Odorants and compositions containing odorants

Abstract

The present invention relates to substituted hexahydro-5H-chromene-5-one and / or substituted tetrahydrobenzofuran-4(2H)-one derivatives which can be used as fragrance or flavor materials.

Description

Technical Field

[0001] The present invention relates to a new class of odorous compounds represented by formula (I), which represent substituted hexahydro-5H-chromen-5-one and / or substituted tetrahydrobenzofuran-4(2H)-one derivatives thereof, which can be used as fragrance or flavor materials, in particular in providing damascone-type or damascenone-type, such as fruity, minty, woody, powdery, amber and / or tobacco-like notes to perfumes, aromas or deodorant / masking compositions. The present invention also relates to fragrance, flavor and / or deodorant / masking compositions comprising said new class of odorous substituted hexahydro-5H-chromen-5-one or its substituted tetrahydrobenzofuran-4(2H)-one derivatives. The present invention further relates to said odorants which can be used in the novel fragrance, flavor and / or deodorant / masking compositions of the present invention. The present invention also relates to methods for producing said odorants / compounds and corresponding fragrance, flavor and / or deodorant / masking compositions containing said odorants / compounds.

[0002] More particularly, the present invention relates to 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one derivatives (Formula A) and / or 3,3-dimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one derivatives (Formula B) (odorants), which can be used as fragrance or flavor materials, especially in providing damascone-type, fruity, minty, woody, powdery, amber and / or tobacco-like notes to perfumes, fragrances and / or deodorizing / masking compositions. Background Art

[0003] The increasing limitations on the supply of natural fragrance ingredients have revolutionized the field of synthetic fragrance ingredients.Today, there is an increasing demand for new odorants / compounds and / or new fragrance, flavor and / or deodorizing / masking compositions comprising the same.

[0004] When fruity and floral notes are needed, various isomers of damascone are used. Typical damascone used include α-damascone, β-damascone and δ-damascone. In addition to the above ingredients, β-damascenone is also used for its fruity profile. However, it is found that all of the above ingredients are skin sensitizers, and therefore IFRA guidelines recommend a large number of restrictions on their use in consumer products. Therefore, there has always been a demand for safe alternatives to damascone.

[0005]

[0006] Damaskone-type fragrances include α-damaskone-type fragrances (called fruity, grassy, ​​seedy, tropical, spicy, apple, and woody), β-damaskone-type fragrances (called fruity, floral, currant, black currant, plum, rose, honey, and tobacco), and δ-damaskone-type fragrances (called fruity, sweet, rose, natural, petal, currant, bud-shaped black currant, and bud-shaped tobacco). Damaskenone-type fragrances include β-damaskenone-type fragrances (called natural sweet, fruity, rose, plum, grape, raspberry, and caramel).

[0007] Examination of the structures of various damascone isomers revealed the presence of an α-β unsaturated keto motif. α-β unsaturated carbonyl compounds are known to be good Michael acceptors, and therefore, many electrophilic α-β unsaturated carbonyl compounds act as skin sensitizers by reacting with nucleophilic proteins on the skin (Aptula, AO et al., Chem. Res. Toxicol. 18 (2005) 1420-1426). It has also been reported that electron-donating substituents such as alkyl groups on the αC atom and, to a lesser extent, on the βC atom, make the C β =C α The bond is deactivated by nucleophilic attack.

[0008] The article from Helvetica Acta - Volume 69 (1986) - Page 1681-4 - entitled "Synthesis of 2,3,4,6,7,8-Hexahydro-5H-1-benzopyran-5-ones and 3-(6-Oxo-1-cyclohexenyl)alkanoicAcids by Reduction of 4,6,7,8-tetrahydro-2H-1-benzopyran-2,5(3H)-diones" provides corresponding comparative results of the reduction.

[0009] The article from Chemische Berichte, volume 123 (1990), pages 101-105, relates to "Light-Induced Conversion of 4,6,7,8-tetrahydro-2H-benzopyran-2,5(3H)-diones into 3,5,6,7-Tetrahydrobenzofuran-4(2H)-ones in Methanol".

[0010] US4268445 (A) relates to a two-step sequential preparation of bicyclic enol-ether (X) (wherein n is 3-12, and R1, R2 and R3 may be H or C1-C4 alkyl) by a free radical adduct formation reaction involving an allyl ether of general formula (V) (wherein R4 is tert-butyl, tetrahydrofuran-2-yl or tetrahydropyran-2-yl) with a cyclic ketone (W), followed by acid-catalyzed cyclization of the obtained compound of general formula (Y); the compounds (X) and (Y) are intermediates for the synthesis of musk-like fragrances.

[0011]

[0012] US4233226 (A) relates to 4a,5,6,7,8,8a-hexahydro-4,7-dimethyl-4H-1-benzopyran (given below) which is used as an odoriferous aromatic compound and a process for its preparation.

[0013]

[0014] EP2848611 (A1) relates to compounds of formula (Z), wherein R = -H, -methyl, ethyl, O-methyl or O-ethyl, R1 = -H, -methyl, ethyl, O-methyl or O-ethyl, and n = 1 or 2, their use as fragrances, preferred mixtures, consumer products containing these compounds and their production.

[0015]

[0016] WO2014064716 (A1) claims protection for substituted hexahydro-(5H)-1-benzopyran-5-one (or hexahydro-(5H)-chromene-5-one) derivatives and substituted tetrahydro-(5H)-1-benzopyran-5-one (or tetrahydro-(5H)-chromene-5-one) derivatives, methods for synthesizing the compounds, and perfumery compositions containing olfactory acceptable amounts of the compounds.

[0017] Surprisingly, it was found that certain compounds represented by formula A (i.e., 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one derivatives) and formula B (i.e., 3,3-dimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one derivatives) impart an exotic fruity, damascone-like or damascenone-type profile. These compounds do not have any α-β unsaturated keto groups in their structure. These compounds still have a geminal dimethyl group, which is a common feature of all damascone isomers. In addition, in these compounds, the keto group is present as part of a six-membered ring fused to a six-membered ring (formula A) or a five-membered ring (formula B) containing a geminal dimethyl group. The six-membered ring (formula A) or the five-membered ring (formula B) containing a geminal dimethyl group also contains an oxygen atom. Interestingly, many of these compounds of formula A and B also advantageously impart minty, woody, powdery, amber and / or tobacco-like notes to perfume, fragrance and / or deodorant / masking compositions. Summary of the invention

[0018] The present invention discloses novel fragrance, flavor and / or deodorizing / masking compositions comprising compounds of formula (I) wherein n is 0 or 1

[0019]

[0020] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 is independently selected from hydrogen, C1-C5 alkyl (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, isobutyl, n-pentyl, cyclopropylmethyl, cyclobutylmethyl, cyclobutyl or cyclopentyl) or C1-C5 alkenyl (e.g., allyl, 3-methylbut-2-en-1-yl, 3-methylbut-3-en-1-yl, but-3-en-1-yl or 2-methylallyl), provided that

[0021] - When n = 1 and R3 = R4 = CH3, the other groups R1, R2 and R5-R 10 cannot be entirely hydrogen; and

[0022] - When n=0 and R3=R4=CH3,

[0023] o the other groups R1, R2 and R5-R8 cannot all be hydrogen; and

[0024] o When R7=R8=CH3, the other groups R1, R2 and R5-R6 cannot all be hydrogen; and

[0025] - When n=0 and R8=CH3, the other groups R1, R2 and R5-R7 cannot all be hydrogen.

