JP7317200B2 - Flavor imparting agent comprising hydroxyaldehyde compound - Google Patents

Description

The present invention relates to flavor imparting agents comprising hydroxyaldehyde compounds. Furthermore, it relates to a perfume composition containing the flavor imparting agent and a novel hydroxyaldehyde compound.

In recent years, consumer demands for foods, beverages, and cosmetics have become sophisticated and diversified, and in particular, attention has been focused on fragrance, and the characteristics of fragrance have become an important factor in the appeal of products. For example, there is an increasing demand for fragrance compounds that can improve flavor by blending, for example, impart or enhance persistence, natural feeling, volume, etc. to fragrance and taste. The search for fragrance compounds has been carried out.

For example, some compounds belonging to the hydroxyaldehyde class are known. Zhen Rohfritsch et al. , J. Agric. Food Chem. 2019, 67, 12, 3511-3520 describes that (E)-4-hydroxy-2-hexenal and (E)-4-hydroxy-2-nonenal were identified as volatile components from milk powder. . Also, (4E)-8-hydroxy-4,8-dimethyldeca-4,9-dienal is prepared according to Schulz, S.; et al. , Zeitschrift fur Naturforschung, C:J. of Biosciences (1988), 43(1-2), 99-104, as an identified substance from butterfly secretions, a synthetic intermediate in JP-A-50-36651 (corresponding to US Pat. No. 3,915,901) and (4E,8E)-10-hydroxy-4,8-dimethyldeca-4,8-dienal is described by Tucker, Samuel P.; Pretty, Jack R.; , Analyst (Cambridge, United Kingdom) (2005), 130(10), 1414-1424 as a possible intermediate in the formation scheme of oxidation products in tobacco smoke.

An object of the present invention is to provide a flavor-imparting agent that exhibits an excellent flavor-imparting effect that cannot be obtained with existing compounds.

The inventor of the present invention conducted intensive research to solve the above problems, and surprisingly discovered that hydroxyaldehydes having a hydroxyl group and an alkyl group at specific positions in the molecule exhibit excellent flavor-imparting effects. bottom. Thus, the present invention provides the following.

[1] A flavor-imparting agent comprising at least one hydroxyaldehyde compound represented by the following formula 1.

[Wherein, the dashed lines at the C4 and C8 positions each independently represent a single bond or a double bond, and in the case of a double bond, a cis-type or a trans-type, or a cis-type and a trans-type Represents a mixture of arbitrary proportions,
When the C8 position is a single bond, R ₁ is an OH group, and R ₂ and R ₃ are each independently hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms; ₂ and R ₃ form a three-membered ring together with the C9 carbon atom to which R 2 and R 3 are attached; or R ₂ and R ₃ together form a methylidene group having a double bond with the C9 carbon; is either
When the C8 position is a double bond, R ₁ is absent, R ₂ is hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms, and R ₃ is an OH group or a CH ₂ OH group. be. ]
[2] The flavor-imparting agent according to [1], comprising at least one hydroxyaldehyde compound represented by the following formulas 1-1 to 1-7.

[In the formula, the wavy line represents a cis-type, a trans-type, or a mixture of the cis-type and the trans-type at any ratio. ]
[3] The flavor imparting agent according to [1] or [2], wherein a double bond is present between the C4 and C5 positions of the hydroxyaldehyde compound.
[4] The flavor imparting agent according to [3], which takes an E form at the double bond between the C4 and C5 positions of the hydroxyaldehyde compound.
[5] Consisting of at least one of a hydroxyaldehyde compound represented by the following formula 1-1-1 (4E) and a hydroxyaldehyde compound represented by the formula 1-2-1 (4E, 8E), [1]- The flavor imparting agent according to any one of [4].

[6] A fragrance composition containing the flavor-imparting agent according to any one of [1] to [5].
[7] A consumable product containing the flavor-imparting agent according to any one of [1] to [5] or the fragrance composition according to [6].
[8] A method for improving the flavor of a flavor composition, comprising blending the flavor-imparting agent according to any one of [1] to [5] into the flavor composition.
[9] A method for imparting flavor to consumer goods, comprising blending the flavor imparting agent according to any one of [1] to [5] or the flavoring composition according to [6] to consumer goods.
[10] A hydroxyaldehyde compound represented by the following formula 1'.

