Aldehyde composition

Abstract

The aldehyde composition contains an aldehyde represented by formula (1) and an aldehyde represented by formula (2), and the mass ratio [(1) / (2)] of the aldehyde represented by formula (1) and the aldehyde represented by formula (2) is 97.00 / 3.00-99.999 / 0.001. The aldehyde composition is useful as a perfume due to having an excellent balance of green, aldehyde, and floral flavors. Further, a perfume composition having excellent diffusivity can be obtained by containing the aldehyde composition. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to an aldehyde composition, a method for producing the same, and a fragrance composition containing the aldehyde composition. Background Art

[0002] It is known that some 3-phenylpropanal aldehydes are useful as raw materials for flavoring.

[0003] For example, Non-Patent Document 1 describes that phenylpropanal (3-phenylpropanal) having a balsamic, green note similar to hyacinth, 3-(p-tert-butylphenyl)-2-methylpropanal (p-tert-butyl-α-methylhydrocinnamaldehyde, lily of the valley aldehyde) having an aroma similar to lily of the valley, 3-(p-isopropylphenyl)-2-methylpropanal (lily of the valley aldehyde) having a honeydew melon and cucumber-like aroma similar to lily of the valley, and 3-(3,4-methylenedioxyphenyl)-2-methylpropanal (neoheitornal) having a sweet floral note similar to heliotrope and anise are useful as flavoring raw materials.

[0004] In addition, a method for producing p-isobutyldihydrocinnamaldehyde having a rabbit ear flower-like odor is disclosed in Patent Document 1. It is disclosed that a product containing 68 to 70% of a para-isomer can be obtained according to the following production method.

[0005]

[0006] Prior art literature

[0007] Non-patent literature

[0008] Non-patent literature 1: Indo Motokazu, "Synthetic Fragrance Chemistry and Product Knowledge, Supplementary Revised Edition", 1996, pp. 211, 213-215, 228, Chemical Industry Daily Press

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Publication No. 42-009135 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] As described above, 3-phenylpropanaldehydes have a characteristic aroma, but new aromas are needed to enhance the value of products such as fragrance products, cosmetics, lotions, sanitary products, sundries, pharmaceuticals, and foods.

[0013] In addition, although Patent Document 1 describes the above-mentioned method for producing p-isobutyldihydrocinnamaldehyde (3-(4-isobutylphenyl)propionaldehyde) and a fragrance composition containing 70% by weight of the product of the para-isomer, the relationship between the detailed composition and the fragrance is not studied.

[0014] Therefore, an object of the present invention is to provide an aldehyde composition and a fragrance composition which have a novel fragrance and are useful as a fragrance.

[0015] Solutions for solving problems

[0016] The present inventors produced various aldehyde compositions and evaluated their aromas. As a result, they found that a specific aldehyde composition has an excellent aroma and is excellent as a raw material for a fragrance composition, thereby 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 formula (1) and an aldehyde represented by the following formula (2), wherein a mass ratio [(1) / (2)] of the aldehyde represented by the formula (1) to the aldehyde represented by the formula (2) is 97.00 / 3.00 to 99.999 / 0.001.

[0019]

[0020] [2] The aldehyde composition according to [1], comprising an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the formula (1) to the aldehyde represented by the formula (2) is 97.00 / 3.00 to 99.90 / 0.10.

[0021]

[0022] [3] The aldehyde composition according to the above [1] or [2], which contains an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) to the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.10% by mass or less relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

[0023]

[0024] [4] The aldehyde composition according to the above [1] or [2], which contains an aldehyde represented by the following formula (1), an aldehyde represented by the following formula (2) and an ester represented by the following formula (4), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) to the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.50 to 2.00 mass % relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

[0025]

[0026] [5] The aldehyde composition according to any one of [1] to [4] above, wherein the total purity of the aldehydes represented by the formula (1) and the formula (2) is 97% by mass or more.

[0027] [6] The aldehyde composition according to any one of [1] to [5], comprising 0.01 to 0.90 mass % of an alcohol represented by the following formula (3).

[0028]

[0029] [7] The aldehyde composition according to any one of [1] to [6], comprising 0.01 to 0.90 mass% of the sulfonic acid ester represented by the following formula (5).

[0030]

[0031] [8] A fragrance composition comprising the aldehyde composition according to any one of [1] to [7] above.

[0032] [9] A method for producing an aldehyde composition according to any one of [1] to [7], comprising the following steps in order:

[0033] A process for formylation of isobutylbenzene with carbon monoxide under superacid conditions to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde;

[0034] A step of subjecting 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde to aldol condensation with acetaldehyde to obtain an aldehyde represented by the following formula (6) and an aldehyde represented by the following formula (7); and

[0035] A step of performing hydrogenation to obtain an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2).

[0036]

[0037]

[10] A method for producing an aldehyde composition according to any one of [1] to [7], comprising the following steps in order:

[0038] A process for formylation of isobutylbenzene with carbon monoxide under superacid conditions to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde;

[0039] A step of acetalizing 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde in the presence of a p-toluenesulfonic acid catalyst;

[0040] A step of reacting the obtained acetal with an alkyl vinyl ether in the presence of an acid catalyst;

[0041] A step of hydrolyzing the product in the presence of an acid catalyst to obtain an aldehyde represented by the following formula (6) and an aldehyde represented by the following formula (7); and

[0042] A step of performing hydrogenation to obtain an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2).

[0043]

[0044] Effects of the Invention

[0045] According to the present invention, an aldehyde composition useful as a fragrance can be provided because it has a well-balanced fragrance of green notes, aldehyde notes, and floral notes. Furthermore, by containing the aldehyde composition, a fragrance composition with excellent diffusibility can be provided. DETAILED DESCRIPTION

[0046] Hereinafter, the description of "XX to YY" in this specification means "XX or more and YY or less".

[0047] [Aldehyde composition]

[0048] The aldehyde composition of the present invention contains an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the formula (1) to the aldehyde represented by the formula (2) is 97.00 / 3.00 to 99.999 / 0.001.

[0049]

[0050] The aldehyde composition has an excellently balanced fragrance of green notes, aldehyde notes, and floral notes, and can impart diffusibility to the fragrance composition.

[0051] The aldehyde composition of the present invention contains the aldehyde represented by the above formula (1) and the aldehyde represented by the above formula (2). The aldehyde composition of the present invention may contain only these two components, but in practice, it may contain by-products and raw materials generated when producing the aldehyde composition.

[0052] Therefore, the total purity of the aldehyde represented by the above formula (1) and the aldehyde represented by the above formula (2) in the aldehyde composition of the present invention is preferably 97% by mass or more, more preferably 97.5% by mass or more, and even more preferably 98% by mass or more. The upper limit is not limited and may be 100% by mass or less, and the aldehyde represented by the above formula (1) and the aldehyde represented by the above formula (2) may be composed only of the aldehyde represented by the above formula (1) and the aldehyde represented by the above formula (2).

[0053] Preferred embodiments of the aldehyde composition of the present invention will be described below.

[0054] [Aldehyde composition (first embodiment)]

[0055] Among the aldehyde compositions of the present invention, the aldehyde composition of the first embodiment as a preferred embodiment (hereinafter also referred to as the first aldehyde composition) contains an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), and the mass ratio [(1) / (2)] of the aldehyde represented by formula (1) and the aldehyde represented by formula (2) is 97.00 / 3.00 to 99.90 / 0.10.

[0056]

[0057] The mass ratio [(1) / (2)] of the aldehyde represented by the above formula (1) and the aldehyde represented by the above formula (2) in the first aldehyde composition is 97.00 / 3.00 to 99.90 / 0.10, preferably 98.00 / 2.00 to 99.90 / 0.10, more preferably 98.50 / 1.50 to 99.90 / 0.10, further preferably 99.00 / 1.00 to 99.80 / 0.20, and further preferably 99.20 / 0.80 to 99.70 / 0.30.

[0058] As described above, the first aldehyde composition has the characteristics of having an excellently balanced fragrance of green notes, aldehyde notes, and floral notes, and also having a strong floral scent, and therefore is useful as a fragrance.

[0059] [Aldehyde composition (second embodiment)]

[0060] Among the aldehyde compositions of the present invention, the aldehyde composition of the second embodiment as a preferred embodiment (hereinafter also referred to as the second aldehyde composition) contains an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.10% by mass or less relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

[0061] It should be noted that if the content of the ester represented by the following formula (4) is 0.10% by mass or less relative to the total amount of the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2), the second aldehyde composition may contain an ester represented by the following formula (4) if the content of the ester represented by the following formula (4) is 0% by mass relative to the total amount of the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2), that is, the second aldehyde composition may contain no ester represented by the following formula (4). However, the second aldehyde composition preferably contains an ester represented by the following formula (4).

[0062] Therefore, the second aldehyde composition preferably contains an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), and does not contain an ester represented by the following formula (4) or contains an ester represented by the following formula (4), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) to the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.10% by mass or less relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2). More preferably, the second aldehyde composition contains an aldehyde represented by the following formula (1), an aldehyde represented by the following formula (2), and an ester represented by the following formula (4), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) to the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.10% by mass or less relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

[0063] It should be noted that the second aldehyde composition may be included in the first aldehyde composition. That is, an aldehyde composition that belongs to the second aldehyde composition and to the first aldehyde composition is also included in the aldehyde composition of the present invention.

