Fragrances and compositions containing fragrances

Abstract

The present invention relates to substituted hexahydro-5H-chromen-5-one and / or substituted tetrahydrobenzofuran-4(2H)-one derivatives that are useful as fragrances or flavoring materials.

Description

[Technical Field]

[0001] The present invention relates to a new class of odoriferous compounds represented by formula (I), which correspond to substituted hexahydro-5H-chromen-5-ones and / or their substituted tetrahydrobenzofuran-4(2H)-one derivatives, which are useful as fragrances or flavoring materials, particularly in imparting damascone- or damascenone-type notes, such as fruity, minty, woody, powdery, ambery, and / or tobacco-like notes, to fragrance, aroma, or deodorizing / masking compositions. The present invention also relates to fragrance, flavor, and / or deodorizing / masking compositions comprising the above-mentioned new class of odoriferous substituted hexahydro-5H-chromen-5-ones or their substituted tetrahydrobenzofuran-4(2H)-one derivatives. The present invention further refers to the odoriferous compounds that can be used in the novel fragrance, flavor, and / or deodorizing / masking compositions of the present invention. The present invention also refers to methods for preparing said odorants / compounds and corresponding fragrance, flavor, and / or deodorizing / masking compositions comprising said odorants / compounds.

[0002] More specifically, 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) (perfuming agents) that are useful as fragrances or flavoring materials, especially in imparting damascone-type notes, fruity notes, minty notes, woody notes, powdery notes, ambery notes, and / or tobacco-like notes to perfume, aroma, and / or deodorizing / masking compositions. [Background technology]

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

[0004] When fruity and floral notes are required, various isomers of damascones are used. Typical damascones 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, all of the above ingredients are known to be skin sensitizers, and IFRA guidelines recommend significant restrictions on their use in consumer products. Therefore, safe alternatives to damascone are constantly sought.

[0005] [ka]

[0006] Damascone-type notes include α-damascone-type notes (known as fruity, green, seedy, tropical, spicy, apple, and woody), β-damascone-type notes (known as fruity, floral, currant, blackcurrant, plum, rose, honey, and tobacco), and δ-damascone-type notes (known as fruity, sweet, rose, natural, petal, currant, blackcurrant bud, and tobacco bud). Damascenone-type notes include β-damascenone-type notes (known as natural sweet, fruity, rose, plum, grape, raspberry, and sugar).

[0007] Examination of the structures of various damascone isomers revealed the presence of an α,β-unsaturated ketone motif. Many electrophilic α,β-unsaturated carbonyl compounds are known to act as skin sensitizers by reacting with nucleophilic proteins on the skin, since α,β-unsaturated carbonyl compounds are good Michael acceptors (Non-Patent Document 1). Also, electron-donating substituents such as alkyl groups on the α-C atom, and to a lesser extent on the β-C atom, can provide C-terminal protection against nucleophilic attack. β =C α It has also been reported to inactivate binding.

[0008] The article entitled "Synthesis of 2,3,4,6,7,8-Hexahydro-5H-1-benzopyran-5-ones and 3-(6-Oxo-1-cyclohexenyl)alkanoic Acids by Reduction of 4,6,7,8-tetrahydro-2H-1-benzopyran-2,5(3H)-diones" from Non-Patent Document 2 provides the corresponding comparative results of the reduction.

[0009] The article in Non-Patent Document 3 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] Patent Document 1 relates to the preparation of bicyclic enol ethers (X) (wherein n is 3-12 and R1, R2, and R3 can be H or C1-C4-alkyl) by a two-step sequence including the free radical addition reaction of an allyl ether of general formula (V) (wherein R4 is tert-butyl, tetrahydrofuran-2-yl, or tetrahydropyran-2-yl) with a cyclic ketone (W) to give a compound of general formula (Y), followed by acid-catalyzed cyclization (the compounds (X) and (Y) are intermediates for the synthesis of musk-like fragrances).

[0011] [ka]

[0012] Patent Document 2 relates to 4a,5,6,7,8,8a-hexahydro-4,7-dimethyl-4H-1-benzopyran (formula shown below), which is useful as an odoriferous fragrance compound, and a method for preparing the same.

[0013] [ka]

[0014] Patent document 3 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 goods containing these compounds, and their manufacture.

[0015] [ka]

[0016] Patent Document 4 claims substituted hexahydro-(5H)-1-benzopyran-5-one (or hexahydro-(5H)-chromen-5-one) derivatives and substituted tetrahydro-(5H)-1-benzopyran-5-one (or tetrahydro-(5H)-chromen-5-one) derivatives, a method for synthesizing the compounds, and a fragrance composition containing an olfactory-acceptable amount of the compounds.

[0017] Surprisingly, it has been 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, confer an exotic fruity, damascone-like, or damascenone-type profile. These compounds lack any α,β-unsaturated ketone groups in their structures. These compounds still possess a geminal dimethyl group, a common feature of all damascone isomers. Furthermore, in these compounds, the ketone group exists as part of a six-membered ring fused to a six-membered ring (Formula A) or five-membered ring (Formula B) containing a geminal dimethyl group. The six-membered ring (Formula A) or five-membered ring (Formula B) containing a geminal dimethyl group also contains an oxygen atom. Interestingly, many of these compounds of Formula A and Formula B also advantageously impart minty, woody, powdery, ambery, and / or tobacco-like notes to perfume, aroma, and / or deodorizing / masking compositions. [Prior art documents] [Patent documents]

[0018] [Patent Document 1] U.S. Patent No. 4,268,445 [Patent Document 2] U.S. Patent No. 4,233,226 [Patent Document 3] European Patent Application Publication No. 2848611 [Patent Document 4] International Publication No. 2014 / 064716 Brochure [Non-patent literature]