[In the formula, the dashed line represents a single bond or a double bond, and in the case of a double bond, it represents a cis-type or a trans-type, or a mixture of the cis-type and the trans-type in an arbitrary ratio. , R ₂ ' and R ₃ ' are each independently hydrogen, or a linear or branched alkyl group having 1 to 3 carbon atoms, or together with the carbon atom at the C9 position to which R ₂ ' and R ₃ ' are bonded Forms a three-membered ring. (Excluding the case where the dashed line is a single bond and R ₂ ' and R ₃ ' are hydrogen.)]
[11] The hydroxyaldehyde compound according to [10], represented by the following formulas 1-3 to 1-7.

[In the formula, the wavy line represents a cis-type, a trans-type, or a mixture of the cis-type and the trans-type at any ratio. ]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with specific examples. In this specification, the range "X to Y" means a range including the lower limit (X) and the upper limit (Y), and means "X or more and Y or less". Concentration and % represent mass concentration and mass %, respectively, unless otherwise specified, and ratios are mass ratios unless otherwise specified. In addition, unless otherwise specified, the operations and physical properties were measured under the conditions of room temperature (20 to 25° C.)/relative humidity of 40 to 50% RH, but the conditions are not limited to these.

(Hydroxyaldehyde compound represented by Formula 1 and flavor imparting agent comprising the compound)
The usefulness of the hydroxyaldehyde compound represented by Formula 1 (sometimes referred to as the compound of Formula 1) as a flavor imparting agent was confirmed by the present inventors for the first time. Among compounds, some isomers with slightly different structures do not exhibit an odor or exhibit an unpleasant odor. Based on the unexpected discovery that blending in an article can impart a desirable flavor to the article. Accordingly, one aspect of the present invention is a flavor imparting agent comprising at least one hydroxyaldehyde compound represented by Formula 1 below. ADVANTAGE OF THE INVENTION According to this invention, the new flavor imparting agent which can impart a flavor to various goods can be provided. Another aspect of the present invention provides an application of the hydroxyaldehyde compound represented by Formula 1 as a flavor imparting agent.

[Wherein, the dashed lines between the C4 and C5 positions and between the C8 and C9 positions each independently represent a single bond or a double bond; or trans-type, or a mixture of cis-type and trans-type in any ratio,
When there is a single bond between the C8 and C9 positions, R ₁ is an OH group, and R ₂ and R ₃ are each independently hydrogen or straight or branched alkyl having 1 to 3 carbon atoms. is a group; forms a three-membered ring with the carbon atom at the C9 position to which R ₂ and R ₃ are bonded; or methylidene, where R ₂ and R ₃ together have a double bond with the carbon atom at the C9 position forming a group;
When there is a double bond between the C8 and C9 positions, R ₁ is absent, R ₂ is hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms, and R ₃ is an OH group. or a CH ₂ OH group. ]
In the hydroxyaldehyde compound represented by Formula 1, when the dashed line between the C8 and C9 positions is a single bond, (i) _R1 is an OH group and _R2 and _R3 are each independently hydrogen or a straight or branched alkyl group having 1 to 3 carbon atoms; (ii) R ₁ is an OH group and forms a three-membered ring together with the carbon atom at the C9 position to which R ₂ and R ₃ are bonded; (iii) R ₁ is an OH group, and R ₂ and R ₃ together form a methylidene group having a double bond with the carbon atom at the C9 position;

The above forms (i) to (iii) are represented by the following formulas (i) to (iii), respectively.

[In the formulas (i) to (iii), the dashed line between the C4 and C5 positions represents a single bond or a double bond, and in the case of a double bond, cis or trans, or cis Represents a mixture of a type and a trans type in an arbitrary ratio, and R ₂ and R ₃ are each independently hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms. ]
In formula 1 and formulas (i) to (iii) above, the linear or branched alkyl group having 1 to 3 carbon atoms as R ₂ and R ₃ includes a methyl group, an ethyl group, an n-propyl group and an isopropyl group. is mentioned. The OH group is a so-called hydroxyl group, and is also called a hydroxyl group or a hydroxyl group.

