Flavoring composition

Abstract

A perfume composition which is useful as a formulated perfume raw material and which has excellent fragrance and fragrance persistence, the perfume composition containing: a compound represented by formula (1); (in the formula, R 1 , R 2 , and R 3 are independently hydrogen or a methyl group, X is an alkyl group having 1 to 4 carbons, R 4 and R 5 are independently hydrogen or a -CHO group, and AA is a single bond or a double bond).

Description

TECHNICAL FIELD

[0001] The present application relates to a flavor composition. BACKGROUND

[0002] It is known that there are compounds useful as a flavor among esters. For example, it is described in Non-Patent Literature 1 that geranyl acetate having a rose-like aroma, methyl jasmonate having a sweet jasmine-like aroma, fructose ester having a fruity aroma, methyl benzoate having a strong dry fruit-like aroma, and the like are useful as a blending flavor raw material.

[0003] PRIOR ART DOCUMENTS

[0004] NON-PATENT LITERATURE

[0005] Non-Patent Literature 1: Shigetoshi Nakajima, "Fundamentals of Flavor and Fragrance", 1995, pp. 215, 235, 244-246, Gyozaburo Industries Publishing Co., Ltd. SUMMARY

[0006] Problem to be solved by the invention

[0007] An object of the present application is to provide a flavor composition useful as a blending flavor raw material, which has excellent aroma and aroma persistence.

[0008] Solution to the problem

[0009] The present inventors have been interested in compounds having a polycyclic structure among terpenes, and synthesized a variety of compounds having a polycyclic structure and evaluated their aroma, and as a result, found that norbornane-2-carboxylate compounds have excellent aroma and are extremely excellent as a blending flavor, thereby completing the present application.

[0010] That is, the present application is as described below. [1]

[0012] A flavor composition comprising a compound represented by formula (1);

[0013]

[0014] (In formula (1), R 1 , R 2 , and R 3 are independently hydrogen or a methyl group,

[0015] X is an alkyl group having 1 to 4 carbons,

[0016] R 4 and R 5 are independently hydrogen or a -CHO group,

[0017] is a single bond or a double bond. [2]

[0019] The perfume composition according to [1], wherein the compound represented by formula (1) is one or more selected from the group consisting of formulae (1-1) to (1-3),

[0020]

[0021] (in formula (1-1), R 1 , R 2 , R 3 are independently hydrogen or methyl,

[0022] X is an alkyl group having 1 to 4 carbons.

[0023]

[0024] (in formula (1-2), R 1 , R 2 , R 3 are independently hydrogen or methyl,

[0025] X is an alkyl group having 1 to 4 carbons.

[0026]

[0027] (in formula (1-3), R 1 , R 2 , R 3 are independently hydrogen or methyl,

[0028] X is an alkyl group having 1 to 4 carbons,

[0029] R 4 and R 5 are hydrogen, and the other is a -CHO group. [3]

[0031] A cosmetic, a health and hygiene material, a commodity, a quasi-drug, or a drug, which contains the perfume composition according to [1] or [2].

[0032] Effects of the invention

[0033] The perfume composition of the present application containing a norbornane-2-carboxylate compound has an excellent fragrance, and has excellent fragrance persistence, and thus is useful as a fragrance-imparting component for a wide range of products such as toiletries, soaps, laundry detergents, and the like. DETAILED DESCRIPTION

[0034] The following describes in detail a mode for carrying out the present application (hereinafter, simply referred to as "the present embodiment"). The present embodiment is an example for describing the present application, and is not intended to limit the present application to the following content. The present application can be carried out with appropriate modifications within the scope of the gist thereof.

[0035] [Perfume composition]

[0036] The perfume composition of the present embodiment contains norbornane-2-carboxylate compounds, i.e., compounds represented by formula (1).

[0037] The perfume composition of the present embodiment can be a perfume composition in which the compounds represented by formula (1) alone or two or more kinds thereof are the main components, or a perfume composition in which the compounds represented by formula (1) alone or two or more kinds thereof are mixed in a blending perfume of other perfume components generally used, a desired composition.

[0038] The main components alone or two or more kinds thereof mean that the compounds represented by formula (1) are contained in an amount of usually 85% by mass or more, preferably 90% by mass or more, more preferably 96% by mass or more, and further preferably 98% by mass or more, relative to the total amount of the perfume composition.

[0039]

[0040] In formula (1), R 1 , R 2 , R 3 are independently hydrogen or methyl,

[0041] X is an alkyl group having 1 to 4 carbons,

[0042] R 4 and R 5 are independently hydrogen or a -CHO group,

[0043]

[0044] is a single bond or a double bond.

[0045] The compounds represented by formula (1) in the present embodiment are preferably the compounds represented by formula (1-1) to formula (1-3) below. The compounds represented by formula (1-1) to formula (1-3) can be one kind alone, or two or more kinds in combination.

[0046]

[0047] In formula (1-1), R 1 , R 2 , R 3 , and X are the same as R 1 , R2 , R 3 and X have the same meaning.

[0048] , R 1 , R 2 , R 3 independently are hydrogen or methyl,

[0049] X is an alkyl group having 1 to 4 carbons.

[0050]

[0051] In formula (1-2), R 1 , R 2 , R 3 and X have the same meaning as R 1 , R 2 , R 3 and X in formula (1).

