JP5107694B2 - Aldehyde compounds - Google Patents

Description

  The present invention relates to an aldehyde compound, a method for producing the same, and a fragrance composition containing the aldehyde compound.

  Conventionally, it is known that cyclohexanecarbaldehyde has a large number of perfume compounds having a floral aroma. For example, it is known that 4- (4-methyl-3-pentenyl) -3-cyclohexenecarbaldehyde has a fresh floral fragrance (see Non-Patent Document 1). However, there was a problem in the fragrance because it had a strong aldehyde feeling at the same time.

On the other hand, synthesis examples of 1,2-dimethylcyclohexanecarbaldehyde and 1,3-dimethylcyclohexanecarbaldehyde (see, for example, Non-Patent Documents 2 and 3), or synthesis examples of 4-t-butyl-1-methylcyclohexanecarbaldehyde (For example, refer nonpatent literature 4).
However, there is no description about aroma in the document, and it has not been known that such an aldehyde compound is useful as a fragrance.

Motoichi Into, “Revised Supplement Synthetic Fragrance Chemistry and Product Knowledge”, Chemical Industry Daily Inc., published March 22, 2005, pp. 197-198 Journal of Organic Chemistry Vol. 31, 2480-2483 (1966) Tetrahedron Letters 13: 1215-1217 (1967) Journal of Organic Chemistry Vol. 43, No. 19, pages 3792-3794 (1978)

  This invention makes it a subject to provide the fragrance composition containing the aldehyde type compound which does not have a strong aldehyde fragrance, and has fresh sweetness and floral fragrance, its manufacturing method, and the said aldehyde type compound.

  The inventors of the present invention synthesized various aldehyde-based compounds and studied their aromas. As a result, compounds having 1 to 4 hydrocarbon groups on a carbon atom having an aldehyde group bonded to a six-membered hydrocarbon skeleton are obtained. It has been found that it does not have a strong aldehyde scent but has a fresh sweetness and a floral scent.

That is, the present invention relates to the following (1) a fragrance composition containing an aldehyde compound, (2) a novel aldehyde compound, and (3) a method for producing the aldehyde compound.
(1) A fragrance composition containing an aldehyde compound represented by the general formula (I).

(In the formula, R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms. R ² represents a saturated hydrocarbon group having 2 to 4 carbon atoms, and is in the 2, 3, or 4 position with respect to the aldehyde group of the cyclohexane ring. Indicates that they are joined.)
(2) An aldehyde compound represented by the general formula (II).

(In the formula, R ³ represents a saturated hydrocarbon group having 1 to ⁴ carbon atoms. R ⁴ represents a saturated hydrocarbon group having 2 to ⁴ carbon atoms, and is 2, 3, or 4 with respect to the aldehyde group on the cyclohexane ring. (Excluding the case where R ⁴ is a tert-butyl group and bonded to the 4-position with respect to the aldehyde group.)
(3) A method for producing an aldehyde compound represented by the general formula (IV), wherein the compound represented by the general formula (III) is alkylated in the presence of a basic compound to introduce an R ³ group.

(In the formula, R ² represents a saturated hydrocarbon group having 2 to 4 carbon atoms and is bonded to the 2, 3 or 4 position with respect to the aldehyde group on the cyclohexane ring.)

(In the formula, R ³ represents a saturated hydrocarbon group having 1 to 4 carbon atoms. R ² is the same as described above.)

  According to the present invention, the aldehyde compound does not have a strong aldehyde scent that restricts the use as a blended fragrance material, has a fresh sweetness and a floral scent, and is useful as a fragrance component for toiletries and the like. A compound, a production method thereof, and a fragrance composition containing the aldehyde compound can be provided.

[Aldehyde compound represented by formula (I)]
The fragrance composition of the present invention contains an aldehyde compound represented by the general formula (I).