In Formula 1, the dashed lines between the C4 and C5 positions and between the C8 and C9 positions may each independently be a single bond or a double bond, but any one is preferably a double bond. That is, preferably, in Formula 1, there are one or two carbon-carbon double bonds represented by dashed lines, and more preferably, at least the dashed lines between the C4 and C5 positions are double bonds is. In this specification, the form in which the dashed line between the C4 and C5 positions is a double bond is simply referred to as "the C4 position is a double bond", and the dashed line between the C8 and C9 positions is double. A double bond form may be simply abbreviated as "the C8 position is a double bond".

In addition, from the viewpoint of making it easier to obtain the desired effect, the hydroxyaldehyde compound represented by formula 1, when the dashed line between the C4 position and the C5 position is a double bond, It is preferred to take the E configuration at the double bond between the positions. That is, the hydroxyaldehyde compound represented by Formula 1 is preferably a 4E form. As detailed in the Examples section, the present inventors have made extensive studies and found that the 4E isomer has a stronger fragrance than the 4Z isomer, and has a fragrance closer to that of fresh flowers of the valley. The 4E form is therefore particularly useful as a flavoring agent. The steric configuration of the hydroxyaldehyde compound represented by Formula 1 (either E-form or Z-form) is mainly determined by high performance liquid chromatography (HPLC) and nuclear magnetic resonance spectroscopy ( ¹ H-NMR, ¹³ C- NMR).

Preferred embodiments of the flavor imparting agent according to the present invention are described below.

(a) When the C4 position is a double bond and the C8 position is a single bond. The imparting agent is preferably in the form of (i) and (iii) above (that is, the hydroxyaldehyde compounds represented by formulas (i) and (iii) above). In addition, the flavor-imparting agent is in the form of (iii) above (that is, represented by the above formula (iii)) in that it is possible to impart a high-quality fragrance reminiscent of fresh flowers, particularly with respect to the lily-of-the-valley-like fragrance. hydroxyaldehyde compounds) are preferred. In the above form (i), R ₂ and R ₃ are each independently preferably hydrogen, a methyl group, or an ethyl group, more preferably hydrogen or a methyl group.

(b) When C4 and C8 are Double Bonds The compound of Formula 1, in which both C4 and C8 are double bonds, particularly improves the natural feeling, diffusibility and longevity of the fragrance in a well-balanced manner. be able to. In addition, the compound can impart a high-quality fragrance reminiscent of fresh flowers, particularly with respect to the lily-of-the-valley-like fragrance. From the viewpoint of further improving the desired effect, R ₂ is preferably hydrogen or a methyl group, more preferably hydrogen. Similarly, R ₃ is preferably a CH ₂ OH group.

The compound of Formula 1 itself exhibits a lily of the valley (also known as muguet, lily of the valley), floral, green, woody, citrus (citrus), rose, ozone-like odor, and is used as a flavor imparting agent such as a perfume compound. It can be used.

Specific examples of preferred structures of the hydroxyaldehyde compound represented by Formula 1 are represented by any one of Formulas 1-1 to 1-7 below. That is, the flavor-imparting agent according to the present invention preferably comprises at least one hydroxyaldehyde compound represented by the following formulas 1-1 to 1-7.

[In the formula, the wavy line represents a cis-type, a trans-type, or a mixture of the cis-type and the trans-type at any ratio. ]
In Formula 1-1, the dashed line between the C8 and C9 positions in Formula 1 is a single bond, R ₁ is an OH group, and R ₂ and R ₃ together are the carbon at the C9 position. When a methylidene group having a double bond is formed (that is, the form (iii) above), Formula 1-7 is a single bond between the C8 and C9 positions in Formula 1, This is the case where R ₁ is an OH group, and R ₂ and R ₃ form a three-membered ring together with the carbon atom at the C9 position to which they are bonded (that is, form (ii) above).