[0026] For the avoidance of doubt, the following groups, namely, R1 and R2, R3 and R4, R5 and R6, R7 and R8, R9 and R10 The reason for excluding the above 4 compounds is that they were found to have no olfactory properties according to the purpose of the present invention.

[0027] In one embodiment, the present invention relates to novel fragrance, flavor and / or deodorizing / masking compositions comprising compounds of formula (I) wherein n is 0 or 1

[0028]

[0029] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are independently selected from hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl or tert-butyl, provided that

[0030] - When n = 1 and R3 = R4 = CH3, the other groups R1, R2 and R5-R 10 cannot be entirely hydrogen; and

[0031] - When n=0 and R3=R4=CH3,

[0032] o the other groups R1, R2 and R5-R8 cannot all be hydrogen; and

[0033] o When R7=R8=CH3, the other groups R1, R2 and R5-R6 cannot all be hydrogen; and

[0034] - When n=0 and R8=CH3, the other groups R1, R2 and R5-R7 cannot all be hydrogen.

[0035] The general formula (I) has been used to represent compounds represented by formula A (i.e., 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one derivatives) and / or formula B (i.e., 3,3-dimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one derivatives), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are independently selected from the groups defined above.

[0036]

[0037] The compound of formula B does not contain R9 and R 10 group, since n=0 in the general formula (I).

[0038] In one embodiment, the invention relates to compounds of formula A or formula B

[0039]

[0040] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 is independently selected from hydrogen, C1-C5 alkyl (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, isobutyl, n-pentyl, cyclopropylmethyl, cyclobutylmethyl, cyclobutyl or cyclopentyl) or C1-C5 alkenyl (e.g., allyl, 3-methylbut-2-en-1-yl, 3-methylbut-3-en-1-yl, but-3-en-1-yl or 2-methylallyl), provided that

[0041] - compounds of formula A excluding compounds of formula A-exc, and

[0042]

[0043] - The compound of formula B does not include compounds of formula B-exc1, B-exc2 and B-exc3

[0044]

[0045] In one embodiment, the invention relates to compounds of formula A or formula B

[0046]

[0047] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are independently selected from hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl or tert-butyl, provided that

[0048] - compounds of formula A excluding compounds of formula A-exc, and

[0049]

[0050] - The compound of formula B does not include compounds of formula B-exc1, B-exc2 and B-exc3

[0051]

[0052] In another embodiment, the present invention relates to a fragrance, flavor and / or deodorizing / masking composition comprising a compound of formula A or formula B

[0053]

[0054] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10is independently selected from hydrogen, C1-C5 alkyl (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, isobutyl, n-pentyl, cyclopropylmethyl, cyclobutylmethyl, cyclobutyl or cyclopentyl) or C1-C5 alkenyl (e.g., allyl, 3-methylbut-2-en-1-yl, 3-methylbut-3-en-1-yl, but-3-en-1-yl or 2-methylallyl), provided that

[0055] - excluding compounds of formula A-exc, and

[0056]

[0057] - Excluding compounds of formula B-exc1, B-exc2 and B-exc3

[0058]

[0059] In another embodiment, the present invention relates to a fragrance, flavor and / or deodorizing / masking composition comprising a compound of formula A or formula B

[0060]

[0061] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are independently selected from hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl or tert-butyl,

[0062] The condition is

[0063] - excluding compounds of formula A-exc, and

[0064]

[0065] - Excluding compounds of formula B-exc1, B-exc2 and B-exc3

[0066]

[0067] In another embodiment of the invention, the compounds of general formula (I) may contain one or more chiral centers and may be chiral, for example they may be used as stereoisomer (enantiomer or diastereoisomer) mixtures. In another embodiment, the compounds of formula (I) may also advantageously be used in pure enantiomer or diastereoisomer form. DETAILED DESCRIPTION

[0068] The term "odorant" characterizing the compounds of the invention means that they induce a preferably pleasant odor sensation in humans; therefore, they are routinely used to perfume industrial and sanitary products, detergents, cleaning agents, personal hygiene products, cosmetics, etc. For the purposes of the present invention and the appended claims, the term "odorant" includes "aroma substances". Aroma substances are terms generally used to designate substances that provide an odor and / or flavor to food.

[0069] The compound of formula A or B can be used alone, as a mixture thereof or in combination with a base material.

[0070] "Base material" as used herein includes all known aroma / flavor materials selected from a wide range of natural products, such as essential oils, extracts, resinoids or isolates and currently available synthetic materials, such as hydrocarbons, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, nitriles, oximes or heterocycles, and / or mixtures with one or more ingredients or excipients / adjuvants conventionally used in combination with odorants in aroma and / or flavor compositions (e.g., solvents / diluents, stabilizers, carrier materials and other adjuvants commonly used in the art).

[0071] The compounds of formula A or B can be used for a wide range of fragrance applications, for example in any fine and functional perfumery industry, such as perfumes, air care products, household products, laundry products, body care products and cosmetics. Depending on the specific application and the nature and amount of other odorant ingredients, the compounds can be employed in widely varying amounts.

[0072] According to a preferred embodiment of the present invention, the fragrance, flavor and / or deodorizing / masking composition of the present invention contains at least one compound of the formula A or B as previously described in an amount of between 0.00001-99.9 wt.%, for example between 0.0001-95 wt.%, for example between 0.001-25 wt.%, preferably between 0.01-15 wt.%, more advantageously between 0.1-10 wt.%, in particular between 1-5 wt.%, in each case relative to the entire composition.

[0073] According to a particularly preferred embodiment of the present invention, in addition to the compounds of formula A or B according to the present invention, the fragrance, flavor and / or deodorizing / masking composition according to the present invention contains further odorants, for example in an amount of 0.1 to 99.9 wt.%, preferably 5 to 90 wt.%, in particular 15 to 70 wt.%, relative to the entire fragrance and / or flavor composition.

