Aldehyde composition

Abstract

An aldehyde composition containing an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), the mass ratio [(1) / (2)] of the aldehyde represented by formula (1) to the aldehyde represented by formula (2) being 96 / 4 to 99.9 / 0.1. (R represents a methyl group or a hydrogen atom)

Description

Technical Field

[0001] This invention relates to aldehyde compositions, methods for their manufacture, and fragrance compositions containing the aldehyde compositions. Background Technology

[0002] It is known that among the 3-(alkylphenyl)-2-alkylpropionaldehyde class of aldehydes, there are substances that are useful as raw materials for blending fragrances.

[0003] For example, Non-Patent Literature 1 describes 3-(p-tert-butylphenyl)-2-methylpropanal (p-tert-butyl-α-methylhydrocinnamaldehyde, lily of the valley aldehyde), which has a fragrance similar to lily of the valley; 3-(p-isopropylphenyl)-2-methylpropanal (rabbit ear aldehyde), which has a fragrance similar to honeydew melon and cucumber; and 3-(3,4-methylenedioxyphenyl)-2-methylpropanal (neo-jasmine aldehyde), which has a fragrance similar to sweet heliotrope and anise. These are useful as blending fragrance ingredients.

[0004] Furthermore, Patent Document 1 discloses that dihydrocinnamaldehyde derivatives can be used as fragrances. Specifically, it discloses a synthesis method using the following formula. It also discloses that when R is a hydrogen atom and R' is n-butyl in the dihydrocinnamaldehyde derivative shown in the following formula, it has a strong floral fragrance with green and pollen notes, and a rabbit's ear floral scent. Furthermore, it discloses that when R is methyl and R' is n-butyl, it has a delicate floral fragrance with green and woody notes, and a rabbit's ear floral scent. Moreover, it discloses that according to the following manufacturing method, a para-isomer of 70% or more and an ortho-isomer of less than 30% can be obtained.

[0005]

[0006] Existing technical documents

[0007] Non-patent literature

[0008] Non-Patent Literature 1: Motokazu Into, *Synthetic Fragrance Chemistry and Commercial Knowledge (New Edition with Supplements)*, 2016, pp. 218-219, 221, 233-234, Chemical Industry Daily.

[0009] Patent documents

[0010] Patent Document 1: Specification of French Patent No. 1460826 Summary of the Invention

[0011] The problem the invention aims to solve

[0012] In particular, floral and blended fragrances are used in a variety of fields, including fragrance products, cosmetics, detergents, hygiene products, groceries, pharmaceuticals, and food. New fragrances are being developed to enhance the value of these products.

[0013] Among them, as mentioned above, there are fragrances with characteristic floral scents in the 3-(alkylphenyl)-2-alkylpropionaldehyde class, but seeking fragrances with more novel scents.

[0014] Here, the subject of the present invention is to provide fragrances and fragrance compositions having novel aromas.

[0015] Solution for solving the problem

[0016] The inventors manufactured various aldehyde compositions and evaluated their aromas, and found that certain aldehyde compositions had excellent aromas and were excellent as raw materials for fragrance compositions, thus completing the present invention.

[0017] That is, the present invention is as follows.

[0018] [1] An aldehyde composition comprising an aldehyde represented by the following general formula (1) and an aldehyde represented by the following general formula (2), wherein the mass ratio of the aldehyde represented by formula (1) to the aldehyde represented by formula (2) [(1) / (2)] is 96 / 4 to 99.9 / 0.1.

[0019]

[0020] (R represents a methyl group or a hydrogen atom)

[0021] [2] The aldehyde composition according to [1] above, wherein R is a hydrogen atom.

[0022] [3] A fragrance composition containing the aldehyde composition described in [1] or [2] above.

[0023] [4] The fragrance composition according to [3] above further contains at least one of the group consisting of a fragrance other than the aldehyde shown in formula (1) or the aldehyde shown in formula (2), a surfactant, a solvent, an antioxidant and a colorant.

[0024] [5] An aldehyde composition for use as a fragrance, the aldehyde composition containing an aldehyde represented by the following general formula (1) and an aldehyde represented by the following general formula (2), wherein the mass ratio of the aldehyde represented by formula (1) to the aldehyde represented by formula (2) [(1) / (2)] is 96 / 4 to 99.9 / 0.1.

[0025]

[0026] (R represents a methyl group or a hydrogen atom)

[0027] [6] A method for manufacturing an aldehyde composition, comprising the following steps in sequence to obtain the aldehyde composition described in [1] or [2] above:

[0028] The process of condensing 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde with acetaldehyde or propionaldehyde to obtain aldehydes of the following general formula (5) and the following general formula (6); and the hydrogenation process.

[0029]

[0030] (R represents a methyl group or a hydrogen atom)

[0031] [7] A method for manufacturing an aldehyde composition, comprising the following steps in sequence to obtain the aldehyde composition described above [2]:

[0032] The process includes: acetalizing 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde under an acid catalyst; reacting the resulting acetal with an alkyl vinyl ether under an acid catalyst; hydrolyzing the acetal under an acid catalyst to obtain an aldehyde of formula (5a) and an aldehyde of formula (6a) below; and a hydrogenation process.

[0033]

[0034] [8] In the method for manufacturing the aldehyde composition according to [6] or [7] above, the mass ratio of 4-n-butylbenzaldehyde to 2-n-butylbenzaldehyde [(4-n-butylbenzaldehyde) / (2-n-butylbenzaldehyde)] is 96 / 4 to 99.9 / 0.1.

[0035] [9] The method for manufacturing the aldehyde composition according to any one of [6] to [8] above, wherein the 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde are 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde manufactured by formylation of n-butylbenzene with carbon monoxide under superacid conditions.

[0036] The effects of the invention

[0037] According to the present invention, an aldehyde composition with floral, green, and lily-of-the-valley notes, exhibiting excellent diffusion, can be provided, making it useful as a fragrance. Furthermore, by containing this aldehyde composition, a fragrance composition with excellent diffusion, potency, and residual aroma can be provided. Detailed Implementation

[0038] In the following, the references to "XX~YY" in this specification refer to "XX and above and YY and below".

[0039] [Aldehyde composition]

[0040] The aldehyde composition of the present invention contains an aldehyde represented by the following general formula (1) and an aldehyde represented by the following general formula (2), wherein the mass ratio of the aldehyde represented by formula (1) to the aldehyde represented by formula (2) [(1) / (2)] is 96 / 4 to 99.9 / 0.1.

[0041]

[0042] (R represents a methyl group or a hydrogen atom)

[0043] The above-mentioned aldehyde composition has a similar floral and green fragrance and a lily of the valley aroma. It has excellent diffusion and can impart diffusibility, strength and substantiality to the fragrance composition.

[0044] In the aforementioned formula (1), R is a methyl group or a hydrogen atom, preferably a hydrogen atom. In the aforementioned formula (2), R is a methyl group or a hydrogen atom, preferably a hydrogen atom. Furthermore, when R in the aforementioned formula (1) is a methyl group, it is preferable that R in the aforementioned formula (2) is also a methyl group; when R in the aforementioned formula (1) is a hydrogen atom, it is preferable that R in the aforementioned formula (2) is also a hydrogen atom; more preferably, both R in the aforementioned formula (1) and R in the aforementioned formula (2) are hydrogen atoms.

[0045] In the aforementioned formula (1), the compound in which R is a hydrogen atom is 3-(4-n-butylphenyl)propanal, and the compound in which R is a methyl group is 3-(4-n-butylphenyl)-2-methylpropanal.

[0046] In the aforementioned formula (2), the compound in which R is a hydrogen atom is 3-(2-n-butylphenyl)propanal, and the compound in which R is a methyl group is 3-(2-n-butylphenyl)-2-methylpropanal.

[0047] The aldehyde composition of the present invention contains the aldehyde shown in formula (1) and the aldehyde shown in formula (2) above. These two components may be used as the components constituting the aldehyde composition of the present invention, but in practice, by-products and raw materials generated during the manufacture of the aldehyde composition are sometimes included.

[0048] Therefore, the total content of the aldehydes represented by formula (1) and formula (2) in the aldehyde composition of the present invention is preferably 95% by mass or more, more preferably 96% by mass or more, and even more preferably 97% by mass or more. There is no upper limit, and it can be 100% by mass or less, or it can consist only of the aldehydes represented by formula (1) and formula (2).

[0049] The mass ratio [(1) / (2)] of the aldehyde in the aldehyde composition of the present invention, representing the aldehyde of formula (1) and the aldehyde of formula (2) is 96 / 4 to 99.9 / 0.1, preferably 98 / 2 to 99.8 / 0.2, more preferably 98.7 / 1.3 to 99.7 / 0.3, even more preferably 99.0 / 1.0 to 99.6 / 0.4, and even more preferably 99.0 / 1.0 to 99.4 / 0.6.

[0050] Furthermore, from the viewpoint of aroma emission and diffusion, the mass ratio [(1) / (2)] of the aldehyde in the aldehyde composition of the present invention to the aldehyde shown in formula (1) above and the aldehyde shown in formula (2) above is preferably 98.7 / 1.3 to 99.9 / 0.1, more preferably 99.0 / 1.0 to 99.8 / 0.2, even more preferably 99.2 / 0.8 to 99.8 / 0.2, and even more preferably 99.3 / 0.7 to 99.7 / 0.3.