More specifically, the hydroxyaldehyde compound represented by Formula 1 may be represented by Formula 1-1-1 (4E) or Formula 1-2-1 (4E, 8E) below. These hydroxyaldehyde compounds are particularly useful as a flavor imparting agent because they give a scent close to that of fresh Lily of the valley and have a strong scent. That is, a preferred embodiment of the present invention provides a flavoring agent comprising at least one hydroxyaldehyde compound represented by the following formula 1-1-1 (4E) or formula 1-2-1 (4E, 8E). be.

As used herein, flavor means the senses that may be stimulated by an odor, including one or more senses, typically smell and taste. As used herein, the term "adding flavor" includes newly adding or enhancing the flavor, and for example, the flavor may be improved as a result of the addition. Furthermore, as a result of imparting flavor, sensations other than olfactory and gustatory sensations, such as cold sensation, warm sensation, texture (such as throat, hardness, viscosity, etc., also referred to as texture), stimulating sensation such as carbonic acid and hotness, etc. may be enhanced, suppressed, or improved.

(Hydroxyaldehyde compound represented by formula 1')
Yet another aspect of the present invention provides a hydroxyaldehyde compound represented by Formula 1' below.

The hydroxyaldehyde compound represented by Formula 1' is included in the hydroxyaldehyde compound represented by Formula 1 above, and is a novel compound not described in conventional literature. Hydroxyaldehyde compounds represented by Formula 1' include forms (i) and (ii) in Formula 1 above. The hydroxyaldehyde compound represented by the formula 1' itself exhibits a lily-of-the-valley, floral, green, woody, citrus-like, rose-like, ozone-like odor, and can be used as a flavor-imparting agent such as a perfume compound. is.

[In the formula, the dashed line represents a single bond or a double bond, and in the case of a double bond, it represents a cis-type or a trans-type, or a mixture of the cis-type and the trans-type in an arbitrary ratio. , R ₂ ' and R ₃ ' are each independently hydrogen, or a linear or branched alkyl group having 1 to 3 carbon atoms, or R ₂ ' and R ₃ ' are the carbon atom at the C9 position to which they are bonded together form a three-membered ring. (Excluding the case where the dashed line is a single bond and R ₂ ' and R ₃ ' are hydrogen.)]
Specific examples and preferred forms of linear or branched alkyl groups having 1 to 3 carbon atoms as R ₂ ' and R ₃ ' in the above formula 1' are the number of carbon atoms as R ₂ and R ₃ in the above formula 1 The same applies to 1 to 3 linear or branched alkyl groups.

The hydroxyaldehyde compound represented by Formula 1' is preferably a compound represented by any one of Formulas 1-3 to 1-7 below.

[In the formula, the wavy line represents a cis-type, a trans-type, or a mixture of the cis-type and the trans-type at any ratio. ]

(Production example of hydroxyaldehyde compound represented by Formula 1)
The means for obtaining the hydroxyaldehyde compound represented by Formula 1 is not particularly limited. The compound can be obtained, for example, by the following methods, but is not limited thereto.
(A) As a starting material, a double providing a compound with a bond and oxidizing the double bond in the second position to an aldehyde group via epoxidation;
(B) as a starting material, having a carbonyl group and double at the second position (between the C2 and C3 positions) and the sixth position (between the C6 and C7 positions) from the carbon chain end; providing a compound having a bond, the carbonyl group being an alkyl group such as methyl, ethyl, isopropyl and a hydroxy group (i.e. a tertiary alcohol) with a Grignard reagent, and the double bond at the second position; is oxidized to an aldehyde group via epoxidation;
(C) Any combination of the reactions described in (A)-(B).

Furthermore, after obtaining a hydroxyaldehyde compound having a double bond at the C4 position by the above (A) to (C), the non-droxyaldehyde compound is subjected to a hydrogenation reaction using an appropriate catalyst, A hydroxyaldehyde compound having a single bond at the C4 position (for example, a compound represented by Formula 1-4 above) can be obtained.