[0074] The compounds of formula A or B as described above can be used in the consumer product base simply by mixing at least one compound of formula (A) and / or at least one compound of formula (B) or a fragrance composition comprising said compounds of formula (A) and / or (B) directly with the consumer product base; or it can be captured in an earlier step using a capturing material such as a polymer, capsule, microcapsule and / or nanocapsule, liposome, film former, absorbent (such as activated carbon or zeolite), cyclic oligosaccharide, cyclic glycoluril and a mixture of two or more thereof, or it can be chemically bonded to a matrix suitable for releasing the fragrance molecules upon application of an external stimulus (such as light, enzyme, air, water, etc.) and then mixed with the consumer product base.

[0075] Thus, the present invention can be used in existing methods of making fragrance, flavor and / or deodorizing / masking compositions, which include incorporating one or more compounds of formula (A) and / or (B) as fragrance, flavor and / or deodorizing / masking ingredients by mixing the compounds directly into a consumer product base, or by mixing a fragrance, flavor and / or deodorizing / masking composition comprising said one or more compounds of formula (A) and / or (B), which can then be mixed with a consumer product base using conventional techniques and methods. By adding an olfactory acceptable amount of at least one compound of formula (A) and / or (B) of the present invention as described above, the odor notes of the consumer product base can be improved, enhanced and / or modified.

[0076] The present invention discloses novel fragrance, flavor and / or deodorizing / masking compositions comprising substituted 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one derivatives (Formula A) and / or 3,3-dimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one derivatives (Formula B) as defined above.

[0077] In a particular embodiment of the present invention, compounds of formula (A) and / or (B) as defined above are claimed; said compounds are useful in the perfume, fragrance and / or deodorizing / masking compositions of the present invention.

[0078] In one embodiment, the compound of formula (A) used in the fragrance, flavor and / or deodorizing / masking composition is selected from the following compounds:

[0079] 1) 4,4-Dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0080] 2) 4,4,6-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0081] 3) 6-ethyl-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0082] 4) 3,3,4,4-Tetramethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0083] 5) 2,3,3,4,4-pentamethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0084] 6) 2,4,4-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0085] 7) 3,3,4,4,6-pentamethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0086] 8) 3,4,4-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0087] 9) 4,4,6,8-Tetramethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0088] 10) 4,4,6,7,7-pentamethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0089] 11) 6-(Cyclopropylmethyl)-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0090] 12) 6-isobutyl-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0091] In one embodiment, the compound of formula (B) used in the fragrance, flavor and / or deodorizing / masking composition is selected from the following compounds:

[0092] 13) 3,3-Dimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one

[0093] 14) 3,3,5-Trimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one

[0094] 15) 3,3,7-Trimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one

[0095] 16) 5-ethyl-3,3-dimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one

[0096] 17) 2,2,3,3-Tetramethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one

[0097] 18) 2,2,3,3,5-pentamethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one

[0098] 19) 2,2,3,3,7-pentamethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one

[0099] 20) 5-ethyl-2,2,3,3-tetramethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one

[0100] In one embodiment of the present invention, the fragrance, flavour and / or deodorising / masking composition comprises a compound of formula (A) or formula (B) selected from any of the above mentioned compounds and / or selected from a mixture of two or more of said compounds.

[0101] The applicant unexpectedly discovered that, from an olfactory point of view, the compounds of formula (A) have a damascone-type or damascenone-type odor profile. In fact, many compounds of formula (A) show exotic fruity and minty notes. Many compounds of formula (A) and (B) also present woody, powdery, amber and / or tobacco-like notes. In fact, some compounds of formula (A) also show a sandalwood profile. Compounds (A) and (B) have a strong retention on blotting paper, lasting more than 4 days. In fact, compounds of formula (A) and (B) perform extremely well in woody, fougere and rose accords.

[0102] In one embodiment of the present invention, the claimed fragrance, flavor and / or deodorizing / masking compositions are advantageously used as perfumery compositions. The perfumery compositions of the present invention typically include perfumes, colognes, eau de toilettes and / or perfumes. In one embodiment of the present invention, the claimed fragrance, flavor and / or deodorizing / masking compositions are advantageously used in cosmetic preparations, personal care products, cleaning products, fabric softeners and / or air fresheners, etc. Furthermore, it is within the scope of embodiments of the present invention that the novel fragrance, flavor and / or deodorizing / masking compositions and / or the novel compounds of formula (A) or formula (B) described herein may be integrated into building materials, wall and floor coverings, automotive parts, etc.

[0103] Typically, in addition to the novel odorants and / or fragrance, flavor and / or deodorizing / masking compositions described herein, suitable fragrance, flavor or deodorizing compositions may advantageously include conventional ingredients such as solvents, carriers, stabilizers, emulsifiers, wetting agents, dispersants, diluents, thickeners, diluents, other odorants and / or adjuvants, etc.

[0104] The compounds of formula (A) or (B) are combined with a number of known natural or synthetic fragrance, flavor and / or deodorizing / masking materials, wherein the range of natural ingredients may include not only readily volatile but also semi-volatile and slightly volatile components, and the range of synthetic ingredients may include representatives from many classes of substances, such as those described in Steffen Arctander, Perfume and Flavor Chemicals, Volumes 1 and 2, Montclair, NJ, 1969; Steffen Arctander, Perfume and Flavor Materials of Natural Origin, Elizabeth, NJ, 1960 or Horst Surburg, Johannes Panten, Common Fragrance and Flavor Materials, Wiley-VCH, Weinheim, 2016 and as is apparent from the following non-limiting compilation:

[0105] Natural products such as:

[0106] Ajowan oil, Amyris oil, Armoise oil, Artemisia oil, Basil oil, Bees wax absolute, Bergamot oil, Birch tar oil, Black pepper oil, Black pepper oleoresin, Camphor oil, Cananga oil, Caraway oil, Cardamom oil, Carrot seed oil, Castoreum absolute, Cedar leaf oil, Cedarwood oil, Celery seed oil, Chamomile oil, Cinnamon bark oil, Cinnamon leaf oil, Cistus absolute, Cistus oil oil, Citronella oil, Citronella terpenes, Clary sage oil, Clove oil rectified, Cognac oil white, Corianderseed oil, Cumin seed oil, Cypress oil, Davana oil, Dill seed oil, Elemi oil, Elemi resinoid, Eucalyptus oil, Fir needle oil, Galbanum oil, Geranium oil, Ginger oil Indian, Grapefruit oil, Guaiacwood oil, Gurjun balsam, Jasmin absolute, Jatamansi oil, Juniper berry oil oil), Juniper leaf oiloil), Kachur oil, Labdanum absolute, Labdanum resinoid, Lavender oil, Lemon oil, Lemon oil terpenes, Lemongrass oil, Lime oil, Litsea cubeba oil, Litsea cubeba terpenes, Lobhan choya resin, Mandarin oil, Mentha arvenisoil, Mentha citrata oil, Mimosa absolute, Myrrh resinoid, Nagarmotha oil, Nutmeg oil, Oakmoss absolute, Oakmoss resinoid, Olibanum oil, Olibanum resinoid, Orange oil oil, Origanum oil, Palma rosa oil, Patchouli oil, Peppermint oil, Peru Balsam resinoid, Petitgrain oil, Pine needle oil, Pink pepper oil, Rose absolut, Rose oil, Rosemary oil, Sandalwood oil, Seaweed absolute, Spearmint oil, Sugandh kokila oil, Sugandh mantri oil, Tagete oil, Tolu Balsam resinoid, Tuberose absolute, Turmeric oil, Turpentine oil, Valerian oil, Vetiver oil oil), Vetiver terpenes.