[0064] The aldehyde composition belonging to the second aldehyde composition and belonging to the first aldehyde composition contains an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.90 / 0.10, and the content of the ester represented by the following formula (4) is 0.10% by mass or less relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

[0065]

[0066] The mass ratio [(1) / (2)] of the aldehyde represented by the above formula (1) to the aldehyde represented by the above formula (2) in the second aldehyde composition is 97.00 / 3.00 to 99.999 / 0.001, preferably 98.00 / 2.00 to 99.999 / 0.001, more preferably 98.50 / 1.50 to 99.999 / 0.001, further preferably 99.50 / 0.50 to 99.998 / 0.002, further preferably 99.90 / 0.10 to 99.998 / 0.002, further preferably 99.96 / 0.04 to 99.997 / 0.003.

[0067] In addition, the content of the ester represented by the above formula (4) in the second aldehyde composition is 0.10% by mass or less, preferably 0.05% by mass or less, and more preferably 0.02% by mass or less, relative to the total amount of the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2). The lower limit is not limited, and the case where the ester represented by the above formula (4) is not included is also included in the second aldehyde composition, but it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more.

[0068] As described above, the second aldehyde composition has the characteristics of having an excellently balanced fragrance of green, aldehyde, and floral notes, and also having a strong aldehyde aroma, and is therefore useful as a fragrance. The ester represented by the aforementioned formula (4) is sometimes obtained as a by-product when the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) are produced. In this case, the second aldehyde composition can be obtained even without adding the ester represented by the aforementioned formula (4), but the second aldehyde composition can also be obtained by adding the ester represented by the aforementioned formula (4) to the aldehyde composition that does not contain the ester represented by the aforementioned formula (4). In addition, for the ester represented by the aforementioned formula (4) obtained as a by-product when the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) are produced, when the amount of the ester represented by the aforementioned formula (4) exceeds 0.10% by mass relative to the total amount of the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2), it can be reduced to 0.10% by mass or less by distillation purification, chromatography, etc.

[0069] [Aldehyde composition (third embodiment)]

[0070] Among the aldehyde compositions of the present invention, the aldehyde composition of the third embodiment which is a preferred embodiment (hereinafter also referred to as the third aldehyde composition) contains an aldehyde represented by the following formula (1), an aldehyde represented by the following formula (2), and an ester represented by the following formula (4), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.50 to 2.00 mass % relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

[0071] It should be noted that the third aldehyde composition may be included in the first aldehyde composition. That is, an aldehyde composition that belongs to the third aldehyde composition and to the first aldehyde composition is also included in the aldehyde composition of the present invention.

[0072] The aldehyde composition belonging to the third aldehyde composition and belonging to the first aldehyde composition contains an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.90 / 0.10, and the content of the ester represented by the following formula (4) is 0.50 to 2.00 mass % relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

[0073]

[0074] The mass ratio [(1) / (2)] of the aldehyde represented by the above formula (1) to the aldehyde represented by the above formula (2) in the third aldehyde composition is 97.00 / 3.00 to 99.999 / 0.001, preferably 98.00 / 2.00 to 99.999 / 0.001, more preferably 98.50 / 1.50 to 99.999 / 0.001, further preferably 99.00 / 1.00 to 99.995 / 0.005, further preferably 99.90 / 0.10 to 99.99 / 0.01, and further preferably 99.92 / 0.08 to 99.98 / 0.02.

[0075] The content of the ester represented by the above formula (4) in the third aldehyde composition is 0.50 to 2.00 mass %, preferably 0.50 to 1.00 mass %, and more preferably 0.50 to 0.80 mass % relative to the total amount of the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2).

[0076] The third aldehyde composition has a well-balanced aroma of green, aldehyde, and floral notes as described above, and also has a powdery feel, and is therefore useful as a fragrance. The ester represented by the above formula (4) is sometimes obtained as a by-product when the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2) are produced. In this case, the third aldehyde composition can be obtained even without adding the ester represented by the above formula (4). However, the third aldehyde composition can be obtained by adding the ester represented by the above formula (4) to an aldehyde composition that does not contain the ester represented by the above formula (4).

[0077] [Other ingredients]

[0078] The aldehyde composition of the present invention contains an aldehyde represented by the aforementioned formula (1) and an aldehyde represented by the aforementioned formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the aforementioned formula (1) to the aldehyde represented by the aforementioned formula (2) is 97.00 / 3.00 to 99.999 / 0.001. The aldehyde composition may also contain an ester represented by the aforementioned formula (4), but may further contain other components shown below. By including these components, when used as a fragrance, the fragrance can be diversified, which is therefore preferred.

[0079] It should be noted that the other components described in this section are common to the first aldehyde composition, the second aldehyde composition, and the third aldehyde composition.

[0080] The aldehyde composition of the present invention may contain 0.01 to 0.90 mass % of an alcohol represented by the following formula (3).

[0081]

[0082] The content of the alcohol represented by the above formula (3) in the aldehyde composition of the present invention is preferably 0.01 to 0.90 mass %, more preferably 0.01 to 0.50 mass %, and further preferably 0.01 to 0.30 mass %. The alcohol represented by the above formula (3) is sometimes obtained as a by-product when producing the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2), but may be added to an aldehyde composition that does not contain the alcohol represented by the above formula (3).

[0083] The aldehyde composition of the present invention may contain 0.01 to 0.90 mass % of a sulfonic acid ester represented by the following formula (5).

[0084]

[0085] The content of the ester represented by the above formula (5) in the aldehyde composition of the present invention is preferably 0.01 to 0.90 mass %, more preferably 0.01 to 0.50 mass %, and even more preferably 0.01 to 0.30 mass %. The ester represented by the above formula (5) is sometimes obtained as a by-product when the aldehyde represented by the above formula (1) and the aldehyde represented by the above formula (2) are produced, but it can also be added to the aldehyde composition not containing the ester represented by the above formula (5).

[0086] The aldehyde composition of the present invention has the above-mentioned composition and has an excellently balanced fragrance of green notes, aldehyde notes and floral notes, and is therefore useful as a fragrance.

[0087] Furthermore, the aldehyde composition is also useful as a raw material for a fragrance composition, can be used as a fragrance component of various products, and can impart diffusibility to the fragrance composition.

[0088] [Fragrance composition]

[0089] The fragrance composition of the present invention contains the above-mentioned aldehyde composition.

[0090] That is, the fragrance composition of the present invention contains an aldehyde composition containing an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the formula (1) to the aldehyde represented by the formula (2) is 97.00 / 3.00 to 99.999 / 0.001.

[0091]

[0092] The fragrance composition of the present invention has a well-balanced fragrance of green notes, aldehyde notes, and floral notes possessed by the aldehyde composition, and has excellent diffusibility, and is therefore useful as a fragrance component for various products.

[0093] As a preferred embodiment, the fragrance composition of the present invention contains the first aldehyde composition.

[0094] That is, a preferred fragrance composition of the present invention contains an aldehyde composition containing an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the formula (1) to the aldehyde represented by the formula (2) is 97.00 / 3.00 to 99.90 / 0.10.

[0095]

[0096] The fragrance composition of the present invention containing the first aldehyde composition has a well-balanced aroma of green, aldehyde and floral notes of the aldehyde composition, a strong floral scent and excellent diffusibility, and is therefore useful as a fragrance component for various products.

[0097] As a preferred embodiment, the fragrance composition of the present invention contains the second aldehyde composition.

[0098] That is, a preferred fragrance composition of the present invention comprises an aldehyde composition comprising an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) to the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.10% by mass or less relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

[0099]

[0100] The fragrance composition of the present invention containing the second aldehyde composition has a well-balanced aroma of green, aldehyde, and floral notes of the aldehyde composition, and also has a strong floral and aldehyde aroma, and is excellent in diffusibility. Therefore, it is useful as a fragrance component for various products.

[0101] As a preferred embodiment, the fragrance composition of the present invention contains the third aldehyde composition.

[0102] That is, a preferred fragrance composition of the present invention comprises an aldehyde composition comprising an aldehyde represented by the following formula (1), an aldehyde represented by the following formula (2), and an ester represented by the following formula (4), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) to the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.50 to 2.00 mass % relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

[0103]

[0104] The fragrance composition of the present invention containing the third aldehyde composition has a well-balanced aroma of green, aldehyde and floral notes of the aldehyde composition, and also has a strong floral and powdery feel and excellent diffusibility, and is therefore useful as a fragrance component for various products.

[0105] The content of the aldehyde composition in the fragrance composition of the present invention may be appropriately adjusted depending on the type of fragrance composition, the type and fragrance intensity of the target fragrance, etc., and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass.

[0106] Examples of other components other than the aldehyde composition contained in the fragrance composition comprising the aldehyde composition include fragrances other than the aldehyde represented by formula (1) or the aldehyde represented by formula (2), surfactants, solvents, antioxidants, and colorants. Preferably, it is at least one member selected from the group consisting of fragrances other than the aldehyde represented by formula (1) or the aldehyde represented by formula (2), surfactants, solvents, antioxidants, and colorants. More preferably, it is at least one member selected from the group consisting of fragrances other than the aldehyde represented by formula (1) or the aldehyde represented by formula (2), and solvents.

[0107] By containing a fragrance other than the aldehyde represented by formula (1) or the aldehyde represented by formula (2), the fragrance can be adjusted according to the target product. In addition, by containing a solvent, it becomes easy to dissolve and permeate into the target product, and the intensity and persistence of the fragrance can be adjusted.

[0108] There are no particular limitations on fragrances other than the aldehyde represented by formula (1) or the aldehyde represented by formula (2) as long as they are conventionally known fragrance components, and a wide range of fragrances can be used. For example, fragrances can be selected from the following substances alone or in combination of two or more at any mixing ratio.