The reagents, solvents, reaction conditions, and the like used in each of the above reactions may be appropriately selected within the range in which the desired product can be obtained. For example, conversion of double bonds to aldehyde groups can be performed using meta-chloroperbenzoic acid, periodic acid, salts thereof, or the like. Alternatively, it can be carried out using N-bromosuccinimide, potassium carbonate, periodate dihydrate and the like. Also, the Grignard reagent used in (B) can be obtained, for example, by reacting a halogenated hydrocarbon with metallic magnesium.

(Flavor composition / method for improving flavor of perfume composition)
A perfume composition according to still another aspect of the present invention contains a flavor imparting agent comprising a hydroxyaldehyde compound represented by formula (1). Furthermore, still another aspect of the present invention also provides an application of the hydroxyaldehyde compound represented by Formula 1 as a perfume composition. Such a fragrance composition can be blended into various articles for the purpose of imparting flavor. Specific examples include fragrance compositions for cosmetics (also referred to as fragrance compositions) and fragrance compositions for food and drink (also referred to as flavor compositions). Examples of articles to be blended include, as described above, various consumer goods such as cosmetics, food and drink, and miscellaneous goods. The form of the perfume composition of the present invention is not particularly limited, and examples thereof include a water-soluble perfume composition, an oil-soluble perfume composition, an emulsified perfume composition, and a powdered perfume composition.

Further, still another aspect of the present invention provides a method for improving the flavor of a flavor composition, which comprises blending the above-mentioned flavor-imparting agent into the flavor composition. The method of blending the flavoring agent is not particularly limited, and can be blended using methods known to those skilled in the art.

The concentration of the flavor-imparting agent comprising the hydroxyaldehyde compound represented by formula 1 in the fragrance composition of the present invention can be arbitrarily determined according to the composition target of the fragrance composition.

As an example of the concentration, in the case of a perfume composition for cosmetics, for example, 0.0005% to 60%, preferably 0.001% to 50%, more preferably 0.0005% to 60%, based on the total weight of the perfume composition. 01% to 20%, more preferably 0.05% to 15%, and particularly preferably 0.1% to 10%. More specifically, any of 0.0005%, 0.001%, 0.01%, 0.05%, 0.1%, 1%, 10%, 20%, 30%, and 40% However, the upper limit is 60%, 50%, 40%, 30%, 20%, 15%, 10%, 1%, 0.1%, or 0.01%, and these lower and upper limits can be in any combination of, but not limited to: Although it depends on the formulation and fragrance tone of the fragrance composition, the concentration of the flavor-imparting agent composed of the hydroxyaldehyde compound represented by formula 1 in the fragrance composition for cosmetics is 0.0005% or more, and further 0.0005% or more. When it is .001% or more, a high blending effect is felt, and when it is 60%, further 50% or less, the scent derived from the hydroxyaldehyde compound represented by formula 1 does not become too strong, and the cosmetic product to be blended. It is possible to suppress unfavorable deterioration of the fragrance characteristics of the fragrance composition for use. However, it may be blended at a concentration below the lower limit or above the upper limit depending on the fragrance tone of the cosmetic fragrance composition to be blended.

In the case of a flavoring composition for food and drink, for example, it is in the range of 10 ppb to 10%, preferably 100 ppb to 1%, more preferably 1 ppm to 0.1%, based on the total mass of the flavoring composition. More specifically, the lower limit is 10 ppb, 100 ppb, 1 ppm, 10 ppm, 100 ppm, 0.1%, or 1%, and the upper limit is 10%, 1%, 0.1%, 100 ppm, 10 ppm, 1 ppm. , 100 ppb, and any combination of these lower and upper limits, but are not limited thereto. Although it depends on the formulation and fragrance tone of the fragrance composition, when the concentration of the flavor-imparting agent composed of the hydroxyaldehyde compound represented by Formula 1 in the fragrance composition for cosmetics is 10 ppb or more, a high blending effect is obtained. When it is 10% or less, the scent derived from the hydroxyaldehyde compound represented by Formula 1 does not become too strong, and it suppresses unfavorable deterioration in the flavor characteristics of the food and drink flavoring composition to be blended. can do. However, it may be added at a concentration below the lower limit or above the upper limit depending on the fragrance tone of the food and drink flavoring composition to be added.

