-1,5-diethoxy-3-methyl-pent-2-ene,

[0585] 3-Methyl-1,5-di-n-propoxy-pentane,

[0586] -3-Methylene-1,5-di-n-propoxy-pentane,

[0587] -(E)-3-methyl-1,5-di-n-propoxy-pent-2-ene,

[0588] -(Z)-3-methyl-1,5-di-n-propoxy-pent-2-ene,

[0589] -1,5-Diisopropoxy-3-methyl-pentane,

[0590] -1,5-Diisopropoxy-3-methylene-pentane

[0591] -1,5-Dibutoxy-3-methyl-pentane,

[0592] -1,5-Di-tert-butoxy-3-methyl-pentane,

[0593] -1,5-Di-tert-butoxy-3-methylene-pentane

[0594] -(E)-1,5-Di-tert-butoxy-3-methyl-pent-2-ene,

[0595] -(Z)-1,5-Di-tert-butoxy-3-methyl-pent-2-ene.

[0596] The general formula compound (Ia) may exist as a mixture of at least two corresponding exo, E, Z or sat derivatives, such as a mixture of exo / E / Z isomers or a mixture of exo / E / Z / sat, or may exist essentially as their exo isomers, their E isomers, their Z isomers or their sat derivatives, respectively.

[0597] For the descriptions of “exo / E / Z isomer mixtures,” “exo / E / Z / sat mixtures,” and “basically existent,” refer to the description of compounds of general formula (I) above.

[0598] Preferably, the compound of general formula (Ia) exists in the form of an exo / E / Z mixture, which may also contain the corresponding saturated derivative (thus obtaining an exo / E / Z / sat mixture). An exo / E / Z isomer mixture is preferred.

[0599] Compounds of general formula (Ia) can be prepared according to the description of compounds of general formula (I).

[0600] Another embodiment of the invention relates to a compound of general formula (Ib), its stereoisomers, or mixtures of stereoisomers thereof, or mixtures of different compounds (Ib):

[0601]

[0602] in:

[0603] Described as One of the keys is a single key, and the other is either a double key or a single key, where R 1b and R 2b It has one of the meanings defined above;

[0604] Exclude the following compounds and mixtures:

[0605] 5-(5-acetoxy-3-methylene-pentyl)acetate,

[0606] -[(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0607] -[(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0608] 5-(5-acetoxy-3-methyl-pentyl)acetate,

[0609] -[(E)-5-formyloxy-3-methyl-pent-3-enyl]carbamate,

[0610] -[(Z)-5-formyloxy-3-methyl-pent-3-enyl]carbamate,

[0611] -(3-methyl-5-propionyloxy-pentyl)propionate,

[0612] -[5-(2,2-dimethylpropionyloxy)-3-methyl-pentyl]2,2-dimethylpropionate,

[0613] -(5-hydroxy-3-methyl-pentyl)3-methylbutyrate,

[0614] -[3-methyl-5-(3-methylbutyryloxy)pentyl]3-methylbutyrate,

[0615] 5-hydroxy-3-methylene-pentyl)acetic acid ester,

[0616] -[(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0617] -[(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate,

[0618] 5-(5-hydroxy-3-methyl-pentyl)carbamate,

[0619] A mixture of [(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate and [(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate,

[0620] A mixture of -[(E)-3-methyl-5-propionyloxy-pent-3-enyl]propionate and [(Z)-3-methyl-5-propionyloxy-pent-3-enyl]propionate, and

[0621] A mixture of (5-hydroxy-3-methylene-pentyl)acetate, [(E)-5-hydroxy-3-methyl-pent-2-enyl]acetate and [(Z)-5-hydroxy-3-methyl-pent-2-enyl]acetate.

[0622] Preferably, in compound (Ib), R 1 and R 2 Neither of them are hydrogen.

[0623] Preferred embodiments of the present invention relate to diester compounds of general formula (Ib), i.e., compounds of general formula (Ib), wherein R 2b -(C=O)-R 4 .

[0624] Further preferred are compounds of general formula (Ib), wherein R 3 and R 4 It is selected from hydrogen and C1-C3 alkyl groups, and particularly from hydrogen, methyl and ethyl.

[0625] More preferably, in compound (Ib), R 1 and R 2 Same, i.e., R 1 -(C=O)-R 3 And R 2 -(C=O)-R 4 , where R 3 and R 4 The same and selected from hydrogen or C1-C4 alkyl, preferably hydrogen, methyl or ethyl.

[0626] Examples of preferred compounds of general formula (Ib) are:

[0627] -(5-formyloxy-3-methylene-pentyl)carbamate,

[0628] -(5-formyloxy-3-methyl-pentyl)carbamate,

[0629] -(3-methylene-5-propionyloxy-pentyl)propionate,

[0630] -[(E)-3-methyl-5-propionyloxy-pent-3-enyl]propionate,

[0631] -[(Z)-3-methyl-5-propionyloxy-pent-3-enyl]propionate,

[0632] -[5-(2,2-dimethylpropionyloxy)-3-methylene-pentyl]2,2-dimethylpropionate,

[0633] -[(E)-5-(2,2-dimethylpropionyloxy)-3-methyl-pent-3-enyl]2,2-dimethylpropionate,

[0634] -[(Z)-5-(2,2-dimethylpropionoxy)-3-methyl-pent-3-enyl]2,2-dimethylpropionate.