[0109] Examples of fragrances other than the aldehyde represented by formula (1) or the aldehyde represented by formula (2) include hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, and natural extracts.

[0110] Examples of the hydrocarbons include limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, and valencene.

[0111] Examples of the alcohol include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, 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, 4-methylcyclohexane -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, isocamphylcyclohexanol, 3,7-dimethyl-7-methoxyoctan-2-ol, etc.

[0112] Examples of the phenols include eugenol, thymol, and vanillin.

[0113] Examples of the esters include linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, pinyl acetate, nopol acetate, bornyl acetate, isobornyl acetate, o-tert-butylcyclohexyl acetate, p-tert-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styroyl acetate, cinnamyl acetate, dimethylbenzyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, tricyclodecenyl propionate, allylcyclopropionate, hexyl ester, ethyl 2-cyclohexylpropionate, benzyl propionate, citronellyl butyrate, dimethylbenzyl orthobutyrate, tricyclodecenyl isobutyrate, methyl 2-nonynoate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, geranyl tiglic acid, leaf alcohol tiglic acid, methyl jasmonate, methyl dihydrojasmonate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl methylphenyl glycidate, methyl anthranilate, ethyl tricyclodecanecarboxylate (fruitate), and the like.

[0114] Examples of the aldehydes include n-octanal, n-decanal, dodecanal, 2-methylundecanal, 10-undecanal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 2-cyclohexylpropanal, p-tert-butyl-α-methylhydrocinnamaldehyde, p-tert-butyl-hydrocinnamaldehyde, p-isopropyl-α-methylhydrocinnamaldehyde, p-ethyl-α,α-dimethylhydrocinnamaldehyde, α-amylcinnamaldehyde, α-hexylcinnamaldehyde, piperonal, and α-methyl-3,4-methylenedioxyhydrocinnamaldehyde.

[0115] Examples of the ketones include methyl heptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptenone, pentylcyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentenolone, rhodone, γ-methylionone, α-ionone, carvone, menthone, camphor, nootkatone, 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, musk ketone, civetone, cyclopentadecanone, and cyclohexadecenone.

[0116] Examples of the acetals and ketals include acetaldehyde ethyl phenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerol acetal, ethyl acetoacetate ethylene glycol ketal, and the like.

[0117] Examples of the ethers include anethole, β-naphthyl methyl ether, β-naphthyl ethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic form or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan.

[0118] Examples of the nitriles include citronellyl nitrile and the like.

[0119] Examples of the lactones include γ-nonalactone, γ-undecalactone, σ-decanolactone, γ-jasminelactone, coumarin, cyclopentadecalactone, cyclohexacalactone, cyperamide, brassic acid ethylene glycol ester, and 11-oxahexadecalactone.

[0120] Examples of natural essential oils and natural extracts include orange, lemon, bergamot, citrus, mint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, sandalwood, vetiver, patchouli, and labdanum.

[0121] Examples of the solvent include dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl citrate.

[0122] Examples of the surfactant include polyoxyethylene lauryl sulfate ether and the like.

[0123] The fragrance composition containing the aldehyde composition can be used as a fragrance component of various products.

[0124] Products that can use the fragrance composition include, for example, aromatic products such as perfumes and colognes; other hair cosmetics such as shampoos, conditioners, hair tonics, hair creams, mousses, hair gels, hair oils, sprays, etc.; skin cosmetics such as lotions, beauty serums, creams, emulsions, facial masks, foundations, pressed powders, lipsticks, and various makeup products; dishwashing detergents, washing detergents, softeners, disinfecting detergents, deodorizing detergents, room fragrances, furniture care agents, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaching agents, fungicides, insect repellents, and various other health and hygiene detergents; quasi-drugs such as toothpastes, mouthwashes, bath preparations, antiperspirants, and perm solutions; sundries such as toilet paper and napkins; pharmaceutical products; food, etc.

[0125] The amount of the fragrance composition blended in the above-mentioned product is not particularly limited, and the amount of the fragrance composition blended can be selected according to the type, properties, and sensory effects of the product to be scented. For example, the amount of the fragrance composition blended in the product 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.

[0126] When the fragrance composition is used as an aromatherapy essential oil, perfume, or the like, the amount of the fragrance composition contained in the product may be 80% by mass or more, or may be 100% by mass.

[0127] [Method for producing aldehyde composition]

[0128] The aldehyde composition of the present invention is not limited in its production method as long as it contains the aldehyde represented by the above formula (1) and the aldehyde represented by the above formula (2) in a mass ratio [(1) / (2)] of 97.00 / 3.00 to 99.999 / 0.001 as described above, but is preferably obtained by the production method described below.

[0129] The following two methods are shown as preferred methods for producing the aldehyde composition of the present invention.

[0130] (First Manufacturing Method)

[0131] The first production method is a method for producing an aldehyde composition, which sequentially comprises the following steps: formylation of isobutylbenzene with carbon monoxide under superacid conditions to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde;

[0132] A step of subjecting 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde to aldol condensation with acetaldehyde to obtain an aldehyde represented by the following formula (6) and an aldehyde represented by the following formula (7); and

[0133] A step of performing hydrogenation to obtain an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2).

[0134]

[0135] (Second Manufacturing Method)

[0136] The second production method is a method for producing an aldehyde composition, which sequentially comprises the following steps: a step of formylation of isobutylbenzene with carbon monoxide under superacid conditions to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde;

[0137] A step of acetalizing 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde in the presence of a p-toluenesulfonic acid catalyst;

[0138] A step of reacting the obtained acetal with an alkyl vinyl ether in the presence of an acid catalyst;

[0139] A step of hydrolyzing the product in the presence of an acid catalyst to obtain an aldehyde represented by the following formula (6) and an aldehyde represented by the following formula (7); and

[0140] A step of performing hydrogenation to obtain an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2).

[0141]

[0142] Each manufacturing method is described below.

[0143] <First Manufacturing Method>

[0144] The first production method is a method for producing an aldehyde composition, which sequentially comprises the following steps: formylation of isobutylbenzene with carbon monoxide under superacid conditions to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde;

[0145] A step of subjecting 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde to aldol condensation with acetaldehyde to obtain an aldehyde represented by the following formula (6) and an aldehyde represented by the following formula (7); and

[0146] A step of performing hydrogenation to obtain an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2).

[0147]

[0148] (Formylation process)

[0149] The first step in the first production method is to formylate isobutylbenzene with carbon monoxide under superacid conditions to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde. "Under superacid conditions" means that a superacid catalyst is used in the reaction.

[0150] The superacid catalyst is preferably based on a combination of a Bronsted acid and a Lewis acid.

[0151] The Bronsted acid is not particularly limited, but is preferably hydrogen fluoride, hydrogen chloride, or hydrogen bromide, and more preferably hydrogen fluoride.

[0152] The Lewis acid is not particularly limited, but is preferably boron trifluoride or aluminum chloride, and more preferably boron trifluoride.

[0153] From the viewpoints of recovery / recycling of the catalyst and positional selectivity of the formyl group, a combination of hydrogen fluoride and boron trifluoride is more preferred.

[0154] When hydrogen fluoride is used as the Bronsted acid, hydrogen fluoride also functions as a solvent for the reaction. As hydrogen fluoride, substantially anhydrous hydrogen fluoride is preferred from the viewpoint of reactivity. 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.

[0155] From the viewpoint of reactivity with carbon monoxide and suppression of side reactions, the molar ratio of hydrogen fluoride to isobutylbenzene [hydrogen fluoride (mole) / isobutylbenzene (mole)] is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 10.0 or more, and 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.

[0156] When boron trifluoride is used as the Lewis acid, the molar ratio of boron trifluoride to isobutylbenzene [boron trifluoride (mole) / isobutylbenzene (mole)] is preferably 1.0 or more, more preferably 2.0 or more, and is preferably 4.0 or less, more preferably 3.0 or less, from the viewpoint of reactivity with carbon monoxide and suppression of side reactions.

[0157] From the viewpoint of improving reactivity, suppressing side reactions, and improving selectivity of the position for introduction of the formyl group, the reaction temperature is preferably -50°C or higher, more preferably -40°C or higher, further preferably -30°C or higher, and is preferably 30°C or lower, more preferably 0°C or lower, further preferably -10°C or lower.

[0158] The reaction of isobutylbenzene and carbon monoxide is preferably carried out under pressure. The pressure during the reaction is preferably 1.0 MPaG or more, more preferably 1.5 MPaG or more, and further preferably 1.8 MPaG or more as a partial pressure of carbon monoxide from the viewpoint of improving reactivity and suppressing side reactions, and is preferably 3.0 MPaG or less, more preferably 2.5 MPaG or less, and further preferably 2.2 MPaG or less.

[0159] In this reaction (formylation reaction), the reaction time is not particularly limited, but from the viewpoint of allowing the reaction to proceed sufficiently, suppressing side reactions and decomposition of the product, and efficiently producing, it is preferably 10 minutes or more, more preferably 20 minutes or more, and further preferably 30 minutes or more, and is preferably 24 hours or less, more preferably 12 hours or less, and further preferably 5 hours or less.

[0160] In addition, this reaction can be carried out in the presence of a solvent. As the solvent used, as long as the solubility of the reaction raw materials is good and it is an inactive solvent to acid catalysts such as hydrogen fluoride and boron trifluoride, there is no particular limitation. For example, saturated aliphatic hydrocarbons such as hexane, heptane, decane, halogenated aliphatic hydrocarbons such as chloroform, methylene chloride, and ethylene dichloride are exemplified. These solvents can be used alone or in combination of two or more. The amount of solvent used is not particularly limited, and can be appropriately selected from the perspective of uniformity of the reaction, reaction speed, and removal of the solvent. It should be noted that in this process, when hydrogen fluoride is used, hydrogen fluoride also functions as a solvent, so a solvent may not be used.