The perfume composition of the present invention contains a flavor-imparting agent consisting of a hydroxyaldehyde compound represented by Formula 1, and the term "comprising" encompasses an aspect in which it is contained in an amount capable of exhibiting the desired aroma. Therefore, the perfume composition of the present invention may contain only the hydroxyaldehyde compound represented by Formula 1, but other perfume ingredients and other additives such as solvents may be added as long as the desired scent is not impaired. and so on. Such other perfume ingredients and other additives are such that the perfume composition (and the hydroxyaldehyde compound represented by Formula 1 contained in the composition) is in the additive at an appropriate concentration, and can be added for the purpose of uniform dispersion.

Examples of such compounds or ingredients include various flavor compounds or flavor compositions, oil-soluble pigments, vitamins, functional substances, fish extracts, livestock meat extracts, plant extracts, yeast extracts, animal and plant proteins. , animal and plant protein decomposition products, starch, dextrin, saccharides, amino acids, nucleic acids, organic acids, solvents and the like. For example, "Patent Office Gazette, Collection of Well-known and Commonly Used Techniques (Fragrance) Part II Food Flavors, Issued on January 14, 2000", "Survey on the Usage of Food Flavoring Compounds in Japan" (2000 Welfare Science Research Report, Japan Perfumery Industry Association, published March 2001) and "Synthetic Perfume Chemistry and Product Knowledge" (published December 20, 2016, enlarged new edition, edited by the Synthetic Perfume Editorial Committee, The Chemical Daily) natural essential oils, natural fragrances, synthetic fragrances, and the like.

Specific examples of synthetic fragrance compounds include hydrocarbon compounds such as monoterpenes such as α-pinene, β-pinene, γ-terpinene, myrcene, camphene and limonene; sesquiterpenes such as valencene, cedrene, caryophyllene and longifolene; 3,5-undecatriene and the like.

Alcohol compounds include saturated alkanols such as butanol, pentanol, 3-octanol and hexanol, unsaturated alcohols such as (Z)-3-hexene-1-ol, prenol and 2,6-nonadienol, linalool, geraniol, citronellol. , tetrahydromyrcenol, farnesol, nerolidol, cedrol, α-terpineol, terpinen-4-ol and borneol; and aromatic alcohols such as benzyl alcohol, phenylethyl alcohol and cinnamyl alcohol.

Examples of aldehyde compounds include saturated aldehydes such as acetaldehyde, hexanal, octanal, decanal and hydroxycitronellal, unsaturated aldehydes such as (E)-2-hexenal and 2,4-octadienal, citronellal, citral, myrtenal and peryl. terpene aldehydes such as aldehydes; aromatic aldehydes such as benzaldehyde, cinnamylaldehyde, vanillin, ethyl vanillin, heliotropine, p-tolylaldehyde;

Ketone compounds include saturated and unsaturated ketones such as 2-heptanone, 2-undecanone, 1-octen-3-one, acetoin, 6-methyl-5-hepten-2-one (methylheptenone), diacetyl, 2,3 - diketones and hydroxyketones such as pentanedione, maltol, ethyl maltol, cyclotene, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, terpene ketones such as carvone, menthone, nootkatone, α-ionone, β- Examples include ketones derived from terpene decomposition products such as ionone and β-damascenone, and aromatic ketones such as raspberry ketone.

Furan or ether compounds include furfuryl alcohol, furfural, rose oxide, linalool oxide, menthofuran, theaspirane, estragole, eugenol, 1,8-cineole, and the like.

Ester compounds include ethyl acetate, isoamyl acetate, octyl acetate, ethyl butyrate, ethyl isobutyrate, isoamyl butyrate, ethyl 2-methylbutyrate, ethyl isovalerate, 2-methylbutyl isobutyrate, ethyl hexanoate, allyl hexanoate, heptane Aliphatic esters such as ethyl acetate, ethyl caprylate, isoamyl isovalerate, ethyl nonanoate, terpene alcohol esters such as linalyl acetate, geranyl acetate, lavandulyl acetate, terpinyl acetate, neryl acetate, benzyl acetate, methyl salicylate, cinnamic acid aromatic esters such as methyl, cinnamyl propionate, ethyl benzoate, cinnamyl isovalerate, and ethyl 3-methyl-2-phenylglycidate;

The lactone compound includes saturated lactones such as γ-decenalactone, γ-dodecalactone, δ-decenalactone and δ-dodecalactone, and unsaturated lactones such as 7-decen-4-olide and 2-decen-5-olide. .