[0051] The aldehyde composition of the present invention is similar to a floral or green fragrance and has the aroma of lily of the valley, exhibiting excellent aroma dissipation properties, and is therefore useful as a fragrance. In particular, by setting the mass ratio of the aldehyde shown in formula (1) to the aldehyde shown in formula (2) within the aforementioned range, the aroma of lily of the valley is strengthened, and the aroma dissipation properties are excellent, thus making it superior as a fragrance.

[0052] The aldehyde composition of the present invention may contain at least one of the compounds selected from the group consisting of the compounds represented by the following general formula (5) and the compounds represented by the following general formula (6).

[0053]

[0054] (R represents methyl or hydrogen)

[0055] The compounds shown in formula (5) and formula (6) above are unsaturated aldehydes used as raw materials or synthetic intermediates in the manufacture of the aldehyde compositions of the present invention.

[0056] The total content of the aldehydes represented by formula (5) and formula (6) in the aldehyde composition of the present invention is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. The lower limit of the total content of the aldehydes represented by formula (5) and formula (6) can be 0% by mass, and more preferably does not contain the aldehydes represented by formula (5) and the compounds represented by formula (6).

[0057] The aldehyde composition of the present invention may contain at least one of the compounds selected from the group consisting of the compounds shown in general formula (12) and the compounds shown in general formula (13).

[0058]

[0059] (R represents methyl or hydrogen)

[0060] The compounds shown in formula (12) and formula (13) are alcohols that can sometimes be obtained as byproducts in the manufacture of the aldehyde compositions of the present invention.

[0061] The total content of the alcohols represented by formula (12) and formula (13) in the aldehyde composition of the present invention is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. The lower limit of the total content of the alcohols represented by formula (12) and formula (13) can be 0% by mass, and more preferably does not contain the alcohols represented by formula (12) and formula (13).

[0062] The aldehyde composition of the present invention has the above-described composition, is similar to a floral or green fragrance and has the aroma of lily of the valley, and has excellent aroma dissipation properties, thus it is useful as a fragrance.

[0063] In addition, the aforementioned aldehyde composition is also useful as a raw material for fragrance compositions. It can be used as an aroma component in various products and can impart diffusion, potency, and residual aroma to fragrance compositions.

[0064] The aldehyde compositions of the present invention also exhibit excellent safety.

[0065] In recent years, the safety requirements for fragrance raw materials have become increasingly stringent. 3-(p-tert-butylphenyl)-2-methylpropanal, with a lily-of-the-valley aroma, is widely used in perfumes, personal care products, and public care products. However, due to concerns about its toxic effects on reproductive organs, it has become a restricted ingredient, prompting a search for alternative fragrance raw materials. Under these circumstances, the aldehyde compositions of the present invention (compositions in formulas (1) and (2) where R is a hydrogen atom) also showed negative results in an in vitro carcinogenicity prediction test using Bhas42 cells based on OECD GD231, demonstrating excellent safety.

[0066] [Uses as a spice]

[0067] Aldehyde compositions containing aldehydes represented by general formula (1) and general formula (2) with a mass ratio of aldehyde (1) to aldehyde (2) of 96 / 4 to 99.9 / 0.1 are similar to floral or green fragrances and have a lily-of-the-valley aroma. They exhibit excellent diffusion and can impart diffusion, potency, and residual aroma to fragrance compositions, thus making them suitable for use as fragrances. This invention also includes the application of aldehyde compositions containing aldehydes represented by general formula (1) and general formula (2) with a mass ratio of aldehyde (1) to aldehyde (2) of 96 / 4 to 99.9 / 0.1 as fragrances.

[0068]

[0069] (R represents a methyl group or a hydrogen atom)

[0070] In the aforementioned formula (1), R is a methyl group or a hydrogen atom, preferably a hydrogen atom. In the aforementioned formula (2), R is a methyl group or a hydrogen atom, preferably a hydrogen atom. Furthermore, when R in the aforementioned formula (1) is a methyl group, it is preferable that R in the aforementioned formula (2) is also a methyl group; when R in the aforementioned formula (1) is a hydrogen atom, it is preferable that R in the aforementioned formula (2) is also a hydrogen atom; more preferably, both R in the aforementioned formula (1) and R in the aforementioned formula (2) are hydrogen atoms.

[0071] In the aforementioned formula (1), the compound in which R is a hydrogen atom is 3-(4-n-butylphenyl)propanal, and the compound in which R is a methyl group is 3-(4-n-butylphenyl)-2-methylpropanal.

[0072] In the aforementioned formula (2), the compound in which R is a hydrogen atom is 3-(2-n-butylphenyl)propanal, and the compound in which R is a methyl group is 3-(2-n-butylphenyl)-2-methylpropanal.

[0073] The aforementioned aldehyde composition contains the aldehyde shown in formula (1) and the aldehyde shown in formula (2). These two components may be used as the constituents of the aforementioned aldehyde composition, but in practice, they are sometimes included as by-products or raw materials generated during the manufacture of the aldehyde composition.

[0074] Therefore, the total content of the aldehydes represented by formula (1) and formula (2) in the aforementioned aldehyde composition is preferably 95% by mass or more, more preferably 96% by mass or more, and even more preferably 97% by mass or more. There is no upper limit, and it can be 100% by mass or less, or it can consist only of the aldehydes represented by formula (1) and formula (2).

[0075] The mass ratio [(1) / (2)] of the aldehyde in the aforementioned aldehyde composition, represented by formula (1) and the aldehyde represented by formula (2), is 96 / 4 to 99.9 / 0.1, preferably 98 / 2 to 99.8 / 0.2, more preferably 98.7 / 1.3 to 99.7 / 0.3, even more preferably 99.0 / 1.0 to 99.6 / 0.4, and even more preferably 99.0 / 1.0 to 99.4 / 0.6.

[0076] Furthermore, from the viewpoint of aroma emission and diffusion, the mass ratio [(1) / (2)] of the aldehyde in the aldehyde composition of the present invention, represented by formula (1) above and the aldehyde represented by formula (2) above, is preferably 98.7 / 1.3 to 99.9 / 0.1, more preferably 99.0 / 1.0 to 99.8 / 0.2, even more preferably 99.2 / 0.8 to 99.8 / 0.2, and even more preferably 99.3 / 0.7 to 99.7 / 0.3.

[0077] The aforementioned aldehyde composition is similar to floral and green notes and has the aroma of lily of the valley, with excellent aroma dispersibility, and therefore can be used as a fragrance. In particular, by making the mass ratio of the aldehyde shown in formula (1) to the aldehyde shown in formula (2) within the aforementioned range, the aroma of lily of the valley is strengthened and the aroma dispersibility is excellent, and therefore it can be suitable for use as a fragrance.

[0078] [Fragrance Composition]

[0079] The fragrance composition of the present invention contains the aforementioned aldehyde composition.

[0080] That is, the fragrance composition of the present invention comprises: an aldehyde composition containing an aldehyde represented by the following general formula (1) and an aldehyde represented by the following general formula (2), wherein the mass ratio of the aldehyde represented by formula (1) to the aldehyde represented by formula (2) [(1) / (2)] is 96 / 4 to 99.9 / 0.1.

[0081]

[0082] (R represents a methyl group or a hydrogen atom)

[0083] The fragrance composition of the present invention contains the aforementioned aldehyde composition as an active ingredient. The aforementioned aldehyde composition can impart a fragrance similar to floral, green, or lily of the valley notes to the fragrance composition, and improve the diffusion, potency, and residual fragrance of the fragrance composition.

[0084] In addition to the floral, green, and lily-of-the-valley aromas found in the aforementioned aldehyde compositions, the fragrance compositions of the present invention also exhibit excellent diffusion, potency, and residual aroma. Therefore, they are useful as aroma components for various products.

[0085] The content of the aforementioned aldehyde composition in the fragrance composition of the present invention can be appropriately adjusted according to the type of fragrance composition, the type of target aroma, and the aroma intensity, etc., preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass.

[0086] Other components contained in the fragrance composition including the aforementioned aldehyde composition besides the aforementioned aldehyde composition may include fragrances other than the aldehyde shown in formula (1) or formula (2), surfactants, solvents, antioxidants and colorants, etc. Preferably, at least one of the group consisting of fragrances other than the aldehyde shown in formula (1) or formula (2), surfactants, solvents, antioxidants and colorants is selected, and more preferably, at least one of the group consisting of fragrances other than the aldehyde shown in formula (1) or formula (2) and solvents is selected.

[0087] By containing an aldehyde other than that shown in Formula (1) or Formula (2), the fragrance can be adjusted according to the target product. In addition, by containing a solvent, it becomes easy to dissolve and impregnate in the target product, thereby adjusting the intensity and persistence of the fragrance.

[0088] For fragrances other than the aldehydes shown in Formula (1) or Formula (2), there are no particular restrictions as long as they are fragrance ingredients known in the past. A wide range of fragrances can be used, for example, one can be selected from the following substances alone or two or more can be selected in any mixing ratio.

[0089] As a fragrance other than the aldehyde shown in formula (1) or formula (2), examples include hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, and natural extracts. Preferably, one or more fragrances are selected from the group consisting of hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, and natural extracts.

[0090] Examples of hydrocarbons include limonene, α-pinene, β-pinene, terpinene, cedrene, longleafene, and valenene.

[0091] Examples of alcohols include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrceneol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, β-phenylethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-tert-butylcyclohexyloxy)-2-butanol, 4-isopropylcyclohexanemethanol, 4-tert-butylcyclohexanol, and 4-methylcyclohexanemethanol. 2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, sandalwood (isocamphylcyclohexanol), 3,7-dimethyl-7-methoxyoctane-2-ol, etc.