[0635] The general formula compound (Ib) may exist as a mixture of at least two corresponding exo, E, Z or sat derivatives, such as a mixture of exo / E / Z isomers or a mixture of exo / E / Z / sat, or may exist essentially as their exo isomers, their E isomers, their Z isomers or their sat isomers, respectively.

[0636] For the expressions “exo / E / Z isomer mixture”, “exo / E / Z / sat isomer mixture”, and “basically existent”, refer to the description of compounds of general formula (I) above.

[0637] Preferably, the compound of general formula (Ib) exists in the form of an exo / E / Z mixture, which may also contain the corresponding saturated derivative (thus obtaining an exo / E / Z / sat mixture). An exo / E / Z isomer mixture is preferred.

[0638] Compounds of general formula (Ib) can be prepared according to the description of ester compounds of general formula (I).

[0639] Another preferred embodiment of the invention is a mixture of compounds selected from at least two of the formulas (I.1), (I.2), (I.3), and (I.4):

[0640]

[0641] Where R 1 and R 2 It has one of the meanings defined in the context.

[0642] The mixture contains each compound in an amount of 1-99% by weight, provided that the sum of the weights of compounds of formulas (I.1), (I.2), (I.3) and (I.4) is 100%.

[0643] Another embodiment is a composition comprising a mixture of at least two compounds selected from those of formulas (I.1), (I.2), (I.3), and (I.4). This composition may, on the one hand, consist of said mixture and contain no other components (and is therefore a mixture). On the other hand, the composition may contain other components, such as small amounts of byproducts from the production process. If such byproducts are present, their amount relative to the total weight of the compounds of formulas (I.1), (I.2), (I.3), and (I.4) and all byproducts is at most 10% by weight, preferably at most 5% by weight, more preferably at most 2% by weight, and particularly at most 1% by weight.

[0644] In a preferred embodiment, the present invention relates to a mixture of at least two compounds selected from compounds of formula (I.1), (I.2) and (I.3), comprising each compound in an amount of 1-99% by weight, provided that the total weight of the compounds of formula (I.1), (I.2) and (I.3) in the mixture is 100%.

[0645] Another preferred embodiment involves a composition comprising such a mixture.

[0646] In certain embodiments, the compositions and mixtures contain either a compound of formula (I.1) or a compound of formulas (I.2) and (I.3), or both of formulas (I.2) and (I.3); in particular, they contain all three compounds (I.1), (I.2) and (I.3).

[0647] More preferably, the mixture comprises all three compounds of formula (I.1), (I.2), and (I.3) in an amount of 1-99% by weight, provided that the total weight of the compounds of formula (I.1), (I.2), and (I.3) in the mixture is 100%, wherein the ratio of (I.1):(I.2):(I.3) is 90:5:5-10:45:45, preferably 80:10:10-20:40:40, especially 55:22.5:22.5-45:27.5:27.5, and even more especially about 50:25:25. The term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0648] Another preferred embodiment involves a composition comprising such a mixture.

[0649] In a particular embodiment, in a composition or mixture comprising at least two compounds selected from formulas (I.1), (I.2), and (I.3), R 1 and R 2 It is a C1-C4 alkyl group.

[0650] In another specific embodiment, in a composition or mixture comprising at least two compounds selected from formulas (I.1), (I.2), and (I.3), R 1 -(C=O)-R 3 R 2 -(C=O)-R 4 And R 3 and R 4 It is a C1-C4 alkyl group.

[0651] Particularly preferably, in all compounds of formulas (I.1), (I.2), and (I.3) present in the mixtures or compositions of the present invention, all groups R 1 and R 2 They are the same.

[0652] A preferred embodiment of the present invention relates to a composition or mixture comprising at least two compounds (I) selected from formulas (I.1), (I.2), and (I.3), wherein

[0653] -(I.1) is present in an amount of 0-75% by weight, preferably 10-75% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0654] -(I.2) is present in an amount of 0-50% by weight, preferably 5-45% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0655] -(I.3) is present in an amount of 0-50% by weight, preferably 0-45% by weight, based on the total weight of (I.1), (I.2) and (I.3), provided that at least two of compounds (I.1), (I.2) and (I.3) are present in an amount of >0% by weight based on the total weight of (I.1), (I.2) and (I.3), and the total weight of compounds (I.1), (I.2) and (I.3) present in the mixture is 100%.

[0656] A more preferred embodiment of the invention relates to a composition or mixture comprising all three compounds of formulas (I.1), (I.2), and (I.3), wherein

[0657] -(I.1) is present in an amount of 25-75% by weight, preferably 30-60% by weight, and especially 35-55% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0658] -(I.2) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0659] -(I.3) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0660] The condition is that the total weight of compounds (I.1), (I.2), and (I.3) is 100%.