Acid compounds include saturated and unsaturated fatty acids such as acetic acid, butyric acid, isovaleric acid, caproic acid, octanoic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid.

Nitrogen-containing compounds include indole, skatole, pyridine, alkyl-substituted pyrazine, methyl anthranilate, trimethylpyrazine, and the like.

Sulfur-containing compounds include methanethiol, dimethylsulfide, dimethyldisulfide, allyl isothiocyanate, 3-methyl-2-butene-1-thiol, 3-methyl-2-butanethiol, 3-methyl-1-butanethiol, 2 -methyl-1-butanethiol, 3-mercaptohexanol, 4-mercapto-4-methyl-2-pentanone, 3-mercaptohexyl acetate, p-mentha-8-thiol-3-one and furfuryl mercaptan. .

Natural essential oils include sweet orange, bitter orange, petitgrain, lemon, bergamot, mandarin, neroli, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, hyacinth, lilac, geranium, jasmine, ylang ylang. , anise, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, labdanum.

Natural flavors include jasmine absolute, hyacinth absolute, rose absolute, tuberose absolute, vanilla absolute, galbanum resinoids, and the like.

Various animal and plant extracts include herb or spice extracts, coffee, green tea, black tea, or oolong tea extracts, milk or processed milk products, and various enzymatic decomposition products thereof such as lipase and/or protease.

Furthermore, in addition to the above, other additives described in the section (Examples of use) described later can also be used as appropriate. In addition, the above other perfume components and other additives may be used singly or in combination of two or more.

The perfume composition of the present invention can be prepared by blending the hydroxyaldehyde compound represented by Formula 1 with an appropriate solvent or dispersion medium by a known method.

As the form of the perfume composition of the present invention, a solution obtained by dissolving the hydroxyaldehyde compound represented by Formula 1 and other components in a water-soluble or oil-soluble solvent, an emulsified formulation, a powder formulation, and other solid formulations (such as solid fat). etc. are preferable.

Examples of water-soluble solvents include ethanol, methanol, acetone, tetrahydrofuran, acetonitrile, 2-propanol, methyl ethyl ketone, glycerin, propylene glycol and dipropylene glycol. Among these, ethanol or glycerin is particularly preferable from the viewpoint of use in foods and drinks. Oil-soluble solvents include vegetable oils, animal oils, refined oils (for example, processed oils such as medium-chain fatty acid triglycerides and short-chain fatty acid triglycerides such as triacetin and tripropionin), various essential oils, and triethyl citrate. etc. can be exemplified.

Moreover, in order to prepare an emulsified formulation, the hydroxyaldehyde compound represented by Formula 1 can be emulsified with a water-soluble solvent and an emulsifier. The method for emulsifying the hydroxyaldehyde compound represented by Formula 1 is not particularly limited, and various types of emulsifiers conventionally used in foods and beverages, such as fatty acid monoglycerides, fatty acid diglycerides, fatty acid triglycerides, and propylene glycol. Fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, lecithin, modified starch, sorbitan fatty acid ester, quillaya extract, gum arabic, tragacanth gum, guar gum, karaya gum, xanthan gum, pectin, alginic acid and its salts, carrageenan, gelatin, casein quillaya A highly stable emulsion can be obtained by emulsifying an emulsifier such as saponin or sodium caseinate using a homomixer, colloid mill, rotating disk homogenizer, high-pressure homogenizer, or the like. The amount of these emulsifiers to be used is not strictly limited, and can be varied over a wide range depending on the type of emulsifier used. A suitable range is from about 0.01 to about 100 parts by weight, preferably from about 0.1 to about 50 parts by weight. In order to stabilize the emulsification, such a water-soluble solvent liquid contains, in addition to water, polyhydric alcohols such as glycerin, propylene glycol, sorbitol, maltitol, sucrose, glucose, trehalose, sugar solution, and reduced starch syrup. One type or a mixture of two or more types can be blended.