[0107] Synthetic raw materials such as:

[0108] Esters such as: C16 aldehyde, galbanum ester, allyl hexanoate, allyl cyclohexyl propionate, allyl heptanoate, allyl phenoxyacetate, isopentyl acetate, amyl benzoate, amyl butyrate, amyl hexanoate, amyl cinnamate, amyl isovalerate, amyl phenylacetate, amyl propionate, isopentyl salicylate, acetylated agarwood oil (Amyris acetate), anisyl acetate, benzyl acetate, benzyl benzoate, benzyl butyrate, benzyl cinnamate, benzyl formate, benzyl isobutyrate, benzylisoeugenol, benzyl propionate, benzyl salicylate, benzyl tiglate, butyl acetate, butyl butyrate, butyl butyrolactate, caryophyllene acetate, cedryl acetate, cinnamyl acetate, cinnamyl butyrate, cis-3-hexenyl acetate, cis-3-hexenyl benzoate, cis-3-hexenyl hexanoate, cis-3-hexenyl formate, cis-3-hexenyl isobutyrate, cis- 3-Hexenyl-2-methylbutyrate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, cis-3-hexenyl tiglate, citronellyl acetate, citronellyl butyrate, citronellyl formate, citronellyl isobutyrate, citronellyl propionate, citronellyl tiglate, cycloclabute, cyclogalbanate, cyclohexyl ethyl acetate, decyl acetate, dibutyl phthalate, diethyl malonate, diethyl phthalate, dihydromyrcenyl acetate, dimethyl octyl acetate, dimethyl phenethyl acetate phenyl ethyl carbinyl acetate), dioctyl adipate, dioctyl phthalate, dimethyl benzyl carbinyl acetate, dimethyl benzyl carbinyl butyrate, ethyl linalyl acetate, ethyl 2-methylbutyrate, ethyl 3-phenylpropionate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethyl decanoate, ethyl hexanoate, ethyl octanoate, ethyl cinnamate, ethyl heptanoate, ethyl hexyl acetate, ethyl isobutyrate, ethyl laurate, ethyl pelargonate, ethyl phenoxyacetate, ethyl phenyl acetate, ethyl phenyl glycidate, ethyl propionate, ethyl crocetin, ethyl salicylate, ethyl valerate, eugenyl acetate, evernyl, fenchyl acetate acetate), Floramat, FrescolatML, ethyl methyl dicyclopentane acetate (Fructone), ethyl tricyclodecane carboxylate (Fruitate), geranyl acetate (Geranyl acetateacetate), Geranyl butyrate, Geranyl formate, Geranyl propionate, Geranyl tiglate, Givescone, Guaiol acetate, Hedione, Helvetolide, Herbanate, Hexyl acetate, Hexyl benzoate, Hexyl butyrate, Hexyl caproate, Hexyl isobutyrate, Hexyl propionate, Hexyl salicylate, Isoborneol acetate, Isobutyl acetate, Isobutylphenyl acetate, Isobutyl salicylate, Isoeugenol acetate, Isononyl acetate, Isopentyrate, Isopropyl 2-methylbutyrate, Isopropyl myristate myristate), Jasmonyl, Liffarome, Linalyl acetate, Mahagonate, Manzanate, Menthanylacetate, Menthyl acetate, Methyl benzoate, 2-methylbutyl acetate, Methyl camomille, Methyl cinnamate, Methyl cyclogeranate, Methyl heptinecarbonate, Methyl laurate, Methyl octine carbonate, Methyl phenyl acetate, Methyl salicylate, Methyl-2-methylbutyrate, Neofolione, Nopyl acetate, Octenyl acetate, Octyl acetate, Octyl isobutyrate, Para cresyl acetate, Para cresyl isobutyrate, Para cresyl phenyl acetate, phenyl acetate), pear ester, peranat, phenoxyethyl isobutyrate, phenethyl acetate, phenethyl butyrate, phenethyl formate, phenethyl isobutyrate, phenethyl phenylacetate, phenethyl propionate, phenethyl salicylate, phenethyl tiglate, phenylpropyl isobutyrate, prenyl acetate, romandolide, sagecete, styrallyl acetate, styrallyl propionatepropionate), Tangerinol, Terpinyl acetate, Thesaron, trans-2-hexenyl acetate, Tropicate, Verdox, Verdyl acetate, Verdyl propionate, Vertenex, Vetikolacetate, Vetiveryl acetate, Yasmolys.

[0109] Lactones such as: Ambrettolide, Arova N, Celeriax, Decanolide δ, Decanolide γ, Dodecanolactone δ, Dodecanolactone γ, Brassic acid glycol ester, Exaltolide, Heptanolide γ, Caprolactone δ, Caprolactone γ, Methyl laitone, Methyl octanolactone, Nonanolide δ, Nonanolide γ, Octahydrocoumarin, Octanolide δ, Octanolide γ, Rootylone, Silvanonesupra, Undecanolide δ, Undecanolide γ, Valerolactone γ, 10-OxaHexaDecanolide (OHD Musk), Coumarin, Habanolide, Jasmolactone.

