Perfume composition

Abstract

The present invention relates to a perfume composition containing at least one alkyl-substituted 4-pentenoic acid ester derivative represented by general formula (1). In general formula (1), R1 to R3 are each independently a hydrogen atom or a C1-C4 alkyl group and R4 is a C1-C5 alkyl group or a C3-C5 alkenyl group. The alkyl-substituted 4-pentenoic acid ester derivative is preferably ethyl 4-methyl-4-hexenoate. General formula (1):

Description

fragrance composition

[0001] The present invention relates to a fragrance composition, and to cosmetics, toiletries, bath additives, tobacco, foods and beverages, and pharmaceuticals containing the fragrance composition.

[0002] Fragrances with fruity aromas such as strawberry, green aromas, milky aromas, and citrus aromas have been widely used as fragrances for various food flavors, various cosmetics, air fresheners, and other health and hygiene materials. It is also widely known that alcohol carboxylic acid esters play an important role in the top note aromas that emerge first among these strawberry-like and other fruity aromas, green aromas, milky aromas, and citrus aromas (see, for example, Non-Patent Document 1). However, most of the alcohol carboxylic acid esters that play an important role in the top note aromas of fruity, green, and floral aromas have already been standardized, and flavorists and perfumers who design fragrances are constantly seeking compounds that exhibit new and different fragrance notes in order to characterize the top notes and differentiate them from existing fragrance compounds.

[0003] Genichi Indo, Synthetic Fragrances: Chemistry and Product Knowledge (revised and expanded edition), Chemical Daily, March 22, 2005, pp. 461-462

[0004] The present invention has been made in view of the above circumstances, and aims to provide a compound exhibiting a new fragrance note different from that heretofore available, and a fragrance composition containing the compound and having at least one of a fruity fragrance such as a strawberry-like fragrance, a green-like fragrance, a milky fragrance, and a citrus-like fragrance.

[0005] Another object of the present invention is to provide cosmetics, toiletries, bath additives, tobacco, foods and beverages, quasi-drugs and pharmaceuticals containing a fragrance composition having at least one of the above-mentioned fruity fragrances such as strawberry-like fragrances, green fragrances, milky fragrances and citrus fragrances.

[0006] Under these circumstances, the present inventors have conducted intensive research and have found that alkyl-substituted 4-pentenoic acid ester derivatives, and particularly ethyl 4-methyl-4-hexenoate, among them, have an unprecedented and excellent fragrance of at least one of a fruity fragrance such as strawberry-like, a green fragrance, a milky fragrance, and a citrus fragrance, have a highly natural feel, and are extremely useful as a fragrance material, thereby completing the present invention.

[0007] That is, the present invention includes the following aspects.

[0008] [1] General formula (1):

[0009]

[0010] (In the formula, R １ ~R ３ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ４ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 3 to 5 carbon atoms.

[0011] [2] The fragrance composition according to [1], wherein the alkyl-substituted 4-pentenoic acid ester derivative is ethyl 4-methyl-4-hexenoate represented by the following formula (2):

[0012]

[0013] [3] The fragrance composition according to [1] or [2], wherein the amount of the alkyl-substituted 4-pentenoic acid ester derivative blended is 0.001 to 30% by weight based on the total weight of the fragrance composition.

[0014] [4] A cosmetic product, toiletry product, bath additive, tobacco, food, drink, or pharmaceutical product, containing 0.0001 to 30% by weight of the fragrance composition according to any one of [1] to [3].

[0015] The alkyl-substituted 4-pentenoic acid ester derivatives can be synthesized by a known method in which the corresponding allyl alcohol and the corresponding orthoester are heated in the presence of an acid catalyst to cause the Johnson-Claisen rearrangement. The raw material allyl alcohol can be synthesized by any known method, such as reduction of the corresponding enone, vinyl Grignard reaction to the corresponding aldehyde, or reduction of the corresponding unsaturated carboxylic acid or unsaturated ester.

[0016] The alkyl-substituted 4-pentenoic acid ester derivative of the present invention is represented by the general formula (1) (wherein R １ ~R ３ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ４ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 3 to 5 carbon atoms. ) and ethyl 4-methyl-4-hexenoate represented by the above formula (2) have a distinctive, strong, excellent, and natural-feeling fragrance that is clearly different from similar fragrances conventionally used, and have at least one of a fruity fragrance such as strawberry-like, a green fragrance, a milky fragrance, and a citrus fragrance. Therefore, the fragrance composition of the present invention containing them can be effectively used as a fragrance for various foods and beverages, various cosmetics, toiletries, bath additives, tobacco, and pharmaceuticals including health and hygiene materials.

[0017] The present invention will be described in detail below.

[0018] The fragrance composition of the present invention is an alkyl-substituted 4-pentenoic acid ester derivative represented by the above general formula (1) (wherein R １ ~R ３ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ４ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 3 to 5 carbon atoms. The alkyl-substituted 4-pentenoic acid ester derivative is preferably ethyl 4-methyl-4-hexenoate represented by the above formula (2).