[0052] , R 1 , R 2 , R 3 independently are hydrogen or methyl,

[0053] X is an alkyl group having 1 to 4 carbons.

[0054]

[0055] In formula (1-3), R 1 , R 2 , R 3 and X have the same meaning as R 1 , R 2 , R 3 and X in formula (1).

[0056] , R 1 , R 2 , R 3 independently are hydrogen or methyl,

[0057] X is an alkyl group having 1 to 4 carbons.

[0058] Either one of R 4 and R 5 is hydrogen, and the other is a -CHO group.

[0059] R 1 , R 2 , R 3 in formula (1), formula (1-1) to formula (1-3) independently are hydrogen or methyl.

[0060] R 2 and R 3 are preferably hydrogen.

[0061] In addition, X in formula (1), formula (1-1) to formula (1-3) is an alkyl group having 1 to 4 carbons. As the alkyl group having 1 to 4 carbons, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a t-butyl group can be given. X is preferably a methyl group and an ethyl group.

[0062] The compound represented by formula (1) and formula (1-1) to formula (1-3) can be a single substance of any one of optical isomers with respect to an asymmetric carbon not embodying a stereoscopic configuration, or can be a mixture containing them in any ratio.

[0063] As the compound represented by formula (1-1), any one of methyl norbornene-2-carboxylate, ethyl norbornene-2-carboxylate, methyl norbornene-2-methyl-2-carboxylate, ethyl norbornene-2-methyl-2-carboxylate is preferable, and any one of methyl norbornene-2-carboxylate, methyl norbornene-2-methyl-2-carboxylate is more preferable.

[0064] The compound represented by formula (1-1) in the present embodiment has a scent having both a strong mature banana and melon-like fruity flavor and an ozone-like marine scent, or even a scent having both a fresh floral green tone and a fruity flavor, and is also excellent in persistence.

[0065] As the compound represented by formula (1-2), any one of methyl norbornane-2-carboxylate, ethyl norbornane-2-carboxylate, methyl norbornane-2-methyl-2-carboxylate, ethyl norbornane-2-methyl-2-carboxylate is preferable, and any one of methyl norbornane-2-carboxylate, methyl norbornane-2-methyl-2-carboxylate is more preferable.

[0066] The compound represented by formula (1-2) in the present embodiment has a scent having a fruity herbal green-like scent, and is also excellent in persistence.

[0067] As the compound represented by formula (1-3), any one of formyl norbornane-2-carboxylate, ethyl formyl norbornane-2-carboxylate, methyl formyl norbornane-2-methyl-2-carboxylate, ethyl formyl norbornane-2-methyl-2-carboxylate is preferable, and any one of methyl formyl norbornane-2-carboxylate, methyl formyl norbornane-2-methyl-2-carboxylate is more preferable.

[0068] The compound represented by formula (1-3) in the present embodiment is a novel scent having both a strong melon and kiwi-like fruity flavor and a fresh marine scent, and a rose-like floral scent, and is also excellent in persistence.

[0069] As above, the compound represented by formula (1) has an excellent aroma such as fruity flavor, and also has excellent persistence, and thus can be used alone or in combination with other ingredients as an aroma component of various products such as cosmetics, health and hygiene materials, miscellaneous goods, quasi drugs, drugs, and the like. Specifically, it can be used as an aroma component of soap, shampoo, hair conditioner, detergent, cosmetic, spray product, fragrance, perfume, or bath agent, and the like.

[0070] [Method for producing compound represented by formula (1)]

[0071] The compound represented by formula (1) in the present embodiment can be produced, for example, by a synthesis method in which a Diels-Alder reaction of heating an olefin and dicyclopentadiene is used as a key process.

[0072] Specifically, the compound represented by formula (1-1) can be produced by a Diels-Alder reaction of heating an olefin and dicyclopentadiene as follows.

[0073]

[0074] (In the formula, R 1 , R 2 , R 3 , and X are the same as R 1 , R 2 , R 3 , and X in formula (1). That is, R 1 , R 2 , R 3 are independently hydrogen or methyl, and X is an alkyl group having 1 to 4 carbons.)

[0075] As the aforementioned olefin, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl crotonate, ethyl crotonate, propyl crotonate, butyl crotonate, methyl 3-methylcrotonate, ethyl 3-methylcrotonate, propyl 3-methylcrotonate, butyl 3-methylcrotonate, and the like can be given. Among these olefins, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl crotonate, ethyl crotonate, methyl 3-methylcrotonate, ethyl 3-methylcrotonate, and the like are preferred, and methyl acrylate, ethyl acrylate, and the like, methyl methacrylate, ethyl methacrylate are more preferred.

[0076] In addition, the aforementioned dicyclopentadiene is preferably high in purity, and it is desirable to avoid as much as possible the content of butadiene, isoprene, and the like. The purity of dicyclopentadiene is preferably 90% or more, and more preferably 95% or more. In addition, it is known that dicyclopentadiene depolymerizes to become cyclopentadiene under heating conditions, and thus cyclopentadiene can also be used instead of dicyclopentadiene.

[0077] In order to make the Diels-Alder reaction proceed efficiently, it is important that cyclopentadiene is present in the reaction system, and therefore the reaction temperature is preferably 100°C or higher, more preferably 120°C or higher, and further preferably 130°C or higher.