Wherein, R ¹ is a hydrocarbon group having 1 to 4 carbon atoms. Specific examples of the hydrocarbon group for R ¹ preferably include an alkyl group having 1 to 4 carbon atoms, an alkenyl group, and an alkynyl group.
Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
Examples of the alkenyl group having 1 to 4 carbon atoms include a vinyl group, an allyl group, a 1-butenyl group, and a 1-methylvinyl group.
Examples of the alkynyl group having 2 to 4 carbon atoms include an ethynyl group, a 2-propynyl group, and a prop-2-yn-1-yl group.
R ¹ is more preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and from the viewpoint of imparting diffusibility and floral-like sweetness, a methyl group, an ethyl group, and an isopropyl group are more preferable. An ethyl group is particularly preferred.
R ² represents a saturated hydrocarbon group having 2 to 4 carbon atoms and is bonded to the 2, 3 or 4 position with respect to the aldehyde group on the cyclohexane ring. In particular, from the viewpoint of odor quality, those bonded to the 4-position with respect to the aldehyde group on the cyclohexane ring are preferred.
Specific examples of the saturated hydrocarbon group having 2 to 4 carbon atoms of R ² include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Is mentioned. Among these, from the viewpoint of imparting floral-like glare, an ethyl group and an isopropyl group are more preferable, and an isopropyl group is particularly preferable.
Preferred compounds represented by the general formula (I) include 4-isopropyl-1-methylcyclohexanecarbaldehyde, 1-ethyl-4-isopropylcyclohexanecarbaldehyde, 1,4-diisopropylcyclohexanecarbaldehyde and the like.

In the aldehyde compound represented by the general formula (I), the mass ratio of the isomer having the cis configuration of the aldehyde group and the R ² group to the isomer having the trans form is preferably 100: 0 to 10:90. Here, the cis form means that the aldehyde group and the R ² group are on the same side with respect to the cyclohexane ring, and that on the opposite side to the trans form. If the mass ratio of the cis form to the trans form is within the above range, an aldehyde compound having both a floral sweetness and a floral feeling can be provided. From the above viewpoint, it is more preferably 100: 0 to 50:50, and further preferably 100: 0 to 90:10.

[Aldehyde compound represented by formula (II)]
The aldehyde compound of the present invention is represented by the general formula (II).

Here, R < ³ > shows a C1-C4 saturated hydrocarbon group. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. R ³ is more preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. From the viewpoint of imparting diffusibility and floral-like sweetness in the use of a fragrance composition, a methyl group, an ethyl group, or an isopropyl group is preferable. More preferred are methyl group and ethyl group.
R ⁴ represents a saturated hydrocarbon group having 2 to ⁴ carbon atoms and is bonded to the 2, 3 or 4 position with respect to the aldehyde group on the cyclohexane ring. In particular, from the viewpoint of odor quality, those bonded to the 4-position with respect to the aldehyde group on the cyclohexane ring are preferred. However, a compound in which R ⁴ is a tert-butyl group and bonded to the 4-position with respect to the aldehyde group is excluded. Specific examples of the hydrocarbon group having 2 to ⁴ carbon atoms in R ⁴ include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Can be mentioned. Among these, from the viewpoint of imparting floral-like glare, an ethyl group and an isopropyl group are more preferable, and an isopropyl group is particularly preferable.
Preferred compounds represented by the general formula (II) include 4-isopropyl-1-methylcyclohexanecarbaldehyde, 1-ethyl-4-isopropylcyclohexanecarbaldehyde, 1,4-diisopropylcyclohexanecarbaldehyde and the like.

[Method for producing aldehyde compound represented by general formula (IV)]
Next, a method for producing an aldehyde compound represented by the following general formula (IV) will be described.
The method for producing the aldehyde compound represented by the general formula (IV) is not particularly limited, but the aldehyde compound represented by the general formula (III) is alkylated in the presence of a basic compound to produce R ^3. It can be efficiently obtained by introducing a group. The aldehyde compound represented by the general formula (II) can also be produced by the same method as the aldehyde compound represented by the general formula (IV).

In general formula (IV), R ² and R ³ are the same as described above.

[Synthesis of Aldehyde Compound Represented by General Formula (III)]
The aldehyde compound represented by the general formula (III) is not particularly limited, but can be produced, for example, by the method described in JP-A-2005-97285. Specifically, as shown by the following formula (A), the aromatic aldehyde represented by the general formula (V) is condensed with an alcohol in the presence of an acid catalyst to form an acetal to obtain an aromatic acetal. Thereafter, hydrogenated alicyclic acetal can be hydrolyzed to produce an aldehyde compound represented by the general formula (III).