[0110] Aldehydes such as: acetaldehyde, adoxal, C10 aldehyde, iso-C11 aldehyde, C11 moa aldehyde (Aldehyde C11moa), C11 undecenal, C11 undecyl aldehyde, C12 lauric aldehyde, C12 MNA aldehyde, anisaldehyde, amyl cinnamaldehyde, benzaldehyde, bourgeonal, campholenaldehyde, cantonal, cetonal, cinnamaldehyde, cis-4-decenal, cis-6-nonenal, citral, citronellal, citronellal, cocal, cuminaldehyde, curgix, cyclal c, cyclamen aldehyde), cyclomyral, cyclovertal, decanal 9, dupical, empetal, ethyl vanillin, floralozone, florhydral, geranaldehyde, neoheterol, heptaldehyde, hexanal, hexylcinnamaldehyde, hivernal neo, hydratropaldehyde, hydroxycitronellal, intreleven aldehyde), Isobutavan, Isocyclocitral, Isovaleraldehyde, Lilial, Limonenal, Maceal, Mefranal, Melonal, Methylcinnamaldehyde, Trans-2-cis-6-nonadienal, Nonanal, Octanal, Oncidal, p-Tolualdehyde, Phenylacetaldehyde, Phenylpropionaldehyde, Methyl Precyclemone B, Safranal, Salicylaldehyde, Scentenal, Syringaaldehyde, Trans-4-Decenal, Trans-2-Dodecenal, Trans-2-Hexenal, Trans-2-Nonenal, Trifernal, Vanillin, Veratraldehyde, Vernaldehyde.

[0111] Ketones such as: Acetanisol, Acetoin, Acetophenone, Aldron, Allyl ionone, Benzophenone, Benzyl acetone, Calone, Camphor, Carvone d-, l-Carvone, Cashmeran, Cedryl methylketone, Cepionate, Claritone, Cosmone, Crysolide, Cyclotene, Damascenone, Damascone alpha, Damascone beta, Damascone delta, Damascone gamma, Diacetyl, Dihydro beta ionone, Dihydroisojasmonate isojasmonate), dimethyl octenone, Dynascone, ethyl amyl ketone, ethyl maltol, fenchone, filbertone, geranyl acetone, 8-cyclohexene-1-one, heptyl cyclopentanone, ionone α, ionone β, pure ionone, iriswood, ironone α, ambergris ketone, isofenchone, isojasmonate, isojasmonate T, isojasmonate K K), Isomenthone, Isophorone, Jasmonecis-, Kambernoir, Kephalis, Koavone, Lavendinal, Maltol, Menthone, Methylacetophenone, Methylamylketone, Methylheptenone, Methylhexylketone, Methylionone gamma, Methylnaphthylketone beta, Methylnonylketonenonylketone), Muscenone, Muscone, Nectaryl, Orinox, OTBC ketone, tert-butylcyclohexanone, Patchwood, Phantolid, Pharaone, Piperitone, Plicatone, Raspberry ketone, Raspberryketone methyl ether, Safraleine, Spirogalbanone pure, Tonalid, Trimofix O, Veloutone, Vetikon.

[0112] Alcohols such as: Alcohol oxo C13, Amber core, Ambermax, Ambrinol, Amyl vinyl carbinol, Anisic alcohol, Bacdanol, Benzyl alcohol, Butyl alcohol, Cedrol crystals, Cinnamyl alcohol, Citronellol, Coranol, Decyl alcohol, Dimethyl benzyl carbinol, Dimethyl octanol, Dimethyl phenethyl carbinol, Dimetol, Fenchol, Hexanol, Isoborneol, Isobornyl cyclohexanol, Javanol, Keflorol, Kohinool, Lauryl alcohol, Lilyflore, Linalool oxide oxide), Mayol, Menthol, Norlimbanol, Octanol, Osyrol, tert-butyl cyclohexanol, Phenoxanol, Phenoxyethanol, Phenylethanol, Phenylpropanol, Propylene glycol, Rosaphen, Rose glycol, Styrallyl alcohol, Tricyclodecanedimethanol, Tetrahydrolinalool, Tetrahydro myrcenol, Timberol, Undecavertol, Citronellol laevo), Cyclofloranol, Dihydrolinalool, Dihydromyrcenol, Dimyrcetol, Ebanol, Geraniol, Isopulegol, Linalool, Nerol, Nerolidol, Trans-2-cis-6-nonadienol, Polysantol, Rosalva, Sandalmysore core, Sandalore, Terpinen-4-ol, Terpineol, Trans-2-hexenol.

[0113] Phenols such as: Butylated hydroxyanisole, dihydroeugenol, dimethylhydroquinone, dimethyl resorcinol, Eugenol pure, guaiacol, isoeugenol, meta cresol, methyl diantilis, paracresol, propenyl guaethol, thymol, ultravanil.

[0114] Ethers such as: Ambroxan, Anethole, Anther, Benzyl Isoamyl Ether, Benzyl Isopropyl Ether, Benzyl Isovalerate, Boisiris, Cedramber, Cetalox, Decyl Methyl Ether, Dibenzyl Ether, Dihydro Rose Oxide, Diphenyl Oxide, Doremox, Estragole, Ethyl Linalool, Eucalyptol, Galaxolide, Gyrane, Herbavert, Lime Oxide, Madrox, Methyl Isoeugenol, β-Naphthyl Isobutyl Ether, Nerol Oxide, Nerolinbromelia, Para cresyl butyl ether, Para cresyl methylether), Petiole, phenethyl methyl ether, 2,4-dimethyl-4-phenyltetrahydrofuran (Rhubafuran), rose oxide (Rose oxide), aromatic rose ether (Rosyrane), Trisamber, Vetylbois K, β-naphthyl methyl ether (Yarayara).

[0115] Acetals such as: Acetal CD, Acetal R, Amberketal, Boisambrene forte, Citrathal, 1,1-diethoxyethane, Emeraldine, Freshopal, Herboxane, Indoflor, Jacinthaflor, Magnolan, Spirambrene, Viridine, Elintaal, Glycolierral, Caraflor, Methyl pamplemousse.

[0116] Hydrocarbons such as: Bisabolene, Camphene, Carene delta 3, Caryophyllene, Cedrene, Cymene para, Dipentene, Diphenylmethane, Isolongifolene, Limonene d-, Longifolene, Myrcene, Naphthalene, Ocimene, Pinene alpha, Pinene beta, Styrene, Terpinenegamma, Terpinolene, Undecatriene, Verdoracine.

[0117] Sulfur-containing compounds such as Corps cassis, dibutyl sulfide, dimethyl sulfide, Exovert, Grapefruit thiol, Oxane, Ribes mercaptan, Sulfurol, Thiocineol.

[0118] Nitriles such as: cinnamon nitrile, citronellyl nitrile, citronitrile, clonal, cumin nitrile, hexylcyclopentanone, iris nitrile, lemon nitrile, peony nitrile, tridecyl nitrile, agrumen nitrile, and n-dodecyl nitrile.

[0119] Oximes such as Buccoxime, Labienoxime, and Stemone.

[0120] Nitrogen-containing heterocyclic rings such as: 2-acetylpyrazine, 2-acetylpyridine, sec-butylquinoline, 2-(3-phenylpropyl)pyridine (Corps racine), 2-ethyl-3,5 (or 6)-dimethylpyrazine, 1-furfurylpyrrole, indole, isobutylquinoline, 2-isobutyl-3 (or 6)-methoxypyrazine, isopropylquinoline, Maritima, p-methylquinoline, skatol, 2,3,5-trimethylpyrazine.