[0078] On the other hand, in order to suppress the generation of high-boiling substances, the reaction temperature is preferably 250°C or lower.

[0079] In addition, as the reaction solvent, a hydrocarbon, an alcohol, an ester, or the like can be used, and it is suitable that an aliphatic hydrocarbon having a carbon number of 6 or more, specifically cyclohexane, toluene, xylene, ethylbenzene, mesitylene, propanol, butanol, or the like.

[0080] As the reaction mode of the Diels-Alder reaction of the present embodiment, various reaction modes such as a batch type using a tank reactor or the like, a semi-batch type in which a substrate or a substrate solution is supplied to a tank reactor under reaction conditions, a continuous flow type in which a substrate is circulated in a pipe reactor under reaction conditions, and the like can be adopted.

[0081] The product obtained in the above reaction can be used as a flavor composition containing the compound represented by formula (1), can be used as a raw material for the following reaction, and can be purified by distillation, extraction, crystallization, or the like and used as a flavor composition, a raw material for the following reaction.

[0082] The obtained product, that is, the compound represented by formula (1-1) can be used as a raw material for the following reaction, and can be used as a raw material for synthesizing the compound represented by formula (1-2) and the compound represented by formula (1-3).

[0083] Specifically, the compound represented by formula (1-2) can be produced by subjecting the compound represented by formula (1-1) to a hydrogenation reaction in the presence of a catalyst, as follows.

[0084]

[0085] (In the formula, R 1 , R 2 , R 3 , and X are the same as R 1 , R 2 , R 3 , and X in formula (1). That is, R 1 , R 2 , R 3 independently are hydrogen or a methyl group, and X is an alkyl group having a carbon number of 1 to 4.)

[0086] The catalyst used in the aforementioned hydrogenation reaction is not particularly limited as long as it is a catalyst used in hydrogenation of a generally unsaturated bond, and is preferably a catalyst containing at least one metal selected from Groups 8 to 11 of the periodic table. Specifically, catalysts containing at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold can be given.

[0087] The aforementioned hydrogenation catalyst can be either a solid catalyst or a homogeneous catalyst, and from the viewpoint of separability from the reaction product, a solid catalyst is preferred. As the solid catalyst, non-supported metal catalysts, supported metal catalysts, and the like can be given.

[0088] As the non-supported metal catalyst, Raney catalysts such as Raney nickel, Raney cobalt, and Raney copper; oxides of platinum, palladium, rhodium, and ruthenium; colloidal catalysts; and the like can be given.

[0089] As the supported metal catalyst, for example, catalysts in which at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold is supported on or mixed with a carrier such as magnesium oxide, zirconium oxide, cerium oxide, diatomaceous earth, activated carbon, alumina, silica, zeolite, and titanium dioxide can be given.

[0090] As the supported metal catalyst, specifically, supported copper catalysts in which copper catalysts such as copper-chromium catalyst (Adkins catalyst), copper-zinc catalyst, copper-iron catalyst, and the like are supported on a carrier; Pt / C, Pt / alumina, and the like supported platinum catalysts; Pd / C, Pd / alumina, and the like supported palladium catalysts; Ru / C, Ru / alumina, and the like supported ruthenium catalysts; Rh / C, Rh / alumina, and the like supported rhodium catalysts; and the like can be given.

[0091] Among these catalysts, from the viewpoints of reactivity and selectivity, catalysts containing copper are more preferred.

[0092] The amount of the hydrogenation catalyst used can be appropriately adjusted depending on the kind of the catalyst, and is preferably 0.001 to 100 mass%, more preferably 0.01 to 30 mass%, and further more preferably 0.1 to 20 mass% relative to the norbornene-2-carboxylate compound as the raw material.

[0093] The hydrogen pressure in the hydrogenation reaction can be either normal pressure or under pressure, and is generally normal pressure to 4.0 MPa, preferably 0.1 to 3.0 MPa, and more preferably 0.1 to 2.0 MPa.

[0094] The hydrogenation reaction can be performed in the absence of a solvent or in the presence of a solvent.

[0095] As the solvent, water, organic acids such as formic acid and acetic acid; esters such as ethyl acetate and butyl acetate; aromatic compounds such as benzene, o-dichlorobenzene, toluene and xylene; hydrocarbons such as hexane, heptane and cyclohexane; alcohols such as methanol, ethanol, isopropanol, tert-butanol, ethylene glycol and diethylene glycol; ethers such as dioxane, tetrahydrofuran, dimethoxyethane and diethylene glycol dimethyl ether; or the like, or a mixture thereof can be mentioned.

[0096] The amount of the solvent used in the hydrogenation reaction is usually 0.1 to 30 mass times, preferably 0.2 to 20 mass times, relative to the norbornene-2-carboxylate compound as the raw material.

[0097] The reaction temperature of the hydrogenation reaction can be usually in the range of -90°C to 200°C. The reaction temperature is preferably in the range of 20°C to 150°C, more preferably in the range of 50°C to 120°C.

[0098] The form of the hydrogenation reaction is not particularly limited as long as it can perform the catalytic hydrogenation reaction, and can be a commonly used known form. As the form of the hydrogenation reaction, for example, a form using a reactor in which the catalyst is fluidized in a fluid to perform the catalytic hydrogenation reaction, a fixed bed reactor in which the catalyst is packed and fixed and a fluid is supplied to perform the catalytic hydrogenation reaction, or the like can be mentioned.