[0019] [Non-Patent Document 1] Aptula, AO et al., Chem. Res. Toxicol., Vol. 18 (2005), pp. 1420-1426 [Non-patent document 2] Helvetica Acta - Volume 69 (1986) - Pages 1681-1684 [Non-patent document 3] Chemische Berichte, Vol. 123 (1990), pp. 101-105 Summary of the Invention [Means for solving the problem]

[0020] The present invention relates to a compound represented by formula (I) in which n is 0 or 1. [ka] (In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are independently selected from the group consisting of hydrogen, C1-C5 alkyl (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, t-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), with the proviso that - when n=1 and R3=R4=CH3, the other groups R1, R2 and R5 to R 10 cannot be all hydrogen, and - when n=0 and R3=R4=CH3, The other groups R1, R2, and R5 to R8 cannot all be hydrogen, and If R7=R8=CH3, the other groups R1, R2, and R5-R6 cannot all be hydrogen; and - when n=0 and R8=CH3, the other groups R1, R2, and R5-R7 cannot all be hydrogen).

[0021] For the avoidance of doubt, the following pairs of groups: R1 and R2, R3 and R4, R5 and R6, R7 and R8, R9 and R 10 are distinct groups, i.e., they do not together form a ring. The exclusion of the above four compounds is justified based on the results that these compounds did not confer olfactory properties according to the objectives of the present invention.

[0022] In one embodiment, the present invention provides a compound of formula (I) wherein n is 0 or 1. [ka] (In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, or t-butyl groups, - when n=1 and R3=R4=CH3, the other groups R1, R2 and R5 to R 10 cannot be all hydrogen, and - when n=0 and R3=R4=CH3, The other groups R1, R2, and R5 to R8 cannot all be hydrogen, and If R7=R8=CH3, the other groups R1, R2, and R5-R6 cannot all be hydrogen; and - when n=0 and R8=CH3, the other groups R1, R2, and R5 to R7 cannot all be hydrogen).

[0023] The general formula (I) is 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 above groups as defined herein.

[0024] [ka]

[0025] The compound of formula B is a compound of general formula (I) in which n=0, and therefore R9 and R 10 Does not contain groups.

[0026] In one embodiment, the present invention provides a compound of formula A or formula B [ka] wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are independently selected from the group consisting of hydrogen, C1-C5 alkyl (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, t-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), with the proviso that - Compounds of formula A have the formula A-exc [ka] The compound Except ,and, Compounds of formula B are represented by the formulas B-exc1, B-exc2, and B-exc3 [ka] The compound except ) regarding.

[0027] In one embodiment, the present invention provides a compound of formula A or formula B [ka] wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, or t-butyl groups, - Compounds of formula A have the formula A-exc [ka] The compound Except ,and, Compounds of formula B are represented by the formulas B-exc1, B-exc2, and B-exc3 [ka] The compound except ) regarding.

[0028] In another embodiment, the present invention provides a compound of formula A or formula B [ka] (In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10are independently selected from the group consisting of hydrogen, C1-C5 alkyl (e.g., methyl, ethyl, isopropyl, n-propyl, n-butyl, t-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), with the proviso that - expression A-exc [ka] and excluding compounds of - Formula B-exc1, Formula B-exc2, and Formula B-exc3 [ka] The present invention relates to a fragrance, flavor, and / or deodorizing / masking composition comprising a compound selected from the group consisting of:

[0029] In another embodiment, the present invention provides a compound of formula A or formula B [ka] (In the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, or t-butyl groups, - expression A-exc [ka] and excluding compounds of - Formula B-exc1, Formula B-exc2, and Formula B-exc3 [ka] The present invention relates to a fragrance, flavor, and / or deodorizing / masking composition comprising a compound selected from the group consisting of:

[0030] In another embodiment of the present invention, the compounds of general formula (I) may contain one or more chiral centers and may be chiral, for example, these compounds may be used as stereoisomeric (enantiomeric or diastereomeric) mixtures. In another embodiment, the compounds of formula (I) may also be advantageously used in pure enantiomeric or diastereomeric form.

[0031] Detailed Description The term "flavoring agent" used to characterize the compounds according to the present invention means that they evoke a preferably pleasant odor sensation in humans. Thus, flavoring agents are conventionally used to flavor industrial and sanitary products, cleaning agents, cleaners, personal hygiene products, cosmetics, etc. For the purposes of this invention and the appended claims, the term "flavoring agent" includes "aromatics," a term commonly used to refer to substances that impart odor and / or flavor to food.

[0032] The compounds of formula A or formula B may be used alone, as mixtures thereof, or in combination with a base material.

[0033] As used herein, "base material" includes any known fragrance / flavoring material selected from a wide range of natural products, such as essential oils, extracts, resinoids, or isolates, as well as currently available synthetic materials, such as hydrocarbons, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, nitriles, oximes, or heterocyclic compounds, and / or mixtures with one or more ingredients or excipients / adjuvants customarily used in combination with flavoring agents in fragrance and / or flavor compositions, such as solvents / diluents, stabilizers, carrier materials, and other adjuvants commonly used in the art.

[0034] The compounds of formula A or formula B can be used in a wide range of fragrance applications, including all areas of fine perfumery and functional fragrance, such as perfumes, air care products, household products, laundry products, body care products, and cosmetics. The compounds can be used in widely varying amounts, depending on the particular application and the nature and amount of other perfume ingredients.

[0035] According to a preferred embodiment of the present invention, the fragrance, flavor and / or deodorizing / masking composition according to the present invention comprises at least one compound according to formula A or formula B as defined above in an amount of between 0.00001% and 99.9% by weight, for example between 0.0001% and 95% by weight, for example between 0.001% and 25% by weight, preferably between 0.01% and 15% by weight, more advantageously between 0.1% and 10% by weight, in each case relative to the total composition.