[0121] Nitro compounds such as Musk Ketone.

[0122] Schiff bases such as: Aurantiol, helianthral, ​​ligantraal, and lingorhizine.

[0123] Other materials include: acetanilide, cyclic amine (Gardamide), fruit amide (Paradisamide), dimethyl anthranilate (Dimethyl anthranilate), methyl anthranilate (Methyl anthranilate), butyric acid, capric acid, caproic acid, caprylic acid, phenylacetic acid, caryophyllene oxide, cedroxyde, and Tobacarol.

[0124] Thus, compounds of formula (A) or (B) and a wide range of known odorants / fragrances, flavors and / or deodorizing / masking materials (as will be apparent from the above compilation) can be used to produce compositions. In the production of such compositions, the previously mentioned known fragrances, flavors and / or deodorizing / masking materials can be used according to methods known to perfumers, such as according to WA Pocket, Perfumes, Cosmetics and Soaps 2, 7th edition, Chapman and Hall, London 1974.

[0125] In one embodiment of the invention, the claimed fragrance, flavor and / or deodorizing / masking composition comprises, in addition to the compound of formula (A) or (B), at least one ester and / or one alcohol, preferably at least one mixture of esters and alcohols; the esters and / or alcohols are preferably selected from the list defined above. In one embodiment of the invention, the claimed odorant composition is characterized in that the total content of the compound(s) of formula (A) or (B) together with the ester(s) and / or the alcohol(s) is higher than 25 wt%, preferably higher than 50 wt%, for example higher than 75 wt%, or even higher than 90 wt%.

[0126] preparation

[0127] As reported by Hombrecher, H. et al. in Helvetica Chimica Acta, Vol. 69, 1961, pp. 1681-1684, compounds of formula (A), such as 4,4,7,7-tetramethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one, are synthesized by LiAlH4-mediated or NaBH4-mediated reduction of 4,4,7,7-tetramethyl-4,6,7,8-tetrahydro-2H-chromene-2,5(3H)-dione, which in turn is synthesized by dimethylcyclohexanedione and an alkylidene-substituted Meldrum acid or a substituted acryloyl chloride.

[0128] We have envisioned a different method in which we synthesize compounds of formula (A) or (B) in one step (method P) or in two steps (methods Q or R). However, we need a method that selectively provides 6-substituted-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one derivatives. Since method Q does not selectively provide the desired 6-substituted derivatives, as it also gives inseparable 8-substituted derivatives; we have also invented a new synthetic method (method S) that only gives 6-substituted-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one derivatives.

[0129] Method P .In a preferred embodiment of the present invention, the compounds represented by the general formula (A) and / or (B) can be advantageously synthesized in one step from the corresponding cyclohexanedione of formula (I) and the alcohol of formula (II) in the presence of an acid, for example in the presence of p-toluenesulfonic acid (0.05 equivalents), using toluene as solvent, at a temperature of 80-90°C.

[0130]

[0131] Method Q In another preferred embodiment of the present invention, the compound of formula (A) can be advantageously prepared in two steps from cyclohexanedione (I) and homoallyl alcohol of formula (III). The first step of this scheme is the reaction of cyclohexanedione (I) with alcohol (III) in the presence of iodine / toluene / THF to obtain vinyl ester (IV). In the second step, compound (IV) is subjected to AlCl3-mediated cyclization in ethylene dichloride (EDC) to obtain products (A) and / or (B).

[0132]

[0133] Method RIn another preferred embodiment of the present invention, the compounds of formula (A) and / or (B) can be advantageously prepared in two steps from cyclohexanedione (I) and an allyl alcohol of formula (II). The first step of this scheme is the reaction of cyclohexanedione (I) with alcohol (II) in the presence of iodine / toluene / THF to obtain vinyl ester (V). In the second step, compound (V) is subjected to AlCl3-mediated cyclization in ethylene dichloride (EDC) to obtain products (A) and / or (B).

[0134]

[0135] In another preferred embodiment of the present invention, if 4-alkylcyclohexane-1,3-dione (XI) and isopentenol are treated with iodine / toluene / THF according to method Q, two isomers (XII) and (XIII) are obtained. This isomer mixture is subjected to AlCl3-mediated cyclization to obtain products (A1) and (A2). These two isomers can be separated by column chromatography, but usually cannot be separated by fractional distillation because their boiling points are very close.

[0136]

[0137] Therefore, a method for selectively obtaining A1 is also desired.

[0138] Method S Ethyl acetoacetate was alkylated using base and alkyl iodide (R1-I). The resulting alkyl derivative (XIV) was treated with methyl acrylate in the presence of potassium tert-butoxide in THF at 0°C to give 4,4-ethoxycarbonyl-alkyl substituted cyclohexane-1,3-dione (XV). Surprisingly, we found that compound (XV) reacted with prenol in the presence of iodine / toluene / THF to give only regioisomer (XVI). LiCl-mediated decarboxylation in DMSO at 170°C selectively gave vinyl ester (XII), and subsequent AlCl3-mediated cyclization of (XII) gave only A1.

[0139]

[0140] Example :

[0141] Embodiment 1:

[0142] 4,4-Dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0143] Synthesis of 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0144] Step 1: Synthesis of 3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one

[0145] Method Q:

[0146] To a mixture of cyclohexane-1,3-dione (25 g, 223 mmol, 1 eq.) in toluene (250 ml) was added 3-methylbut-3-en-1-ol (23.04 g, 268 mmol, 1.2 eq.) and iodine (2.72 g, 10.71 mmol, 0.048 eq.). After stirring the reaction mixture for 16 h, the reaction was quenched with 200 mL of 10% sodium thiosulfate solution. The toluene layer was then separated and the aqueous layer was extracted with ethyl acetate (2 x 50 mL). The combined organic layers were washed with water (1 x 50 mL) and dried over anhydrous sodium sulfate. The organic solvent was evaporated on a rotary evaporator to give 30 gm of crude material, which gave 32 g of 3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one (80%) based on flash chromatography.

[0147] 1 H-NMR (400MHz, CDCl3): δ5.39 (s, 1H), 4.85 (s, 1H), 4.76 (s, 1H), 3.96 (t, J = 6.8Hz, 2H), 2.47-2.35 (m, 6H), 2.02-1.96 (m, 2H), 1.78 (s, 3H).