[0099] The reaction product obtained in the hydrogenation reaction is subjected to removal of low-boiling substances or the like using a rotary evaporator or the like, and then subjected to distillation using a distillation column, whereby it can be used as a flavor composition containing the compound represented by formula (1-2).

[0100] The compound represented by formula (1-3) can be synthesized by subjecting carbon monoxide and hydrogen to a hydroformylation reaction in the presence of a rhodium compound and an organophosphorus compound, for example, for the compound represented by formula (1-1).

[0101]

[0102] (In the formula, R 1 , R 2 , R 3 and X are the same as R 1 , R 2 , R 3 and X in formula (1). That is, in the formula, R 1 , R 2 , R 3 are independently hydrogen or methyl, and X is an alkyl group having 1 to 4 carbons. Either one of R 4 and R 5 is hydrogen, and the other is a -CHO group.)

[0103] The rhodium compound used in the hydroformylation reaction is not limited in form as long as it is a compound that forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of carbon monoxide and hydrogen. Catalyst precursor materials such as rhodium acetylacetonate dicarbonyl (hereinafter, referred to as Rh(acac)(CO)2), Rh2O3, Rh4(CO) 12 , Rh6(CO) 16 , Rh(NO3)3, and the like can be introduced into the reaction mixture together with the organophosphorus compound, and a rhodium metal hydride carbonyl phosphine complex having catalytic activity is formed in the reaction vessel, or a rhodium metal hydride carbonyl phosphine complex can be prepared in advance and introduced into the reactor. As a preferred method for producing the rhodium compound used in the hydroformylation reaction, a method in which Rh(acac)(CO)2 is reacted with an organophosphorus compound in the presence of a solvent and then introduced into the reactor together with excess organophosphorus compound to form a rhodium-organophosphorus complex having catalytic activity can be mentioned as a specific example.

[0104] The amount of the rhodium compound used in the hydroformylation reaction is preferably 0.1 to 30 micromoles, more preferably 0.2 to 20 micromoles, and further preferably 0.5 to 10 micromoles, per 1 mole of the olefin that is the substrate of the hydroformylation reaction. By making the amount of the rhodium compound less than 30 micromoles per 1 mole of the olefin, the cost of the rhodium catalyst can be reduced even without providing a recycling device for the rhodium complex, and thus the economic burden of the recycling device can be reduced. In addition, by making the amount of the rhodium compound more than 0.1 micromole per 1 mole of the olefin, the hydroformylation reaction product can be obtained at a high yield.

[0105] As the organophosphorus compound that forms a catalyst for the hydroformylation reaction with the rhodium compound in the hydroformylation reaction, a phosphine represented by the general formula P(-R 6 )(-R 7 )(-R 8 ) or a phosphite represented by the general formula P(-OR 6 )(-OR 7 )(-OR 8 ) and the like can be mentioned as specific examples.

[0106] As specific examples of R 6 , R 7 , and R 8 , an aryl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, an alicyclic alkyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the like can be mentioned.

[0107] As the organophosphorus compound, specifically, triphenylphosphine, triphenylphosphite is suitably used.

[0108] The amount of the organophosphorus compound is preferably 500 times the molar amount of the rhodium metal to 10,000 times the molar amount of the rhodium metal, more preferably 700 times the molar amount of the rhodium metal to 5,000 times the molar amount of the rhodium metal, and further preferably 900 times the molar amount of the rhodium metal to 2,000 times the molar amount of the rhodium metal. In the case where the amount of the organophosphorus compound is less than 500 times the molar amount of the rhodium metal, the stability of the rhodium hydride carbonyl-phosphine complex of the catalytically active species tends to be impaired, and the reaction tends to proceed slowly. In addition, in the case where the amount of the organophosphorus compound is more than 10,000 times the molar amount of the rhodium metal, the cost of the organophosphorus compound tends to increase.

[0109] The hydroformylation reaction can also be performed without using a solvent, and can be more suitably performed by using a solvent that is not reactive to the reaction. As the solvent, there is no particular limitation as long as the olefin, dicyclopentadiene or cyclopentadiene, and the aforementioned rhodium compound, and the aforementioned organophosphorus compound are dissolved, for example.

[0110] As the solvent, specifically, there can be mentioned hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons; esters such as aliphatic esters, alicyclic esters, and aromatic esters; alcohols such as aliphatic alcohols, and alicyclic alcohols; aromatic halides; and the like. Among these solvents, hydrocarbons are preferred, and alicyclic hydrocarbons and aromatic hydrocarbons are more preferred.

[0111] As the temperature in the case where the hydroformylation reaction is performed, 40°C to 160°C is preferred, and 80°C to 140°C is more preferred. By making the reaction temperature 40°C or higher, a sufficient reaction rate can be obtained, and the residual amount of the olefin as the raw material can be suppressed. In addition, by making the reaction temperature 160°C or lower, the generation of by-products derived from the raw material olefin, the reaction product can be suppressed, and the decrease in the reaction effect can be prevented.