[0036] According to a particularly preferred embodiment of the present invention, in addition to the compound according to formula A or formula B according to the present invention, the fragrance, flavor and / or deodorizing / masking composition according to the present invention comprises an additional odorant, for example in an amount of 0.1% to 99.9% by weight, preferably 5% to 90% by weight, in particular 15% to 70% by weight, based on the total fragrance and / or flavor composition.

[0037] The compounds of formula A or B above may be used in a consumer product base material by simply directly mixing the consumer product base material with at least one compound of formula (A) and / or at least one compound of formula (B) or a fragrance composition comprising one or more compounds of formula (A) and / or formula (B) above, or they may be entrapped at an earlier stage by an entrapment material, for example, a polymer, a capsule, a microcapsule, and / or a nanocapsule, a liposome, a film-forming agent, an absorbent such as activated carbon or zeolite, a cyclic oligosaccharide, a cyclic glycouril, and mixtures of two or more thereof, or they may be chemically bound to a substrate adapted to release the fragrance molecules upon application of an external stimulus such as light, an enzyme, air, water, etc., and then mixed with the consumer product base material.

[0038] Thus, the present invention may be useful in existing methods of manufacturing fragrance, flavor, and / or deodorizing / masking compositions, which involve incorporating one or more compounds of Formula (A) and / or Formula (B) as a fragrance, flavor, and / or deodorizing / masking composition by directly incorporating the compound into the 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 Formula (B), which can then be mixed with the consumer product base using conventional techniques and methods. By adding an olfactory-acceptable amount of at least one compound of Formula (A) and / or Formula (B) of the present invention as described above, the odor notes of the consumer product base may be improved, enhanced, and / or modified.

[0039] 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 herein above.

[0040] In particular embodiments according to the present invention, compounds of formula (A) and / or formula (B) as defined above are claimed, said compounds being useful in the perfume, aroma and / or deodorizing / masking compositions of the present invention.

[0041] In one embodiment, the compounds of formula (A) useful in fragrance, flavor, and / or deodorizing / masking compositions are 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.

[0042] In one embodiment, the compounds of formula (B) useful in the fragrance, flavor, and / or deodorizing / masking compositions are 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.

[0043] In an embodiment according to the present invention, the fragrance, flavor, and / or deodorizing / masking composition comprises a compound of formula (A) or formula (B) selected from any compound and / or mixtures of two or more of said compounds set out above.

[0044] The applicants have surprisingly 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) exhibit exotic fruity notes and mint notes. Many compounds of formula (A) and (B) also exhibit woody notes, powdery notes, ambery notes, and / or tobacco-like notes. In fact, some compounds of formula (A) also exhibit a sandalwood profile. Compounds (A) and (B) have sufficient retention on blotters for a long period of time, for more than four days. Indeed, compounds of formula (A) and formula (B) function extremely well in woody accords, fougere accords, and rose accords.

[0045] In embodiments of the present invention, the claimed fragrances, flavors, and / or deodorizing / masking compositions are advantageously used as perfume compositions. Fragrance compositions according to the present invention generally include fragrances, colognes, eau de toilettes, and / or eau de parfums. In embodiments of the present invention, the claimed fragrances, flavors, and / or deodorizing / masking compositions are advantageously used in cosmetic formulations, personal care products, cleansing products, fabric softeners, and / or air fresheners, etc. Furthermore, it is within the scope of embodiments of the present invention that the novel fragrances, flavors, and / or deodorizing / masking composition(s) and / or novel compound(s) of Formula (A) or Formula (B) described herein may be incorporated into building materials, wall and floor coverings, vehicle parts, etc.

[0046] Generally, in addition to the novel fragrance and / or fragrance, flavor, and / or deodorizing / masking compositions described herein, suitable fragrance, flavor, or deodorizing compositions may advantageously include conventional ingredients such as, for example, solvents, carriers, stabilizers, emulsifiers, humectants, dispersants, diluents, thickeners, thinning agents, other flavoring agents, and / or adjuvants.

[0047] By combining the compounds of formula (A) or formula (B) with many known natural or synthetic fragrances, flavors, and / or deodorizing / masking materials, the range of natural ingredients can be incorporated, not only of readily volatile components, but also of semi-volatile and less volatile components, and the range of synthetic ingredients can be incorporated, as described in Steffen Arctander, Perfume and Flavor Chemicals, Vols. 1 and 2, Montclair, NJ, 1969; Steffen Arctander, Perfume and Flavor Materials of Natural Origin, Elizabeth, NJ, 1960; or Horst Surburg and Johannes Panten, Common Fragrance and Flavor Materials. Representatives of many classes of substances can be taken from the following non-limiting compilations, such as those described in the following: (1) "Chemical Materials", Wiley-VCH, Weinheim, 2016;

[0048] Natural products such as: Ajowan oil, Amyris oil, Armoise oil, Artemisia oil, Basil oil, Beeswax 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, Citronella oil, Citronella terpenes, Clary sage oil, Rectified clove oil, White cognac oil, Coria Underwood seed oil, cumin seed oil, cypress oil, davana oil, dill seed oil, elemi oil, elemi resinoids, eucalyptus oil, fir needle oil, galbanum oil, geranium oil, Indian ginger oil, grapefruit oil, guaiac wood oil, guruyun balsam, jasmine absolute, jatamansi oil, juniper berry oil, juniper leaf oil, kachur oil, labdanum absolute, labdanum resinoids, lavender oil, lemon oil, lemon oil terpenes, lemongrass oil, lime oil, litsea cubeba oil, litsea cubeba terpenes, choya loban choya resinoid, mandarin oil, Mentha arvenis oil, bergamot mint oil, mimosa absolute, myrrh resinoid, nagarmot oil, nutmeg oil, oakmoss absolute, oakmoss resinoid, olibanum oil, olibanum resinoid, orange oil, origanum oil, palmarosa oil, patchouli oil, peppermint oil, Peru balsam resinoid, petitgrain oil, pine needle oil, pink pepper oil, rose absolute, rose oil, rosemary oil, sandalwood oil, seaweed absolute, spearmint oil, sugandha kokila oil, sugandha mantri oil, taget oil, tolu balsam resinoid, tuberose absolute, turmeric oil, turpentine, valerian oil, vetiver oil, vetiver terpenes.