[0148] Step 2: Synthesis of 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0149] Method Q: To a stirred solution of AlCl3 (266 g, 2 mol, 1.2 eq) in 1,2-dichloroethane (200 mL) at 15°C was added a solution of 3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one (300 g, 1.66 mol, 1 eq) in EDC (100 mL) dropwise. The reaction mixture was warmed to 25°C and stirred for 6 h. The reaction mixture was slowly poured into ice water with vigorous stirring. The aqueous layer was separated and extracted with DCM (500 mL). The combined organic layers were washed with water (2 x 1 L) and then stirred with aqueous sodium bicarbonate solution (1 L) for 1 hour. This was repeated twice. The organic layer was separated and dried over sodium sulfate and concentrated on a rotary evaporator to give 220 g of crude product. The crude product was purified by fractional distillation (81-83°C / 1 mm) to give 189 g of pure 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (63%).

[0150] 1H-NMR (400MHz, CDCl3): δ4.10-4.07(m,2H),2.37-2.29(m,4H),1.90-1.84(m,2H),1.69-1.66(m,2H),1.29(s,6H). 13 C-NMR (100MHz, CDCl3): δ197.4,170.9,119.3,63.9,39.6,38.1,29.1,27.3,20.1.

[0151] Odor profile: tobacco, leather, fruity, woody

[0152] Embodiment 2:

[0153] 4,4,6-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0154] Synthesis of 4,4,6-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0155] Method S:

[0156] Step 1: Synthesis of ethyl 1-methyl-2,4-dioxocyclohexane-1-carboxylate:

[0157] Potassium tert-butoxide (35.8 g, 319 mmol, 1.1 eq.) was added to a solution of ethyl 2-methyl-3-oxobutanoate (49.3 ml, 348 mmol, 1.2 eq.) in tetrahydrofuran (400 ml) at room temperature. The reaction mixture was cooled to 0 ° C., and methyl acrylate (26.3 ml, 290 mmol, 1 eq.) was then added. After stirring the reaction mixture for 16 h, 2M HCl was added to adjust the pH to 3-4, and the mixture was extracted with EtOAc (3 x 50 mL). The organic layer was washed with water, brine, and then concentrated to give a crude material, which was purified by column chromatography using 30-35% EtOAc in hexane to give 1-methyl-2,4-dioxocyclohexane-1-carboxylic acid ethyl ester (47 g, 82%).

[0158] Step 2 Synthesis of ethyl 1-methyl-4-((3-methylbut-3-en-1-yl)oxy)-2-oxocyclohex-3-ene-1-carboxylate:

[0159] 3-methylbut-3-ene-1-ol (61.1ml, 605mmol) and 4-methylbenzenesulfonic acid (17.37g, 101mmol) were added to a solution of 1-methyl-2,4-dioxocyclohexane-1-carboxylic acid ethyl ester (100g, 504mmol) in toluene (1600mL) at 25°C. After stirring the reaction mixture for 16h at 25°C, it was quenched with saturated NaHCO3 solution. The mixture was extracted with EtOAc (3x 100mL) and the combined organic layer was washed with brine, dried and filtered with anhydrous Na2SO4. The organic layer was concentrated to obtain crude 1-methyl-4-((3-methylbut-3-ene-1-yl)oxy)-2-oxocyclohex-3-ene-1-carboxylic acid ethyl ester (89g), which was used as is for the next step reaction.

[0160] Step 3 Synthesis of 6-methyl-3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one:

[0161] To a stirred solution of crude ethyl 1-methyl-4-((3-methylbut-3-en-1-yl)oxy)-2-oxocyclohex-3-ene-1-carboxylate (89 g, 334 mmol) in DMSO (355 ml) and water (14 mL) was added lithium chloride (70.8 g, 1671 mmol). The reaction mixture was stirred at 170 °C for 8 h. The reaction mixture was diluted with water and then extracted with EtOAc (3 x 50 mL). The combined organic layers were washed with brine, filtered and concentrated to give a crude residue which was purified by column chromatography to give 6-methyl-3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one (30 g, 46%).

[0162] Step 4:

[0163] Synthesis of 4,4,6-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0164] To a stirred solution of 6-methyl-3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one (30 g, 154 mmol) in 1,2-dichloroethane (250 ml) was added aluminum chloride (41.2 g, 309 mmol) at 25°C. The reaction was stirred at 25°C for 20 min. The reaction mixture was slowly added to ice water and the mixture was stirred for 30 min, then it was extracted with dichloromethane (3 x 50 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and filtered. The organic layer was concentrated and the crude compound was purified by column chromatography using 5% EtOAc in hexane to give 4,4,6-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one (18 g, 60%).

[0165] 1 H-NMR (400MHz, CDCl3): δ4.06-4.02(m,1H),3.98-3.92(m,1H),2.37-2.23(m,2H),2.18-2.14(m,1H),1.91-1.84(m,1H),1.66-1.47(overlapping m,3H),1.22(s,3H),1.18(s,3H),1.04(d,J=6.8Hz,3H). 13 C-NMR (100MHz, CDCl3): δ200.1,169.9,118.7,64.0,41.1,39.8,29.4,28.3,28.2,28.1,27.0,15.8.

[0166] Odor profile: exotic fruity, delta-damascena type, woody

[0167] Embodiment 3:

[0168] 6-Ethyl-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0169] Synthesized in 4 steps from ethyl 2-ethyl-3-oxobutanoate according to Method S.

[0170] 1 H-NMR (400 MHz, CDCl3): δ4.04-3.93 (m, 2H), 2.34-2.21 (m, 2H), 1.98-1.85 (s, 2H), 1.81-1.71 (m, 1H), 1.66-1.49 (partial overlap m, 3H), 1.39-1.28 (m, 1H), 1.20 (s, 3H), 1.19 (s, 3H), 0.84 (t, J = 7.2 Hz, 3H).

[0171] Odor profile: Fruity, plum, woody, beta-damascena-like

[0172] Embodiment 4:

[0173] 2,3,3,4,4-Pentamethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0174] Synthesized in 2 steps according to Method Q from cyclohexane-1,3-dione and 3,3,4-trimethylpent-4-en-2-ol.

[0175] 1H-NMR (400 MHz, CDCl3): δ 3.98 (q, J = 6.4 Hz, 1H), 2.33-2.24 (partial overlap m, 3H), 2.21-2.15 (m, 1H), 1.84-1.70 (m, 2H), 1.17 (d, J = 6.8 Hz, 3H), 1.15 (s, 3H), 1.09 (s, 3H), 0.71 (s, 3H), 0.67 (s, 3H). 13 C-NMR (100MHz, CDCl3): δ198.1,170.4,118.8,75.7,38.9,38.2,37.2,29.3,23.6,20.6,20.5,18.4,15.6,15.0.