[0161] The above reaction may be carried out by any method such as a batch method, a semi-batch method, or a continuous method. However, a continuous method is preferred from the viewpoint of enabling recovery and reuse of the catalyst and from the viewpoint of production efficiency.

[0162] In addition, the apparatus used in the production method is a reaction apparatus capable of sufficiently mixing a liquid phase and a gas phase while adjusting the temperature under pressure.

[0163] For example, in the continuous method, 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 an appropriate temperature, and after the temperature is kept constant, the pressure is increased to an appropriate reaction pressure using carbon monoxide, and the carbon monoxide is supplied in a manner that the pressure is kept constant. Thereafter, a semi-batch reaction is performed in which isobutylbenzene dissolved in a solvent as required is supplied. Then, hydrogen fluoride, boron trifluoride, and isobutylbenzene dissolved in a solvent as required are started to be supplied, and the reaction product liquid is continuously extracted.

[0164] Hydrogen fluoride and boron trifluoride are removed from the obtained reaction product liquid containing 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde, and the resultant liquid is purified by distillation or extraction as necessary to obtain the target 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde.

[0165] When the obtained 4-isobutylbenzaldehyde contains 2-isobutylbenzaldehyde, it may be further purified to obtain higher-purity 4-isobutylbenzaldehyde and higher-purity 2-isobutylbenzaldehyde, or a mixture thereof may be used as a raw material for the next step as it is.

[0166] In particular, when the mass ratio of 4-isobutylbenzaldehyde to 2-isobutylbenzaldehyde [4-isobutylbenzaldehyde / 2-isobutylbenzaldehyde] is 97.00 / 3.00 to 99.999 / 0.001, it is preferable to use it as a raw material directly because the mass ratio of the final product can be adjusted to the aforementioned range (mass ratio of the aldehyde represented by formula (1) to the aldehyde represented by formula (2) [(1) / (2)]) of 97.00 / 3.00 to 99.999 / 0.001.

[0167] The mass ratio of 4-isobutylbenzaldehyde to 2-isobutylbenzaldehyde [4-isobutylbenzaldehyde / 2-isobutylbenzaldehyde] is preferably adjusted according to the target aroma. For example, in order to obtain the first aldehyde composition, it is preferably 97.00 / 3.00 to 99.90 / 0.10, more preferably 98.00 / 2.00 to 99.90 / 0.10, further preferably 98.50 / 1.50 to 99.90 / 0.10, further preferably 99.00 / 1.00 to 99.80 / 0.20, and further preferably 99.20 / 0.80 to 99.70 / 0.30. In order to obtain the second aldehyde composition, it is preferably 97.00 / 3.00 to 99.999 / 0.001, more preferably 98.00 / 2.00 to 99.999 / 0.001, further preferably 98.50 / 1.50 to 99.999 / 0.001, further preferably 99.50 / 0.50 to 99.998 / 0.002, further preferably 99.90 / 0.10 to 99.998 / 0.002, further preferably 99.96 / 0.04 to 99.997 / 0.003. In order to obtain the third aldehyde composition, it is preferably 97.00 / 3.00 to 99.999 / 0.001, more preferably 98.00 / 2.00 to 99.999 / 0.001, further preferably 98.50 / 1.50 to 99.999 / 0.001, further preferably 99.00 / 1.00 to 99.995 / 0.005, further preferably 99.90 / 0.10 to 99.99 / 0.01, further preferably 99.92 / 0.08 to 99.98 / 0.02.

[0168] 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 in the present production method. Specifically, the ratio of positional isomers of the raw materials in each step corresponding to the target aldehyde can be adjusted.

[0169] (Cinnamaldehyde Synthesis Process Using Aldol Condensation)

[0170] In the first production method, the next step is to subject the 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde obtained in the previous step to aldol condensation with acetaldehyde to obtain the aldehyde represented by the above formula (6) and the aldehyde represented by the above formula (7) (isobutylcinnamaldehyde).

[0171] In the aldol condensation reaction of this step, a basic compound is preferably used as a catalyst.

[0172] Examples of the basic compound used as the catalyst include sodium hydroxide, potassium hydroxide, sodium bicarbonate, and mixtures thereof. The amount of the basic compound is preferably 0.05 mol or more, more preferably 0.1 mol or more, and further preferably 0.2 mol or more, and is preferably 3 mol or less, more preferably 1 mol or less, and further preferably 0.5 mol or less, relative to 1 mol of isobutylbenzaldehyde as the raw material.

[0173] The amount of acetaldehyde added is preferably 0.5 mol or more, more preferably 0.8 mol or more, and preferably 1.5 mol or less, more preferably 1.1 mol or less, relative to 1 mol of 4-isobutylbenzaldehyde as a raw material. Acetaldehyde is preferably added sequentially or continuously over time, for example, preferably by dropwise addition.

[0174] The aldol condensation reaction of this step is preferably carried out in a solvent. As the solvent, various water-miscible organic solvents are exemplified, and specifically, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, allyl alcohol, ethylene glycol, propylene glycol, and diethylene glycol are preferably exemplified, and methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, ethylene glycol, propylene glycol, and diethylene glycol are more preferably exemplified.

[0175] The reaction temperature in the aldol condensation reaction of this step is not particularly limited, but is preferably 0° C. or higher, more preferably 10° C. or higher, from the viewpoint of reaction rate, and is preferably 50° C. or lower, more preferably 40° C. or lower, and further preferably 30° C. or lower, from the viewpoint of suppressing side reactions.

[0176] The reaction time is not particularly limited, and may be a time during which condensation can proceed sufficiently, and is preferably 10 minutes or more, more preferably 30 minutes or more, and even more preferably 1 hour or more, and is preferably 24 hours or less, more preferably 12 hours or less, even more preferably 6 hours or less, and even more preferably 4 hours or less.

[0177] The reaction may be stopped by neutralization. For example, the reaction may be stopped by adding an acid such as acetic acid.

[0178] The method for separating the aldehyde represented by the above formula (6) and the aldehyde represented by the formula (7) from the solution after completion of the reaction is not particularly limited, and the method can be carried out by appropriately combining liquid separation, extraction operation, and distillation purification.

[0179] For example, a low-polarity or non-polar organic solvent is added to the solution after completion of the reaction to transfer the aldehyde mixture to an oil phase, the obtained oil phase is dried over, for example, magnesium sulfate, and the filtrate obtained by filtration is concentrated and further purified by distillation to allow separation.

[0180] (Hydrogenation process)

[0181] In the first production method, the next step is a step of performing hydrogenation to obtain the aldehyde represented by the above formula (1) and the aldehyde represented by the above formula (2).

[0182] This hydrogenation step is a step of hydrogenating the aldehyde represented by the above formula (6) and the aldehyde represented by the formula (7) (isobutylcinnamaldehyde) obtained in the previous step to obtain the target aldehyde composition containing the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2).

[0183] The method of hydrogenation is not particularly limited, and the hydrogenation can be carried out by a known method using a hydrogenation catalyst.

[0184] The hydrogenation catalyst is not particularly limited, and a known catalyst can be used, for example, a supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like; a so-called Ziegler-type hydrogenation catalyst using an organic acid salt of Ni, Co, Fe, or Cr, or a transition metal salt such as acetylacetonate, and a reducing agent such as an organic aluminum; a homogeneous hydrogenation catalyst such as an organic metal complex such as an organic metal compound of Ti, Ru, Rh, or Zr, etc., and the like.

[0185] From the viewpoint of reactivity and suppression of side reactions, the temperature of the hydrogenation reaction in this step is preferably 0°C or higher, more preferably 10°C or higher, further preferably 20°C or higher, and is preferably 150°C or lower, further preferably 100°C or lower.

[0186] The pressure of hydrogen used for the hydrogenation reaction is preferably 0.01 MPaG or more, more preferably 0.03 MPaG or more, further preferably 0.05 MPaG or more, and is preferably 10 MPaG or less, more preferably 3 MPaG or less, further preferably 1 MPaG or less, and further preferably 0.5 MPaG or less.

[0187] The reaction time is not particularly limited, but is preferably 3 minutes or longer, more preferably 10 minutes or longer, and even more preferably 30 minutes or longer, and is preferably 24 hours or shorter, more preferably 12 hours or shorter, and even more preferably 8 hours or shorter.

[0188] The hydrogenation reaction can be carried out in the presence of a solvent. The solvent used is not particularly limited as long as it does not hinder the hydrogenation reaction, and examples thereof include aliphatic hydrocarbons such as pentane, hexane, isopentane, heptane, octane, isooctane, etc.; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, etc. These solvents can be used alone or in combination of two or more.

[0189] The method for purifying the target aldehyde represented by formula (1) and the aldehyde represented by formula (2) from the solution after the reaction is completed is not particularly limited, and a known method can be appropriately selected. Specifically, filtration, chromatography, distillation purification, etc. are exemplified, and by purifying by appropriately combining them, a target aldehyde or aldehyde composition with high purity can be obtained.

[0190] As described above, when the mass ratio of 4-isobutylbenzaldehyde to 2-isobutylbenzaldehyde [4-isobutylbenzaldehyde / 2-isobutylbenzaldehyde] as the product of the formylation step is 97.00 / 3.00 to 99.999 / 0.001, it is used as a raw material as it is, and it is preferred that the mass ratio of the positional isomers of the final product (the mass ratio of the aldehyde represented by the formula (1) to the aldehyde represented by the formula (2) [(1) / (2)]) is 97.00 / 3.00 to 99.999 / 0.001. However, the product after the hydrogenation step or a purified product thereof may be used to adjust the mass ratio to the above range, as long as the mass ratio finally obtained is within the above range.