[0661] Specific embodiments involve compositions or mixtures comprising all three compounds of general formulas (I.1), (I.2), and (I.3), comprising each compound in an amount of 1-99% by weight, provided that the total weight of compounds of formulas (I.1), (I.2), and (I.3) is 100%, wherein the ratio of (I.1):(I.2):(I.3) is 90:5:5-10:45:45, preferably 80:10:10-20:40:40, especially 55:22.5:22.5-45:27.5:27.5, and more especially about 50:25:25. The term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0662] Preferred embodiments of the present invention relate to compositions or mixtures comprising at least two ether compounds (Ia) selected from formulas (I.1), (I.2), and (I.3), wherein R 1 and R 2 As defined in the first embodiment above relating to ether compounds, wherein

[0663] -(I.1) is present in an amount of 0-75% by weight, preferably 10-75% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0664] -(I.2) is present in an amount of 0-50% by weight, preferably 5-45% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0665] -(I.3) is present in an amount of 0-50% by weight, preferably 0-45% by weight, based on the total weight of (I.1), (I.2) and (I.3), provided that at least two of compounds (I.1), (I.2) and (I.3) are present in an amount of >0% by weight based on the total weight of (I.1), (I.2) and (I.3), and the total weight of compounds (I.1), (I.2) and (I.3) present in the mixture is 100%.

[0666] A more preferred embodiment of the invention relates to a composition or mixture comprising all three ether compounds selected from formulas (I.1), (I.2), and (I.3), wherein R 1 and R 2As defined in the second embodiment above involving ester compounds, wherein

[0667] -(I.1) is present in an amount of 25-75% by weight, preferably 30-60% by weight, and especially 35-55% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0668] -(I.2) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0669] -(I.3) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0670] The condition is that the total weight of compounds (I.1), (I.2), and (I.3) is 100%.

[0671] Specific embodiments involve compositions or mixtures comprising all three general formulas (I.1), (I.2), and (I.3) ether compounds, comprising each compound in an amount of 1-99% by weight, provided that the total weight of the compounds of formulas (I.1), (I.2), and (I.3) is 100%, wherein the ratio of (I.1):(I.2):(I.3) is 90:5:5-10:45:45, preferably 80:10:10-20:40:40, especially 55:22.5:22.5-45:27.5:27.5, and more especially about 50:25:25. The term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0672] Preferred embodiments of the present invention relate to compositions or mixtures comprising at least two ester compounds (Ib) selected from formulas (I.1), (I.2), and (I.3), wherein R 1 and R 2 As defined in the second embodiment above involving ester compounds, wherein

[0673] -(I.1) is present in an amount of 0-75% by weight, preferably 10-75% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0674] -(I.2) is present in an amount of 0-50% by weight, preferably 5-45% by weight, based on the total weight of (I.1), (I.2) and (I.3).

[0675] -(I.3) is present in an amount of 0-50% by weight, preferably 0-45% by weight, based on the total weight of (I.1), (I.2) and (I.3), provided that at least two of compounds (I.1), (I.2) and (I.3) are present in an amount of >0% by weight based on the total weight of (I.1), (I.2) and (I.3), and the total weight of compounds (I.1), (I.2) and (I.3) present in the mixture is 100%.

[0676] A more preferred embodiment of the invention relates to a composition or mixture comprising all three ester compounds selected from formulas (I.1), (I.2), and (I.3), wherein R 1 and R 2 As defined in the second embodiment above involving ester compounds, wherein

[0677] -(I.1) is present in an amount of 25-75% by weight, preferably 30-60% by weight, and especially 35-55% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0678] -(I.2) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0679] -(I.3) is present in an amount of 15-35% by weight, preferably 18-30% by weight, and especially 20-28% by weight, based on the total weight of (I.1), (I.2), and (I.3).

[0680] The condition is that the total weight of compounds (I.1), (I.2), and (I.3) is 100%.

[0681] Another specific embodiment relates to a composition or mixture comprising all three general formulas (I.1), (I.2), and (I.3) ester compounds, comprising each compound in an amount of 1-99% by weight, provided that the total weight of the compounds of formulas (I.1), (I.2), and (I.3) is 100%, wherein the molar ratio of (I.1):(I.2):(I.3) is 90:5:5-10:45:45, preferably 80:10:10-20:40:40, especially 55:22.5:22.5-45:27.5:27.5, and more especially about 50:25:25. The term "about" takes into account measurement errors that may occur in determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0682] Specifically, the mixtures of the present invention are selected from the following mixtures:

[0683] A mixture of (5-formyloxy-3-methylene-pentyl)carbamate, [(E)-5-formyloxy-3-methyl-pent-3-enyl]carbamate and [(Z)-5-formyloxy-3-methyl-pent-3-enyl]carbamate;

[0684] A mixture of (5-acetoxy-3-methylene-pentyl)acetate, [(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate and [(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate;

[0685] A mixture of -(3-methylene-5-propionyloxy-pentyl)propionate, [(E)-3-methyl-5-propionyloxy-pent-3-enyl]propionate and [(Z)-3-methyl-5-propionyloxy-pent-3-enyl]propionate;

[0686] A mixture of (E)-1,5-dimethoxy-3-methylene-pentane, (E)-1,5-dimethoxy-3-methyl-pent-2-ene and (Z)-1,5-dimethoxy-3-methyl-pent-2-ene;

[0687] A mixture of -1,5-diethoxy-3-methylene-pentane, (E)-1,5-diethoxy-3-methyl-pent-2-ene and (Z)-1,5-diethoxy-3-methyl-pent-2-ene, and

[0688] A mixture of -1,5-di-n-butoxy-3-methylene-pentane, (E)-1,5-di-n-butoxy-3-methyl-pent-2-ene and (Z)-1,5-di-n-butoxy-3-methyl-pent-2-ene.