[0019] The alkyl-substituted 4-pentenoic acid ester derivatives and ethyl 4-methyl-4-hexenoate may exist as geometric isomers of the (E)- and (Z)-isomers due to the presence of a double bond in the molecule. The alkyl-substituted 4-pentenoic acid ester derivatives and ethyl 4-methyl-4-hexenoate may be either the (E)- or (Z)-isomer alone, or may be a mixture of these in any proportions.

[0020] When geometric isomers exist, most of the alkyl-substituted 4-pentenoate derivatives and ethyl 4-methyl-4-hexenoate structures are (E)-isomers due to the synthetic method, and therefore, the alkyl-substituted 4-pentenoate derivatives and ethyl 4-methyl-4-hexenoate are preferably (E)-isomers.

[0021] In formula (1), R １ From R ３ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a 1,1-dimethylethyl group. １ From R ３ are limited to these. １ is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group. ２ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. ３ is preferably a hydrogen atom or a propyl group, and more preferably a hydrogen atom.

[0022] In addition, in formula (1), R ４is an acid residue of an ester, and is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 3 to 5 carbon atoms. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a 1,1-dimethylethyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, and a 1-ethylpropyl group. Examples of the alkenyl group having 3 to 5 carbon atoms include an allyl group, a 1-methylallyl group, a 2-methylallyl group, a 2-butenyl group, a 3-butenyl group, a 1,1-dimethylallyl group, a 1,2-dimethylallyl group, a 1-methyl-2-butenyl group, a 2-methyl-2-butenyl group, a 3-methyl-2-butenyl group, a 3-pentenyl group, a 1-methyl-3-butenyl group, a 2-methyl-3-butenyl group, a 3-methyl-3-butenyl group, and a 4-pentenyl group. ４ are limited to these. ４ is preferably an ethyl group, an isopropyl group, or a butyl group, and more preferably an ethyl group.

[0023] Examples of alkyl-substituted 4-pentenoate derivatives represented by the general formula (1) include ethyl 4-methyl-4-hexenoate, ethyl 4-octenoate, ethyl 4-methyl-4-heptenoate, ethyl 4-methyl-4-nonenoate, ethyl 3-vinylhexanoate, isopropyl 4-methyl-4-hexenoate, and butyl 4-methyl-4-hexenoate. Of these, ethyl 4-methyl-4-hexenoate is particularly preferred.

[0024] When these geometric isomers exist, one or both of these isomers may be used as a mixture in any ratio. Furthermore, when optical isomers exist, one or both of these isomers may be used as a mixture in any ratio.

[0025] The alkyl-substituted 4-pentenoic acid ester derivative represented by the above general formula (1) is represented by the following general formula (3):

[0026]

[0027] an alkyl-substituted allylic alcohol represented by the formula: １ ~R ３ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and trialkyl orthoacetate (here, the alkyl group usually refers to a saturated hydrocarbon group having 1 to 4 carbon atoms), more preferably triethyl orthoacetate, is heated in the presence of an acid catalyst to cause the known Johnson-Claisen rearrangement, and if necessary, hydrolysis and esterification can be carried out to obtain the compound.

[0028] Examples of the acid catalyst necessary for causing the Johnson-Claisen rearrangement include, but are not limited to, carboxylic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, and valeric acid; sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; and inorganic acids such as phosphoric acid and sulfuric acid.

[0029] The Johnson-Claisen rearrangement usually proceeds at a reaction temperature of 50 to 280° C., more preferably 90 to 180° C., under normal pressure. However, when the reaction is carried out under high pressure or as a gas phase reaction, the temperature is not limited to these temperature ranges.

[0030] In addition to the alkyl-substituted 4-pentenoic acid ester derivative, which is the target product, an ester having the alkyl-substituted allyl alcohol used as a raw material in the reaction as an ester acid residue may also be produced as a by-product of the Johnson-Claisen rearrangement reaction. For example,

[0031]

[0032] When allyl alcohol represented by the following formula (2) is reacted with triethyl orthoacetate in the presence of an acid catalyst,

[0033]

[0034] In addition to producing ethyl 4-methyl-4-hexenoate represented by the following formula (5):

[0035]

[0036] However, even if this by-product is present, it does not have any particular effect on the aroma. Furthermore, the use of a raw material represented by general formula (3) results in the production of a similar by-product, but if the molecular weight of the by-product exceeds the molecular weight of the compound represented by formula (5), the aroma will not be perceived.