[0092] Examples of phenols include eugenol, thymol, and vanillin.

[0093] Examples of esters include linaloyl formate, citronellol formate, geraniol formate, n-hexyl acetate, cis-3-hexenyl acetate, linaloyl acetate, citronellol acetate, geraniol acetate, neroliyl acetate, terpineol acetate, norborneol acetate, borneol acetate, isoborneol acetate, o-tert-butylcyclohexyl acetate, p-tert-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrax acetate, cinnamyl acetate, dimethyl benzyl acetate, 3-pentyltetrahydropyran-4-ylacetate, citronellol propionate, tricyclodecenyl propionate, and allylcyclopropionate. Hexyl ester, ethyl 2-cyclohexylpropionate, benzyl propionate, citronellol butyrate, dimethyl benzyl butyrate, tricyclodecenyl isobutyrate, methyl 2-nonyneate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, geraniol ester, geraniol ester, methyl jasmone, methyl dihydrojasmone, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl methylphenyl glycidyl ester, methyl anthranilate, ethyl tricyclodecanecarboxylate (fruitate), etc.

[0094] Examples of aldehydes include n-octanal, n-decanal, dodecaldehyde, 2-methylundecaldehyde, 10-undecenal, citronellol, citral, hydroxycitronellol, dimethyltetrahydrobenzaldehyde, 4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde, 2-cyclohexylpropanal, p-tert-butyl-α-methylhydrocinnamaldehyde, p-isopropyl-α-methylhydrocinnamaldehyde, p-ethyl-α,α-dimethylhydrocinnamaldehyde, α-pentylcinnamaldehyde, α-hexylcinnamaldehyde, piperaldehyde, and α-methyl-3,4-methylenedioxyhydrocinnamaldehyde.

[0095] Examples of ketones include methylheptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptenone, pentylcyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentenolone, rose ketone, γ-methylionone, α-ionone, carvone, menthone, camphor, nocaketone, benzylacetone, anisylacetone, methyl β-naphthone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, muscone, civetone, cyclopentadecanone, and cyclohexaenoone.

[0096] Examples of acetals and ketals include acetaldehyde ethyl phenyl propyl acetal, citral diethyl acetal, phenyl acetaldehyde glycerol acetal, and ethyl acetoacetate ethylene glycol ketal.

[0097] Examples of ethers include anethole, β-naphthylmethyl ether, β-naphthylethyl ether, limonene oxide, rose ether, 1,8-cineole, racemic mixtures, or optically active dodecylhydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan.

[0098] Examples of nitriles include citronellol.

[0099] Examples of lactones include γ-nonanolactone, γ-undecanolactone, σ-decanolactone, γ-jasmine lactone, coumarin, cyclopentadecanolactone, cyclohexadecylolactone, asterolactone, ethylene glycol brassinolate, and 11-oxahexadecylolactone.

[0100] Examples of natural essential oils and extracts include orange, lemon, bergamot, citrus, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedarwood, cypress, sandalwood, vetiver, patchouli, and rockrose.

[0101] In addition, dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, triethyl citrate, etc. can be cited as solvents.

[0102] Examples of surfactants include polyoxyethylene lauryl sulfate.

[0103] Fragrance compositions containing the aforementioned aldehyde compositions can be used as aroma components in various products.

[0104] Products that can use fragrance compositions include, for example, perfumes, colognes, and other aromatic products; shampoos, conditioners, hair growth products, hair creams, mousses, hair gels, hair oils, sprays, and other hair cosmetics; lotions, serums, creams, emulsions, masks, foundations, powders, lipsticks, and various makeup products for the skin; dishwashing liquids, detergents, fabric softeners, disinfectants, deodorants, room fresheners, furniture cleaners, glass cleaners, floor cleaners, disinfectants, insecticides, bleach, bactericides, insect repellents, and other various health and hygiene detergents; toothpaste, mouthwash, bath salts, antiperspirants, perming solutions, and other quasi-medicines; toilet paper, napkins, and other groceries; pharmaceuticals; and food.

[0105] The amount of the fragrance composition in the above-mentioned products is not particularly limited, and can be selected according to the type, properties, and functional effects of the products to be scented. For example, the amount of the fragrance composition in the products is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more. In addition, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.

[0106] It should be noted that when the fragrance composition is used as aromatherapy essential oil, perfume, etc., the amount of the fragrance composition in the product can be 80% by mass or more, or it can be 100% by mass.

[0107] [Method for manufacturing aldehyde compositions]

[0108] If the aldehyde composition of the present invention contains the aldehyde represented by the aforementioned general formula (1) and the aldehyde represented by the aforementioned general formula (2) as described above, and their mass ratio [(1) / (2)] is 96 / 4 to 99.9 / 0.1, then the manufacturing method is not limited, but it is preferably obtained by the manufacturing method shown below.

[0109] As a preferred method for manufacturing the aldehyde composition of the present invention, the following two methods are shown, each of which uses 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde as raw materials and sequentially includes step 1, which obtains the aldehyde shown in the following general formula (5) and the aldehyde shown in the following general formula (6) (cinnamaldehyde), and a hydrogenation step, i.e., step 2.

[0110] Through the aforementioned hydrogenation process, an aldehyde composition containing the target aldehyde represented by the aforementioned general formula (1) and the aldehyde represented by the aforementioned general formula (2) can be obtained.

[0111]

[0112] (R represents a methyl group or a hydrogen atom)

[0113] Furthermore, the 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde supplied to the aforementioned step 1 are preferably 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde produced by formylation of n-butylbenzene with carbon monoxide under superacid conditions.

[0114] Summarize the above processes as follows:

[0115]

[0116] (R represents methyl or hydrogen)

[0117] Here, the compound shown in formula (7) is n-butylbenzene, the compound shown in formula (3) is 4-n-butylbenzaldehyde, and the compound shown in formula (4) is 2-n-butylbenzaldehyde.

[0118] <Formylation process>

[0119] The 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde supplied to the aforementioned step 1 are preferably 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde produced by formylation of n-butylbenzene with carbon monoxide under superacid conditions.

[0120] Therefore, as the initial step in the method for manufacturing the aldehyde composition of the present invention, a formylation step is preferably performed, in which n-butylbenzene is reacted with carbon monoxide under a superacid catalyst to obtain 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde. That is, "under superacid conditions" means that a superacid catalyst is used in the reaction.

[0121] The preferred superacid catalyst is a combination of Brønsted acid and Lewis acid.

[0122] Brønsted acid is not particularly limited, but hydrogen fluoride, hydrogen chloride, and hydrogen bromide are preferred, with hydrogen fluoride being more preferred.

[0123] Lewis acids are not particularly limited, but boron trifluoride and aluminum chloride are preferred, with boron trifluoride being more preferred.

[0124] From the perspective of catalyst recovery / reuse and the position selectivity of formyl groups, the combination of hydrogen fluoride and boron trifluoride is further preferred.

[0125] When hydrogen fluoride is used as a Brønsted acid, it also functions as a solvent in the reaction. From a reactivity point of view, substantially anhydrous hydrogen fluoride is preferred. It should be noted that "substantially anhydrous" means that the water content is 5% by mass or less, preferably 1% by mass or less, and more preferably 0.1% by mass or less.

[0126] From the viewpoint of reactivity with carbon monoxide and suppression of side reactions, the molar ratio of hydrogen fluoride to n-butylbenzene [hydrogen fluoride (moles) / n-butylbenzene (moles)] is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 10.0 or more. Furthermore, from the viewpoint of economy and production efficiency, it is preferably 30.0 or less, more preferably 20.0 or less, and even more preferably 15.0 or less.

[0127] When boron trifluoride is used as a Lewis acid, from the viewpoint of reactivity with carbon monoxide and suppression of side reactions, the molar ratio of boron trifluoride to n-butylbenzene [boron trifluoride (moles) / n-butylbenzene (moles)] is preferably 1.0 or more, more preferably 2.0 or more, and preferably 4.0 or less, more preferably 3.0 or less.

[0128] From the viewpoint of improving reactivity, suppressing side reactions, and improving the selectivity of formyl group introduction site, the reaction temperature is preferably -50°C or higher, more preferably -40°C or higher, even more preferably -30°C or higher, and preferably 30°C or lower, more preferably 0°C or lower, even more preferably -10°C or lower.

[0129] The reaction of n-butylbenzene with carbon monoxide is preferably carried out under pressure. From the viewpoint of improving reactivity and suppressing side reactions, the partial pressure of carbon monoxide is preferably 1.0 MPaG or more, more preferably 1.5 MPaG or more, even more preferably 1.8 MPaG or more, and preferably 3.0 MPaG or less, more preferably 2.5 MPaG or less, even more preferably 2.2 MPaG or less. Here, "MPaG" represents "MPa (gauge pressure)".

[0130] In this reaction (formylation reaction), the reaction time is not particularly limited, but from the viewpoint of ensuring that the reaction proceeds fully, suppressing side reactions and product decomposition, and producing the product efficiently, it is preferred to be 10 minutes or more, more preferably 20 minutes or more, even more preferably 30 minutes or more, and preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 5 hours or less.

[0131] Furthermore, this reaction can be carried out in the presence of a solvent. There are no particular limitations on the solvent used, as long as the reactants are well-soluble and the solvent is inactive against acid catalysts such as hydrogen fluoride and boron trifluoride. Examples include saturated aliphatic hydrocarbons such as hexane, heptane, and decane, and halogenated aliphatic hydrocarbons such as chloroform, dichloromethane, and dichloroethane. One or more of these solvents can be used alone. There are no particular limitations on the amount of solvent used; it can be appropriately selected from the perspective of reaction uniformity, reaction rate, and solvent removal. It should be noted that in this process, when hydrogen fluoride is used, hydrogen fluoride also functions as a solvent, so it is not necessary to use a solvent.