[0689] Specifically, the compositions of the present invention comprise one of the specific mixtures described above.

[0690] More specifically, the mixtures of the present invention are selected from the following mixtures:

[0691] - A mixture of (5-formyloxy-3-methylene-pentyl)carbamate, [(E)-5-formyloxy-3-methyl-pent-3-enyl]carbamate and [(Z)-5-formyloxy-3-methyl-pent-3-enyl]carbamate in a weight ratio of about 50:25:25;

[0692] - A mixture of (5-acetoxy-3-methylene-pentyl) acetate, [(E)-5-acetoxy-3-methyl-pent-3-enyl] acetate and [(Z)-5-acetoxy-3-methyl-pent-3-enyl] acetate in a weight ratio of about 50:25:25;

[0693] A mixture of (3-methylene-5-propionyloxy-pentyl)propionate, [(E)-3-methyl-5-propionyloxy-pent-3-enyl]propionate and [(Z)-3-methyl-5-propionyloxy-pent-3-enyl]propionate in a weight ratio of approximately 50:25:25.

[0694] - A mixture of 1,5-dimethoxy-3-methylene-pentane, (E)-1,5-dimethoxy-3-methyl-pent-2-ene and (Z)-1,5-dimethoxy-3-methyl-pent-2-ene in a weight ratio of approximately 50:25:25.

[0695] A mixture of 1,5-diethoxy-3-methylene-pentane, (E)-1,5-diethoxy-3-methyl-pent-2-ene and (Z)-1,5-diethoxy-3-methyl-pent-2-ene in a weight ratio of approximately 50:25:25, and

[0696] - A mixture of 1,5-di-n-butoxy-3-methylene-pentane, (E)-1,5-di-n-butoxy-3-methyl-pent-2-ene and (Z)-1,5-di-n-butoxy-3-methyl-pent-2-ene in a weight ratio of about 50:25:25.

[0697] The term “about” above takes into account measurement errors that may occur when determining the ratio and includes a deviation of ±10%, preferably ±5%.

[0698] More specifically, the compositions of the present invention comprise one of the specific mixtures described above.

[0699] Another embodiment relates to a method for preparing a compound of formula (I) as defined above, its stereoisomers, or mixtures thereof, comprising the following steps:

[0700] (i)make

[0701]

[0702] and

[0703] The reaction, in which

[0704] Described as One of the keys is a single key, and the other is either a double key or a single key.

[0705] R 1 It has one of the meanings given above.

[0706] R 2 It has one of the meanings given above.

[0707] R 5 For X or –OC(=O)-R 2,and

[0708] X represents a leaving group.

[0709] To obtain a mixture of crude products, and

[0710] (ii) Optionally, the crude product mixture obtained in step (i) is subjected to a purification step.

[0711] Therefore, the present invention also relates to a method for preparing a compound of formula (Ia), its stereoisomers, or mixtures thereof (or as defined above), comprising:

[0712] (i) To make compound (II) or a mixture thereof:

[0713]

[0714] With alkylating agent R 1a -X and optional alkylating agent R 2a -X reacts in the presence of a base to give a mixture of crude products, wherein R 1a and R 2a It has one of the meanings given above, and X represents a leaving group selected from halogens, such as Cl, Br, I, and sulfonates, such as toluenesulfonate, methanesulfonate, trifluoromethanesulfonate, or perfluorobutylsulfonate.

[0715] (ii) subject the crude product mixture obtained in step (i) to a purification step.

[0716] The alkylation reaction in step (i) is carried out under conventional alkylation reaction conditions familiar to those skilled in the art.

[0717] Suitable bases that can be used in alkylation reactions are as defined above.

[0718] To prepare monoether compounds of general formula (Ia), compound (II) or mixtures thereof is typically mixed with a sub-equimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9, or 0.95 equivalents of alkylating agent R. 1a -X reaction to give monosubstituted compound (Ia-OH):

[0719]

[0720] Where R 1a It has one of the meanings given above.

[0721] This further involves purification steps as defined above to remove unwanted byproducts or impurities, such as residual feedstocks or corresponding disubstituted compounds.

[0722] Wherein group R 1a and R 2aThe preparation of diether compounds of the same general formula (Ia) is generally carried out by reacting compound (II) or mixtures thereof with at least 2 equivalents, for example 2.0, 2.1, 2.5 or 3.0 equivalents, of an alkylating agent R. 1a -X or R 2a The reaction proceeds via the -X reaction, where the group R... 1a R 2a X has one of the meanings given above, and the resulting crude product is then subjected to purification steps as defined above.

[0723] Wherein group R 1a and R 2a Different general formula (Ia) diether compounds are typically prepared by first reacting compound (II) or a mixture thereof with a sub-equimolar or nearly equimolar amount, for example, 0.7, 0.8, 0.9, or 0.95 equivalents of alkylating agent R. 1 The -X reaction yields a monosubstituted compound (I.-a-OH), which, after purification, is further reacted with a second alkylating agent R. 2a -X reaction proceeds.