[0037] The alkyl-substituted 4-pentenoic acid ester derivatives represented by general formula (1) and ethyl 4-methyl-4-hexenoate represented by formula (2) of the present invention have at least one of a strong, excellent, and natural-feeling fruity odor (such as strawberry-like), a green odor, a milky odor, and a citrus odor, which are clearly different from conventionally used compounds having a fruity or green odor, as described above. Therefore, these may be used alone or in combination of two or more as fragrance components, but generally, a fragrance composition is prepared by blending the alkyl-substituted 4-pentenoic acid ester derivatives or ethyl 4-methyl-4-hexenoate with, as additional fragrance components, ketones, aldehydes, esters, alcohols, ethers, terpenes, natural essential oils, synthetic musks, and the like, which are conventionally known or well-known as fragrance components, either alone or in appropriate combination. The additional perfume ingredients are incorporated into the perfume composition in an amount of 0.001% to 99.999% by weight, or 0.001% to 99.9% by weight, or 0.01% to 99% by weight, or 0.1% to 99% by weight, or 0.1% to 90% by weight, or 0.1% to 80% by weight, or 1% to 70% by weight, or 2% to 60% by weight, or 5% to 50% by weight, or 10% to 40% by weight, or 15% to 30% by weight, or 20% to 25% by weight.

[0038] The fragrance composition of the present invention may further comprise a solvent. Some non-limiting examples of solvents include dipropylene glycol, propylene glycol, diethyl phthalate (DEP), diisononyl phthalate (DINP), benzyl benzoate, benzyl alcohol, isopropyl myristate (IPM), isopropyl palmitate (IPP / Deltylprim), butyl stearate, dioctyl adipate, triethyl citrate, hydrogenated methyl rosinate (CAS No. 8050-15-5), terpenes (e.g., Glidsol 100), paraffinic naphthenic solvents (e.g., LPA-170 solvent), isoalkanes (e.g., Soltrol 170 isoparaffin), isoparaffins, isooctadecanol (e.g., Tego Alkanol 66), phenoxyethanol, diethylene glycol monoethyl ether (Carbitol low gravity), glycol ether (methyl carbitol), dipropylene glycol methyl ether (e.g., Dowanol DPM), dipropylene glycol methyl ether acetate (e.g., Dowanol DPMA), propylene glycol methyl ether (e.g., Dowanol PM Glycol Ether), tripropylene glycol methyl ether, diisoheptyl phthalate (e.g., Jayflex® 77 available from Exxon), deionized or distilled water, especially denatured ethyl alcohol (e.g., SDA 40B), dimethyl adipate / dimethyl glutarate (e.g., DBE®-LVP ester available from FLEXISOLV®), racemic mixture (+ / -)-2,2-dimethyl-4-hydroxymethyl-1,3-Dioxolane (e.g., Augo Clean Multi Solvent), Alcohol 40B Anhydrous 200 Proof, Alcohol SDA 40B 190 Proof, triacetin, 3-methoxy-3-methyl-1-butanol (Solfit), benzyl laurate, tripropylene glycol methyl ether (e.g., Dowanol TPM), dipropylene glycol n-butyl ether (e.g., Dowanol DPNB), dimethylsiloxane, trimethylsiloxy-terminated (e.g., Dowanol Corning 200 Fluid), caprylic / capric triglyceride (e.g., Neobee M-5), propylene glycol and glyceryl oleate (e.g., Arlacel 186), Uniceth-IC20L (e.g., Arlasolve 200L), 1,3 propanediol, butyl cellosolve, hexylene glycol, glycerin, N-methyl stearate, isopropyl alcohol, 2-methyl-1,3-propanediol (e.g., MP diol glycol), diethyl citrate, triethyl acetyl citrate, isopentyl diacetate (IPD-AC). , dimethyl 2-methylpentanedioate (e.g., Rhodiasolve Iris), medium-chain triglycerides (MTC), terpene hydrocarbons (e.g., dipentene 5100), DL-limonene (e.g., dipentene 122), 3,5,5-trimethylhexyl acetate, diethyl malonate, limonene (e.g., Unitene D), cyclohexyl acetate, para-tert-butyl ether (e.g., Vertenex), ethyl acetate, diethyl succinate, and natural solvents (including, but not limited to, vegetable oils such as sunflower oil).

[0039] The amounts of the alkyl-substituted 4-pentenoic acid ester derivative and ethyl 4-methyl-4-hexenoate to be blended in the fragrance composition of the present invention are determined appropriately depending on the fragrance composition to be used, or on the form and usage mode of the product to which the fragrance composition is further applied. Generally, the amounts are preferably blended in the fragrance composition in an amount of 0.001 to 30% by weight, and particularly preferably 0.01 to 10% by weight.

[0040] Fragrance compositions containing the alkyl-substituted 4-pentenoic acid ester derivative represented by general formula (1) or ethyl 4-methyl-4-hexenoate represented by formula (2) can be suitably used as fragrances in various products, such as cosmetics, toiletries, bath additives, tobacco, foods and beverages, and pharmaceuticals. The amount of the fragrance composition obtained by the present invention to be blended into a product and the method of application can be appropriately changed depending on the type of product, the purpose of use, etc. Typically, the amount of the fragrance composition to be blended into a product is 0.0001 to 30 wt %, preferably 0.001 to 10 wt %, of the final product composition.

[0041] Cosmetics, toiletries, bath additives, tobacco, foods, beverages and pharmaceuticals to which the fragrance composition of the present invention can be applied will be described in more detail below.