In the formula (A), R ² is the same as in the general formula (I).
The aldehyde compound represented by the general formula (III) can also be produced, for example, by the method described in JP-A-2-188549.
Specifically, as shown by the following formula (B), the alcohol represented by the general formula (VII) is heated in the presence of a dehydrogenation catalyst, or is reacted with an oxidizing agent in an organic solvent. Thus, an aldehyde compound represented by the general formula (III) can be produced.

In the formula (B), R ² is the same as in the general formula (I).

[Synthesis of Aldehyde Compound Represented by General Formula (IV)]
The aldehyde compound represented by the general formula (IV) of the present invention is not particularly limited. For example, as shown in the following formula (C), the compound represented by the general formula (III) It can be obtained by reacting an alkylating agent in the presence of a functional compound.

In the formula (C), R ² is the same as the above general formula (I), and R ³ is the same as the above general formula (II). R ³ X represents an alkylating agent described later.
Specific examples of basic compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride, potassium hydride, lithium hydride, methyl lithium, ethyl lithium, n-butyl lithium, tert-butyl lithium, lithium Diisopropylamine, sodium methoxide, sodium ethoxide, potassium tert-butoxide and the like can be used.
The amount of the basic compound used is preferably in the range of 50 to 1000 mol%, more preferably in the range of 100 to 500 mol%, relative to the aldehyde compound represented by the general formula (III) as the raw material.

In the method represented by the above formula (C), the alkylating agent is a compound having an alkyl group having 1 to 4 carbon atoms, such as alkyl halides such as alkyl chloride, alkyl bromide and alkyl iodide, and dimethyl Preferred examples include dialkyl sulfuric acid such as sulfuric acid. Among these, alkyl bromide and alkyl iodide are more preferable from the viewpoint of reactivity.
The amount of the alkylating agent used is preferably 50 to 1000 mol%, more preferably 100 to 500 mol%, based on the aldehyde compound represented by the general formula (III) as a raw material.

The alkylation reaction represented by the above formula (C) can be performed without solvent, but can also be performed using an organic solvent. The organic solvent is not particularly limited as long as it can be used under basic conditions. Halogenated hydrocarbons such as dichloromethane, ether solvents such as tetrahydrofuran and diethyl ether, aliphatic hydrocarbon solvents such as hexane, benzene And aromatic hydrocarbon solvents such as toluene.
The reaction temperature is usually −78 to 110 ° C., preferably −20 to 100 ° C., more preferably 0 to 80 ° C.

[Synthesis of Aldehyde Compound Represented by General Formula (I)]
There is no restriction | limiting in particular as a manufacturing method of the aldehyde type compound represented by general formula (I), It can obtain by the method similar to the manufacturing method of the aldehyde type compound represented by general formula (IV) mentioned above. it can. For example, reacting an aldehyde compound represented by the general formula (III) with an alkylating agent, alkenylating agent or alkynylating agent having an R ¹ group in the presence of a basic compound to introduce the R ¹ group Can be obtained.

Examples of the alkylating agent include those exemplified above. Examples of the alkenylating agent include alkenyl chloride, alkenyl bromide, alkenyl iodide and the like. Examples of the alkynylating agent include alkynyl chloride, alkynyl bromide, alkynyl iodide and the like. The amount of the alkylating agent, alkenylating agent and alkynylating agent used is preferably 50 to 1000 mol%, preferably 100 to 500 mol%, relative to the aldehyde compound represented by the general formula (III) as a raw material. More preferred.
The reaction temperature, the type and amount of basic compound used, and the type of organic solvent are the same as in the method of the above formula (C).

The aldehyde compounds represented by the above general formulas (I), (II) and (IV) can be used as perfumes, whether purified or unpurified. There is no restriction | limiting in particular as a purification method, It can refine | purify by normal distillation, column chromatography, etc., and can be made the purity which can be used as a fragrance | flavor.
Aldehyde compounds represented by the above general formulas (I), (II) and (IV) do not have a strong aldehyde fragrance and have a floral fragrance having a fresh sweetness, so that alone or with other components In combination, it can be used as a perfuming ingredient for soaps, shampoos, rinses, detergents, cosmetics, spray products, fragrances, perfumes, bathing agents and the like.
The aldehyde compound represented by the general formula (II) of the present invention is a synthetic intermediate of an alcohol compound having a floral fragrance represented by the following general formula (VIII) (for example, see Japanese Patent Application No. 2006-174994). It is also useful.
Specifically, as shown in the following formula (D), an alcohol compound represented by the general formula (VIII) can be obtained by reducing the compound (IV).