[0049] Synthetic raw materials, such as: esters, such as: aldehyde C16, allyl amyl glycolate, allyl caproate, allyl cyclohexylpropionate, allyl heptanoate, allyl phenoxyacetate, isoamyl acetate, amyl benzoate, amyl butyrate, amyl caproate, amyl cinnamate, amyl isovalerate, amyl phenylacetate, amyl propionate, isoamyl salicylate, amyris acetate, anisyl acetate, benzyl acetate, benzyl benzoate, benzyl butyrate, benzyl cinnamate, benzyl formate, benzyl isobutyrate, benzyl isoeugenol, benzyl propionate Benzyl salicylate, benzyl tiglate, butyl acetate, butyl butyrate, butyl butyryl lactate, caryophyllene acetate, cedryl acetate, cinnamyl acetate, cinnamyl butyrate, cis-3-hexenyl acetate, cis-3-hexenyl benzoate, cis-3-hexenyl caproate, cis-3-hexenyl formate, cis-3-hexenyl isobutyrate, cis-3-hexenyl-2-methyl butyrate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, cis-3-hexenyl tiglate, citronellyl acetate, citronellyl butyrate, citronellyl formate, citronellyl isobutyrate Ronellyl, citronellyl propionate, citronellyl tiglate, cyclabute, cyclogalbanate, cyclohexylethyl acetate, decyl acetate, dibutyl phthalate, diethyl malonate, diethyl phthalate, dihydromyrcenyl acetate, octanyl dimethyl acetate, dimethylphenylethylcarbinyl acetate, dioctyl adipate, dioctyl phthalate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, linalyl acetate, ethyl 2-methylbutyrate, ethyl 3-phenylpropionate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, Ethyl butyrate, ethyl caprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethyl heptanoate, ethyl hexyl acetate, ethyl isobutyrate, ethyl laurate, ethyl pelargonate, ethyl phenoxyacetate, ethyl phenylacetate, ethyl phenylglycidate, ethyl propionate, ethyl saffronate, ethyl salicylate, ethyl valerate, eugenyl acetate, evernyl, fenchyl acetate, Floramat, Frescolate ML, fractone, fruitate, geranyl acetate, geranyl butyrate, geranyl formate, geranyl propionate, geranyl tiglate,Divescon, Guaiol Acetate, Hedionate, Hedione, Helbetolide, Herbanate, Hexyl Acetate, Hexyl Benzoate, n-Hexyl Butyrate, Hexyl Caproate, Hexyl Isobutyrate, Hexyl Propionate, Hexyl Salicylate, Isobornyl Acetate, Isobutyl Acetate, Isobutyl Phenylacetate, Isobutyl Salicylate, Isoeugenyl Acetate, Isononyl Acetate, Isopentylate , isopropyl 2-methylbutyrate, isopropyl myristate, jasmonyl, rifarom, linalyl acetate, mahagonate, manzanate, menthyl acetate, menthyl acetate, methyl benzoate, 2-methylbutyl acetate, methyl chamomile, methyl cinnamate, methyl cyclogeranate, methyl heptine carbonate, methyl laurate, methyl octyne carbonate, methyl phenylacetate, methyl salicylate, methyl 2-methylbutyrate, neofolion (neof olione), nopyr acetate, octenyl acetate, octyl acetate, octyl isobutyrate, paracresyl acetate, paracresyl isobutyrate, paracresyl phenylacetate, pear esters, peranat, phenoxyethyl isobutyrate, phenylethyl acetate, phenylethyl butyrate, phenylethyl formate, phenylethyl isobutyrate, phenylethyl phenylacetate, phenylethyl propionate, phenylethyl salicylate, phenylethyl tiglate, phenylpropyl isobutyrate, prenyl acetate, romandride, sagecete, styrallyl acetate, styrallyl propionate, tangerinol, terpinyl acetate, thesalone, trans-2-hexenyl acetate, tropicate, verdox, verdyl acetate, verdyl propionate, vertenex, veticol acetate, vetiveryl acetate, Yasmolys.

[0050] Lactones, such as: Ambrettolide, Arova N, Celeriax, Delta Decalactone, Gamma Decalactone, Delta Dodecalactone, Gamma Dodecalactone, Ethylene Brassilelate, Exaltolide, Gamma Heptalactone, Delta Hexalactone, Gamma Hexalactone, Methyl Laitone, Methyl Octalactone, Delta Nonalactone, Gamma Nonalactone, Octahydrocoumarin, Delta Octalactone, Gamma Octalactone, Rootylone, Silvanone Supra, Deltaun Decalactone, Gamma Undecalactone, Gamma Valerolactone, 10-Oxahexadecanolide (OHD Musk), Coumarin, Habanolide, Jasmolactone.