[0042] Examples of cosmetics to which the fragrance composition of the present invention can be applied include fragrance products, basic cosmetics, finishing cosmetics, hair cosmetics, sunscreen cosmetics, medicated cosmetics, hair care products, soaps, body cleansers, detergents, fabric softeners, cleaning agents, kitchen detergents, bleaches, aerosols, deodorizers / fragrances, repellents, and other miscellaneous goods.

[0043] More specifically, examples of fragrance products include perfume, eau de parfum, eau de toilette, and eau de cologne; basic cosmetics include facial cleansing cream, vanishing cream, cleansing cream, cold cream, massage cream, emulsion, lotion, serum, pack, and makeup remover; finishing cosmetics include foundation, powder, solid powder, talcum powder, lipstick, lip balm, blush, eyeliner, mascara, eye shadow, eyebrow pencil, eye pack, nail enamel, and enamel remover; hair cosmetics include pomade, Brilantine, setting lotion, hair stick, hair solid, hair oil, hair treatment, hair cream, hair tonic, hair liquid, hair spray, Bandolin, hair tonic, and hair dye.

[0044] - Tanning cosmetics include suntan products and sunscreen products; - Medicated cosmetics include antiperspirants, aftershave lotions and gels, permanent wave agents, medicated soaps, medicated shampoos, medicated skin cosmetics, etc.; - Hair care products include shampoos, rinses, rinse-in shampoos, conditioners, treatments, hair packs, etc.; - Soaps include cosmetic soaps, bath soaps, perfumed soaps, transparent soaps, synthetic soaps, etc.; - Body cleansers include body soaps, body shampoos, hand soaps, etc.; - Detergents include heavy-duty laundry detergents, light-duty laundry detergents, liquid detergents, laundry soaps, compact detergents, powdered soaps, etc.

[0045] - Fabric softeners include softeners and furniture care products; - Detergents include cleansers, house cleaners, toilet cleaners, bathroom cleaners, glass cleaners, mold removers, drain cleaners, etc.; - Kitchen detergents include kitchen soap, synthetic kitchen soap, dishwashing detergent, etc.; - Bleaching agents include oxidation bleaches (chlorine bleaches, oxygen bleaches, etc.), reduction bleaches (sulfur bleaches, etc.), optical bleaches, etc.; - Aerosol agents include spray types and powder sprays; - Deodorizers and air fresheners include solid types, gel types, liquid types, etc.; - Repellents include mist spray types and aqueous liquid types; - Miscellaneous items include tissue paper and toilet paper.

[0046] Examples of toiletry products to which the fragrance composition of the present invention can be applied include toothpaste, mouthwash, mouthwash, shaving cream, and lotion.

[0047] Furthermore, examples of bath additives to which the fragrance composition of the present invention can be applied include bath additives (bath salts, bath tablets, bath liquids, etc.), foam baths (bubble baths, etc.), bath oils (bath perfumes, bath capsules, etc.), milk baths, bath jellies, bath cubes, etc.

[0048] Tobacco to which the flavor composition of the present invention can be applied includes cigarettes, cigars, pipes, hookahs, water pipes, smokeless tobacco, heated tobacco, and electronic cigarettes.

[0049] Examples of foods and beverages to which the flavoring composition of the present invention can be applied include beverages such as fruit juice drinks, fruit liquors, dairy drinks, carbonated drinks, soft drinks, and energy drinks; frozen desserts such as ice creams, sorbets, and popsicles; desserts such as jellies and puddings; Western confectioneries such as cakes, cookies, chocolates, and chewing gum; Japanese confectioneries such as buns, yokan, and yuzu; jams; candies; breads; tea drinks or beverages such as green tea, oolong tea, black tea, persimmon leaf tea, chamomile tea, kumazasa tea, mulberry tea, houttuynia tea, pu-erh tea, yerba mate tea, rooibos tea, gymnema tea, guava tea, coffee, and cocoa; soups such as Japanese-style soups, Western-style soups, and Chinese-style soups; flavor seasonings; various instant drinks and foods; and various snack foods.

[0050] Examples of pharmaceutical products to which the fragrance composition of the present invention can be applied include topical skin preparations such as poultices and ointments, oral preparations, medicated cosmetics, medicated lotions, etc. However, the products to which the fragrance composition of the present invention can be applied are not limited to those described above.

[0051] Furthermore, products to which the compounds are applied are appropriately blended with ingredients according to the intended use of each product, and are provided as fragrances, toiletries, bath additives, tobacco, foods and beverages, pharmaceuticals, etc. When blended into a product, the alkyl-substituted 4-pentenoate derivative represented by the general formula (1) above or the ethyl 4-methyl-4-hexenoate represented by the formula (2) above is preferably blended in a state contained in a fragrance composition, but it is also possible to blend the alkyl-substituted 4-pentenoate derivative or the ethyl 4-methyl-4-hexenoate and a fragrance composition that does not contain them as separate blending ingredients.