[0112] In the case where the hydroformylation reaction is performed, it is necessary to perform the reaction under pressurization with carbon monoxide (CO) and hydrogen (H2) gases. The CO and H2 gases can be independently introduced into the reaction system, or can be introduced into the reaction system in the form of a mixed gas prepared in advance. The molar ratio (= CO / H2) of the CO and H2 gases introduced into the reaction system is preferably 0.2 to 5, more preferably 0.5 to 2, and further preferably 0.8 to 1.2. When the molar ratio of the CO and H2 gases deviates from this range, the reaction activity of the hydroformylation reaction and the selectivity to the target aldehyde sometimes decrease. The CO and H2 gases introduced into the reaction system gradually decrease as the reaction proceeds, and therefore, if a mixed gas of CO and H2 prepared in advance is used, the reaction control is sometimes facilitated.

[0113] As the reaction pressure in the hydroformylation reaction, 1 to 12 MPa, more preferably 1.2 to 9 MPa, further preferably 1.5 to 5 MPa is preferred. By making the reaction pressure 1 MPa or more, a sufficient reaction rate can be obtained, and the residual olefin as a raw material can be suppressed. In addition, by making the reaction pressure 12 MPa or less, it becomes unnecessary to use an expensive device having excellent pressure resistance, and thus it is economically advantageous. In particular, in the case of performing the reaction in a batch system or a semi-batch system, it is necessary to discharge CO and H2 gas and depressurize after the reaction is completed, and the lower the pressure, the less the loss of CO and H2 gas, and thus it is economically advantageous.

[0114] As the reaction mode in the case of performing the hydroformylation reaction, a batch system reaction or a semi-batch system reaction is suitable. The semi-batch system reaction can be performed as follows: a rhodium compound, an organophosphorus compound, and the aforementioned solvent are added to a reactor, and pressurization with CO / H2 gas, heating, or the like is performed to form the aforementioned reaction conditions, and then an olefin as a raw material or a solution thereof is supplied to the reactor.

[0115] The reaction product obtained in the aforementioned hydroformylation reaction can be subjected to distillation by removing low-boiling substances or the like using a rotary evaporator or the like, and thus used as a flavor composition containing a compound represented by formula (1-3).

[0116] As for the flavor composition of the present embodiment, the aforementioned compound represented by formula (1) can be mixed alone or two or more of the aforementioned compounds represented by formula (1) can be mixed and compounded in a blending flavor of other flavor ingredients, a desired composition, which is usually used.

[0117] The compounding amount of the compound represented by formula (1) in the flavor composition of the present embodiment can be appropriately adjusted depending on the type of the blending flavor, the type and intensity of the target aroma, and the like, and 0.01 to 90% by mass, more preferably 0.1 to 50% by mass is preferably added to the blending flavor.

[0118] In the flavor composition of the present embodiment, as the flavor ingredient used in combination with the compound represented by formula (1), surfactants such as polyoxyethylene lauryl ether sulfate; solvents such as dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, triethyl citrate; hydrocarbons such as limonene, a-pinene, β-pinene, terpinolene, cedrene, longifolene, valencene; alcohols such as linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cypressene, menthol, borneol, β-phenyl ethanol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-tert-butylcyclohexyloxy)-2-butanol, 4-isopropylcyclohexanemethanol, 4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-butene-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-butene-1-ol, isocamphyl cyclohexanol, 3,7-dimethyl-7-methoxyoctan-2-ol; phenols such as eugenol, thymol, vanillin; esters such as linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpinyl acetate, nopyl acetate, borneol acetate, isoborneol acetate, o-tert-butylcyclohexyl acetate, p-tert-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrallyl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, tricyclodecenyl propionate, allylcyclohexyl propionate, ethyl 2-cyclohexyl propionate, benzyl propionate, citronellyl butyrate, dimethylbenzylcarbinyl n-butyrate, tricyclodecenyl isobutyrate, methyl 2-nonenate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, geranyl tiglate, cis-3-hexenyl tiglate, methyl jasmonate, methyl dihydrojasmonate, methyl-2,4-dihydroxy-3,6-dimethylbenzoate, ethyl methylphenylglycidate, methyl anthranilate, fruitate; and the like are not limited to the following ingredients, but can be mentioned, for example.aldehydes such as n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, dimethyl tetrahydrosalicylaldehyde, 4(3)- (4-hydroxy-4-methylpentyl)-3-cyclohexen-1-carboxaldehyde, 2-cyclohexylpropanal, p-tert-butyl-α-methylhydrocinnamaldehyde, p-isopropyl-α-methylhydrocinnamaldehyde, p-ethyl-α,α-dimethylhydrocinnamaldehyde, α-amylcinnamaldehyde, α-hexylcinnamaldehyde, heliotropin, α-methyl-3,4-methylenedioxyhydrocinnamaldehyde, and the like; ketones such as methylheptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, amylcyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentenyl ketone, rose ketone, γ-methylionone, α-ionone, carvone, menthone, camphor, nucifone, benzylacetone, anisalacetone, methyl β-naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene, muscone, civetone, cyclopentadecanone, cyclohexadecenone, and the like; acetal and ketal such as acetaldehyde ethyl phenyl propyl acetal, citral diethyl acetal, phenylacetaldehyde glycerol acetal, ethyl acetoacetate ethylene ketal, and the like; ethers such as anethole, β-naphthyl methyl ether, β-naphthyl ethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan, and the like; nitriles such as citronitrile, and the like; lactones such as γ-nonalactone, γ-undecalactone, σ-decalactone, γ-jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, helenandiolide, tridecanedioic acid cyclohexylidene ester, 11-oxahexadecanolide, and the like; natural essential oils such as orange, lemon, bergamot, mandarin, mint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, patchouli, labdanum, and the like, natural extracts, and other perfume materials. The other perfume materials can be used alone or in combination of a plurality of kinds.