[0724] Generally, the starting compound (II) or a mixture thereof is used as a mixture of exo / E / Z / sat isomers, particularly the exo / E / Z isomer. Therefore, compound (Ia) is usually obtained as a mixture of exo / E / Z / sat isomers, particularly the exo / E / Z isomer.

[0725] In step (ii) of the method for preparing compound (Ia), the crude product mixture obtained in step (i) is subjected to a purification step to remove unwanted byproducts or impurities, such as residual monosubstituted compounds (Ia-OH), and, if necessary, to separate exo / E / Z isomers.

[0726] Generally, the purification in step (ii) can be carried out using conventional purification methods, such as crystallization, distillation, or chromatography, such as column chromatography or high-performance liquid chromatography. If only minor amounts of impurities and byproducts are present in the crude product mixture, the purification step can also be carried out with a simple post-extraction treatment. If necessary, the cis / trans isomers can be separated by fractional crystallization, column chromatography, or high-performance liquid chromatography.

[0727] Therefore, the present invention also relates to a method for preparing a compound of formula (Ib) as defined above, its stereoisomers, or mixtures thereof, comprising:

[0728] (i) To make compound (II) or a mixture thereof:

[0729]

[0730] With acylation reagent and optionally with acylation reagents The reaction, in which R 5 For OH, X, or –OC(=O)-R 3 Where X represents a leaving group, selected from halogens, for example...

[0731] Such as Cl, Br, or I, especially Cl or Br, and R 3 and R 4 It has one of the meanings given above, in particular

[0732] Compound (II) or a mixture thereof is reacted with carboxylic acid R 3 -COOH or its anhydride or with an acyl halide R 3 -(C=O)X′ in the presence of an organic base and optionally with carboxylic acid R 4 -COOH or its anhydride, or with an acyl halide R 4 The -(C=O)X′ reaction yields a crude product mixture, wherein R 3 and R 4 It has one of the meanings given above, and X′ represents a halogen atom, such as Cl, Br, or I, especially Cl or Br, and

[0733] (ii) Optionally, the crude product mixture obtained in step (i) is subjected to a purification step.

[0734] The reaction conditions for the ester compounds of general formula (Ib) in step (i) are well known to those skilled in the art.

[0735] To prepare monoester compounds of general formula (Ib), compound (II) or mixtures thereof are typically reacted with a sub-equimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9, or 0.95 equivalents of an acylation agent to give a monosubstituted compound (Ib-OH):

[0736]

[0737] Where R 1b -C(=O)R 3 ,

[0738] If necessary, it may be further subjected to purification steps as defined above to remove unwanted byproducts or impurities, such as residual feedstock or corresponding disubstituted compounds.

[0739] Wherein group R 1b and R 2b The preparation of diester compounds of the same general formula (Ib) is generally carried out by reacting compound (II) or mixtures thereof with at least 2 equivalents, such as 2.0, 2.1, 2.5 or 3.0 equivalents, of an acylation agent such as carboxylic acid R. 3-COOH or its anhydride or acyl halide R 3 -(C=O)X′ in the presence of an organic base and optionally with carboxylic acid R 4 -COOH or its anhydride or with an acyl halide R 4 The -(C=O)X′ reaction yields a crude product mixture, wherein R 3 and R 4 Having one of the meanings given above, and X′ representing a halogen atom, such as Cl, Br, or I, especially Cl or Br, the crude product is then subjected to purification steps as defined above, if necessary.

[0740] Wherein group R 1b and R 2b Different general formula (Ib) diester compounds are typically prepared by first reacting compound (II) or a mixture thereof with a sub-equimolar or nearly equimolar amount, for example 0.7, 0.8, 0.9, or 0.95 equivalents of carboxylic acid R. 3 -COOH or its anhydride or with an acyl halide R 3 -(C=O)X′ reacts in the presence of an organic base to give a crude product mixture to yield a monosubstituted compound (I.-b-OH), which, after purification, is further reacted with a second carboxylic acid R. 4 -COOH or its anhydride or with an acyl halide R 4 -(C=O)X′ reacts in the presence of an organic base to give a crude product mixture (where R) 3 and R 4 It has one of the meanings given above, and X′ represents a halogen atom, such as Cl, Br or I, especially Cl or Br).

[0741] In step (ii) of the method for preparing compound (Ib), if necessary, the crude product mixture obtained in step (i) is subjected to a purification step to remove unwanted byproducts or impurities, such as residual monosubstituted compounds (Ib-OH), and if necessary, to separate exo / E / Z isomers.

[0742] Generally, the purification in step (ii) can be carried out using conventional purification methods, such as crystallization, distillation, or chromatography, such as column chromatography or high-performance liquid chromatography. If only minor amounts of impurities and byproducts are present in the crude product mixture, the purification step can also be carried out with a simple post-extraction treatment. If necessary, the exo / E / Z isomers can be separated by fractional crystallization, column chromatography, or high-performance liquid chromatography.

[0743] The starting material compound (II) may be a pure compound (II.1), (II.2), (II.3) or (II.4) or a mixture of different stereoisomers [E / Z mixture; E = (II.2); Z = (II.3)] or a mixture of double bond position isomers [mixtures such as (II.1) = exo with (II.2) and / or (II.3)], or a mixture of saturated and unsaturated compounds [[II.4] with at least one of (II.1), (II.2) and (II.3)].