[0191] <Second Manufacturing Method>

[0192] The second production method is a method for producing an aldehyde composition, which sequentially comprises the following steps: a step of formylation of isobutylbenzene with carbon monoxide under superacid conditions to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde;

[0193] A step of acetalizing 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde in the presence of a p-toluenesulfonic acid catalyst;

[0194] A step of reacting the obtained acetal with an alkyl vinyl ether in the presence of an acid catalyst;

[0195] A step of hydrolyzing the product in the presence of an acid catalyst to obtain an aldehyde represented by the following formula (6) and an aldehyde represented by the following formula (7); and

[0196] A step of performing hydrogenation to obtain an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2).

[0197]

[0198] (Formylation process)

[0199] The first step in the second manufacturing method is: under super acid conditions, isobutylbenzene is formylated using carbon monoxide to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde. This formylation step is the same as the formylation step in the first manufacturing method, and the preferred conditions are also the same. The formylation step is specifically described below. It should be noted that "under super acid conditions" means that a super acid catalyst is used in the reaction.

[0200] The superacid catalyst is preferably based on a combination of a Bronsted acid and a Lewis acid.

[0201] The Bronsted acid is not particularly limited, but is preferably hydrogen fluoride, hydrogen chloride, or hydrogen bromide, and more preferably hydrogen fluoride.

[0202] The Lewis acid is not particularly limited, but is preferably boron trifluoride or aluminum chloride, and more preferably boron trifluoride.

[0203] From the viewpoints of recovery / recycling of the catalyst and positional selectivity of the formyl group, a combination of hydrogen fluoride and boron trifluoride is more preferred.

[0204] When hydrogen fluoride is used as the Bronsted acid, hydrogen fluoride also functions as a solvent for the reaction. As hydrogen fluoride, substantially anhydrous hydrogen fluoride is preferred from the viewpoint of reactivity. 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.

[0205] From the viewpoint of reactivity with carbon monoxide and suppression of side reactions, the molar ratio of hydrogen fluoride to isobutylbenzene [hydrogen fluoride (mole) / isobutylbenzene (mole)] is preferably 3.0 or more, more preferably 5.0 or more, and even more preferably 10.0 or more, and 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.

[0206] When boron trifluoride is used as the Lewis acid, the molar ratio of boron trifluoride to isobutylbenzene [boron trifluoride (mole) / isobutylbenzene (mole)] is preferably 1.0 or more, more preferably 2.0 or more, and is preferably 4.0 or less, more preferably 3.0 or less, from the viewpoint of reactivity with carbon monoxide and suppression of side reactions.

[0207] From the viewpoint of improving reactivity, suppressing side reactions, and improving selectivity of the position for introduction of the formyl group, the reaction temperature is preferably -50°C or higher, more preferably -40°C or higher, further preferably -30°C or higher, and is preferably 30°C or lower, more preferably 0°C or lower, further preferably -10°C or lower.

[0208] The reaction of isobutylbenzene and carbon monoxide is preferably carried out under pressure. The pressure during the reaction is preferably 1.0 MPaG or more, more preferably 1.5 MPaG or more, and further preferably 1.8 MPaG or more as a partial pressure of carbon monoxide from the viewpoint of improving reactivity and suppressing side reactions, and is preferably 3.0 MPaG or less, more preferably 2.5 MPaG or less, and further preferably 2.2 MPaG or less.

[0209] In this reaction (formylation reaction), the reaction time is not particularly limited, but from the viewpoint of allowing the reaction to proceed sufficiently, suppressing side reactions and decomposition of the product, and efficiently producing, it is preferably 10 minutes or more, more preferably 20 minutes or more, and further preferably 30 minutes or more, and is preferably 24 hours or less, more preferably 12 hours or less, and further preferably 5 hours or less.

[0210] In addition, this reaction can be carried out in the presence of a solvent. As the solvent used, as long as the solubility of the reaction raw materials is good and it is an inactive solvent to acid catalysts such as hydrogen fluoride and boron trifluoride, there is no particular limitation. For example, saturated aliphatic hydrocarbons such as hexane, heptane, decane, halogenated aliphatic hydrocarbons such as chloroform, methylene chloride, and ethylene dichloride are exemplified. These solvents can be used alone or in combination of two or more. The amount of solvent used is not particularly limited, and can be appropriately selected from the perspective of uniformity of the reaction, reaction speed, and removal of the solvent. It should be noted that in this process, when hydrogen fluoride is used, hydrogen fluoride also functions as a solvent, so a solvent may not be used.

[0211] The above reaction may be carried out by any method such as a batch method, a semi-batch method, or a continuous method. However, a continuous method is preferred from the viewpoint of enabling recovery and reuse of the catalyst and from the viewpoint of production efficiency.

[0212] In addition, the apparatus used in the production method is a reaction apparatus capable of sufficiently mixing a liquid phase and a gas phase while adjusting the temperature under pressure.

[0213] For example, in the continuous method, 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 an appropriate temperature, and after the temperature is kept constant, the pressure is increased to an appropriate reaction pressure using carbon monoxide, and the carbon monoxide is supplied in a manner that the pressure is kept constant. Thereafter, a semi-batch reaction is performed in which isobutylbenzene dissolved in a solvent as required is supplied. Then, hydrogen fluoride, boron trifluoride, and isobutylbenzene dissolved in a solvent as required are started to be supplied, and the reaction product liquid is continuously extracted.

[0214] Hydrogen fluoride and boron trifluoride are removed from the obtained reaction product liquid containing 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde, and the resultant liquid is purified by distillation or extraction as necessary to obtain the target 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde.

[0215] When the obtained 4-isobutylbenzaldehyde contains 2-isobutylbenzaldehyde, it may be further purified to obtain higher-purity 4-isobutylbenzaldehyde and higher-purity 2-isobutylbenzaldehyde, or a mixture thereof may be used as a raw material for the next step as it is.

[0216] In particular, when the mass ratio of 4-isobutylbenzaldehyde to 2-isobutylbenzaldehyde [4-isobutylbenzaldehyde / 2-isobutylbenzaldehyde] is 97.00 / 3.00 to 99.999 / 0.001, it is preferable to use it as a raw material directly because the mass ratio of the final product can be adjusted to the aforementioned range (mass ratio of the aldehyde represented by formula (1) to the aldehyde represented by formula (2) [(1) / (2)]) of 97.00 / 3.00 to 99.999 / 0.001.

[0217] The mass ratio of 4-isobutylbenzaldehyde to 2-isobutylbenzaldehyde [4-isobutylbenzaldehyde / 2-isobutylbenzaldehyde] is preferably adjusted according to the target aroma. For example, in order to obtain the first aldehyde composition, it is preferably 97.00 / 3.00 to 99.90 / 0.10, more preferably 98.00 / 2.00 to 99.90 / 0.10, further preferably 98.50 / 1.50 to 99.90 / 0.10, further preferably 99.00 / 1.00 to 99.80 / 0.20, and further preferably 99.20 / 0.80 to 99.70 / 0.30. In order to obtain the second aldehyde composition, it is preferably 97.00 / 3.00 to 99.999 / 0.001, more preferably 98.00 / 2.00 to 99.999 / 0.001, further preferably 98.50 / 1.50 to 99.999 / 0.001, further preferably 99.50 / 0.50 to 99.998 / 0.002, further preferably 99.90 / 0.10 to 99.998 / 0.002, further preferably 99.96 / 0.04 to 99.997 / 0.003. In order to obtain the third aldehyde composition, it is preferably 97.00 / 3.00 to 99.999 / 0.001, more preferably 98.00 / 2.00 to 99.999 / 0.001, further preferably 98.50 / 1.50 to 99.999 / 0.001, further preferably 99.00 / 1.00 to 99.995 / 0.005, further preferably 99.90 / 0.10 to 99.99 / 0.01, further preferably 99.92 / 0.08 to 99.98 / 0.02.

[0218] 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 in the present production method. Specifically, the ratio of positional isomers of the raw materials in each step corresponding to the target aldehyde can be adjusted.

[0219] (Cinnamaldehyde Synthesis Process Using Muller-Conradi-Pieroh Conditions)

[0220] In the second production method, the following steps are: a step of acetalizing the 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde obtained in the previous step in the presence of a p-toluenesulfonic acid catalyst; a step of reacting the obtained acetal with an alkyl vinyl ether in the presence of an acid catalyst; and a step of hydrolyzing in the presence of an acid catalyst to obtain the aldehyde represented by the above formula (6) and the aldehyde represented by the above formula (7) (isobutylcinnamaldehyde).

[0221] This step is a step of synthesizing isobutylcinnamaldehyde using Muller-Conradi-Pieroh conditions.

[0222] The acetalization step which is the first step of this step is specifically represented by the following formula.

[0223]

[0224] 4-isobutylbenzaldehyde represented by the above formula (9) and 2-isobutylbenzaldehyde represented by the above formula (10) are acetalized to obtain acetal represented by the above formula (11) and acetal represented by the above formula (12), respectively.

[0225] Acetalization can be performed using a known method, for example, a method of reacting methanol or ethanol in the presence of a p-toluenesulfonic acid catalyst, or a method of reacting with triethyl orthoformate in the presence of a p-toluenesulfonic acid catalyst.

[0226] Next, there is a step of reacting the obtained acetal with an alkyl vinyl ether in the presence of an acid catalyst to add the alkyl vinyl ether.