[0132] The above-mentioned reaction can be carried out by any method, such as batch, semi-batch, or continuous, but from the perspective of making catalyst recovery / reuse possible and from the point of view of production efficiency, continuous reaction is preferred.

[0133] In addition, the apparatus used in the manufacturing method is a reaction apparatus that can fully mix the liquid phase and the gas phase under pressure while adjusting the temperature.

[0134] For example, in a continuous reaction, hydrogen fluoride and boron trifluoride are first added to a reactor equipped with a stirring device. The contents are stirred and the liquid temperature is set to a suitable temperature. After maintaining a constant temperature, carbon monoxide is used to pressurize the mixture to a suitable reaction pressure, ensuring that carbon monoxide is supplied at a constant pressure. Then, a semi-batch reaction is carried out, with n-butylbenzene dissolved in a solvent as needed. Subsequently, hydrogen fluoride, boron trifluoride, and n-butylbenzene dissolved in a solvent as needed are then supplied, and the reaction product is continuously extracted.

[0135] Hydrogen fluoride and boron trifluoride are removed from the reaction product containing 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde, and purified by distillation and extraction as needed to obtain the target 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde.

[0136] When the obtained 4-n-butylbenzaldehyde contains 2-n-butylbenzaldehyde, it can be further purified to obtain 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde with higher purity. Alternatively, the mixture of them can be used directly as raw material for the next process.

[0137] In particular, when the mass ratio of 4-n-butylbenzaldehyde (formula (3)) to 2-n-butylbenzaldehyde (formula (4)) [(3) / (4)] is 96 / 4 to 99.9 / 0.1, the mass ratio of the final product can be set to the aforementioned range (the mass ratio of the aldehyde shown in formula (1) to the aldehyde shown in formula (2) [(1) / (2)] is 96 / 4 to 99.9 / 0.1) by using it directly as a raw material, which is therefore preferred.

[0138] The mass ratio of 4-n-butylbenzaldehyde (formula (3)) to 2-n-butylbenzaldehyde (formula (4)) [(3) / (4)] is preferably 96 / 4 to 99.9 / 0.1, more preferably 98 / 2 to 99.8 / 0.2, even more preferably 98.7 / 1.3 to 99.7 / 0.3, even more preferably 99.0 / 1.0 to 99.6 / 0.4, and even more preferably 99.0 / 1.0 to 99.4 / 0.6.

[0139] Furthermore, from the viewpoint of aroma emission and diffusion of the obtained aldehyde composition, the mass ratio of 4-n-butylbenzaldehyde (formula (3)) to 2-n-butylbenzaldehyde (formula (4)) [(3) / (4)] is preferably 98.7 / 1.3 to 99.9 / 0.1, more preferably 99.0 / 1.0 to 99.8 / 0.2, even more preferably 99.2 / 0.8 to 99.8 / 0.2, and even more preferably 99.3 / 0.7 to 99.7 / 0.3.

[0140] It should be noted that the mass ratio of positional isomers in the final product is not limited to this step and can be adjusted in any step of this manufacturing method. Specifically, the ratio of positional isomers of the raw materials in each step corresponding to the target aldehyde can be adjusted.

[0141] <Step 1 (Part 1): Synthesis of Cinnamaldehyde using Aldol Condensation>

[0142] As previously described, the manufacturing method of the present invention includes two methods. Both methods use 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde as raw materials, and sequentially include step 1, which yields the aldehyde represented by the following general formula (5) and the aldehyde represented by the following general formula (6) (cinnamaldehyde), and a hydrogenation step, i.e., step 2.

[0143] The first method is to use an aldehyde-alcohol condensation method in the aforementioned step 1.

[0144] Step 1 is a step of performing an aldol condensation of 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde with acetaldehyde or propionaldehyde to obtain an aldehyde as shown in formula (5) and an aldehyde as shown in formula (6). That is, the first method is a method of producing an aldehyde composition containing an aldehyde as shown in the aforementioned general formula (1) and an aldehyde as shown in the aforementioned general formula (2), and whose mass ratio [(1) / (2)] is 96 / 4 to 99.9 / 0.1, by sequentially performing the following steps: using 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde as raw materials, performing an aldol condensation of 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde with acetaldehyde or propionaldehyde to obtain an aldehyde as shown in formula (5) and an aldehyde as shown in formula (6), and a hydrogenation step.

[0145]

[0146] (R represents a methyl group or a hydrogen atom)

[0147] Specifically, it is the method shown in the following formula.

[0148]

[0149] (R represents methyl or hydrogen)

[0150] In this process, the aldol condensation reaction preferably uses a basic compound as a catalyst.

[0151] Examples of basic compounds used as catalysts include sodium hydroxide, potassium hydroxide, sodium bicarbonate, and mixtures thereof. The amount of the basic compound relative to 1 mole of n-butylbenzaldehyde as a raw material is preferably 0.05 moles or more, more preferably 0.1 moles or more, even more preferably 0.2 moles or more, and preferably 3 moles or less, more preferably 1 mole or less, and even more preferably 0.5 moles or less.

[0152] The amount of acetaldehyde or propionaldehyde added is preferably 0.5 moles or more, more preferably 0.8 moles or more, and more preferably 1.5 moles or less, more preferably 1.1 moles or less, relative to 1 mole of 4-n-butylbenzaldehyde as a raw material. The addition of acetaldehyde or propionaldehyde is preferably carried out gradually or continuously over time, for example, preferably by dropwise addition.

[0153] The aldol condensation reaction in this step is preferably carried out in a solvent. Examples of solvents include various water-miscible organic solvents, and more preferably include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, allyl alcohol, ethylene glycol, propylene glycol, and diethylene glycol. More preferably, methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, ethylene glycol, propylene glycol, and diethylene glycol are also mentioned.

[0154] The reaction temperature in the aldehyde-alcohol condensation reaction of this process is not particularly limited, but from the viewpoint of reaction rate, it is preferably 0°C or higher, more preferably 10°C or higher, and from the viewpoint of suppressing side reactions, it is preferably 50°C or lower, more preferably 40°C or lower, and even more preferably 30°C or lower.

[0155] Furthermore, the reaction time is not particularly limited, as long as the condensation can proceed sufficiently. It is preferably 10 minutes or more, more preferably 30 minutes or more, even more preferably 1 hour or more, and preferably 24 hours or less, more preferably 12 hours or less, even more preferably 6 hours or less, and even more preferably 3 hours or less.

[0156] The reaction can be stopped by neutralization, for example by adding an acid such as acetic acid.

[0157] In addition, there are no particular limitations on the method for separating the aldehydes shown in formula (5) and formula (6) from the solution after the reaction is completed. They can be carried out by appropriately combining liquid-liquid separation, extraction, and distillation purification.

[0158] For example, by adding a low-polarity or non-polar organic solvent to the solution after the reaction, the aforementioned aldehyde or aldehyde mixture is transferred to the oil phase. The resulting oil phase is dried, for example, using magnesium sulfate. The filtrate obtained by filtration is then concentrated and purified by distillation, thereby achieving separation.

[0159] <Step 1 (Part 2): Cinnamaldehyde Synthesis under Muller-Conradi-Pieroh Conditions>

[0160] The second method of the manufacturing method of the present invention is a method of using the Muller-Conradi-Pieroh condition in the aforementioned step 1.

[0161] Step 1 comprises the following steps: sequentially performing acetalization of 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde under an acid catalyst; reacting the resulting acetal with an alkyl vinyl ether under an acid catalyst; and hydrolyzing the acetal under an acid catalyst. It should be noted that in the second method, R in the aforementioned formulas (1) and (2) of the obtained aldehyde composition represents a hydrogen atom. That is, the second method is a method of obtaining an aldehyde composition containing the aldehyde shown in the aforementioned general formula (1) and the aldehyde shown in the aforementioned general formula (2) in a mass ratio [(1) / (2)] of 96 / 4 to 99.9 / 0.1, wherein R in the aforementioned formula (1) and the aforementioned formula (2) is a hydrogen atom: a step of acetalizing 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde under an acid catalyst; a step of reacting the obtained acetal with an alkyl vinyl ether under an acid catalyst; a step of hydrolyzing under an acid catalyst to obtain the aldehyde shown in the following formula (5a) and the following formula (6a); and a hydrogenation step.

[0162] Specifically, the initial step of this process, namely the acetalization step, is represented by the following formula.

[0163]

[0164] (R 1 (Indicates methyl or ethyl)

[0165] The 4-n-butylbenzaldehyde shown in formula (3) and the 2-n-butylbenzaldehyde shown in formula (4) are acetalized to obtain the acetal shown in formula (8) and the acetal shown in formula (9), respectively.

[0166] Acetalization can be carried out using well-known methods. Examples include reacting methanol or ethanol under an acid catalyst, and reacting it with trimethyl orthoformate or triethyl orthoformate under an acid catalyst.

[0167] There are no particular limitations on the acid catalyst used in this acetalization process, but Brønsted acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, and toluenesulfonic acid, as well as Lewis acids such as boron trifluoride, zinc chloride, and aluminum chloride can be used.

[0168] The process then involves reacting the obtained acetal with an alkyl vinyl ether under an acid catalyst to form an alkyl vinyl ether.

[0169] Specifically, the alkyl vinyl ether addition process is represented by the following formula.