[0119] In order to impart a fragrance and in order to improve the fragrance of a blending target, the perfume composition containing the compound represented by formula (1) can be used as a fragrance component of various products such as cosmetics, health and hygiene materials, miscellaneous goods, quasi drugs, drugs, and the like.

[0120] The fragrance composition containing the compound represented by formula (1) can be used, for example, as a fragrance ingredient of a perfume, a cologne, or the like; a hair cosmetic product such as a shampoo, a hair rinse, a hair tonic, a hair cream, a mousse, a gel, a hair wax, a spray, or the like; a skin cosmetic product such as a lotion, a serum, a cream, an emulsion, a pack, a foundation, a powder, a lipstick, a cosmetic, or the like; a health and sanitary detergent such as a dishwashing detergent, a laundry detergent, a softener, a disinfectant, a deodorant, an indoor fragrance, a furniture care agent, a glass cleaner, a furniture cleaner, a floor cleaner, a disinfectant, a pesticide, a bleaching agent, or the like; a quasi-drug such as a toothpaste, a mouthwash, a bath agent, an antiperspirant, a permanent wave solution, or the like; a miscellaneous goods such as a toilet paper, a tissue, or the like; or a medicine.

[0121] In addition, the compounding amount of the fragrance or the fragrance composition of the present embodiment in the above-mentioned product is preferably 0.001 to 50% by mass, and more preferably 0.01 to 20% by mass, of the formyl norbornane-2-carboxylate compound represented by formula (1) relative to the total amount of the product.

[0122] Examples

[0123] Hereinafter, the method of the present application will be further described in detail based on examples, but the present application is not limited to these examples.

[0124] The measurement methods in the following examples are shown below.

[0125] <Gas Chromatography Analysis Conditions>

[0126] • Analysis device: Capillary Chromatograph GC-2010 Plus manufactured by Shimadzu Corporation

[0127] • Analysis column: InertCap1 (30 m, 0.32 mm I.D., film thickness 0.25 μm manufactured by GL Sciences, Inc.

[0128] • Column oven temperature: 60°C (0.5 minutes) - temperature increase rate 15°C / minute - 280°C (4 minutes)

[0129] • Detector: FID, temperature 280°C

[0130] <Yield and Selectivity of Carboxylate Compound>

[0131] The area ratio (GC%) of the carboxylate compound as a product was found by gas chromatography analysis, and the yield and selectivity of the norbornene-2-carboxylate and norbornane-2-carboxylate compound were calculated from the following formula by the internal standard method.

[0132] • Yield (mole%) based on olefin = amount (mole) of norbornene-2-carboxylate obtained / amount (mole) of olefin charged x 100

[0133] • Yield (mole%) based on dicyclopentadiene = amount (mole) of norbornene-2-carboxylate obtained / amount (mole) of dicyclopentadiene charged x 100 / 2

[0134] • Selectivity (mole%) based on olefin = amount (mole) of norbornene-2-carboxylate obtained / amount (mole) of olefin reacted x 100

[0135] • Selectivity (mole%) based on dicyclopentadiene = amount (mole) of norbornene-2-carboxylate obtained / amount (mole) of dicyclopentadiene reacted x 100 / 2

[0136] • Yield (mole%) of hydrogenation reaction = amount (mole) of norbornane-2-carboxylate obtained / (amount (mole) of norbornene-2-carboxylate charged x 100

[0137] • Selectivity (mole%) of hydrogenation reaction = amount (mole) of norbornane-2-carboxylate obtained / amount (mole) of norbornene-2-carboxylate reacted x 100

[0138] • Yield (mole%) of hydroformylation reaction = amount (mole) of formyl norbornane-2-carboxylate obtained / amount (mole) of norbornene-2-carboxylate charged x 100

[0139] • Selectivity (mole%) of hydroformylation reaction = amount (mole) of formyl norbornane-2-carboxylate obtained / amount (mole) of norbornene-2-carboxylate reacted x 100

[0140] <GC-MS measurement conditions>

[0141] • Analysis device: GCMS-QP2010 Plus, Shimadzu Corporation

[0142] • Ionization voltage: 70 eV

[0143] • Analysis column: DB-1 (30 m, 0.32 mm I.D., film thickness 1.00 μm), Agilent Technologies

[0144] • Column oven temperature: 60°C (0.5 minutes) - temperature increase rate 15°C / minute - 280°C (4 minutes)

[0145] [Example 1]

[0146] (Synthesis method of norbornene-2-carboxylic acid methyl ester)

[0147]

[0148] The synthesis was performed using a stainless steel autoclave having a magnetic induction type stirrer and three inlet nozzles at the upper portion, with a content volume of 500 ml.

[0149] First, dodecane (Tokyo Chemical Industry Co., Inc. special grade) 101.2 g was charged in the autoclave, and after nitrogen gas replacement, the liquid temperature was set to 195°C.