[0052] The present invention will be specifically explained below with reference to synthesis examples and examples, but the present invention is not limited thereto in any way.

[0053] In the following synthesis examples, nuclear magnetic resonance spectra (NMR) and mass spectra (MS) were measured using the following instruments. １ H NMR, １３ C NMR): DRX-500 type device (manufactured by Bruker Japan) Mass spectrum (MS): GCMS-QP2010 type device (manufactured by Shimadzu Corporation)

[0054] Synthesis Example 1 Synthesis of ethyl 4-methyl-4-hexenoate 103.4 g of 3-methyl-3-buten-2-ol (molecular weight 86.13, 1.20 mol), 253.1 g of triethyl orthoacetate (molecular weight 162.23, 1.56 mol), and 0.5 g of propionic acid (molecular weight 74.08, 6.75 mmol) were placed in a 500 ml reaction flask equipped with a thermometer, a Dean-Stark apparatus, and a reflux condenser, and heated in an oil bath at 180° C. under a nitrogen stream for 4 hours while removing the resulting ethanol from the Dean-Stark apparatus. Unreacted 3-methyl-3-buten-2-ol and triethyl orthoacetate were removed by rotary evaporation under reduced pressure, followed by distillation under reduced pressure to obtain 154.11 g of the target ethyl 4-methyl-4-hexenoate (molecular weight 156.23, 0.98 mol) as a colorless, transparent oil (yield 82.2%). bp: 70-72°C / 1400 Pa

[0055] MS of the obtained compound: １ H NMR, １３ C NMR results were as follows: GC / MS (m / e): 156 (M+), 125, 110, 83, 82, 69, 67, 55, 43, 41, 40, 29, 27. １ H NMR (500 MHz, CDCl ３ ): δ = 5.23 (m, 1H), 4.12 (q, J = 7.2Hz, 2H), 2.40-2.32 (m, 2H), 2.32-2 .25 (m, 2H), 1.61 (s, 3H), 1.58-1.54 (m, 3H), 1.25 (t, J=7.2Hz, 3H). １３ C NMR (125 MHz, CDCl ３): δ=173.56(s), 134.01(d), 119.19(d), 60.21(t), 34.65(q), 33.19(q), 15.52(t), 14.22(t), 13.32(q).

[0056] Synthesis Example 2 (Synthesis of Ethyl 4-Octenoate) 100.2 g of 1-hexen-3-ol (molecular weight 100.16, 1.00 mol), 210.9 g of triethyl orthoacetate (molecular weight 162.23, 1.30 mol), and 0.4 g of propionic acid (molecular weight 74.08, 5.40 mmol) were placed in a 500 ml reaction flask equipped with a thermometer, a Dean-Stark tube, and a reflux condenser. The mixture was heated in an oil bath at 180° C. under a nitrogen stream for 4 hours while removing the resulting ethanol from the Dean-Stark tube. Unreacted 1-hexen-3-ol and triethyl orthoacetate were removed by rotary evaporation under reduced pressure, followed by distillation under reduced pressure to obtain 133.82 g of the target ethyl 4-octenoate (molecular weight 170.25, 0.79 mol) as a colorless, transparent oil. (Yield 78.6%) bp. 85-87°C / 1400Pa

[0057] MS of the obtained compound: １ H NMR, １３ C NMR measurements were as follows: GC / MS (m / e): 170 (M+), 125, 124, 96, 88, 84, 82, 81, 71, 70, 67, 55, 43, 41, 29, 27. １ H NMR (500MHz, CDCl ３ ): δ = 5.50-5.35 (m, 4H), 4.12 (q, J = 7.2Hz, 2H), 2.38-2.27 (m, 2H), 1.94 (q, J = 7.2Hz, 2H), 1.40-1.31 (m, 4H), 1.24 (t, J=7.2Hz, 3H), 0.87 (t, J=7.4Hz, 3H). １３ C NMR (125 MHz, CDCl ３ ): δ=173.38(s), 131.57(d), 128.12(d), 60.21(t), 34.57(t), 34.45(t), 27.95(t), 22.54(t), 14.24(q), 13.58(q).

[0058] Synthesis Example 3 Synthesis of ethyl 4-methyl-4-heptenoate 100.2 g of 2-methyl-1-penten-3-ol (molecular weight 100.16, 1.00 mol), 210.9 g of triethyl orthoacetate (molecular weight 162.23, 1.30 mol), and 0.4 g of propionic acid (molecular weight 74.08, 5.40 mmol) were placed in a 500 ml reaction flask equipped with a thermometer, a Dean-Stark apparatus, and a reflux condenser, and heated in an oil bath at 180° C. under a nitrogen stream for 4 hours while removing the generated ethanol from the Dean-Stark apparatus. Unreacted 2-methyl-1-penten-3-ol and triethyl orthoacetate were removed by rotary evaporation under reduced pressure, followed by distillation under reduced pressure to obtain 130.07 g of the target ethyl 4-methyl-4-heptenoate (molecular weight 170.25, 0.76 mol) as a colorless, transparent oil (yield 76.4%). bp: 82-83°C / 1300-1400 Pa