[0744]

[0745] A byproduct of citral production is a mixture of exo / E / Z isomers of II [(II.1), (II.2), and (II.3)], which is a suitable starting material for the preparation of compound (I). Therefore, when using this mixture, compound Ib is usually obtained as a mixture of exo / E / Z isomers.

[0746] The invention will now be described in further detail through the following embodiments, but without imposing any limitations thereon. Example

[0747] abbreviation:

[0748] DMAP: 4-(N,N'-dimethylamino)-pyridine

[0749] MTBE: 2-Methoxy-2-methylpropane (methyl tert-butyl ether)

[0750] RT: Room temperature (20-25℃)

[0751] THF: Tetrahydrofuran

[0752] Citral SS Diol: A mixture of 3-methylene-1,5-pentanediol, (E)-3-methylpent-2-ene-1,5-diol, and (Z)-3-methylpent-2-ene-1,5-diol (can be used as a side fraction in citral production).

[0753] analyze:

[0754] The purity of the product was determined by gas chromatography (area %).

[0755] GC architecture: Agilent 7890B;

[0756] GC column: DB-WAX (30m (length), 0.32mm (ID), 0.25μm (membrane));

[0757] Temperature program: from 85°C to 230°C at a rate of 5°C / min

[0758] A. Preparation

[0759] Example 1:

[0760]

[0761]

[0762] DMAP was added to a THF solution of a citral-ss diol mixture under RF conditions. The mixture was set to reflux (53 °C), and acetic anhydride (2.25 equivalents) was slowly added at this temperature. After 1 hour, a diol conversion of 99% was observed by GC. The reaction was cooled to room temperature and slowly quenched with 100 mL of water, followed by the addition of 100 mL of ethyl acetate. The organic phase was separated and washed with NaHCO3 and brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 37.1 g of crude product containing approximately 90% diacetate (based on GC area %) was obtained. The product was purified by distillation. The corresponding diacetate mixture was given with a purity of 93.2% (GC area %). NMR confirmed that the mixture was a 1:1 E / Z mixture of 50% 3-methylene diacetate and 50% 2-pentene derivative.

[0763]

[0764]

[0765]

[0766]

[0767] Example 2:

[0768] -

[0769]

[0770] Formic acid was slowly added to acetic anhydride at 0 °C. The mixture was stirred at 55 °C for 1.5 h, then cooled to 0 °C, and 50 mL of THF was added. At this temperature, a solution of citral SS diol in 50 mL of THF was slowly added, followed by the addition of DMAP. The reaction was stirred at room temperature for 4 h, and complete conversion was observed by GC. 100 mL of toluene was added to the mixture, and the organic phase was washed three times with 30 mL of water. The organic phase was dried with sodium sulfate, and the solvent was removed in a rotary evaporator to give 19.6 g of crude product containing approximately 90% dicarboxylate, according to GC (area %). The product was purified by distillation. The corresponding mixture of dicarboxylates was given with a purity of 98.1% (GC area %). NMR confirmed that the mixture was a 1:1 E / Z mixture of 50% 3-methylene dicarboxylate and 50% 2-pentene derivative.

[0771]

[0772]

[0773] Example 3:

[0774]

[0775]

[0776] A solution of citral SS diol mixture, triethylamine, and DMAP in hexane was cooled to 0 °C. At this temperature, propionyl chloride was slowly added. The reaction was stirred at room temperature for 1 hour, 50 mL of hexane was added, and the reaction was refluxed (67 °C) for 4 hours. After this time, complete conversion was observed by GC. The reaction was cooled to room temperature and slowly quenched with 100 mL of water, 100 mL of ethyl acetate was added, and the organic phase was washed with NaHCO3 and an aqueous brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 38.4 g of crude product containing approximately 90% dipropionate (based on GC area %) was given. The product was purified by distillation. The corresponding mixture of dipropionates was given with a purity of 97.8% (GC area %). NMR confirmed that the mixture was a 1:1 E / Z mixture of 50% 3-methylene dipropionate and 50% 2-pentene derivative.

[0777]

[0778]

[0779] Example 4:

[0780]

[0781]

[0782]

[0783] At 0°C, a solution of citral SS2 diol in 30 mL of THF was slowly added to a dispersion of sodium hydride (2.3 equivalents) in 75 mL of THF. The mixture was stirred at 0°C for 30 minutes. Then, 2.3 equivalents of methyl iodine were slowly added at RT, followed by stirring at 40°C for 4 hours. The reaction mixture was cooled to 0°C, and the addition of 0.75 equivalents of NaH, followed by 0.75 equivalents of methyl iodine, was repeated. The mixture was then stirred at 40°C for 20 hours. The reaction was then slowly quenched with 50 mL of water. The organic phase was extracted three times with 50 mL of MTBE. The organic extracts were combined and washed with 50 mL of NH3 solution and 50 mL of brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 20 g of crude product containing 98% diether (based on GC area %) was obtained. The product was purified by distillation. The corresponding dimethyl ether mixture was given with a purity of >99% (GC area %). NMR confirmed that the mixture consisted of a 1:1 E / Z mixture of 50% exo-dimethyl ether and 50% 2-pentene derivative.