[0150] While maintaining the reaction temperature at 195°C, a mixed solution of methyl acrylate 96.4 g (1.12 mol) and dicyclopentadiene 105.7 g (0.80 mol) was supplied from the upper portion of the autoclave over 1 hour, and further, stirring was continued for 2 hours.

[0151] The reaction liquid was cooled, and the obtained liquid 301.0 g was analyzed by gas chromatography by internal standard method, and as a result, it contained the target methyl norbornene-2-carboxylate compound 133.2 g. The results based on methyl acrylate were as follows: yield 78.2 mol%, selectivity 79.0 mol%, and the results based on dicyclopentadiene were as follows: yield 54.7 mol%, selectivity 59.3 mol%.

[0152] The obtained liquid was subjected to rectification using a rectification column having 20 theoretical plates (distillation temperature 88°C, vacuum degree 2.7 kPa), and as a result, 120.5 g (distillation yield 90.5 mol%) was obtained as a main fraction which was 98.5 GC% in gas chromatography analysis.

[0153] The obtained fraction was analyzed by GC-MS, and as a result, the molecular weight of the target substance was 152.

[0154] The obtained fraction had a new type of aroma having both mature banana and cantaloupe-like fruity aroma and ozone-like marine aroma, and had the characteristic of excellent aroma persistence compared to other known esters or geranyl acetate having only fruity aroma or only rose-like aroma.

[0155] (Fragrance composition having apricot-like fruity aroma with floral sensation)

[0156] First, a fragrance composition (control) having the composition shown in Table 1 was prepared. Next, 10 parts by mass of the methyl norbornene-2-carboxylate prepared above was added to 90 parts by mass of the control, and a fragrance composition was prepared.

[0157] The obtained fragrance composition was confirmed to have an apricot-like fruity aroma with a strong gardenia-like floral sensation in a fragrance evaluation based on a perfumer.

[0158] [Table 1]

[0159]

[0160] [Example 2]

[0161] (Synthesis method of norbornene-2-methyl-2-carboxylic acid methyl ester)

[0162]

[0163] The Diels-Alder reaction and the treatment were carried out in the same manner as in Example 1, except that 112.1 g (1.12 moles) of methyl methacrylate was used as the olefin.

[0164] After the reaction liquid was cooled, the obtained liquid 316.9 g was analyzed by gas chromatography by the internal standard method, and as a result, it contained 140.0 g of the target norbornene-2-methyl-2-carboxylic acid methyl ester compound. The yield based on methyl methacrylate was 75.2 mole%, and the selectivity was 75.9 mole%, and the yield based on dicyclopentadiene was 52.7 mole%, and the selectivity was 57.4 mole%.

[0165] The obtained liquid was subjected to rectification (distillation temperature 90°C, vacuum degree 2.7 kPa) using a rotating band distillation column having 40 theoretical plates, and as a result, 127.5 g (distillation yield 91.1 mole%) of 98.5 GC% as analyzed by gas chromatography was obtained as the main fraction.

[0166] The obtained fraction was analyzed by GC-MS, and as a result, the molecular weight of the target substance was 166.

[0167] The obtained fraction had a novel aroma having both a fresh green floral-like fragrance and a fruity fragrance, and had the characteristic of having excellent aroma persistence compared to other known esters or geranyl acetate having only a rose-like fragrance, unlike the known fruit ester having only a fruity fragrance or the known geranyl acetate having only a rose-like fragrance.

[0168] (Fragrance composition considered to be a fruit type of fresh pear)

[0169] First, a fragrance composition (control) having the composition shown in Table 2 was prepared. Next, 10 parts by mass of the norbornene-2-methyl-2-carboxylic acid methyl ester prepared in the above was added to 90 parts by mass of the control, and a fragrance composition was prepared.

[0170] The obtained fragrance composition was confirmed to have a fragrance considered to be a fruit type of fresh pear in a fragrance evaluation based on a perfumer.

[0171] [Table 2]

[0172]

[0173] [Example 3]

[0174] (Synthesis of methyl norbornene-2-carboxylate)

[0175]

[0176] A hydrogenation reaction was performed using a stainless steel autoclave having a magnetic induction type stirrer and three inlet nozzles at the upper portion, with a content volume of 500 ml.

[0177] In the aforementioned autoclave, Cu-Cr catalyst (N-203S manufactured by Nippon Kagaku) 6.0 g and isopropyl alcohol (special grade manufactured by Wako Pure Chemical Industries) 120.0 g were charged, and activation was performed at 170°C under a hydrogen pressure of 2 MPa for 1 hour. After cooling, methyl norbornene-2-carboxylate 60.0 g prepared in the above was charged, and reduction was performed by stirring at 120°C under a hydrogen pressure of 2 MPa for 3 hours. The reaction liquid was filtered to remove the catalyst, and reaction liquid 173.9 g containing methyl norbornane-2-carboxylate 57.6 g was obtained (conversion 100%, yield 96.2%). The results of the methyl norbornene-2-carboxylate reference were as follows: yield 96.2 mol%, selectivity 100 mol%.