In the formula (D), R ² is the same as the above general formula (I), and R ³ is the same as the above general formula (II).

[Perfume composition]
The fragrance composition of the present invention is a mixture of other fragrance components that are usually used and blended fragrances of a desired composition, with the aldehyde compound represented by the general formula (I) alone or in combination of two or more. It is obtained.
The blending amount varies depending on the type of the blended fragrance, the type of the target fragrance, the intensity of the fragrance, etc., but it is preferable to add 0.01 to 90% by weight in the blended fragrance, and 0.1 to 50% by weight. More preferably, it is added.
Perfume ingredients that can be used in combination with the aldehyde system of the present invention include hydrocarbons, alcohols, phenols, esters, carbonates, aldehydes, ketones, acetals, ethers, nitriles, carboxylic acids And natural essential oils such as lactones, natural effluents, and synthetic fragrances.

Examples of the hydrocarbons include limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, and valencene.
Alcohols include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, phenylethyl alcohol, benzyl alcohol, dimethylbenzylcarbi Nol, phenylethyldimethylcarbinol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, amber core (trade name of Kao Corporation) and the like.
Examples of phenols include guaiacol, eugenol, isoeugenol, thymol, paracresol, vanillin and the like.

  Esters include formic acid ester, acetic acid ester, propionic acid ester, butyric acid ester, nonenic acid ester, benzoic acid ester, cinnamic acid ester, salicylic acid ester, brassylic acid ester, tiglic acid ester, jasmonic acid ester, glycidic acid ester, anthranil Acid ester etc. are mentioned.

  As formic acid ester, linalyl formate, citronellyl formate, geranyl formate, etc. As acetic acid ester, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, tellurium acetate Pinyl acetate, nopylacetate, bornyl acetate, isobornyl acetate, ot-butylcyclohexyl acetate, pt-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, phenylethyl acetate, styrylyl acetate , Cinnamyl acetate, dimethylbenzylcarbinyl acetate, phenylethylphenylacetate, 3-pentyltetrahydropyran-4-yl acetate, para-credit As a propionate such as phenyl acetate, citronellyl propionate, tricyclodecenyl propionate, allyl cyclohexyl propionate, ethyl 2-cyclohexyl propionate, benzyl propionate, etc. Citronellyl butyrate, dimethyl benzylcarbinyl n-butyrate, tricyclodecenyl isobutyrate and the like can be mentioned.

Further, as nonenoic acid ester, methyl 2-nonenoate, ethyl 2-nonenoate, ethyl 3-nonenoate, etc., and as benzoic acid ester, methyl benzoate, benzyl benzoate, 3,6-dimethylbenzoate, etc., methyl cinnamate, cinnamic acid, etc. Examples of the ester include benzyl cinnamate, and examples of the salicylic acid ester include methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, cyclohexyl salicylate, and benzyl salicylate.
Further, as the brassic acid ester, ethylene brushate, etc., as the tiglic acid ester, geranyl tiglate, 1-hexyl tiglate, cis-3-hexenyl tiglate, etc., as the jasmonic acid ester, methyl jasmonate, methyl Dihydrojasmonate, etc., as glycidic acid ester, methyl 2,4-dihydroxy-ethylmethylphenyl glycidate, 4-methylphenylethyl glycidate, etc., as anthranilic acid ester, methyl anthranilate, ethyl anthranilate, Examples thereof include dimethyl anthranilate and fruitate (trade name of Kao Corporation).

Examples of carbonates include Jasma Cyclat (trade name of Kao Corporation), Flora Mat (trade name of Kao Corporation), and the like as commercially available products.
Examples of aldehydes include n-octanal, n-nonal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, benzaldehyde, phenylacetaldehyde, phenylpropional. Lualdehyde, cinnamic aldehyde, dimethyltetrahydrobenzaldehyde, Lilal (trade name of IFF), 2-cyclohexylpropanal, pt-butyl-α-methylhydrocinnamic aldehyde, p-isopropyl-α-methylhydrocinnamic aldehyde P-ethyl-α, α-dimethylhydrocinnamic aldehyde, α-amylcinnamic aldehyde, α-hexylcinnamic aldehyde, heliotropin, α-methyl-3,4-methylene Etc. oxyhydrocarbyl cinnamic aldehyde and the like.