[0051] Aldehydes, for example: Acetaldehyde, Adoxal, Aldehyde C10, Aldehyde C11 iso, Aldehyde C11 moa, Undecylenic aldehyde C11, Undecyl aldehyde C11, Lauryl aldehyde C12, Aldehyde C12 MNA, Anisaldehyde, Amyl Cinnamaldehyde, Benzaldehyde, Bourgeonal, Campholenaldehyde, Cantonal, Cetnal, Cinnamic Aldehyde, Cis-4-Decenal, Cis-6-Nonenal, Citral, Citronellal, Citronellyloxyacetaldehyde, Cocal, Cuminaldehyde, Curgix, Cyclal C, Cyclamen Aldehyde, Cyclomyral, Cycloberthal, Decenal 9, Dupical, Empethal, Ethyl Vanillin, Floralozone, Florhydral, Geraldehyde, Helional, Heliotropin, Heptanal, Hexanal, Hexyl Cinnamaldehyde, Hibernal Neo , hydratropaldehyde, hydroxycitronellal, intrelevenaldehyde, isobutan, isocyclocitral, isovaleraldehyde, lilial, limonenal, maceal, mefranal, melonal, methyl cinnamaldehyde, trans,cis-2,6-nonadienal, nonanal, octanal, oncidal, para-tolylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, precyclemone B, safranal, salicylic aldehyde, centenal, syringaldehyde, trans-4-decenal, trans-2-dodecenal, trans-2-hexenal, trans-2-nonenal, triphenal, vanillin, veratraldehyde, verniciflua.

[0052] Ketones, such as: acetanisole, acetoin, acetophenone, aldron, allylionone, benzophenone, benzylacetone, chalone, camphor, d-carvone, l-carvone, cashmeran, cedryl methyl ketone, sepionate, Claritone, cosmon, chrysolide, cyclotene, damascenone, damascone alpha, damascone beta, damascone delta, damascone gamma, diacetyl, dihydro beta ionone, dihydro isojasmonate, dimethyl octenone, dynascone, ethyl amyl ketone, ethyl maltol, fenchone, filbertone, geranyl acetone, globanone, heptyl cyclopentanone, alpha ionone, beta ionone, pure ionone, iris wood, alpha ionone, iso E super, isofenchone, iso Jasmone T, Isolone K, Isomenthone, Isophorone, cis-Jasmone, Kambernoir, Cephalis, Coavon, Lavendinal, Maltol, Menthone, Methylacetophenone, Methyl Amyl Ketone, Methylheptenone, Methylhexyl Ketone, Gamma Methyl Ionone, Methyl Naphthyl Ketone Beta, Methyl Nonyl Ketone, Muscenone, Muscone, Nectaryl, Orinox, OTBC Ketone, Para-Tertbutylcyclohexanone, Patchwood, Phantolide, Pharaon, Piperitone, Plicatone, Raspberry Ketone, Raspberry Ketone Methyl Ether, Safralein, Pure Spirogalbanone, Tonalide, Trimofix O, Veloutone, Vetikon.

[0053] Alcohols such as: Oxoalcohol C13, Ambercore, Ambermax, Ambrinol, Amylvinylcarbinol, Anise Alcohol, Bacdanol, Benzyl Alcohol, Butanol, Cedrol Crystal, Cinnamal Alcohol, Citronellol, Kolanol, Decanol, Dimethylbenzylcarbinol, Dimethyloctanol, Dimethylphenylethylcarbinol, Dimetol, Fenchol, Hexanol, Isoborneol, Isobornylcyclohexanol, Javanol, Keflorol, Kohinool, Lauryl Alcohol, Lilyflore, Linalool Oxide, Mayol, Menthol, Norlimbanol, Octanol, Oscilol, Para-tertbutyl Cyclohexanol, phenoxanol, phenoxyethanol, phenylethyl alcohol, phenylpropyl alcohol, propylene glycol, rosafen, rose glycol, styrallyl alcohol, tricyclodecane dimethanol, tetrahydrolinalool, tetrahydromyrcenol, timberol, undecavertol, cis-3-hexenol, levocitronellol, cyclofloranol, dihydrolinalool, dihydromyrcenol, dimyrcetol, evaporol, geraniol, isopulegol, linalool, nerol, nerolidol, trans,cis-2,6-nonadienol, polysanthol, rosalva, sandalwood, sandalwood, terpinen-4-ol, terpineol, trans-2-hexenol.

[0054] Phenols, for example: butylhydroxyanisole, dihydroeugenol, dimethylhydroquinone, dimethylresorcinol, pure eugenol, guaiacol, isoeugenol, metacresol, methyldianthrix, paracresol, propenylguaethol, thymol, ultravanil.

[0055] Ethers, such as: Ambroxan, Anethole, Anthracene, Benzyl Isoamyl Ether, Benzyl Isopropyl Ether, Benzyl Isovalerate, Boyalis, Cedrumbar, Cetalox, Decyl Methyl Ether, Dibenzyl Ether, Dihydrorose Oxide, Diphenyl Oxide, Dremox, Estragole, Ethyl Linalool, Eucalyptol, Galaxolide, Gyrane, Herbavert, Lime Oxide, Madrox, Methyl Isoeugenol, Naphthyl Isobutyl Ether Beta, Nerol Oxide, Neroline Bromeliad, Paracresyl Butyl Ether, Paracresyl Methyl Ether, Petiole, Phenylethyl Methyl Ether, Rhubarb, Rose Oxide, Rosilan, Trisamber, Vetylbois K, Yara Yara.

[0056] Acetals, such as: Acetal CD, Acetal R, Amberketal, Boisambrene Forte, Citrathal, 1,1-Diethoxyethane, Emeraldine, Freshopal, Halboxane, Indoflor, Jacinthaflor, Magnolan, Spirambrene, Viridine, Ellinthal, Glycoleural, Methyl Pamplemousse.