[0170]

[0171] (R 1 Indicates methyl or ethyl, R 2 (representing alkyl groups with 2 to 8 carbon atoms)

[0172] By reacting the acetals shown in formula (8) and formula (9) with alkyl vinyl ethers in the presence of an acid catalyst, alkyl vinyl ethers are added to obtain the acetals shown in formula (10) and formula (11), respectively.

[0173] As alkyl vinyl ethers, vinyl ethers having alkyl groups having 2 to 8 carbons, such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, and 2-ethylhexyl vinyl ether, are preferred. From a reactivity point of view, at least one selected from the group consisting of ethyl vinyl ether and propyl vinyl ether is more preferred.

[0174] There are no particular limitations on the acid catalyst used in the addition process of this alkyl vinyl ether, but Brønsted acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, and toluenesulfonic acid, as well as Lewis acids such as boron trifluoride, zinc chloride, and aluminum chloride can be used.

[0175] From the viewpoint of reaction yield, the amount of alkyl vinyl ether added relative to 1 mole of the matrix (acetal) is preferably 1 mole or more, more preferably 1.2 moles or more. Furthermore, from the viewpoint of economy, it is preferably 2 moles or less, more preferably 1.7 moles or less.

[0176] From the viewpoint of reactivity, the reaction temperature is preferably 0°C or higher, more preferably 10°C or higher. Furthermore, from the viewpoint of suppressing side reactions, the temperature is preferably 50°C or lower, more preferably 40°C or lower.

[0177] The next step involves hydrolyzing the acetal obtained in the aforementioned alkyl vinyl ether addition process under an acid catalyst.

[0178] Specifically, the hydrolysis process is represented by the following formula.

[0179]

[0180] (R 1 Indicates methyl or ethyl, R 2 (representing alkyl groups with 2 to 8 carbon atoms)

[0181] By hydrolyzing the acetals shown in formula (10) and (11) in the presence of an acid catalyst, the aldehydes shown in formula (5a) and (6a) are obtained, respectively. It should be noted that the aldehyde shown in formula (5a) is a compound in which R is a hydrogen atom in the aldehydes shown in general formula (5), and the aldehyde shown in formula (6a) is a compound in which R is a hydrogen atom in the aldehydes shown in general formula (6).

[0182] There are no particular limitations on the acid catalyst used in this hydrolysis process, but hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, toluenesulfonic acid, etc. can be used.

[0183] Furthermore, from the viewpoint of the efficiency of the hydrolysis reaction, the amount of acid catalyst added relative to the matrix (acetal) is preferably 0.5% by mass or more, preferably 1% by mass or more, and more preferably 3% by mass or more. Moreover, from the viewpoint of suppressing side reactions, it is preferably 20% by mass or less, and more preferably 15% by mass or less.

[0184] The reaction temperature is preferably 60°C or higher, more preferably 80°C or higher. Furthermore, it is preferably carried out under reflux. Additionally, it is preferably 100°C or lower.

[0185] <Process 2: Hydrogenation Process>

[0186] As described above, the preferred method for manufacturing the aldehyde composition of the present invention includes a hydrogenation step, namely step 2, after the aforementioned step 1.

[0187] This hydrogenation process involves hydrogenating the aldehydes (5) and (6) obtained in process 1 to obtain an aldehyde composition containing the aldehydes (1) and (2) as the target substances.

[0188] There are no particular limitations on the method of hydrogenation; it can be carried out using known methods that employ hydrogenation catalysts.

[0189] There are no particular limitations on the hydrogenation catalyst; known catalysts can be used, such as supported heterogeneous hydrogenation catalysts that support metals such as Ni, Pt, Pd, and Ru on carbon, silica, alumina, diatomaceous earth, etc.; so-called Ziegler-type hydrogenation catalysts that use transition metal salts such as organic acid salts or acetylacetonates of Ni, Co, Fe, and Cr with reducing agents such as organoaluminum; and so-called organometallic complexes such as organometallic compounds of Ti, Ru, Rh, and Zr, etc., etc.

[0190] From the viewpoint of reactivity and suppression of side reactions, the temperature of the hydrogenation reaction in this process is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and preferably 150°C or lower, even more preferably 100°C or lower.

[0191] The pressure of hydrogen used in the hydrogenation reaction is preferably 0.01 MPaG or more, more preferably 0.03 MPaG or more, even more preferably 0.05 MPaG or more, and preferably 10 MPaG or less, more preferably 3 MPaG or less, even more preferably 1 MPaG or less, and even more preferably 0.5 MPaG or less.

[0192] The reaction time is not particularly limited, but is preferably 3 minutes or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and preferably 24 hours or less, more preferably 12 hours or less, even more preferably 8 hours or less.

[0193] Hydrogenation reactions can be carried out in the presence of a solvent. There are no particular limitations on the solvent used, as long as it does not hinder the hydrogenation reaction. Examples of solvents include aliphatic hydrocarbons such as pentane, hexane, isopentane, heptane, octane, and isooctane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene. One solvent can be used alone, or two or more can be used in combination.

[0194] There are no particular limitations on the method for purifying the target aldehydes, namely the aldehydes shown in formula (1) and formula (2), from the solution after the reaction. Any known method can be selected appropriately. Specifically, examples include filtration, chromatography, and distillation purification. By appropriately combining these methods, the target aldehydes or aldehyde compositions with high purity can be obtained.

[0195] As described above, when the mass ratio of 4-n-butylbenzaldehyde (formula (3)) to 2-n-butylbenzaldehyde (formula (4)) [(3) / (4)] is 96 / 4 to 99.9 / 0.1, it can be used directly as a raw material. It is preferable to set the mass ratio of the positional isomers of the final product to the aforementioned range (the mass ratio of the aldehyde shown in formula (1) to the aldehyde shown in formula (2) [(1) / (2)] is 96 / 4 to 99.9 / 0.1). However, the product after the hydrogenation process or the purified product that generates it can also be used to adjust it to the aforementioned range. The final mass ratio can be within the aforementioned range.

[0196] Example

[0197] The present invention will be specifically described based on the embodiments shown below, but the present invention is not limited to these embodiments.

[0198] [Analysis / Evaluation]

[0199] <Gas Chromatography Analysis (Compositional Analysis)>

[0200] The composition of each process, the composition of the product, and the composition of the composition were determined using gas chromatography (GC-2010Plus, manufactured by Shimadzu Corporation) with n-decane (reagent grade, manufactured by Fujifilm and Koden Pharmaceutical Co., Ltd.) as an internal standard to create a standard curve.

[0201] It should be noted that, as a capillary column, the HR-1701 (inner diameter) manufactured by Agilent Technologies Japan, Ltd. was used. Length: 30 m). For the heating program, heat from 100 °C to 280 °C at a rate of 5 °C per minute and hold for 30 minutes.

[0202] <NMR Spectral Analysis>

[0203] Apparatus: Varian NMR System PS600 600 MHz

[0204] Solvent: Chloroform-d (CDCl3)

[0205] Measurement Mode: 1 H, 13 C

[0206] Internal Standard Substance: Tetramethylsilane (TMS)

[0207] <Evaluation of Fragrance / Odor Note>

[0208] For the fragrance and odor note of the aldehyde composition and the perfume composition obtained in the examples and comparative examples, evaluation was carried out by the method of impregnating a filter paper with a width of 8 mm and a length of 15 cm and having professional evaluators smell it. It should be noted that for the aroma diffusibility, the intensity of the fragrance immediately after impregnation in the filter paper was compared with the reference examples (Example 1 and Example 7). If they were the same, the aroma diffusibility was "good". In addition, the intensity of the fragrance immediately after impregnation in the filter paper was compared with the reference examples (Example 1 and Example 7), and the stronger one was taken as the aroma diffusibility "very good". In addition, the intensity of the fragrance immediately after impregnation in the filter paper was compared with the reference examples (Example 1 and Example 7), and the weaker one (lower than the equivalent one) was taken as the aroma diffusibility "bad".

[0209] <Evaluation of Odor Threshold>

[0210] The aldehyde composition obtained in the examples and lily aldehyde (Lilial, 3-(p-tert-butylphenyl)-2-methylpropanal) were respectively diluted to concentrations of 10 ppm, 1 ppm, 0.1 ppm, 0.01 ppm, and 0.001 ppm with dipropylene glycol. By the method of impregnating this dilution in a filter paper with a width of 8 mm and a length of 15 cm and having professional evaluators smell it, the lower limit concentration at which the odor can be discriminated was evaluated. The lower the lower limit concentration, the lower the odor threshold, and the more excellent the intensity and diffusibility of the aroma.

[0211] <Evaluation of Residual Scent>

[0212] The aldehyde composition obtained in the examples and lilial (3-(p-tert-butylphenyl)-2-methylpropanal) were impregnated in filter paper with a width of 8 mm and a length of 15 cm. The longest period during which the odor could be perceived was evaluated by having a specialist smell the paper every week. The longer the longest period during which the odor could be perceived, the better the residual aroma.

[0213] <Carcinogenicity Prediction Trial>

[0214] Using the aldehyde composition obtained in the examples and lilial (3-(p-tert-butylphenyl)-2-methylpropanal), a transformation assay (an in vitro carcinogenicity prediction assay using Bhas42 cells) was performed according to OECD GD231 to determine whether the carcinogenicity was negative or positive. If the result of this assay is negative, it is predicted that there is no possibility of it being a cause of carcinogenicity, indicating high safety.