[0178] The obtained liquid was subjected to rectification using a rotating band distillation column having 40 theoretical plates (distillation temperature 89°C, vacuum degree 2.7 kPa), and as a result, 53.5 g (distillation yield 91.5 mol%) of 98.5 GC% in gas chromatography analysis was obtained as a main fraction.

[0179] The obtained fraction was analyzed by GC-MS, and as a result, the molecular weight of the target substance was 154.

[0180] The obtained fraction had a novel aroma having a strong fruity feeling of a grassy green type, and had a characteristic of excellent aroma persistence compared to other known esters or geranyl acetate having only a fruity aroma or a rose-like aroma.

[0181] (Fruity perfume composition having a fresh feeling of green apple)

[0182] First, a perfume composition (control) having the composition shown in Table 3 was prepared. Next, 10 parts by mass of the methyl norbornane-2-carboxylate prepared in the above was added to 90 parts by mass of the control, and a perfume composition was prepared.

[0183] The obtained perfume composition was confirmed to have a fruity aroma having a fresh feeling of green apple in an aroma evaluation based on a perfumer.

[0184] [Table 3]

[0185]

[0186] [Example 4]

[0187] (Synthesis method of formyl norbornane-2-carboxylic acid methyl ester)

[0188]

[0189] A hydrogenation formylation reaction was performed using a stainless steel autoclave having a magnetic induction type stirrer and three inlet nozzles at the upper portion, with a content volume of 500 ml.

[0190] In the aforementioned autoclave, 60.0 g of the norbornene-2-carboxylic acid methyl ester prepared in the above, 116.9 g of toluene, 0.37 g of triphenyl phosphite, and 3.10 g of the Rh(acac)(CO)2toluene solution prepared separately (concentration 0.01 wt%) were added. After displacement with nitrogen gas and CO / H2mixed gas was performed three times each, the system was pressurized with CO / H2mixed gas, and a reaction was performed at 100°C, 2 MPa for 5 hours. After the reaction was completed, the reaction liquid was analyzed by gas chromatography, and 186.9 g of the reaction liquid containing 69.0 g of formyl norbornane-2-carboxylic acid methyl ester (a mixture of 5-formyl norbornane-2-carboxylic acid methyl ester and 6-formyl norbornane-2-carboxylic acid methyl ester) was obtained. The results based on norbornene-2-carboxylic acid methyl ester were as follows: yield 96.2 mol%, selectivity 100 mol%.

[0191] The obtained liquid was subjected to rectification using a rotating band distillation column having 40 theoretical plates (distillation temperature 112°C, vacuum degree 0.19 kPa), and as a result, 63.5 g (distillation yield 90.7 mol%) of 98.4 GC% as analyzed by gas chromatography was obtained as a main fraction.

[0192] The obtained fraction was analyzed by GC-MS, and as a result, the molecular weight of the target substance was 182.

[0193] The obtained fraction was different from a known fructose ester having only a fruity aroma or a known geranyl acetate having only a rose-like aroma, and was a novel aroma having a strong melon, kiwi-like fruity flavor and a fresh marine tone, and a rose-like floral scent. In addition, the aroma persistence was excellent compared to other known esters or geranyl acetates.

[0194] (Fruit-type flavor composition having a floral scent of gardenia flowers considered to be sweet and rich)

[0195] First, a flavor composition (control) having the composition shown in Table 4 was prepared. Next, 10 parts by mass of the formyl norbornane-2-carboxylic acid methyl ester prepared in the above was added to 90 parts by mass of the control, and a flavor composition was prepared.

[0196] The resulting flavor composition was confirmed to have a fruity flavor with a floral sense of gardenia that was considered to be sweet and rich in a flavor evaluation based on a perfumer's sense of smell.

[0197] [Table 4]

[0198]

[0199] This application is based on Japanese Patent Application (Tokugan 2016-180434) filed on September 15, 2016, Japanese Patent Application (Tokugan 2016-180435) filed on September 15, 2016, and Japanese Patent Application (Tokugan 2016-180436) filed on September 15, 2016, the contents of which are incorporated herein by reference.

[0200] Industrial applicability

[0201] The carboxylic acid ester compound having a norbornane skeleton of the present application has a fruity aroma and excellent aroma persistence, and is thus useful as a fragrance-imparting component in a wide range of products such as toiletries, soaps, and laundry detergents.

Claims

1. A perfume composition containing a mixture of methyl 5-formyl norbornane-2-carboxylate and methyl 6-formyl norbornane-2-carboxylate, or a mixture of methyl 5-formyl norbornane-2-carboxylate and methyl 6-formyl norbornane-2-carboxylate and the following formula (1-2), ###0001### X is an alkyl group having 1 to 4 carbons, In formula (1-2), R 1 , R 2 , R 3 are independently hydrogen, the compounding amount of the mixture of methyl 5-formyl norbornane-2-carboxylate and methyl 6-formyl norbornane-2-carboxylate in the perfume composition is 0.01 to 90 mass%, or the compounding amount of the mixture of methyl 5-formyl norbornane-2-carboxylate and methyl 6-formyl norbornane-2-carboxylate and formula (1-2) is 0.01 to 90 mass%.

2. A cosmetic, a sanitary paper, a toilet paper, a toothpaste, a mouthwash, a bath agent, an antiperspirant product, a permanent wave liquid, or a pharmaceutical product containing the perfume composition according to claim 1. ​

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