[0057] Hydrocarbons, for example: bisabolene, camphene, delta 3 carene, caryophyllene, cedrene, para-cymene, dipentene, diphenylmethane, isolongifolene, d-limonene, longifolene, myrcene, naphthalene, ocimene, alpha-pinene, beta-pinene, styrene, gamma-terpinene, terpinolene, 1,3,5-undecatriene, verdracin.

[0058] Sulfur compounds, for example: Corpus cassis, dibutyl sulfide, dimethyl sulfide, Exovert, grapefruit thiol, oxane, Ribes mercaptan, sulfurol, thiocineol.

[0059] Nitriles, for example: cinnamyl nitrile, citronellyl nitrile, citronitrile, clonal, cumin nitrile, hexylcyclopentanone, iris nitrile, lemonyl, pionyl, tridecyl nitrile, agrumen nitrile, n-decyl nitrile.

[0060] Oximes, for example: buccoxim, labienoxim, stemone.

[0061] Nitrogen heterocycles, for example: 2-acetylpyrazine, 2-acetylpyridine, sec-butylquinoline, Corpus Racine, 2-ethyl-3,5(or 6)-dimethylpyrazine, furfurylpyrrole, indole, isobutylquinoline, 2-isobutyl-3(or 6)-methoxypyrazine, isopropylquinoline, maritime, p-methylquinoline, skatole, 2,3,5-trimethylpyrazine.

[0062] Nitro compounds, for example: musk ketone.

[0063] Schiff bases, for example: Aurantiol, Helianthral, ​​Ligantral, Verdantiol.

[0064] Other materials include: Acetanilide, Gardamide, Paradisamide, Dimethyl Anthranilate, Methyl Anthranilate, n-Butyric Acid, Capric Acid, Caproic Acid, Caprylic Acid, Phenylacetic Acid, Caryophyllene Oxide, Cedroxide, Tovacarol.

[0065] Thus, the compounds of formula (A) or formula (B) can be used in the preparation of compositions, as well as a wide range of known fragrances / fragrances, flavors, and / or deodorizing / masking materials, as is evident from the above-mentioned compilations. In the preparation of such compositions, the known fragrances, flavors, and / or deodorizing / masking materials mentioned above can be used according to methods known to perfumers, for example, according to W. A. ​​Poucher, Perfumes, Cosmetics and Sorps 2, 7th Edition, Chapman and Hall, London, 1974.

[0066] In an embodiment of the present invention, the claimed fragrance, flavor and / or deodorizing / masking compositions comprise, in addition to the compound(s) of formula (A) or formula (B), at least one ester and / or one alcohol, preferably a mixture of at least an ester and an alcohol, said ester and / or alcohol being preferably selected from the list defined herein above. In an embodiment of the present invention, the claimed perfume compositions are characterized in that the total content of the compound(s) of formula (A) or formula (B) together with the ester(s) and / or alcohol(s) is more than 25% by weight, preferably more than 50% by weight, for example more than 75% by weight or even more than 90% by weight.

[0067] preparation As reported in Hombrecher, H., 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, were synthesized by reduction with LiAlH or NaBH of 4,4,7,7-tetramethyl-4,6,7,8-tetrahydro-2H-chromene-2,5(3H)-dione, which was further synthesized with dimedone and either an alkylidene-substituted Meldrum's acid or a substituted acryloyl chloride.

[0068] We envisioned different approaches to synthesize compounds of Formula (A) or Formula (B) in either one step (Method P) or two steps (Method Q or Method R). However, a method was needed that would selectively afford the 6-substituted 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one derivative. Because Method Q did not selectively afford the desired 6-substituted derivative and also afforded the inseparable 8-substituted derivative, we also devised a new synthetic approach (Method S) that would exclusively afford the 6-substituted 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one derivative.

[0069] Method P In a preferred embodiment according to the present invention, the compounds represented by general formula (A) and / or general formula (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, such as p-toluenesulfonic acid (0.05 equivalents), using toluene as a solvent at a temperature of 80°C to 90°C.

[0070] [ka]

[0071] Method QIn another preferred embodiment according to the present invention, compounds of formula (A) can be advantageously prepared in two steps from cyclohexanedione (I) and homoallylic alcohols of formula (III). The first step in this scheme is the reaction of cyclohexanedione (I) with alcohol (III) in the presence of iodine / toluene / THF to give vinylogous ester (IV). In the second step, compound (IV) is subjected to AlCl-mediated cyclization in ethylene dichloride (EDC) to give product (A) and / or product (B).

[0072] [ka]

[0073] Method R In another preferred embodiment according to the present invention, compounds of formula (A) and / or formula (B) can be advantageously prepared in two steps from cyclohexanedione (I) and allylic alcohol of formula (II). The first step in this scheme is the reaction of cyclohexanedione (I) with alcohol (II) in the presence of iodine / toluene / THF to give vinylogous ester (V). In the second step, compound (V) is subjected to AlCl-mediated cyclization in ethylene dichloride (EDC) to give product (A) and / or product (B).

[0074] [ka]

[0075] In another preferred embodiment according to the present invention, 4-alkylcyclohexane-1,3-dione (XI) and isoprenol were treated with iodine / toluene / THF according to Method Q to give two isomers (XII) and (XIII). This isomer mixture was subjected to AlCl-mediated cyclization to give product (A1) and product (A2). While the two isomers can be separated by column chromatography, they often cannot be separated by fractional distillation due to their very close boiling points.

[0076] [ka] Therefore, a method for selectively obtaining A1 was also desired.