[0215] [raw material]

[0216] Manufacturing Example 1 (Synthesis of n-Butylbenzaldehyde)

[0217] The raw material used in the following synthesis examples and comparative examples is n-butylbenzaldehyde.

[0218] The experiment was conducted using a 10L stainless steel autoclave equipped with a magnetic induction stirrer, three inlet nozzles at the top, one outlet nozzle at the bottom, and a jacket for internal temperature control. First, the autoclave was purged with carbon monoxide. Then, hydrogen fluoride (1193g, 59.6 mol) and boron trifluoride (809g, 11.9 mol) were added. The liquid temperature was set to -25°C, and the pressure was increased to 2 MPa using carbon monoxide. The reaction temperature was maintained at -25°C and the reaction pressure at 2 MPa. Simultaneously, n-butylbenzene (800g, 4.93 mol) was supplied from the top of the autoclave over 60 minutes. Stirring continued for approximately 30 minutes until no further carbon monoxide absorption was observed. The reaction mixture in the autoclave was drained into ice water. After thorough mixing by shaking, the oil layer was separated. After washing the obtained oil layer with water, the oil layer was purified by distillation (107℃, 5 Torr) to obtain n-butylbenzaldehyde (purity 98.7% by mass, mass ratio of 4-n-butylbenzaldehyde to 2-n-butylbenzaldehyde [(4-n-butylbenzaldehyde) / (2-n-butylbenzaldehyde)] = 99.3 / 0.7, 677 g).

[0219] [Aldehyde composition]

[0220] Example 1 (Preparation of an aldehyde composition containing 3-(4-n-butylphenyl)propionaldehyde and 3-(2-n-butylphenyl)propionaldehyde: using an aldol condensation method)

[0221] (Aldehyde condensation process)

[0222] In a 1000 mL round-bottom flask equipped with a stirrer, thermometer, and dropping funnel, methanol (400.0 g), potassium hydroxide (18.1 g, manufactured by Fujifilm and Kohden Chemical Co., Ltd.), and n-butylbenzaldehyde (200.0 g) obtained in Preparation Example 1 were added. The mixture was stirred and cooled to 10°C, and then acetaldehyde (56.4 g, manufactured by Fujifilm and Kohden Chemical Co., Ltd.) was added dropwise over 3 hours. After the addition was complete, the reaction was maintained at 10°C for 1 hour to complete the reaction. Acetic acid (16.4 g) was added for neutralization, followed by the addition of water and heptane, followed by shaking. The mixture was separated and the aqueous phase was removed. Next, the heptane was distilled off to obtain a crude intermediate. This crude intermediate was subjected to simple distillation (138–143°C / 3 torr) to obtain 3-(n-butylphenyl)propenal (51.0 g, purity 94.6% by mass).

[0223] (Hydrogenation process)

[0224] 50.0 g of 3-(n-butylphenyl)propenal, 30.0 g of 2-propanol, and 0.5 g of 5% palladium-carbon catalyst (prepared by NECHEMCAT CORPORATION, aqueous, PE type) obtained through the aforementioned aldol condensation process were added to a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and internal temperature control via a jacket. The reaction was carried out at 25°C and a hydrogen pressure of 0.05 MPa for 5 hours to induce hydrogenation. The reaction solution was filtered to remove the catalyst, and heptane was added and shaken. The aqueous phase was separated by liquid-liquid separation. Subsequently, the heptane was distilled off to obtain a crude composition. The crude composition was distilled using a 20-plate distillation column at 10 torr, yielding an aldehyde composition (9.3 g, mass ratio [3-(4-n-butylphenyl)propionaldehyde / 3-(2-n-butylphenyl)propionaldehyde] = 99.3 / 0.7) containing 3-(4-n-butylphenyl)propionaldehyde and 3-(2-n-butylphenyl)propionaldehyde) at 138–141 °C. The aroma / flavor profile of the obtained aldehyde composition is shown in Table 1.

[0225] It should be noted that 3-(4-n-butylphenyl)propanal is the compound in formula (1) where R is a hydrogen atom, and 3-(2-n-butylphenyl)propanal is the compound in formula (2) where R is a hydrogen atom.

[0226] Furthermore, the obtained composition was purified by column chromatography to separate 3-(4-n-butylphenyl)propanal (purity 98.8%, mass ratio [3-(4-n-butylphenyl)propanal / 3-(2-n-butylphenyl)propanal] = 100.0 / 0.0), and NMR spectra were measured. The results are shown below. It should be noted that the 3-(4-n-butylphenyl)propanal separated here was used as Comparative Example 1 for aroma / flavor evaluation. The results are shown in Table 1.

[0227] [Results of NMR spectral determination of 3-(4-n-butylphenyl)propionaldehyde]

[0228] 1 H NMR(600MHz, CDCl3)δ0.92(3H,t,J=7.5Hz),1.31-1.38(2H,m),1.55-1.60(2H,m),2.57(2H,t,J=7.8Hz) ,2.76(2H,t,J=7.8Hz),2.92(2H,t,J=7.8Hz),7.09(2H,d,J=9.0Hz),7.11(2H,d,J=9.0Hz),9.71(1H,s)

[0229] 13 C NMR (150MHz, CDCl3) δ14.0,22.4,27.7,33.7,35.2,45.4,128.1,128.6,137.4,140.9,201.8

[0230] Example 2 (Preparation of an aldehyde composition containing 3-(4-n-butylphenyl)propionaldehyde and 3-(2-n-butylphenyl)propionaldehyde: a method using Muller-Conradi-Pieroh conditions)

[0231] (Ethyl vinyl ether addition process of p-acetal based on Muller-Conradi-Pieroh conditions)

[0232] Methanol (139.0 g), trimethyl orthoformate (393.0 g, manufactured by Fujifilm and Kohden Chemical Co., Ltd.), and n-butylbenzaldehyde (500.0 g) obtained in Preparation Example 1 were added to a 1000 mL round-bottom flask equipped with a stirrer, thermometer, and dropping funnel. The mixture was stirred and cooled to 10°C, then 35% hydrochloric acid (0.5 g, manufactured by Fujifilm and Kohden Chemical Co., Ltd.) was added, and the temperature was raised to 25°C. The mixture was maintained at 25°C for 30 minutes. Then, boron trifluoride diethyl ether complex (0.6 g, manufactured by Fujifilm and Kohden Chemical Co., Ltd.) was added dropwise over 4 hours, followed by the dropwise addition of ethyl vinyl ether (276.0 g, manufactured by Tokyo Chemical Industry Co., Ltd.). After the dropwise addition was complete, the mixture was stirred for another hour to complete the reaction. Sodium acetate (16.4 g) was added for neutralization, and the low-boiling components were distilled off. 37% hydrochloric acid (manufactured by Fujifilm and Kojun Chemical Co., Ltd., 58.0 g) and water (520.0 g) were added to the crude reaction solution, and the mixture was heated to 90°C and stirred for 24 hours. Then, heptane was added, and the aqueous phase was separated by liquid-liquid extraction. Next, the heptane was distilled off to obtain a crude intermediate. This crude intermediate was then subjected to simple distillation (138–143°C / 3 torr) to give 3-(n-butylphenyl)propenal (220 g, purity 95.4% by mass).

[0233] (Hydrogenation process)

[0234] The 3-(n-butylphenyl)propenal (50.0 g), 2-propanol (30.0 g), and 5% palladium-carbon catalyst (prepared by NECHEMCAT CORPORATION, aqueous, PE type, 0.5 g) obtained in the previous process were added to a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and internal temperature control via a jacket. The reaction was carried out at 25°C and 0.05 MPa for 5 hours with stirring. The reaction solution was filtered to remove the catalyst, heptane was added and shaken, and the aqueous phase was separated by liquid-liquid separation. The heptane was then distilled off to obtain the crude composition. The crude composition was distilled using a 20-plate distillation column at 10 torr, yielding an aldehyde composition (9.3 g, mass ratio [3-(4-n-butylphenyl)propionaldehyde / 3-(2-n-butylphenyl)propionaldehyde] = 99.2 / 0.8) containing 3-(4-n-butylphenyl)propionaldehyde and 3-(2-n-butylphenyl)propionaldehyde) at 138–141 °C. The aroma / flavor profile of the obtained aldehyde composition is shown in Table 1.

[0235] Comparative Example 2 (Preparation of an aldehyde composition containing 3-(4-n-butylphenyl)propionaldehyde and 3-(2-n-butylphenyl)propionaldehyde: via an acetoxyenol intermediate)

[0236] (Synthetic process of acetoxyenol intermediate)

[0237] In a 200 mL round-bottom flask equipped with a stirrer, thermometer, and dropping funnel, 50.0 g of n-butylbenzene, 20.9 g of acrolein (manufactured by Tokyo Chemical Industry Co., Ltd.), and 25.7 g of acetic anhydride (manufactured by Fujifilm and Wakamitsu Chemical Co., Ltd.) were added, and the mixture was cooled to -20°C while stirring. A mixture of 50.0 g of titanium tetrachloride (manufactured by Fujifilm and Wakamitsu Chemical Co., Ltd.) and 16.8 g of n-butylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. After the addition was complete, the mixture was kept at -20°C for 3 hours to allow the reaction to proceed. Water and heptane were added and the mixture was shaken, and the aqueous phase was separated by liquid-liquid chromatography. The heptane was then distilled off to obtain a crude intermediate. The crude intermediate was subjected to simple distillation (95–102 °C / 2 torr) to obtain 3-(n-butylphenyl)-1-acetoxy-1-propene (26.0 g, purity 70.1% by mass).