[0176] Odor profile: Fruity, woody, cashmeran (cashmeran includes floral and fruity notes)

[0177] Embodiment 5:

[0178] 2,4,4-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0179] Odor profile: sweet, sandalwood, woody

[0180] Embodiment 6:

[0181] 3,4,4-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0182] According to Method Q, synthesized in two steps from cyclohexane-1,3-dione and 3-methyl-2-methylenebutan-1-ol.

[0183] Odor Profile: Strong minty, woody, animalic background

[0184] Embodiment 7:

[0185] 4,4,6,8-Tetramethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0186] Synthesized from 4,6-dimethylcyclohexane-1,3-dione and 3-methylbut-3-en-1-ol according to Method Q.

[0187] Odor Profile: Minty, Dry, Woody

[0188] Embodiment 8:

[0189] 6-(Cyclopropylmethyl)-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0190] Synthesized from 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and (bromomethyl)cyclopropane in one step.

[0191] 1 H-NMR (300MHz, CDCl3): δ4.08-4.01(m,2H),2.38-2.34(m,2H),2.2-2.05(m,2H),1.74- 1.56(m,4H),1.37-1.35(m,1H),1.25(s,6H),0.68-0.66(m,1H),0.45-0.37(m,2H),0.07 -0.01(m,2H). 13 C-NMR (100MHz, CDCl3): δ199.8,169.4,119.1,64.1,47.0,40.0,35.0,29.5,28.1(2C),27.5,25.3,8.95.5.36,4.24.

[0192] Scent profile: Woody, amber

[0193] Example 9

[0194] 6-Isobutyl-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one

[0195] Synthesized from 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 1-bromo-2-methylpropane in one step, yield = 15%.

[0196] 1 H-NMR (300MHz, CDCl3): δ4.09-3.99(m,2H),2.40-2.34(m,2H),2.25-2.16(m,1H),2.23-1.99(m,1H ),1.97-1.61(m,4H),1.58-1.33(m,2H),1.27(s,6H),0.94(d,J=6.6Hz,3H),0.89(d,J=6.3Hz,3H).

[0197] Odor profile: Dry woody amber

[0198] Example 10

[0199] 2,2,3,3-Tetramethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one

[0200] 1H-NMR (400MHz, CDCl3): δ2.27(t,J=6.4Hz,2H), 2.22(t,J=6.8Hz,2H), 1.91-1.93(m,2H), 1.21(s,6H), 1.10(s,6H).

[0201] Odor profile: Woody, Musk

[0202] Composition Evaluation Example 1:

[0203] In the following invention, Example (A) containing the compound from Example 2 (4,4,6-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one) and Comparative Example B containing the commercially available compound ethyl crocetin (C = Blank) illustrate a composition evaluation study for a woody blend fragrance for shampoo (IPM = isopropyl myristate).

[0204]

[0205] Introducing 5.5% by weight of 4,4,6-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one as a 10% w / w solution in IPM gave a rounded, punchy woody effect. On the other hand, when 10% by weight of ethyl crocetin in IPM was used in the above blend, only a normal rose effect was observed.

[0206] Composition Evaluation Example 2:

[0207] In another evaluation involving a rose accord fragrance for a shampoo, when the compound from Example 2 (4,4,6-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one) was included in the rose accord, it imparted very well-toned and very powerful rose and spicy notes; this was much stronger than the effect imparted by ethyl crocetin under the same conditions.

Claims

1. A compound of the following formula A or formula B Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are independently selected from hydrogen, C1-C5 alkyl or C1-C5 alkenyl, provided that - compounds of formula A excluding compounds of formula A-exc, and - The compound of formula B does not include compounds of formula B-exc1, B-exc2 and B-exc3 2. The compound of formula A or formula B according to claim 1, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 independently selected from hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, isobutyl, n-pentyl, cyclopropylmethyl, cyclobutylmethyl, cyclobutyl, cyclopentyl, allyl, 3-methylbut-2-en-1-yl, 3-methylbut-3-en-1-yl, but-3-en-1-yl or 2-methylallyl.

3. The compound of formula A or formula B according to claim 1 Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are independently selected from hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl or tert-butyl.

4. The compound according to claim 1, which is selected from the following compounds: 1) 4,4-Dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 2) 4,4,6-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 3) 6-ethyl-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 4) 3,3,4,4-Tetramethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 5) 2,3,3,4,4-pentamethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 6) 2,4,4-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 7) 3,3,4,4,6-pentamethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 8) 3,4,4-Trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 9) 4,4,6,8-Tetramethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 10) 4,4,6,7,7-pentamethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 11) 6-(Cyclopropylmethyl)-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 12) 6-isobutyl-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one.

5. The compound according to claim 1, which is selected from the following compounds: 13) 3,3-Dimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one 14) 3,3,5-Trimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one 15) 3,3,7-Trimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one 16) 5-ethyl-3,3-dimethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one 17) 2,2,3,3-Tetramethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one 18) 2,2,3,3,5-pentamethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one 19) 2,2,3,3,7-pentamethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one 20) 5-ethyl-2,2,3,3-tetramethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one.

6. A mixture of a compound of formula A according to any one of claims 1 to 4 together with a compound of formula B according to any one of claims 1 to 3 or 5.

7. Odorants consisting of the compounds according to any one of claims 1 to 5 or the mixture according to claim 6.

8. A fragrance, flavour and / or deodorising / masking composition comprising a compound according to any one of claims 1 to 5 or a mixture according to claim 6.

9. A fragrance, flavour and / or deodorising / masking composition according to claim 8, wherein the compound of formula A or formula B is present in an amount of at least 0.1 wt.%.

10. A fragrance, flavour and / or deodorising / masking composition according to claim 9, wherein the compound of formula A or formula B is present in an amount of at least 1 wt.%.

11. A fragrance, flavour and / or deodorising / masking composition according to any one of claims 8 to 10, wherein the content of compounds of formula A and formula B is less than 50 wt.%.

12. A fragrance, flavour and / or deodorising / masking composition according to claim 11, wherein the content of compounds of formula A and formula B is less than 25 wt.%.

13. A fragrance, flavour and / or deodorising / masking composition according to claim 8, comprising at least one ester or one alcohol, or at least one mixture of an alcohol and an ester, wherein the total content of compounds of formula (A) and formula (B) together with the ester and the alcohol is higher than 25 wt%.

14. A fragrance, flavour and / or deodorising / masking composition according to claim 13, wherein the total content of compounds of formula (A) and (B) together with the ester and alcohol is greater than 50 wt%.

15. Use of a fragrance, flavour and / or deodorising / masking composition according to claim 8 in perfumed or flavoured products.

16. Use of a compound according to any one of claims 1 to 5 or a mixture according to claim 6 for perfuming or flavoring a product.

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