[0059] MS of the obtained compound: １ H NMR, １３ C NMR measurements were as follows: GC / MS (m / e): 170 (M+), 125, 124, 97, 96, 95, 88, 83, 82, 81, 70, 69, 67, 55, 41, 29, 27. １ H NMR (500MHz, CDCl ３ ): δ = 5.15 (dt, J = 1.3Hz, J = 7.1Hz, 1H), 4.11 (q, J = 7.2, 2H), 2.40 (dt, J = 1.3Hz, J = 7.7Hz, 2H), 2.29 ( t, J=7.7Hz, 2H), 1.98 (dq, J=7.1, J=7.6, 2H), 1.60 (s, 3H), 1.24 (t, J=7.2, 3H), 0.92 (t, J=7.6, 3H). １３ C NMR (125 MHz, CDCl ３ ): δ=173.53(s), 132.60(s), 127.20(d), 60.19(t), 34.65(t), 33.26(t), 21.12(t), 15.70(q), 14.24(q).

[0060] Synthesis Example 4 Synthesis of ethyl 4-methyl-4-nonenoate 128.2 g of 2-methyl-1-hepten-3-ol (molecular weight 128.22, 1.00 mol), 210.9 g of triethyl orthoacetate (molecular weight 162.23, 1.30 mol), and 0.4 g of propionic acid (molecular weight 74.08, 5.40 mmol) were placed in a 500 ml reaction flask equipped with a thermometer, a Dean-Stark apparatus, and a reflux condenser, and heated in an oil bath at 180° C. under a nitrogen stream for 4 hours while removing the resulting ethanol from the Dean-Stark apparatus. Unreacted 2-methyl-1-penten-3-ol and triethyl orthoacetate were distilled off, followed by vacuum distillation to obtain 148.34 g of the target ethyl 4-methyl-4-nonenoate (molecular weight 198.31, 0.75 mol) as a colorless, transparent oil (yield 74.8%). bp: 94-96°C / 700 Pa

[0061] MS of the obtained compound: １ H NMR, １３ C NMR results were as follows: GC / MS (m / e): 198 (M+), 153, 142, 124, 111, 110, 109, 96, 95, 88, 81, 70, 69, 68, 67, 55, 43, 41, 29, 27. １ H NMR (500MHz, CDCl ３ ): δ = 5.16 (dt, J = 1.2Hz, J = 7.2Hz, 1H), 4.11 (q, J = 7.2, 2H), 2.40 (dt, J = 1.20Hz, J = 8.2Hz, 2H), 2.29 (t, J =8.2Hz, 2H), 2.01-1.93 (m, 2H), 1.60 (s, 3H), 1.33-1.26 (m, 4H), 1.24 (t, J = 7.2, 3H), 0.94-0.85 (m, 3H). １３ C NMR (125 MHz, CDCl ３ ): δ=173.54(s), 133.07(s), 125.59(d), 60.20(t), 34.72(t), 33.30 (t), 31.90 (t), 27.55 (t), 22.28 (t), 15.85 (q), 14.24 (q), 13.99 (q).

[0062] Synthesis Example 5 (Synthesis of Ethyl 3-Vinylhexanoate) 100.2 g of 2-hexen-3-ol (molecular weight 100.16, 1.00 mol), 210.9 g of triethyl orthoacetate (molecular weight 162.23, 1.30 mol), and 0.4 g of propionic acid (molecular weight 74.08, 5.40 mmol) were placed in a 500 ml reaction flask equipped with a thermometer, a Dean-Stark tube, and a reflux condenser. The mixture was heated in an oil bath at 180°C under a nitrogen stream for 4 hours while removing the resulting ethanol from the Dean-Stark tube. The unreacted 2-hexen-3-ol and triethyl orthoacetate were distilled off, followed by vacuum distillation to obtain 139.26 g of the target ethyl 3-vinylhexanoate (molecular weight 170.25, 0.82 mol) as a colorless, transparent oil. (Yield 81.8%) bp. 76-78℃ / 1600Pa

[0063] MS of the obtained compound: １ H NMR, １３ C NMR measurements were as follows: GC / MS (m / e): 170 (M+), 155, 141, 127, 124, 96, 88, 83, 81, 68, 43, 41, 29, 27. １ H NMR (500MHz, CDCl ３ ): δ = 5.56 (ddd, J = 10.2Hz, J = 8.4Hz, J = 17.2Hz, 1H), 5.05-4.97 (m, 2H), 4.12 (q, J = 7.1Hz, 2H), 2.35 (dd, J = 6.2Hz, J=7.3Hz, 1H), 2.26 (dd, J=8.4Hz, J=7.3Hz, 1H), 1.40-1.20 (m, 4H), 1.24 (t, J=7.1Hz, 3H), 0.89 (t, J=6.8Hz, 3H). １３ C NMR (125 MHz, CDCl ３ ): δ=172.61(s), 141.13(d), 114.86(t), 60.15(t), 40.24(d), 40.16(t), 36.68(t), 20.04(t), 14.27(q), 13.96(q).