[0238] (Deacetylation process)

[0239] In a 200 mL round-bottom flask equipped with a stirrer, thermometer, and dropping funnel, 26.0 g of 3-(n-butylphenyl)-1-acetoxy-1-propene (obtained through the aforementioned synthesis of the acetoxyenol intermediate), 1.1 g of potassium carbonate (manufactured by Fujifilm and Koujun Pharmaceutical Co., Ltd.), and 60.0 g of methanol were added, and the mixture was stirred at 25 °C for 2 hours. Water and heptane were added and shaken, and the aqueous phase was separated by separation. Then, the heptane was distilled off to obtain a crude composition. The crude composition was distilled using a 20-plate distillation column at 6 torr, and the fraction at 130–134 °C was used to obtain an aldehyde composition containing 3-(4-n-butylphenyl)propanal and 3-(2-n-butylphenyl)propanal (mass ratio [3-(4-n-butylphenyl)propanal / 3-(2-n-butylphenyl)propanal] = 95.5 / 4.5). The results of the aroma / flavor evaluation of the obtained aldehyde compositions are shown in Table 1.

[0240] Examples 3 and 4 (Preparation of aldehyde compositions containing 3-(4-n-butylphenyl)propionaldehyde and 3-(2-n-butylphenyl)propionaldehyde: based on a method of mixing the compositions)

[0241] The 3-(4-n-butylphenyl)propanal of Comparative Example 1 and the aldehyde composition of Comparative Example 2 (mass ratio [3-(4-n-butylphenyl)propanal / 3-(2-n-butylphenyl)propanal] = 95.5 / 4.5) were mixed in such a manner as shown in Table 1 to obtain an aldehyde composition. The results of the aroma / fragrance evaluation of the obtained aldehyde composition are shown in Table 1.

[0242] Examples 5 and 6 (Preparation of aldehyde compositions containing 3-(4-n-butylphenyl)propionaldehyde and 3-(2-n-butylphenyl)propionaldehyde: based on a method of mixing the compositions)

[0243] The 3-(4-n-butylphenyl)propanal of Comparative Example 1 was mixed with the aldehyde composition of Example 2 (mass ratio [3-(4-n-butylphenyl)propanal / 3-(2-n-butylphenyl)propanal] = 99.2 / 0.8) in such a manner as shown in Table 1 to obtain the aldehyde composition. The results of the aroma / fragrance evaluation of the obtained aldehyde composition are shown in Table 1.

[0244] [Table 1]

[0245] Table 1

[0246]

[0247] The aldehyde compositions of Examples 1-6 are similar to floral and green fragrances and have an excellent lily of the valley scent, and their aroma dissipation is also excellent. On the other hand, the aldehyde composition of Comparative Example 1 has poor aroma dissipation. In addition, the aldehyde composition of Comparative Example 2 has a strong green fragrance and does not have the scent of lily of the valley.

[0248] Example 7 (Preparation of an aldehyde composition containing 3-(4-n-butylphenyl)-2-methylpropanal and 3-(2-n-butylphenyl)-2-methylpropanal: using an aldol condensation method)

[0249] (Aldehyde condensation process)

[0250] In a 500 mL round-bottom flask equipped with a stirrer, thermometer, and dropping funnel, methanol (100.0 g), 50% sodium hydroxide aqueous solution (11.8 g, manufactured by Fujifilm and Kohden Chemical Co., Ltd.), and n-butylbenzaldehyde obtained in Preparation Example 1 (100.0 g) were added. The mixture was stirred and cooled to 15°C, and then propionaldehyde (35.9 g, manufactured by Fujifilm and Kohden Chemical Co., Ltd.) was added dropwise over 2 hours. After the addition was complete, the reaction was maintained at 15°C for 1 hour to complete the reaction. Acetic acid (8.9 g) was added for neutralization, followed by the addition of water and heptane, followed by shaking and separation to remove the aqueous phase. Heptane was then distilled off to obtain a crude intermediate. This crude intermediate was subjected to simple distillation (145–149°C / 3 torr) to obtain 3-n-butylphenyl-2-methylpropenal (76.0 g, purity 97.6% by mass).

[0251] (Hydrogenation process)

[0252] 59.0 g of 3-n-butylphenyl-2-methylpropenal, obtained through an aldol condensation process, 60.0 g of 5% sodium carbonate aqueous solution, and 1.0 g of 10% palladium-carbon catalyst (prepared by NECHEMCAT CORPORATION, aqueous, PE type) were added to a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and internal temperature control via a jacket. The reaction was carried out at 75°C and 0.4 MPa for 28 hours with stirring. The catalyst was removed by filtration of the reaction solution. Heptane was added and shaken, and the aqueous phase was separated by liquid-liquid separation. Heptane was then distilled off to obtain a crude composition. The crude composition was distilled using a 20-plate distillation column at 10 torr, yielding an aldehyde composition (17.0 g, mass ratio [3-(4-n-butylphenyl)-2-methylpropanal / 3-(2-n-butylphenyl)-2-methylpropanal] = 99.6 / 0.4) containing 3-(4-n-butylphenyl)-2-methylpropanal and 3-(2-n-butylphenyl)-2-methylpropanal] at 145–147 °C. The aroma / flavor profile of the obtained aldehydes is shown in Table 2.

[0253] Furthermore, the obtained composition was purified by column chromatography to separate 3-(4-n-butylphenyl)-2-methylpropanal (purity 98.9%, mass ratio [3-(4-n-butylphenyl)-2-methylpropanal / 3-(2-n-butylphenyl)-2-methylpropanal] = 100.0 / 0.0), and NMR spectroscopy was performed. The results are shown below. It should be noted that the 3-(4-n-butylphenyl)-2-methylpropanal separated here was used as Comparative Example 3 for aroma / fragrance evaluation. The results are shown in Table 2.

[0254] [Results of NMR spectral determination of 3-(4-n-butylphenyl)-2-methylpropionaldehyde]

[0255] 1 H NMR(600MHz, CDCl3)δ0.92(3H,t,J=7.2Hz),1.08(3H,d,J=9.6Hz),1.31-1.38(2H,m),1.55-1.60(2H,m),2.55-2.62 (3H,m),2.62-2.68(1H,m),3.05(1H,dd,J=6.0Hz,13.8Hz),7.07(2H,d,J=8.1Hz),7.11(2H,d,J=8.1Hz),9.71(1H,s)

[0256] 13C NMR (150MHz, CDCl3) δ13.2,14.0,22.4,33.7,35.2,36.3,48.1,128.5,128.9,135.9,141.0,204.7

[0257] Example 8 (Preparation of an aldehyde composition containing 3-(4-n-butylphenyl)-2-methylpropanal and 3-(2-n-butylphenyl)-2-methylpropanal: via an acetoxyenol intermediate)

[0258] (Synthetic process of acetoxyenol intermediate)

[0259] In a 200 mL round-bottom flask equipped with a stirrer, thermometer, and dropping funnel, 50.0 g of n-butylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 17.5 g of methacrolein (manufactured by Tokyo Chemical Industry Co., Ltd.), and 25.7 g of acetic anhydride were added while stirring and cooling to -10 °C. A mixture of 50.0 g of titanium tetrachloride (manufactured by Fujifilm and Wako Pure Chemical Industries Co., Ltd.) and 16.8 g of n-butylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. After the addition was complete, the mixture was maintained at -10 °C for 3 hours to allow the reaction to proceed. Water and heptane were added and the mixture was shaken, and the aqueous phase was separated by liquid-liquid extraction. The heptane was then distilled off to obtain a crude intermediate. The crude intermediate was subjected to simple distillation (100-110 °C / 2 tor) to obtain 3-n-butylphenyl-2-methyl-1-acetoxy-1-propene (40.0 g, purity 72.0% by mass).

[0260] (Deacetylation process)

[0261] In a 200 mL round-bottom flask equipped with a stirrer, thermometer, and dropping funnel, 40.0 g of 3-n-butylphenyl-2-methyl-1-acetoxy-1-propene (obtained through the synthesis of acetoxyenol intermediates), 1.8 g of potassium carbonate (manufactured by Fujifilm and Koichi Chemical Co., Ltd.), and 60.0 g of methanol were added and stirred at 25 °C for 2 hours. Water and heptane were added, and the aqueous phase was separated by liquid-liquid extraction. The heptane was then distilled off to obtain the crude composition. The crude composition was distilled using a 20-plate distillation column at 6 torr, yielding an aldehyde composition containing 3-(4-n-butylphenyl)-2-methylpropanal and 3-(2-n-butylphenyl)-2-methylpropanal as the fraction at 139–140 °C (mass ratio [3-(4-n-butylphenyl)-2-methylpropanal / 3-(2-n-butylphenyl)-2-methylpropanal] = 99.0 / 1.0). The aroma / flavor profile evaluation results of the obtained aldehydes are shown in Table 2.

[0262] Comparative Example 4 (Preparation of an aldehyde composition containing 3-(4-n-butylphenyl)-2-methylpropanal and 3-(2-n-butylphenyl)-2-methylpropanal: via an acetoxyenol intermediate)

[0263] After obtaining the crude composition using the same method as in Example 4, it was distilled at 6 torr using a distillation column with 20 theoretical plates, yielding an aldehyde composition containing 3-(4-n-butylphenyl)-2-methylpropanal and 3-(2-n-butylphenyl)-2-methylpropanal (mass ratio [3-(4-n-butylphenyl)-2-methylpropanal / 3-(2-n-butylphenyl)-2-methylpropanal] = 95.1 / 4.9) at 137–139 °C. The results of the aroma / flavor evaluation of the obtained aldehydes are shown in Table 2.