[0077] Method S Ethyl acetoacetate was alkylated using base and an 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 the 4,4-ethoxycarbonyl-alkyl-substituted cyclohexane-1,3-dione (XV). Surprisingly, it was found that the reaction of compound (XV) with isoprenol in the presence of iodine / toluene / THF afforded only one regioisomer (XVI). LiCl-mediated decarboxylation in DMSO at 170 °C selectively afforded the vinylogous ester (XII), followed by AlCl-mediated cyclization of (XII) to afford only A1.

[0078] [ka] [Example]

[0079] Example 1: 4,4-Dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one Synthesis of 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one Step 1: Synthesis of 3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one Method Q: To a mixture of cyclohexane-1,3-dione (25 g, 223 mmol, 1 equiv.) in toluene (250 mL) was added 3-methylbut-3-en-1-ol (23.04 g, 268 mmol, 1.2 equiv.) and iodine (2.72 g, 10.71 mmol, 0.048 equiv.). After stirring the reaction mixture for 16 hours, the reaction was diluted with 200 mL of 10% sodium thiosulfate solution. The toluene layer was then separated, and the aqueous layer was extracted with ethyl acetate (2 × 50 mL). The combined organic layers were washed with water (1 × 50 mL) and dried over anhydrous sodium sulfate. The organic solvent was evaporated on a rotary evaporator to give 30 grams of crude material, which was subjected to flash chromatography to give 32 g of 3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one (80%). 1 H-NMR (400MHz, CDCl3): δ 5.39(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).

[0080] Step 2: Synthesis of 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one Method Q: To a stirred solution of AlCl3 (266 g, 2 mol, 1.2 equiv.) in 1,2-dichloroethane (200 mL) was added dropwise a solution of 3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one (300 g, 1.66 mol, 1 equiv.) in EDC (100 mL) at 15 °C. The reaction mixture was warmed to 25 °C and stirred for 6 h. The reaction mixture was poured slowly 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 × 1 L) and then stirred with aqueous sodium bicarbonate (1 L) for 1 h. This was repeated twice. The organic layer was separated, dried over sodium sulfate, and concentrated on a rotary evaporator to give 220 g of crude product. The crude material was purified by fractional distillation (81° C.-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%). 1 H-NMR (400MHz, CDCl3): δ 4.10-4.07 (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): δ 197.4,170.9,119.3,63.9,39.6,38.1,29.1,27.3,20.1. Odor profile: Tobacco, leathery, fruity, woody.

[0081] Example 2: 4,4,6-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one Synthesis of 4,4,6-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one Method S: Process 1 Synthesis of ethyl 1-methyl-2,4-dioxocyclohexane-1-carboxylate: To a solution of ethyl 2-methyl-3-oxobutanoate (49.3 ml, 348 mmol, 1.2 equiv.) in tetrahydrofuran (400 ml) was added potassium tert-butoxide (35.8 g, 319 mmol, 1.1 equiv.) at room temperature. The reaction mixture was cooled to 0 °C, and then methyl acrylate (26.3 ml, 290 mmol, 1 equiv.) was added. After stirring the reaction mixture for 16 h, 2 M HCl was added to adjust the pH to 3-4, and the mixture was extracted with EtOAc (3 × 50 mL). The organic layer was washed with water, brine, and then concentrated to give the crude material, which was purified by column chromatography using 30%-35% EtOAc in hexanes to give ethyl 1-methyl-2,4-dioxocyclohexane-1-carboxylate (47 g, 82%).

[0082] Process 2 Synthesis of ethyl 1-methyl-4-((3-methylbut-3-en-1-yl)oxy)-2-oxocyclohex-3-ene-1-carboxylate: To a solution of ethyl 1-methyl-2,4-dioxocyclohexane-1-carboxylate (100 g, 504 mmol) in toluene (1600 mL) was added 3-methylbut-3-en-1-ol (61.1 mL, 605 mmol) and 4-methylbenzenesulfonic acid (17.37 g, 101 mmol) at 25 °C. The reaction mixture was stirred at 25 °C for 16 h, after which it was diluted with a saturated solution of NaHCO. The mixture was extracted with EtOAc (3 × 100 mL), and the combined organic layers were washed with brine, dried over anhydrous NaSO, and filtered. The organic layers were concentrated to give crude ethyl 1-methyl-4-((3-methylbut-3-en-1-yl)oxy)-2-oxocyclohex-3-ene-1-carboxylate (89 g), which was used directly in the subsequent reaction.

[0083] Process 3 Synthesis of 6-methyl-3-((3-methylbut-3-en-1-yl)oxy)cyclohex-2-en-1-one: 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 (3×50 mL). The combined organic layers were washed with brine, filtered, and concentrated to give the 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%).

[0084] Step 4: Synthesis of 4,4,6-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one 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 trichloride (41.2 g, 309 mmol) at 25° C. The reaction was stirred at 25° C. for 20 minutes. The reaction mixture was slowly added to ice water, and after stirring the mixture for 30 minutes, it was extracted with methylene dichloride (3×50 mL). The combined organic layers were washed with brine, dried over anhydrous NaSO, and filtered. The organic layers were concentrated, and the resulting 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%). 1 H-NMR (400 MHz, CDCl): δ 4.06-4.02 (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 = 6.8 Hz, 3H). 13C-NMR (100MHz, CDCl3): δ 200.1,169.9,118.7,64.0,41.1,39.8,29.4,28.3,28.2,28.1,27.0,15.8. Odor profile: Exotic fruity, delta-damascone type, woody.

[0085] Example 3: 6-Ethyl-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one It was synthesized in four steps according to Method S from ethyl 2-ethyl-3-oxobutanoate. 1 H-NMR(400MHz, CDCl3):δ 4.04-3.93(m,2H),2.34-2.21(m,2H),1.98-1.85(s,2H),1.81-1.71(m,1H),1.66-1 .49 (overlapping m, 3H), 1.39-1.28 (m, 1H), 1.20 (s, 3H), 1.19 (s, 3H), 0.84 (t, J=7.2Hz, 3H). Odor profile: Fruity, plum, woody, beta-damascone-like.