[0064] Synthesis Example 6 Synthesis of 4-methyl-4-hexenoic acid 31.25 g (molecular weight 156.23, 0.20 mol) of ethyl 4-methyl-4-hexenoate obtained in Synthesis Example 1 and a 30% aqueous solution of sodium hydroxide (16.00 g (molecular weight 40.0, 0.4 mol) as sodium hydroxide) were placed in a 200 ml reaction flask equipped with a thermometer and stirred at room temperature. The reaction was monitored by gas chromatography, and the starting material ethyl 4-methyl-4-hexenoate had disappeared within 2 hours of stirring. After removing the organic layer, the residue was washed twice with hexane and then neutralized by adding 20% ​​sulfuric acid (19.60 g (molecular weight 98.0, 0.2 mol) as sulfuric acid). The organic layer was extracted twice with ethyl acetate and washed twice with water, and the solvent was then removed using a rotary evaporator to obtain 24.84 g of crude 4-methyl-4-hexenoic acid (molecular weight 128.17) as a pale yellow, transparent oil. This crude was used directly in the following esterification reaction.

[0065] Synthesis Example 7 (Synthesis of isopropyl 4-methyl-4-hexenoate) 20 ml of toluene, 1.0 g of 4-methyl-4-hexenoic acid (molecular weight 128.17, 7.8 mmol) obtained in Synthesis Example 6, 938 mg of isopropanol (molecular weight 60.10, 15.6 mmol), and 3.22 g of dicyclohexylcarbodiimide (molecular weight 206.33, 15.6 mmol) were placed in a 50 ml reaction flask equipped with a thermometer, and the mixture was stirred at room temperature for 3 hours. The resulting salt was filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The residue was then purified by silica gel chromatography to obtain 1.12 g of the target isopropyl 4-methyl-4-hexenoate (molecular weight 170.25, 6.58 mol) as a colorless, transparent oil. (Yield: 84.3%)

[0066] MS of the obtained compound: １ H NMR, １３ C NMR measurements were as follows: GC / MS (m / e): 170 (M+), 128, 113, 111, 110, 85, 83, 82, 69, 67, 55, 43, 41, 29, 27. １ H NMR (500MHz, CDCl ３): δ = 5.23 (dq, J = 6.6Hz, J = 1.1Hz, 1H), 5.00 (sep, J = 6.3Hz, 1H), 2.40-2.32 (m, 2H ), 2.32-2.25 (m, 2H), 1.61 (s, 3H), 1.56 (d, J=6.7Hz, 3H), 1.22 (d, J=6.3Hz, 6H). １３ C NMR (125 MHz, CDCl ３ ): δ=173.07(s), 134.06(s), 119.20(d), 67.38(d), 34.77(t), 33.51(t), 21.83(q), 15.50(q), 13.30(q).

[0067] Synthesis Example 8 (Synthesis of butyl 4-methyl-4-hexenoate) 20 ml of toluene, 1.0 g of 4-methyl-4-hexenoic acid (molecular weight 128.17, 7.8 mmol) obtained in Synthesis Example 6, 1.16 g of 1-butanol (molecular weight 74.12, 15.6 mmol), and 3.22 g of dicyclohexylcarbodiimide (molecular weight 206.33, 15.6 mmol) were placed in a 50 ml reaction flask equipped with a thermometer and stirred at room temperature for 3 hours. The resulting salt was filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The residue was then purified by silica gel chromatography to obtain 1.19 g of the target butyl 4-methyl-4-hexenoate (molecular weight 184.28, 6.46 mol) as a colorless, transparent oil. (Yield: 82.8%)

[0068] MS of the obtained compound: １ H NMR, １３ C NMR results were as follows: GC / MS (m / e): 184 (M+), 128, 111, 110, 95, 85, 83, 82, 69, 67, 57, 55, 43, 41, 39, 29, 27. １ H NMR (500MHz, CDCl ３ ): δ=5.23 (dq, J=6.6Hz, J=1.1Hz, 1H), 4.06 (t, J=6.7Hz, 2H), 2.43-2.35 (m, 2H), 2.35-2 .26 (m, 2H), 1.66-1.52 (m, 8H), 1.38 (td, J=7.4Hz, J=14.9Hz, 2H), 0.93 (t, J=7.4Hz, 3H). １３C NMR (125 MHz, CDCl ３ ): δ=173.64(s), 134.04(s), 119.19(d), 64.14(t), 34.70(t), 33.21(t), 30.70(t), 19.21(t), 15.52(q), 13.69(q), 13.32(q).