[0227] Specifically, the alkyl vinyl ether addition step is represented by the following formula.

[0228]

[0229] (wherein R represents an alkyl group having 2 to 8 carbon atoms)

[0230] The acetal represented by the above formula (11) and the acetal represented by the above formula (12) are reacted with an alkyl vinyl ether in the presence of an acid catalyst to add the alkyl vinyl ether, thereby obtaining the acetal represented by the above formula (13) and the acetal represented by the above formula (14), respectively.

[0231] As the alkyl vinyl ether, vinyl ethers having an alkyl group having 2 to 8 carbon atoms, such as ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and 2-ethylhexyl vinyl ether, are preferred. Among them, at least one selected from the group consisting of ethyl vinyl ether and propyl vinyl ether is more preferred from the viewpoint of reactivity.

[0232] The acid catalyst used in the alkyl vinyl ether addition step is not particularly limited, but Bronsted acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, and toluenesulfonic acid, and Lewis acids such as boron trifluoride, zinc chloride, and aluminum chloride can be used.

[0233] From the viewpoint of reaction yield, the amount of alkyl vinyl ether added is preferably 1 mol or more, more preferably 1.2 mol or more, per mol of the substrate (acetal), and from the viewpoint of economic efficiency, preferably 2 mol or less, more preferably 1.7 mol or less.

[0234] From the viewpoint of reactivity, the reaction temperature is preferably 0° C. or higher, more preferably 10° C. or higher. From the viewpoint of suppressing side reactions, the reaction temperature is preferably 50° C. or lower, more preferably 40° C. or lower.

[0235] Next, there is a step of hydrolyzing the acetal obtained in the above-mentioned alkyl vinyl ether addition step in the presence of an acid catalyst.

[0236] Specifically, the hydrolysis step is represented by the following formula.

[0237]

[0238] (wherein R represents an alkyl group having 2 to 8 carbon atoms)

[0239] The acetal represented by the above formula (13) and the acetal represented by the above formula (14) are hydrolyzed in the presence of an acid catalyst to obtain the aldehyde represented by the above formula (6) and the aldehyde represented by the above formula (7), respectively.

[0240] The acid catalyst used in the hydrolysis step is not particularly limited, but hydrochloric acid, hydrobromic acid, sulfuric acid, acetic acid, toluenesulfonic acid, etc. can be used.

[0241] In addition, from the viewpoint of the efficiency of the hydrolysis reaction, the amount of the acid catalyst added is preferably 0.5% by mass or more, preferably 1% by mass or more, and more preferably 3% by mass or more relative to the substrate (acetal). Furthermore, from the viewpoint of suppressing side reactions, it is preferably 20% by mass or less, and more preferably 15% by mass or less.

[0242] The reaction temperature is preferably 60°C or higher, more preferably 80°C or higher. Furthermore, it is preferably carried out under reflux. Also, it is preferably 100°C or lower.

[0243] (Hydrogenation process)

[0244] In the second production method, the next step is a step of performing hydrogenation to obtain the aldehyde represented by the above formula (1) and the aldehyde represented by the above formula (2).

[0245] This hydrogenation step is a step of hydrogenating the aldehyde represented by the above formula (6) and the aldehyde represented by the formula (7) (isobutylcinnamaldehyde) obtained in the previous step to obtain the target aldehyde composition containing the aldehyde represented by the formula (1) and the aldehyde represented by the formula (2). This hydrogenation step is the same as the hydrogenation step in the first production method, and the preferred conditions are also the same. The specific hydrogenation step is described below.

[0246] The method of hydrogenation is not particularly limited, and the hydrogenation can be carried out by a known method using a hydrogenation catalyst.

[0247] The hydrogenation catalyst is not particularly limited, and a known catalyst can be used, for example, a supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like; a so-called Ziegler-type hydrogenation catalyst using an organic acid salt of Ni, Co, Fe, or Cr, or a transition metal salt such as acetylacetonate, and a reducing agent such as an organic aluminum; a homogeneous hydrogenation catalyst such as an organic metal complex such as an organic metal compound of Ti, Ru, Rh, or Zr, etc., and the like.

[0248] From the viewpoint of reactivity and suppression of side reactions, the temperature of the hydrogenation reaction in this step is preferably 0°C or higher, more preferably 10°C or higher, further preferably 20°C or higher, and is preferably 150°C or lower, further preferably 100°C or lower.

[0249] The pressure of hydrogen used for the hydrogenation reaction is preferably 0.01 MPaG or more, more preferably 0.03 MPaG or more, further preferably 0.05 MPaG or more, and is preferably 10 MPaG or less, more preferably 3 MPaG or less, further preferably 1 MPaG or less, and further preferably 0.5 MPaG or less.

[0250] The reaction time is not particularly limited, but is preferably 3 minutes or longer, more preferably 10 minutes or longer, and even more preferably 30 minutes or longer, and is preferably 24 hours or shorter, more preferably 12 hours or shorter, and even more preferably 8 hours or shorter.

[0251] The hydrogenation reaction can be carried out in the presence of a solvent. The solvent used is not particularly limited as long as it does not hinder the hydrogenation reaction, and examples thereof include aliphatic hydrocarbons such as pentane, hexane, isopentane, heptane, octane, isooctane, etc.; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, etc. These solvents can be used alone or in combination of two or more.

[0252] The method for purifying the target aldehyde represented by formula (1) and the aldehyde represented by formula (2) from the solution after the reaction is completed is not particularly limited, and a known method can be appropriately selected. Specifically, filtration, chromatography, distillation purification, etc. are exemplified, and by purifying by appropriately combining them, a target aldehyde or aldehyde composition with high purity can be obtained.

[0253] As described above, when the mass ratio of 4-isobutylbenzaldehyde to 2-isobutylbenzaldehyde [4-isobutylbenzaldehyde / 2-isobutylbenzaldehyde] as the product of the formylation step is 97.00 / 3.00 to 99.999 / 0.001, it is preferably used as a raw material as it is, and the mass ratio of the positional isomers of the final product (the mass ratio of the aldehyde represented by the formula (1) to the aldehyde represented by the formula (2) [(1) / (2)]) is 97.00 / 3.00 to 99.999 / 0.001. However, the product after the hydrogenation step or a purified product thereof may be used to adjust the mass ratio to the above range, and the mass ratio finally obtained may be within the above range.

[0254] Example

[0255] The present invention will be specifically described based on the following examples, but the present invention is not limited to these examples.

[0256] [Analysis / Evaluation]

[0257] <Gas chromatography analysis (composition analysis)>

[0258] The composition in each step described below, the composition of the product and the composition of the composition were determined by preparing a calibration curve using a gas chromatograph (GC-2010 Plus, manufactured by Shimadzu Corporation) with n-decane (reagent grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an internal standard.

[0259] As a capillary column, HR-1701 (inner diameter Length: 30 m). For the temperature program, the temperature was increased from 100°C to 280°C at a rate of 5°C / min and maintained for 30 minutes.

[0260] <Evaluation of fragrance / note>

[0261] The flavor and fragrance of the aldehyde compositions and fragrance compositions obtained in Examples and Comparative Examples were evaluated by impregnating the compositions with a width of 8 mm and a length of 15 cm with filter paper and allowing specialized panelists to smell the compositions.

[0262] It should be noted that, among the fragrance notes, regarding the floral scent, based on Example 1, the equivalent was designated as A, the stronger than Example 1 was designated as A+, the weaker than Example 1 was designated as B, and the non-floral scent was designated as C.

[0263] In addition, regarding the aldehyde scent in the fragrance note, those equivalent to Example 1 were designated as A, those stronger than Example 1 were designated as A+, those weaker than Example 1 were designated as B, and those without aldehyde scent were designated as C.

[0264] Furthermore, among the fragrance notes, those having a powdery feel were given a P.

[0265] <Evaluation of Odor Threshold>

[0266] The aldehyde composition obtained in the example and lilial (Lilial, 3-(p-tert-butylphenyl)-2-methylpropanal) were diluted with dipropylene glycol to concentrations of 10ppm, 1ppm, 0.1ppm, 0.01ppm, and 0.001ppm, respectively, and impregnated into filter paper with a width of 8mm and a length of 15cm. The lower limit concentration at which the odor can be distinguished was evaluated by a method in which a specialized evaluator smelled. The lower the lower limit concentration, the lower the threshold of the odor, and the better the intensity and diffusivity of the aroma.

[0267] <Evaluation of residual fragrance>

[0268] The aldehyde composition obtained in the example and lilial (Lilial, 3-(p-tert-butylphenyl)-2-methylpropanal) were impregnated into filter paper of 8 mm width and 15 cm length, and the longest period during which the odor could be perceived was evaluated by a method in which a specialized evaluation panel smelled the odor every week. The longer the longest period during which the odor could be perceived, the better the residual fragrance.

[0269] <Carcinogenicity prediction test>

[0270] Using the aldehyde composition obtained in the example and lilial (Lilial, 3-(p-tert-butylphenyl)-2-methylpropanal), a conversion test (in vitro carcinogenicity prediction test using Bhas42 cells) was performed in accordance with OECD231GD to determine whether the carcinogenicity was negative or positive. If the result of this test is negative, it is predicted that there is no possibility of being a cause of carcinogenicity, and the safety is high.