[0784]

[0785]

[0786] Example 5:

[0787]

[0788]

[0789] At 0 °C, a solution of citral SS2 diol in 30 mL THF was slowly added to a dispersion of sodium hydride (2.3 equivalents) in 75 mL THF. The mixture was stirred at 0 °C for 30 min, and then 2.3 equivalents of ethyl iodine was slowly added at RT. After the addition, the mixture was stirred at 40 °C for 4 h. The reaction mixture was cooled to 0 °C, and 0.75 equivalents of NaH were added repeatedly, followed by 0.75 equivalents of ethyl iodine. The mixture was then stirred at 40 °C for 20 h, and the reaction was slowly quenched with 50 mL of water. The organic phase was extracted three times with 50 mL of MTBE. The organic extracts were combined and washed with 50 mL of NH3 solution and 50 mL of brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 24.6 g of crude product containing 93% diether (based on GC area %) was given. The product was purified by distillation. The corresponding mixture of diethyl ethers was given with a purity of >96% (GC area %). NMR confirmed that the mixture consisted of a 1:1 E / Z mixture of 50% exo-diethyl ether and 50% 2-pentene derivative.

[0790]

[0791]

[0792]

[0793] Example 6:

[0794]

[0795] compound MW mass / volume Moore 3-Methyl-1,5-pentanediol 118.17 10g 0.085 Ethyl iodine 155.97 30.35g 0.195 Sodium hydride 23.99 4.67g 0.195 Tetrahydrofuran 105mL

[0796] At 0 °C, a solution of 3-methyl-1,5-pentanediol in 30 mL THF was slowly added to a dispersion of sodium hydride (2.3 equivalents) in 75 mL THF. The mixture was stirred at 0 °C for 30 min, and then 2.3 equivalents of ethyl iodine was slowly added at RT. After the addition, the mixture was stirred at 40 °C for 4 h. The reaction mixture was cooled to 0 °C, and 0.75 equivalents of NaH were added repeatedly, followed by 0.75 equivalents of ethyl iodine. The mixture was then stirred at 40 °C for 20 h, and the reaction was slowly quenched with 50 mL of water. The organic phase was extracted three times with 50 mL of MTBE. The organic extracts were combined and washed with 50 mL of NH3 solution and 50 mL of brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 15.7 g of crude product containing 92% diether (based on GC area %) was given. The product was purified by distillation. The corresponding mixture of diethyl ethers was obtained with a purity of >97% (GC area%).

[0797]

[0798] Example 7:

[0799]

[0800]

[0801] At 0 °C, a solution of citral-ss diol mixture in 30 mL THF was slowly added to a dispersion of sodium hydride (2.3 equivalents) in 75 mL THF. The mixture was stirred at 0 °C for 30 min, and then 2.3 equivalents of ethyl iodine was slowly added at RT. After the addition, the mixture was stirred at 50 °C for 4 h. The reaction mixture was cooled to 0 °C, and 0.75 equivalents of NaH were added repeatedly, followed by 0.75 equivalents of 1-iodobutane. The mixture was then stirred at 50 °C for 90 h, and the reaction was slowly quenched with 50 mL of water. The organic phase was extracted three times with 50 mL of MTBE. The organic extracts were combined and washed with 50 mL of NH3 solution and 50 mL of brine solution. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 26.2 g of crude product containing 37% di-n-butyl ether (based on GC area %) was given, with the remainder being monoether derivatives. The product was purified by column chromatography. The corresponding mixture of diethyl ethers was obtained with a purity of >95% (GC area %). NMR confirmed that the mixture was a 1:1 E / Z mixture of 50% exo-di-n-butyl ether and 50% 2-pentene derivative.

[0802]

[0803]

[0804]

[0805] B. Olfactory evaluation

[0806] To test the odor quality and intensity of the compounds obtained in the preparation examples, perfume strip tests were conducted.

[0807] For this purpose, absorbent paper strips were immersed in a solution containing 1-10% by weight ethanol of the compound to be tested (I). After the solvent evaporated (approximately 30 seconds), the aroma impression was assessed by smell by a skilled perfumer. The results are summarized in Table 1.

[0808] Table 1: Results of the Aroma Test

[0809]

[0810]

Claims

1. Use of a compound of formula (I) or a stereoisomer thereof or a mixture thereof or a mixture of different compounds of formula (I) as a synthetic fragrance: in: symbol One represents a single bond, and the other represents either a double bond or a single bond. R 1 and R 2 They are all the same and all C1-C4 alkyl groups, or R 1 -(C=O)-R 3 And R 2 -(C=O)-R 4 , where R 3 and R 4 They are the same and are either hydrogen or C1-C4 alkyl.