[0069] [Example 1] (Sensory Evaluation) Seven expert panelists evaluated the aroma on a blotter for the ethyl 4-methyl-4-hexenoate, ethyl 4-octenoate, ethyl 4-methyl-4-heptenoate, ethyl 4-methyl-4-nonenoate, ethyl 3-vinylhexanoate, isopropyl 4-methyl-4-hexenoate, and butyl 4-methyl-4-hexenoate obtained in Synthesis Examples 1 to 5 and 7 to 8. The results are shown in Table 1.

[0070]

[0071] Example 2 and Comparative Example 1 Using the ethyl 4-methyl-4-hexenoate obtained in Synthesis Example 1, 100 g of a fruity strawberry-like fragrance composition was prepared according to the following recipe (Example 2). Also, 100 g of a fragrance composition not containing ethyl 4-methyl-4-hexenoate was prepared (Comparative Example 1). The scents of these fragrance compositions were evaluated by seven expert panelists. In the tables, the blend amounts are expressed in grams.

[0072]

[0073] As a result of the evaluation, all seven expert panelists reported that the fragrance composition of Example 2 exhibited a more palatable, natural, strawberry-like, fruity green fragrance than the fragrance composition of Comparative Example 1.

[0074] Example 3 and Comparative Example 2 (Strawberry Flavor) Using the ethyl 4-methyl-4-hexenoate obtained in Synthesis Example 1, a fragrance composition (strawberry flavor) was prepared according to the following recipe (Example 3). In addition, a fragrance composition (strawberry flavor) not containing ethyl 4-methyl-4-hexenoate was prepared (Comparative Example 2). The fragrances of these fragrance compositions were evaluated by seven expert panelists. In the tables, the amounts are expressed in parts by weight.

[0075]

[0076] As a result of the evaluation, all seven expert panelists reported that the fragrance composition of Example 3 exhibited a more palatable, natural strawberry-like fragrance note than the fragrance composition of Comparative Example 2.

[0077] Example 4 and Comparative Example 3 (Mango Flavor) A fragrance composition (mango flavor) was prepared according to the following recipe using the ethyl 4-methyl-4-hexenoate obtained in Synthesis Example 1 (Example 4). In addition, a fragrance composition (mango flavor) not containing ethyl 4-methyl-4-hexenoate was prepared (Comparative Example 3). The fragrances of these fragrance compositions were evaluated by seven expert panelists. In the tables, the amounts are expressed in parts by weight.

[0078]

[0079] As a result of the evaluation, all seven expert panelists reported that the fragrance composition of Example 4 exhibited a more palatable, natural mango-like fragrance note than Comparative Example 3.

[0080] [Example 5] (Shampoo) Using the fruity strawberry-like fragrance composition obtained in Example 2, a shampoo was prepared according to the formulation shown in Table 5 below. In the table, the units of blending amounts are parts by weight. As a result, a shampoo was obtained that had a natural feel and a fruity strawberry-like fragrance note with excellent palatability.

[0081]

[0082] [Example 6] (Body Shampoo) Using the fruity strawberry-like fragrance composition obtained in Example 2, a body shampoo was prepared according to the formulation shown in Table 6 below. In the table, the units of blending amounts are parts by weight. As a result, a body shampoo was obtained that had a natural feel and a fruity strawberry-like fragrance note with excellent palatability.

[0083]

[0084] [Example 7] (Toothpaste) Using the strawberry flavor composition obtained in Example 3, toothpaste was prepared according to the formulation shown in Table 7 below. In the table, the units of blending amounts are parts by weight. As a result, a strawberry flavor toothpaste with a natural feel and excellent palatability was obtained.

[0085]

[0086] Example 8 (Strawberry-flavored beverage) A strawberry-flavored beverage was prepared using the strawberry-flavored flavor composition obtained in Example 3 according to the formulation shown in Table 8 below. In the table, the units of blending amounts are parts by weight. As a result, a strawberry-flavored beverage with a natural taste and excellent palatability was obtained.

[0087]

[0088] [Example 9] (Mango Flavored Chewing Gum) Using the mango flavor fragrance composition obtained in Example 4, mango flavored chewing gum was prepared according to the formulation shown in Table 9 below. In the table, the unit of blending amount is gram (g). As a result, a mango flavored chewing gum with a natural feel and excellent palatability was obtained.

[0089]

[0090] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on U.S. patent application Ser. No. 63 / 606,884, filed Dec. 6, 2023, the entire contents of which are incorporated by reference.

Claims

1. General formula (1): (In the formula, R １ ~R ３ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ４ is an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 3 to 5 carbon atoms.

2. The fragrance composition according to claim 1, wherein the alkyl-substituted 4-pentenoic acid ester derivative is ethyl 4-methyl-4-hexenoate represented by the following formula (2):

3. The fragrance composition according to claim 1 or 2, wherein the amount of the alkyl-substituted 4-pentenoic acid ester derivative is 0.001 to 30% by weight based on the total weight of the fragrance composition.

4. A cosmetic product, a toiletry product, a bath agent, a cigarette, a food, a drink or a medicine, containing 0.0001 to 30% by weight of the fragrance composition according to claim 1 or 2.

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