Examples of ketones include α-ionone, β-ionone, γ-ionone, α-methylionone, β-methylionone, γ-methylionone, damasenone, methylheptenone, 4-methylene-3,5,6,6-tetramethyl-2- Heptanone, amylcyclopentanone, dihydrojasmon, rose ketone, carvone, menthone, camphor, acetyl cedrene, isolongifolanone, nootkatone, benzylacetone, anisylacetone, methyl β-naphthylketone, 2,5-dimethyl-4 -Hydroxy-3 (2H) -furanone, maltol, muscone, sibeton, cyclopentadecanone, and the like.
Examples of acetals include formaldehyde cyclododecylethyl acetal, acetaldehyde ethylphenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, ethyl acetoacetate ethylene glycol acetal, and the like.

Examples of ethers include cedol methyl ether, anethole, β-naphthyl methyl ether, β-naphthyl ethyl ether, limonene oxide, rose oxide, nerol oxide, 1,8-cineole, rose furan, ambroxan (product of Kao Corporation) Name), Herbaval (trade name of Kao Corporation), Boazin Brenforte (trade name of Kao Corporation) and the like.
Examples of nitriles include geranyl nitrile, citronellyl nitrile, and dodecane nitrile.
Examples of carboxylic acids include benzoic acid, phenylacetic acid, cinnamic acid, hydrocinnamic acid, butyric acid, and 2-hexenoic acid.
Examples of lactones include γ-decalactone, δ-decalactone, γ-valerolactone, γ-nonalactone, γ-undecalactone, δ-hexalactone, γ-jasmolactone, whiskey lactone, coumarin, cyclopentadecanolide, Examples include cyclohexadecanolide, ambretlide, ethylene brushate, 11-oxahexadecanolide, butylidenephthalide, and the like.

  Natural essential oils and natural extracts include orange, lemon, lime, bergamot, vanilla, mandarin, peppermint, spearmint, lavender, camomil, rosemary, eucalyptus, sage, basil, rose, rock rose, geranium, jasmine, ylang ylang, Anise, cloves, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, lemongrass, lovedanum and the like.

(1) Identification of sample The structure of the aldehyde compound obtained in the Examples was identified by nuclear magnetic resonance spectrum ( ¹ H-NMR, ¹³ C-NMR) and IR. The nuclear magnetic resonance spectrum was measured with Mercury 400 manufactured by Varian using chloroform-d as a solvent, and IR was measured with FT-710 manufactured by Horiba, Ltd.
The mass ratio of cis isomer / trans isomer was measured by gas chromatography manufactured by Gerstel.

Example 1 (Synthesis of 4-isopropyl-1-methylcyclohexanecarbaldehyde)
After adding 331 g of potassium tert-butoxide and 700 g of tetrahydrofuran to the flask and stirring at 0 ° C. for several minutes, 350 g of 4-isopropylcyclohexanecarbaldehyde was added dropwise at 0 ° C. over 2.5 hours. Thereafter, 483 g of iodomethane was added dropwise at 0 ° C. over 3 hours. After stirring at 0 ° C. for 30 minutes, the mixture was warmed to room temperature and further stirred for 30 minutes. The reaction solution was washed with 700 g of water three times, added with magnesium sulfate, dried, filtered, and concentrated to obtain 357 g of an aldehyde mixture. 83 g of the aldehyde mixture was distilled under the conditions of a pressure of 70 to 150 Pa and a temperature of 60 to 65 ° C. to obtain 66 g of 4-isopropyl-1-methylcyclohexanecarbaldehyde.