2. The use according to claim 1, wherein in formula (I), R 1 It is a C1-C4 alkyl group. R 2 It is a C1-C4 alkyl group.

3. The use according to claim 1, wherein R 1 and R 2 It is a C1-C3 alkyl group.

4. The use according to claim 1, wherein R 1 and R 2 It can be methyl or ethyl.

5. The use according to claim 1, wherein R 1 and R 2 It is a methyl group.

6. The use according to claim 1, wherein in formula (I), R 1 -(C=O)-R 3 ,and R 2 -(C=O)-R 4 .

7. The use according to claim 6, wherein R 3 and R 4 It is hydrogen or C1-C3 alkyl.

8. The use according to claim 6, wherein R 3 and R 4 It can be hydrogen, methyl, or ethyl.

9. The use according to any one of claims 1-8, wherein the mixture contains two or three isomers of the compound of formula I, wherein the isomers have formulas (I.1), (I.2) and (I.3):

10. The use according to any one of claims 1-8, for imparting an olfactory impression.

11. As claimed in claim 10, used as a spice.

12. Use of a compound of formula (I) as defined in any one of claims 1-8, or a stereoisomer thereof, or a mixture of stereoisomers thereof, or a mixture of different formula (I) compounds, in improving the aroma characteristics of a flavoring composition.

13. Use of a compound of formula (I) as defined in any one of claims 1-8, or a stereoisomer thereof, or a mixture of stereoisomers thereof, or a mixture of different formula (I) compounds, in improving the flavor characteristics of a flavored ready-to-use composition.

14. The use according to any one of claims 1-8, for use in a composition selected from fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food, food supplements, pharmaceutical compositions, and crop protection compositions.

15. A composition comprising at least one compound of formula (I) as defined in any one of claims 1-8, a stereoisomer thereof, or a mixture thereof, and at least one other component selected from synthetic fragrances and non-synthetic fragrance carriers other than compound (I); The carrier material can be a liquid or oily carrier material, a waxy or solid carrier material; The liquid or oily carrier material is selected from methanol, ethanol, ethylene glycol, glycerol, diglycerol, propylene glycol, dipropylene glycol, 1,2-butanediol, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, diethylene glycol monoethyl ether, diethyl phthalate, isopropyl myristate, triethyl citrate, benzyl benzoate, fractionated coconut oil, tetradecyl acetate, tetradecyl lactate, glyceryl esters with a melting temperature below 20°C, and isopropyl myristate.

16. The composition of claim 15, wherein the composition is selected from fragrance compositions, body care compositions, oral and dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, perfume dispenser compositions, food, food supplements, pharmaceutical compositions, and crop protection compositions.

17. A composition comprising any one of the compounds of formula (I.1) and (I.2) and (I.3) or a mixture of the compounds of formula (I.1) and (I.2) and (I.3): In all compounds of formulas (I.1), (I.2), and (I.3) present in the mixture, all groups R 1 and R 2 Are the same and are C1-C4 alkyl, or all groups R 1 -(C=O)-R 3 All groups R 2 -(C=O)-R 4 And all groups R 3 and R 4 They are the same and are either hydrogen or C1-C4 alkyl. The mixture contains each compound present in the mixture in an amount of 1-99% by weight, provided that the total weight of the compounds of formulas (I.1), (I.2) and (I.3) present in the mixture is 100%.

18. The composition according to claim 17, wherein R 3 and R 4 It can be hydrogen, methyl, or ethyl.

19. The composition according to claim 17, comprising all three compounds (I.1), (I.2) and (I.3).

20. The composition according to claim 17, wherein R 1 and R 2 It is a C1-C4 alkyl group, or R 1 -(C=O)-R 3 R 2 -(C=O)-R 4 And R 3 and R 4 It is a C1-C4 alkyl group.

21. The composition according to claim 19, wherein R 3 and R 4 It can be hydrogen, methyl, or ethyl.

22. The composition of claim 17, comprising a mixture selected from the following: A mixture of (5-formyloxy-3-methylene-pentyl)carbamate, [(E)-5-formyloxy-3-methyl-pent-3-enyl]carbamate and [(Z)-5-formyloxy-3-methyl-pent-3-enyl]carbamate; A mixture of (5-acetoxy-3-methylene-pentyl)acetate, [(E)-5-acetoxy-3-methyl-pent-3-enyl]acetate and [(Z)-5-acetoxy-3-methyl-pent-3-enyl]acetate; A mixture of -(3-methylene-5-propionyloxy-pentyl)propionate, [(E)-3-methyl-5-propionyloxy-pent-3-enyl]propionate and [(Z)-3-methyl-5-propionyloxy-pent-3-enyl]propionate; A mixture of (E)-1,5-dimethoxy-3-methylene-pentane, (E)-1,5-dimethoxy-3-methyl-pent-2-ene and (Z)-1,5-dimethoxy-3-methyl-pent-2-ene; A mixture of -1,5-diethoxy-3-methylene-pentane, (E)-1,5-diethoxy-3-methyl-pent-2-ene and (Z)-1,5-diethoxy-3-methyl-pent-2-ene, and A mixture of -1,5-di-n-butoxy-3-methylene-pentane, (E)-1,5-di-n-butoxy-3-methyl-pent-2-ene and (Z)-1,5-di-n-butoxy-3-methyl-pent-2-ene.

23. The composition according to any one of claims 17-18 and 20-22, wherein when the mixture comprises all three compounds of formula (I.1), (I.2) and (I.3), the ratio of (I.1):(I.2):(I.3) is 90:5:5-10:45:

45.

24. The composition according to any one of claims 17-18 and 20-22, wherein when the mixture comprises all three compounds of formula (I.1), (I.2) and (I.3), the ratio of (I.1):(I.2):(I.3) is 80:10:10-20:40:40.

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