[0271] [Synthesis of raw materials]

[0272] Preparation Example 1 (Synthesis of isobutylbenzaldehyde)

[0273] The following synthesis was performed using a stainless steel autoclave with a magnetic induction stirrer, 3 inlet nozzles at the top, 1 extraction nozzle at the bottom, and a capacity of 10L capable of controlling the internal temperature through a jacket. First, the interior of the autoclave was replaced with carbon monoxide, and then hydrogen fluoride (Morita Chemical Industry Co., Ltd., 1128g, 56.4 mol) and boron trifluoride (STELLA CHEMIFA CORPORATION, 765g, 11.3 mol) were added. After the liquid temperature was set to -25°C, it was pressurized to 2MPa with carbon monoxide. The reaction temperature was maintained at -25°C, and the reaction pressure was maintained at 2MPa. At the same time, isobutylbenzene (Tokyo Chemical Industry Co., Ltd., 946g, 7.05 mol) was supplied from the top of the autoclave over 60 minutes, and stirring was continued for about 30 minutes until no absorption of carbon monoxide was observed. The reaction mixture in the autoclave was drained into ice water. After the drained liquid was fully shaken and mixed, the oil layer was separated. The obtained oil layer was washed with water and then purified by distillation (95°C, 3 Torr) using a distillation tower with 20 theoretical plates to obtain isobutylbenzaldehyde as a colorless transparent liquid (purity 99.5% by mass, mass ratio of 4-isobutylbenzaldehyde to 2-isobutylbenzaldehyde [(4-isobutylbenzaldehyde) / (2-isobutylbenzaldehyde)]=99.95 / 0.05, 650 g).

[0274] Preparation Example 2 (Synthesis of isobutylbenzaldehyde)

[0275] The following synthesis was performed using a stainless steel autoclave with a magnetic induction stirrer, 3 inlet nozzles at the top, 1 extraction nozzle at the bottom, and a capacity of 500 mL, which could control the internal temperature through a jacket. First, isobutylbenzene (100 g, 0.75 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1,2-dichloroethane (295 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), aluminum chloride (149 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 37% hydrochloric acid (1.0 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the inside of the autoclave was replaced with carbon monoxide. After the liquid temperature was set to 20°C, the pressure was increased to 2 MPa with carbon monoxide. The reaction temperature was maintained at 20°C, and the reaction pressure was maintained at 2 MPa, while stirring was continued for about 60 minutes until no carbon monoxide absorption was observed. The reaction mixture in the autoclave was drained into ice water. After the drained liquid was fully shaken and mixed, the oil layer was separated. The obtained oil layer was washed with water and then purified by distillation (95°C, 3 Torr) using a distillation tower with 20 theoretical plates to obtain isobutylbenzaldehyde as a colorless transparent liquid (purity 99.5% by mass, mass ratio of 4-isobutylbenzaldehyde to 2-isobutylbenzaldehyde [(4-isobutylbenzaldehyde) / (2-isobutylbenzaldehyde)]=99.0 / 1.0, 50 g).

[0276] Preparation Example 3 (Synthesis of isobutylbenzaldehyde)

[0277] The following synthesis was performed using a stainless steel autoclave with a magnetic induction stirrer, three inlet nozzles at the top, one extraction nozzle at the bottom, and a capacity of 10 L, which could control the internal temperature by a jacket. First, isobutylbenzene (Tokyo Chemical Industry Co., Ltd., 1000 g, 7.5 mol), 1,2-dichloroethane (Fujifilm Wako Pure Chemical Industries, Ltd., 2950 g), aluminum chloride (Fujifilm Wako Pure Chemical Industries, Ltd., 1490 g), and 37% hydrochloric acid (Fujifilm Wako Pure Chemical Industries, Ltd., 10 g) were added, and the inside of the autoclave was replaced with carbon monoxide. After the liquid temperature was set to 20°C, the pressure was increased to 2 MPa with carbon monoxide. The reaction temperature was maintained at 20°C and the reaction pressure was maintained at 2 MPa, and stirring was continued for about 60 minutes until no carbon monoxide absorption was observed. The reaction mixture in the autoclave was drained into ice water. After the drained liquid was fully shaken and mixed, the oil layer was separated. The obtained oil layer was washed with water and then purified by distillation (95°C, 3 Torr) using a distillation tower with 20 theoretical plates to obtain isobutylbenzaldehyde as a colorless transparent liquid (purity 98.5% by mass, mass ratio of 4-isobutylbenzaldehyde to 2-isobutylbenzaldehyde [(4-isobutylbenzaldehyde) / (2-isobutylbenzaldehyde)]=95.5 / 4.5, 205 g).

[0278] [Manufacturing of aldehyde composition]

[0279] Example 1 (Production of an aldehyde composition containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal: Method using aldol condensation)

[0280] (Aldol condensation step)

[0281] Methanol (400.0 g), sodium hydroxide (18.1 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and isobutylbenzaldehyde (200.0 g) obtained in Preparation Example 1 were added to a round-bottom flask with a stirring device, a thermometer, and a dropping funnel. After cooling to 10°C while stirring, acetaldehyde (56.4 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise over 3 hours. After the addition was completed, the temperature was kept at 10°C for 1 hour to terminate the reaction. After neutralization by adding acetic acid (16.4 g), water and heptane were added and shaken, and the aqueous phase was separated and removed. Then, the heptane was distilled off to obtain a crude intermediate. The crude intermediate was simply distilled (154-161°C / 7 torr) to obtain 3-(isobutylphenyl) acrolein (54.0 g, purity 94.0% by mass).

[0282] (Hydrogenation process)

[0283] 3-(isobutylphenyl) acrolein (50.0 g), 2-propanol (30.0 g), and 5% palladium-carbon catalyst (manufactured by NECHEMCAT CORPORATION, water-containing product, PE type, 0.5 g) obtained by the aldol condensation step were placed in a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature by a jacket, and stirred for 5 hours at 25° C. and a hydrogen pressure of 0.05 MPa to carry out a hydrogenation reaction. The reaction solution was filtered to remove the catalyst, heptane was added and shaken, and the aqueous phase was separated and removed. Then, the heptane was distilled off to obtain a crude composition. The crude composition was distilled at 1 torr using a distillation column with 20 theoretical plates, and an aldehyde composition containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal (8.0 g, mass ratio [3-(4-isobutylphenyl)propanal / 3-(2-isobutylphenyl)propanal] = 99.95 / 0.05) was obtained as a fraction at 108 to 110°C. The results of the fragrance / fragrance evaluation of the obtained aldehyde composition are shown in Table 1.

[0284] Example 2 (Production of an aldehyde composition containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal: method using Muller-Conradi-Pieroh conditions)

[0285] (Addition process of ethyl vinyl ether to acetal based on Muller-Conradi-Pieroh conditions)

[0286] In a round-bottom flask with a content of 300 mL equipped with a stirring device, a thermometer, and a dropping funnel, triethyl orthoformate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 87.2 g) and isobutylbenzaldehyde (86.0 g) obtained in Preparation Example 1 were added, and after cooling to 10°C while stirring, p-toluenesulfonic acid monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 0.5 g) was added, and the temperature was raised to 25°C. Maintain at 25°C for 30 minutes. Thereafter, boron trifluoride diethyl ether complex (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 0.2 g) was added, and ethyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., 57.3 g) was added dropwise over 4 hours. After the addition was completed, stirring was continued for another hour to terminate the reaction. After adding sodium acetate (4.0 g) for neutralization, low-boiling components were distilled off. 37% hydrochloric acid (Fujifilm Wako Pure Chemical Industries, Ltd., 8.0 g) and water (50.0 g) were added to the obtained crude reaction solution, and the temperature was raised to 90°C and stirred for 24 hours. After that, heptane was added and the aqueous phase was separated by liquid separation. Then, the heptane was distilled off to obtain a crude intermediate. The crude intermediate was subjected to simple distillation (156-161°C / 7 torr) to obtain 3-(isobutylphenyl) acrolein (54.0 g, purity 95.4% by mass).

[0287] (Hydrogenation process)

[0288] 3-(isobutylphenyl)propenal (50.0 g), 2-propanol (30.0 g), and 5% palladium-carbon catalyst (manufactured by NECHEMCAT CORPORATION, water-containing product, PE type, 0.5 g) obtained in the previous step were placed in a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature by a jacket, and stirred for 5 hours at 25°C and a hydrogen pressure of 0.05 MPa for hydrogenation reaction. The reaction solution was filtered to remove the catalyst, heptane was added and shaken, and the aqueous phase was separated and removed. Then, the heptane was distilled off to obtain a crude composition. The crude composition was distilled at 1 torr using a distillation tower with a theoretical plate number of 20 stages, and an aldehyde composition (9.3 g) containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal was obtained as a fraction of 108 to 110°C. The results of the fragrance / fragrance evaluation of the obtained aldehyde composition are shown in Table 1.

[0289] Example 3 (Production of an aldehyde composition containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal: method using Muller-Conradi-Pieroh conditions)

[0290] (Addition process of ethyl vinyl ether to acetal based on Muller-Conradi-Pieroh conditions)

[0291] 3-(isobutylphenyl)acrolein (52.0 g, purity 94.4% by mass) was obtained by the same method as in Example 2 except that 3.5 g of p-toluenesulfonic acid monohydrate was used and no boron trifluoride diethyl ether complex was added after the reaction with triethyl orthoformate.

[0292] (Hydrogenation process)

[0293] Using 3-(isobutylphenyl)propenal (50.0 g) obtained in the previous step, an aldehyde composition (9.0 g) containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal was obtained in the same manner as in Example 2. The results of the evaluation of the flavor and fragrance of the obtained aldehyde composition are shown in Table 1.