The resulting 4-isopropyl-1-methylcyclohexanecarbaldehyde has a floral-like fragrance reminiscent of jasmine and muguet with a fresh sweetness. The identified results are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz, δ ppm): 0.81 (s, 3H), 0.83 (s, 3H), 0.95 (s, 3H), 0.94-0.99 (m, 2H), 1.19-1.25 (m, 2H ), 1.36-1.41 (m, 2H), 1.59-1.62 (m, 2H), 2.08 (d, 2H, J = 12.8Hz), 9.43 (s, 1H)
¹³ C-NMR (CDCl ₃ , 100 MHz, δ ppm): 20.21 (q), 24.36 (t), 24.54 (t), 27.04 (q), 27.04 (q), 32.95 (d), 33.88 (t), 33.88 ( t), 43.70 (s), 46.99 (d), 206.97 (d)
IR (neat, cm ^-1 ): 2956, 2927, 2870, 2688, 1728, 1456, 1385, 1367, 1124, 933, 741
Cis isomer: trans isomer = 91: 9 (mass ratio)

Example 2 (Synthesis of 1-ethyl-4-isopropylcyclohexanecarbaldehyde)
A flask was charged with 19 g of potassium tert-butoxide and 40 g of tetrahydrofuran and stirred at 0 ° C. for several minutes, and then 20 g of 4-isopropylcyclohexanecarbaldehyde was added dropwise at 0 ° C. over 2.5 hours. Thereafter, 22 g of bromoethane was added dropwise at 0 ° C. over 3 hours. After stirring at 0 ° C. for 30 minutes, the mixture was warmed to room temperature and further stirred for 30 minutes. The reaction solution was washed with 40 g of water three times, added with magnesium sulfate, dried, filtered and concentrated to obtain 21 g of an aldehyde mixture. The aldehyde mixture was distilled under the conditions of a pressure of 70 to 150 Pa and a temperature of 60 to 85 ° C. to obtain 17 g of 1-ethyl-4-isopropylcyclohexanecarbaldehyde.

The obtained 1-ethyl-4-isopropylcyclohexanecarbaldehyde has a sweet fruity, floral-like fragrance. The identified results are as follows.
¹ H-NMR (CDCl ₃ , 400MHz, δppm): 0.78 (t, 3H, J = 7.6Hz), 0.81 (s, 3H), 0.83 (s, 3H), 0.87-0.92 (m, 2H), 0.94- 0.99 (m, 2H), 1.14-1.17 (m, 2H), 1.38-1.44 (m, 2H), 1.60-1.64 (m, 2H), 2.09-2.13 (m, 2H), 9.39 (s, 1H)
¹³ C-NMR (CDCl ₃ , 100 MHz, δ ppm): 8.36 (q), 20.21 (q), 20.35 (q), 26.92 (t), 26.92 (t), 31.17 (t), 31.70 (t), 33.03 ( d), 36.93 (t), 44.10 (d), 50.49 (s), 207.46 (d)
IR (neat, cm ^-1 ): 2956, 2937, 2870, 1726, 1462, 1385, 1367, 1001, 937, 806
Cis isomer: trans isomer = 90: 10 (mass ratio)

Example 3 (Synthesis of 1,4-diisopropylcyclohexanecarbaldehyde)
After 14 g of potassium tert-butoxide and 30 g of tetrahydrofuran were added to the flask and stirred at 0 ° C. for several minutes, 15 g of 4-isopropylcyclohexanecarbaldehyde was added dropwise at 0 ° C. over 2.5 hours. Thereafter, 25 g of 2-iodopropane was added dropwise at 0 ° C. over 3 hours. After stirring at 0 ° C. for 30 minutes, the mixture was warmed to room temperature and further stirred for 30 minutes. The reaction solution was washed with 30 g of water three times, added with magnesium sulfate, dried, filtered and concentrated to obtain 13 g of an aldehyde mixture. 13 g of the aldehyde mixture was purified by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 50/1) to obtain 3 g of 1,4-diisopropylcyclohexanecarbaldehyde.

The resulting 1,4-diisopropylcyclohexanecarbaldehyde has a sweet fruity, floral, greenish aroma. The identified results are as follows.
¹ H-NMR (CDCl ₃ , 400 MHz, δ ppm): 0.81 (s, 3H), 0.82 (s, 3H), 0.87 (s, 3H), 0.89 (s, 3H), 0.90-0.99 (m, 4H), 1.21-1.44 (m, 2H), 1.59-1.64 (m, 2H), 2.05-2.08 (m, 2H), 9.45 (s, 1H)
¹³ C-NMR (CDCl ₃ , 100 MHz, δ ppm): 17.66 (q), 17.71 (q), 20.20 (q), 20.31 (q), 27.08 (t), 28.91 (t), 30.04 (t), 34.29 ( t), 39.00 (d), 44.07 (d), 44.19 (d), 52.73 (s), 208.53 (d)
IR (neat, cm ⁻¹ ): 2958, 2939, 2870, 1724, 1468, 1387, 1367, 939, 806
Cis isomer: trans isomer = 94: 6 (mass ratio)