[0086] Example 4: 2,3,3,4,4-pentamethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one It was synthesized in two steps from cyclohexane-1,3-dione and 3,3,4-trimethylpent-4-en-2-ol according to Method Q.

[0087] 1 H-NMR (400 MHz, CDCl): δ 3.98 (q, J = 6.4 Hz, 1H), 2.33-2.24 (overlapping 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). 13C-NMR (100MHz, CDCl3): δ 198.1,170.4,118.8,75.7,38.9,38.2,37.2,29.3,23.6,20.6,20.5,18.4,15.6,15.0. Odor profile: Fruity, woody, cashmeran-type (cashmeran has floral-fruity notes).

[0088] Example 5: 2,4,4-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one Odor profile: Sweet, sandal, woody.

[0089] Example 6: 3,4,4-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one It was synthesized in two steps from cyclohexane-1,3-dione and 3-methyl-2-methylenebutan-1-ol according to Method Q. Odor profile: Strong minty, woody, animalic in the background.

[0090] Example 7: 4,4,6,8-Tetramethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one Synthesized according to Method Q from 4,6-dimethylcyclohexane-1,3-dione and 3-methylbut-3-en-1-ol. Odor profile: Minty, dry, woody.

[0091] Example 8: 6-(Cyclopropylmethyl)-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one It was synthesized in one step from 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and (bromomethyl)cyclopropane. 1H-NMR(300MHz, CDCl3):δ 4.08-4.01(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): δ 199.8,169.4,119.1,64.1,47.0,40.0,35.0,29.5,28.1(2C),27.5,25.3,8.95.5.36,4.24. Odor profile: Woody, ambery.

[0092] Example 9 6-Isobutyl-4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one It was synthesized in one step from 4,4-dimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one and 1-bromo-2-methylpropane (yield=15%). 1 H-NMR(300MHz, CDCl3):δ 4.09-3.99(m,2H),2.40-2.34(m,2H),2.25-2.16(m,1H),2.23-1.99(m,1H),1.97-1.6 1(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). Odor profile: Dry, woody, ambery.

[0093] Example 10 2,2,3,3-tetramethyl-3,5,6,7-tetrahydrobenzofuran-4(2H)-one 1 H-NMR (400MHz, CDCl3): δ 2.27 (t, J = 6.4 Hz, 2H), 2.22 (t, J = 6.8 Hz, 2H), 1.91-1.93 (m, 2H), 1.21 (s, 6H), 1.10 (s, 6H). Odor profile: Woody, musky.

[0094] Composition Evaluation Example 1 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 saffronate illustrate a compositional evaluation study in woody accord fragrances used in shampoos (C = blank, IPM = isopropyl myristate).

[0095] [Table 1]

[0096] The incorporation of 5.5 wt. % of 4,4,6-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one as a 10% (w / w) solution in IPM provides an excellent rounded, powerful woody effect, whereas only an average rosy effect was observed when 10 wt. % of ethyl saffronate in IPM was used in the above accord.

[0097] Composition Evaluation Example 2 In another evaluation of a rose accord fragrance used in a shampoo, the compound from Example 2 (4,4,6-trimethyl-2,3,4,6,7,8-hexahydro-5H-chromen-5-one) imparted excellent and sufficiently powerful rosy and spicy notes to the accord when included in the rose accord, which was much stronger than the effect imparted by ethyl saffronate under the same conditions.

Claims

1. Formula A or Formula B 【Chemical 1】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are independently hydrogen, C 1 ~C 5 Alkyl, or C 1 ~C 5 alkenyl) provided that Compounds of formula A have the formula A-exc 【Chemistry 2】 and excluding compounds of Compounds of formula B have the formulas B-exc1, B-exc2, and B-exc3 【Chemistry 3】 (excluding compounds of the above).

2. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-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. Formula A or Formula B according to claim 1 【Chemistry 4】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 are independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, or t-butyl.

4. 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 2. The compound of claim 1 selected from:

5. 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 2. The compound of claim 1 selected from:

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

7. A fragrance comprising the compound according to any one of claims 1 to 5 or the mixture according to claim 6.

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

9. 9. The fragrance, flavor, and / or deodorizing / masking composition of claim 8, wherein the content of the compound of formula A or formula B is at least 0.1% by weight.

10. 10. The fragrance, flavor, and / or deodorizing / masking composition of claim 9, wherein the content of the compound of formula A or formula B is at least 1% by weight.

11. 11. The fragrance, flavor, and / or deodorizing / masking composition according to any one of claims 8 to 10, wherein the content of the compounds of formula A and formula B is below 50% by weight.

12. 12. The fragrance, flavor, and / or deodorizing / masking composition of claim 11, wherein the content of the compounds of formula A and formula B is below 25% by weight.

13. 13. The fragrance, flavor, and / or deodorizing / masking composition according to any one of claims 8 to 12, comprising at least one ester and / or one alcohol, or a mixture of at least an ester and an alcohol, wherein the total content of said compound(s) of formula (A) and formula (B) together with said ester(s) and said alcohol(s) is / are greater than 25% by weight.

14. 14. The fragrance, flavor, and / or deodorizing / masking composition according to claim 13, wherein the total content of the compound(s) of formula (A) and formula (B), the ester(s) and the alcohol(s) combined is greater than 50% by weight.

15. Use of the fragrance, flavor and / or deodorizing / masking composition according to any one of claims 8 to 14 in perfumed or flavored products.

16. Use of a compound according to any one of claims 1 to 5 or a mixture according to claim 6 in a perfumed or flavored product.

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