[0294] Example 4 (Production of an aldehyde composition containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal)

[0295] The content of 3-(4-isobutylphenyl)propanal in the composition obtained in Example 1 was increased by column chromatography to obtain an aldehyde composition (0.9 g) containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal (mass ratio [3-(4-isobutylphenyl)propanal / 3-(2-isobutylphenyl)propanal]=99.996 / 0.004). The fragrance / aroma evaluation was performed. The results are shown in Table 1.

[0296] Example 5 (Production of an aldehyde composition containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal: method using Muller-Conradi-Pieroh conditions)

[0297] (Addition process of ethyl vinyl ether to acetal based on Muller-Conradi-Pieroh conditions)

[0298] An aldehyde composition (8.0 g) containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal was obtained in the same manner as in Example 2 except that isobutylbenzaldehyde (50.0 g) obtained in Production Example 2 was used. The results of the evaluation of the flavor and fragrance of the obtained aldehyde composition are shown in Table 1.

[0299] Example 6

[0300] The aldehyde composition obtained in Example 2 and the aldehyde composition obtained in Example 5 were mixed at a mass ratio of 1:1 to obtain an aldehyde composition containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal. The results of the fragrance / fragrance evaluation of the obtained aldehyde composition are shown in Table 1.

[0301] Example 7 (Production of an aldehyde composition containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal: method using Muller-Conradi-Pieroh conditions)

[0302] (Addition process of ethyl vinyl ether to acetal based on Muller-Conradi-Pieroh conditions)

[0303] A crude reaction liquid was obtained by the same method as in Example 2 using isobutylbenzaldehyde (50.0 g) obtained in Production Example 1. The obtained crude reaction liquid was used in the hydrogenation step as it was.

[0304] (Hydrogenation process)

[0305] The crude reaction solution (50.0 g) obtained in the previous step was used to obtain an aldehyde composition (4.0 g) containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal by the same method as in Example 2. The results of the flavor / fragrance evaluation of the obtained aldehyde composition are shown in Table 1.

[0306] Example 8

[0307] Using column chromatography, the content of the ester compound (formula (4)) in the composition obtained in Example 2 was increased to obtain an aldehyde composition (0.8 g) containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal. The results of the fragrance / aroma evaluation of the obtained aldehyde composition are shown in Table 1.

[0308] Example 9

[0309] An aldehyde composition was prepared by adding ethyl p-toluenesulfonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to the aldehyde composition obtained in Example 3. Table 1 shows the results of the evaluation of the flavor and fragrance of the obtained aldehyde composition.

[0310] Example 10

[0311] The aldehyde composition obtained in Example 1 and the aldehyde composition obtained in Comparative Example 1 were mixed at a mass ratio of 6:4 to obtain an aldehyde composition containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal. The results of the fragrance / fragrance evaluation of the obtained aldehyde composition are shown in Table 1.

[0312] Comparative Example 1

[0313] An aldehyde composition (7.0 g) containing 3-(4-isobutylphenyl)propanal and 3-(2-isobutylphenyl)propanal was obtained in the same manner as in Example 1 except that isobutylbenzaldehyde (200.0 g) obtained in Production Example 3 was used. The results of the evaluation of the flavor and fragrance of the obtained aldehyde composition are shown in Table 1.

[0314] [Table 1]

[0315] Table 1

[0316]

[0317] The aldehyde composition of the embodiment has an excellently balanced fragrance of green notes, aldehydes, and floral notes. Furthermore, the first aldehyde composition (Examples 5 and 6) has an excellently balanced fragrance of green notes, aldehydes, and floral notes, and also has a strong floral scent. In addition, the second aldehyde composition (Examples 1, 4, and 10) has an excellently balanced fragrance of green notes, aldehydes, and floral notes, and also has a strong aldehyde scent. The third aldehyde composition (Examples 2 and 8) has an excellently balanced fragrance of green notes, aldehydes, and floral notes, and also has a powdery feel. As described above, it can be seen that the aldehyde composition of the embodiment has an excellent fragrance and is therefore useful as a fragrance.

[0318] [Evaluation of odor threshold, evaluation of residual fragrance, and carcinogenicity prediction test]

[0319] The threshold value of the odor, the evaluation of the residual aroma, and the carcinogenicity prediction test of the aldehyde composition of Example 1 were evaluated. In addition, as Comparative Example 2, the threshold value of the odor, the evaluation of the residual aroma, and the carcinogenicity prediction test of lilial (3-(p-tert-butylphenyl)-2-methylpropanal) were evaluated.

[0320] [Table 2]

[0321] Table 2

[0322]

[0323] It can be seen that the aldehyde composition of the example has a lower threshold of odor than lily of the valley aldehyde, which has a similar structure and fragrance, and has better fragrance intensity and diffusion. It can also be seen that the aldehyde composition of the example has better residual fragrance than lily of the valley aldehyde. It can also be seen that the aldehyde composition of the example is negative in the carcinogenicity prediction test and is also excellent in safety.

[0324] Example 11 and Comparative Example 3 (lemongrass-like spice composition)

[0325] As Example 11, the aldehyde composition of Example 1 was added to the blended fragrance base shown in Table 3 in an amount of 1% by mass, and the fragrance / note evaluation was performed. In addition, as Comparative Example 3, MEFRANAL (3-methyl-5-phenyl-1-pentanal, a floral fragrance with aldehyde and green aroma) was added to the blended fragrance base shown in Table 3 in an amount of 1% by mass, and the fragrance / note evaluation was performed.

[0326] [Table 3]

[0327] Table 3 (parts by mass)

[0328] Embodiment 11 Comparative Example 3 MEFRANAL(3-Methyl-5-phenyl-1-pentanal) - 10 Aldehyde composition of Example 1 ((1) / (2)=99.95 / 0.05) 10 - Aldehyde (ALDEHYDE) C-10 6 6 BLACK PEPPER OIL INDIA 0.8 0.8 Caryophyllene 40 40 Synthetic Citral (CITRAL SYNTHETIC) 640 640 CITRONELLA OIL 50 50 CITRONELLAL 8 8 CITRONELLOL 8 8 CITRONELLYL NITRILE 2 2 CUMINIC ALDEHYDE 0.8 0.8 Dipropylene glycol (DPG) 98 98 GERANIOL 40 40 GERANYL ACETATE 10 10 Ginger Oil (GINGER OIL CHINESE) 2 2 Isoeugenol (ISO EUGENOL) 4 4 Lemononitrile (LEMONILE) 2 2 LIME TERPENE 10 10 Linalool 6 6 METHYL HEPTENONE 10 10 ORANGE OIL FLORIDA 40 40 Para Cymene 4 4 PLICATONE974482 2 2 TAGETES OIL 0.4 0.4 TERPINOLENE 20 6 6 1000 1000

[0329] The results of the fragrance / note evaluation showed that the fragrance composition of Example 11 had a softer and more natural feel than MEFRANAL, which had a relatively harsh fragrance, and also had the effect of adding a gentle floral fragrance overall. In addition, the diffusibility was significantly improved compared to the fragrance composition of Comparative Example 3.

[0330] The results in Table 3 show that the fragrance composition of the present invention further containing the aldehyde composition has improved fragrance and better diffusibility. In other words, it is known that the aldehyde composition of the present invention can impart not only the fragrance but also diffusibility to the fragrance composition.

Claims

1. An aldehyde composition comprising an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the formula (1) to the aldehyde represented by the formula (2) is 97.00 / 3.00 to 99.999 / 0.001, 2. The aldehyde composition according to claim 1, comprising an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) to the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.90 / 0.10, 3. The aldehyde composition according to claim 1, comprising an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) to the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.10 mass % or less relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2), 4. The aldehyde composition according to claim 1, comprising an aldehyde represented by the following formula (1), an aldehyde represented by the following formula (2), and an ester represented by the following formula (4), wherein the mass ratio [(1) / (2)] of the aldehyde represented by the following formula (1) to the aldehyde represented by the following formula (2) is 97.00 / 3.00 to 99.999 / 0.001, and the content of the ester represented by the following formula (4) is 0.50 to 2.00 mass % relative to the total amount of the aldehyde represented by the following formula (1) and the aldehyde represented by the following formula (2).

5. The aldehyde composition according to claim 1, wherein The total purity of the aldehydes represented by the formula (1) and the formula (2) is 97% by mass or more.

6. The aldehyde composition according to claim 1, comprising 0.01 to 0.90 mass % of an alcohol represented by the following formula (3):

7. The aldehyde composition according to claim 1, comprising 0.01 to 0.90 mass% of a sulfonic acid ester represented by the following formula (5): 8 . A fragrance composition comprising the aldehyde composition according to claim 1 .

9. A method for producing the aldehyde composition according to claim 1, comprising the following steps in sequence: A process for formylation of isobutylbenzene with carbon monoxide under superacid conditions to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde; A step of subjecting 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde to aldol condensation with acetaldehyde to obtain an aldehyde represented by the following formula (6) and an aldehyde represented by the following formula (7); and A step of hydrogenating to obtain an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2), 10. A method for producing the aldehyde composition according to claim 1, comprising the following steps in sequence: A process for formylation of isobutylbenzene with carbon monoxide under superacid conditions to obtain 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde; A step of acetalizing 4-isobutylbenzaldehyde and 2-isobutylbenzaldehyde in the presence of p-toluenesulfonic acid catalyst; A step of reacting the obtained acetal with an alkyl vinyl ether in the presence of an acid catalyst; A step of hydrolyzing the product in the presence of an acid catalyst to obtain an aldehyde represented by the following formula (6) and an aldehyde represented by the following formula (7); and A step of hydrogenating to obtain an aldehyde represented by the following formula (1) and an aldehyde represented by the following formula (2),

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