Comparative Example 1
4-Isopropyl-1-methylcyclohexanecarbaldehyde obtained in Example 1, 1-ethyl-4-isopropylcyclohexanecarbaldehyde obtained in Example 2, 1,4-diisopropylcyclohexanecarbacarb obtained in Example 3 The fragrance of aldehyde was compared with 4-isopropylcyclohexanecarbaldehyde.

  From the comparison of the fragrance of the components shown in Comparative Example 1, it was confirmed that the fragrance changed significantly by introducing an alkyl group into 4-isopropylcyclohexanecarbaldehyde.

Example 4 and Comparative Example 2:
Using 4-isopropyl-1-methylcyclohexanecarbaldehyde obtained in Example 1, blended as shown in Table 2 to prepare a perfume for a product of floral Mugue-like. The numerical values in Table 2 are parts by mass.

  Recalling lily of the valley fragrance by adding 20 parts by mass of 4-isopropyl-1-methylcyclohexanecarbaldehyde of the compound of the present invention in place of 20 parts by mass of dipropylene glycol in the floral perfume-like fragrance shown in Comparative Example 2. A floral muguet-like blended fragrance with enhanced fresh floral aroma was obtained.

Example 5 and Comparative Example 3:
Using 1-ethyl-4-isopropylcyclohexanecarbaldehyde obtained in Example 2, blending was carried out as shown in Table 3 to prepare a floral mugue-like product fragrance. The numerical values in Table 3 are parts by mass.

  By adding 22 parts by mass of 1-ethyl-4-isopropylcyclohexanecarbaldehyde of the compound of the present invention instead of 22 parts by mass of dipropylene glycol in the floral bouquet-like fragrance shown in Comparative Example 3, a fruity floral aroma A floral bouquet-like blended fragrance with enhanced

Example 6 and Comparative Example 4
Using 1,4-diisopropylcyclohexanecarbaldehyde obtained in Example 3, blended as shown in Table 4 to prepare a floral green-like product fragrance. The numerical values in Table 4 are parts by mass.

  By adding 35 parts by mass of 1,4-diisopropylcyclohexanecarbaldehyde of the compound of the present invention instead of 35 parts by mass of dipropylene glycol in the floral green-like blended fragrance shown in Comparative Example 4, the fruity green aroma is enhanced. A floral green-like blended fragrance was obtained.

Claims (4)

A fragrance composition containing an aldehyde compound represented by formula (I).

(In the formula, R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms. R ² represents a saturated hydrocarbon group having 2 to 4 carbon atoms, and is in the 2, 3, or 4 position relative to the aldehyde group on the cyclohexane ring. Indicates that it is bound to.) In the aldehyde compound represented by the general formula (I), the mass ratio of the isomer having the cis configuration of the aldehyde group and the R ² group to the isomer having the trans form is 100: 0 to 10: The fragrance composition according to claim 1, wherein the fragrance composition is 90. An aldehyde compound represented by the general formula (II).

(In the formula, R ³ represents a saturated hydrocarbon group having 1 to ⁴ carbon atoms. R ⁴ represents a saturated hydrocarbon group having 2 to ⁴ carbon atoms, and is 2, 3, or 4 with respect to the aldehyde group on the cyclohexane ring. (Excluding the case where R ⁴ is a tert-butyl group and bonded to the 4-position with respect to the aldehyde group.) A method for producing an aldehyde-based compound represented by the general formula (IV), wherein the compound represented by the general formula (III) is alkylated in the presence of a basic compound to introduce an R ³ group.

(In the formula, R ² represents a saturated hydrocarbon group having 2 to 4 carbon atoms and is bonded to the 2, 3 or 4 position with respect to the aldehyde group on the cyclohexane ring.)

(In the formula, R ³ represents a saturated hydrocarbon group having 1 to 4 carbon atoms. R ² is the same as described above.)