[0264] [Table 2]

[0265] Table 2

[0266]

[0267] The aldehyde compositions of Examples 7 and 8 are similar to floral and green fragrances and have an excellent lily of the valley scent. On the other hand, the aldehyde composition of Comparative Example 3 has poor aroma dissipation. In addition, the aldehyde composition of Comparative Example 4 has a metallic fragrance and does not have the scent of lily of the valley.

[0268] As can be seen from the results in Tables 1 and 2, the aldehyde composition of the present invention is similar to floral and green fragrances and has the aroma of lily of the valley. It has excellent aroma dissipation properties and is therefore useful as a fragrance.

[0269] [Evaluation of odor threshold, evaluation of residual aroma, and carcinogenicity prediction tests]

[0270] The odor threshold, residual aroma, and carcinogenicity prediction tests of the aldehyde composition of Example 1 were performed. Furthermore, the odor threshold and residual aroma of the aldehyde composition of Example 7 were evaluated. Additionally, as Comparative Example 5, the odor threshold, residual aroma, and carcinogenicity prediction tests of lily aldehyde (3-(p-tert-butylphenyl)-2-methylpropanal) were evaluated.

[0271] [Table 3]

[0272] Table 3

[0273]

[0274] It is known that the aldehyde composition of the examples has a lower odor threshold and superior aroma intensity and diffusion compared to lily aldehyde, which has a similar structure and fragrance. Furthermore, it is known that the aldehyde composition of the examples has superior residual aroma compared to lily aldehyde. Consequently, it is also known that the aldehyde composition of Example 1 was negative in the carcinogenicity prediction test, demonstrating excellent safety.

[0275] Example 9 and Comparative Example 6 (fragrance compositions similar to floral / green fragrances)

[0276] As Example 9, the aldehyde composition of Example 1 was added to the blending fragrance base ingredients shown in Table 4 at a mass of 18%, and the aroma / fragrance was evaluated. Additionally, as Comparative Example 6, lily aldehyde (3-(p-tert-butylphenyl)-2-methylpropanal) was added to the blending fragrance base ingredients shown in Table 4 at a mass of 18%, and the aroma / fragrance was evaluated.

[0277] [Table 4]

[0278] Table 4 (mass%)

[0279] Example 9 Comparative Example 6 lily aldehyde (3-(p-tert-butylphenyl)-2-methylpropanal) - 18 The aldehyde composition of Example 1 ((1) / (2) = 99.3 / 0.7) 18 - Aldehyde (C-10) 0.4 0.4 Allyl caproate 0.4 0.4 Benzyl acetate 1.5 1.5 cis-jasmone 0.04 0.04 Citronellol 3 3 Cyclamen Aldehyde 2 2 Cyclaprop tricyclodecenyl propionate 2.5 2.5 Dimethyl benzyl acetate (DMBCACETATE) 0.15 0.15 Diphenyl ether 0.04 0.04 Dipropylene glycol (DPG) 27.07 27.07 Ethyl salicylate 0.04 0.04 Floralozone 0.8 0.8 2-Octynyl methyl ester (FOLIONE) 0.02 0.02 Geraniol 2 2 Geranyl acetate 4 4 Helional (New Ocean Jasmine Aldehyde) 0.4 0.4 Hexyl acetate 0.4 0.4 Hexyl Cinnamic Aldehyde 8 8 Hexyl salicylate 4 4 β-Ionone (IONONE BETA) 2 2 Jasmacyclene tricycloacetate 4.5 4.5 Linalool 8 8 2-Methylvalerate (MANZANATE) 0.08 0.08 Melonal 0.08 0.08 γ-Methylionone (METHYL IONONE GAMMA) 3.5 3.5 Phenyl ethyl alcohol 5 5 Styraxyl acetate 2 2 UNDECAVERTOL (methyldecenol) 0.08 0.08 total 100 100

[0280] The results of the fragrance / note evaluation were as follows: The fragrance composition of Example 9 has a similar fragrance / note to that of lily aldehyde with added aldehyde (Aldehyde) C-12, and its diffusion, potency and residual fragrance are significantly greater than those of the fragrance composition of Comparative Example 6.

[0281] Example 10 and Comparative Example 7 (fragrance compositions similar to floral / green fragrances)

[0282] As Example 10, the aldehyde composition obtained in Example 7 was added to the blending fragrance base ingredients shown in Table 5 at a rate of 10% by mass, and the aroma / fragrance was evaluated. Additionally, as Comparative Example 7, lily aldehyde (3-(p-tert-butylphenyl)-2-methylpropanal) was added to the blending fragrance base ingredients shown in Table 5 at a rate of 10% by mass, and the aroma / fragrance was evaluated.

[0283] [Table 5]

[0284] Table 5 (mass%)

[0285] Example 10 Comparative Example 7 lily aldehyde (3-(p-tert-butylphenyl)-2-methylpropanal) - 10 The aldehyde composition of Example 7 ((1) / (2) = 99.6 / 0.4) 10 - Aldehyde (C-14) 1.8 1.8 Allyl heptaate 1.4 1.4 Ambroxol (ISO E SUPER) 8.5 8.5 Anisyl acetone 0.4 0.4 BACDANOL 0.8 0.8 Benzyl acetate 3.5 3.5 cis-3-hexenol (CIS-3-HEXENOL) 0.2 0.2 CIS-3-HEXENYL ACETATE 0.2 0.2 Cyclamen Aldehyde 1.5 1.5 delta-damascone (DAMASCONE DELTA) 0.4 0.4 γ-Decalactone (GAMMA) 1.8 1.8 Dihydromyrcenol 4 4 Dipropylene glycol (DPG) 13.75 13.75 Ethyl maltol 0.04 0.04 Ethyl vanillin 0.1 0.1 2-Methylbutyrate (ETHYL-2-METHYL BUTYRATE) 0.1 0.1 Flourydral 0.15 0.15 Heliotropine 1 1 Hexyl acetate 0.8 0.8 Hexyl Cinnamic Aldehyde 16 16 Hexyl salicylate 7 7 β-Ionone (IONONE BETA) 1.5 1.5 Ligustral 1 1 Methyl anthranilate 0.6 0.6 γ-nonalactone (GAMMA) 0.3 0.3 Norlimabanol 0.04 0.04 2,4-Dimethyl-4-phenyltetrahydrofuran (RHUBAFURAN) 0.12 0.12 Styraxyl acetate 0.3 0.3 Tetrahydrolinalool 7 7 UNDECAVERTOL (methyldecenol) 0.3 0.3 o-tert-butylcyclohexyl acetate (VERDOX) 8 8 p-tert-butylcyclohexyl acetate (VERTENEX) 6 6 β-Naphthylmethyl ether (YARA YARA) 0.4 0.4 FRUITATE (tricyclodecane carboxylic acid ethyl ester) 1 1 100 100

[0286] The results of the fragrance / note evaluation were as follows: The fragrance composition of Example 10 has a fragrance / note similar to that of woody amber added to lily aldehyde, and its sillage, potency and residual properties are superior to those of the fragrance composition of Comparative Example 7.

[0287] As can be seen from the results in Tables 4 and 5, the fragrance compositions of the present invention containing the aforementioned aldehyde compositions, in addition to the aforementioned fragrance, also exhibit excellent diffusivity, potency, and residual aroma. That is, it can be seen that the aldehyde compositions of the present invention can impart the aforementioned fragrance to fragrance compositions, and also impart diffusivity, potency, and residual aroma.

Claims

1. A method for manufacturing an aldehyde composition, said aldehyde composition comprising an aldehyde represented by general formula (1) and an aldehyde represented by general formula (2), wherein the mass ratio of the aldehyde represented by formula (1) to the aldehyde represented by formula (2) [(1) / (2)] is 96 / 4 to 99.9 / 0.

1. R represents a methyl or hydrogen atom. The manufacturing method comprises the following steps in sequence: The process of condensing 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde with acetaldehyde or propionaldehyde to obtain aldehydes of the following general formula (5) and the following general formula (6); and the hydrogenation process, 。 2. The method for manufacturing the aldehyde composition according to claim 1, wherein, 4-n-Butylbenzaldehyde and 2-n-Butylbenzaldehyde are subjected to an aldol condensation with acetaldehyde, wherein R represents a hydrogen atom.

3. A method for manufacturing an aldehyde composition, said aldehyde composition comprising an aldehyde represented by general formula (1) and an aldehyde represented by general formula (2), wherein the mass ratio of the aldehyde represented by formula (1) to the aldehyde represented by formula (2) [(1) / (2)] is 96 / 4 to 99.9 / 0.

1. R represents a hydrogen atom. The manufacturing method comprises the following steps in sequence: The process includes: acetalizing 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde under an acid catalyst; reacting the resulting acetal with an alkyl vinyl ether under an acid catalyst; hydrolyzing the acetal under an acid catalyst to obtain the aldehydes shown in formula (5a) and (6a) below; and a hydrogenation process. 。 4. The method for manufacturing the aldehyde composition according to any one of claims 1 to 3, wherein, The mass ratio of 4-n-butylbenzaldehyde to 2-n-butylbenzaldehyde [(4-n-butylbenzaldehyde) / (2-n-butylbenzaldehyde)] is 96 / 4 to 99.9 / 0.

1.

5. The method for producing the aldehyde composition according to any one of claims 1 to 3, wherein, The 4-n-butylbenzaldehyde and 2-n-butylbenzaldehyde are produced by formylation of n-butylbenzene with carbon monoxide under superacid conditions.

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