Moreover, the emulsion thus obtained can be made into a powder formulation by drying if desired. At the time of pulverization, saccharides such as gum arabic, trehalose, dextrin, sugar, lactose, glucose, starch syrup, reduced starch syrup, etc., can be added as appropriate. The amount of these agents to be used can be appropriately selected according to the desired properties of the powder formulation.

The perfume composition of the present invention may further contain ingredients commonly used in perfume compositions, if desired. For example, solvents such as water and ethanol, and perfume retention such as ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexyl glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hacoline, medium chain fatty acid triglyceride, medium chain fatty acid diglyceride, etc. agent.

(Application example)
A flavor imparting agent comprising a hydroxyaldehyde compound represented by Formula 1 or a perfume composition containing the same may be blended into any article such as various consumer goods. That is, still another aspect of the present invention provides consumer goods containing the above flavor imparting agent or the above fragrance composition. The above-mentioned flavor-imparting agent and the above-mentioned perfume composition are preferably used in consumer goods such as cosmetics, foods and drinks, and particularly preferably in cosmetics.

Still another aspect of the present invention provides a method for imparting flavor to consumer goods, comprising blending the above flavor imparting agent or the above perfume composition into consumer goods. The method of blending the flavor-imparting agent and/or the fragrance composition is not particularly limited, and can be blended using methods known to those skilled in the art.

Examples of cosmetics as consumer goods include, but are not limited to, perfumes such as eau de cologne, eau de toilette, eau de parfum, and parfums; hair care products such as shampoos, rinses, and hair styling products (hair creams, pomades, etc.); Cosmetics such as foundation, lipstick, lip balm, lip gloss, lotion, milky lotion, cosmetic cream, cosmetic gel, beauty essence, face pack; deodorant such as antiperspirant spray, deodorant sheet, deodorant cream, and deodorant stick Products: Inorganic salt-based, refreshing, carbon dioxide-based, skin-care, enzyme-based, herbal medicine-based bath additives; Suntan products, sunscreen products, and other suntanning cosmetics; Cleaning agents such as soap, body wash, laundry soap, laundry detergent, disinfectant detergent, deodorant detergent, fabric softener, kitchen detergent, cleaning detergent, disinfectant, bleach, toothpaste, mouthwash; dry or wet Hygiene products or quasi-drugs such as tissue paper, toilet paper, masks, bandages, bandages, poultices; deodorant deodorants for rooms and cars;

Moreover, the form (dosage form) of cosmetics is not particularly limited. For example, it can be applied in various forms such as liquid, milky lotion, cream, paste, solid and multilayer. In addition to these, it can also be applied as a sheet agent, a spray agent, or a mousse agent.

Such cosmetics containing a flavor imparting agent comprising a hydroxyaldehyde compound represented by Formula 1 or a perfume composition containing the same can be produced using techniques known to those skilled in the art.

The cosmetic according to one aspect of the present invention contains a flavor-imparting agent comprising a hydroxyaldehyde compound represented by Formula 1 or the perfume composition of the present invention containing the same at an appropriate concentration as long as the desired scent is not impaired. , and may contain other additives so as to be uniformly dispersed.

Other additives are not particularly limited, and known ones can be used. Examples include hydrocarbons such as squalane, petrolatum, microcrystalline wax; jojoba oil, carnauba wax, octyldodecyl oleate, phenylethyl acetate. , phenylethyl butyrate, phenylethyl formate, phenylethyl phenylacetate, phenylethyl isobutyrate, benzyl benzoate, phenylethyl propionate, phenylpropyl acetate; phenylacetaldehyde, benzaldehyde, cinnamic aldehyde, hexyl cinnamic aldehyde, etc. aldehydes; triglycerides such as olive oil, beef tallow, and coconut oil; fatty acids such as stearic acid, oleic acid, and ritinoleic acid; Alcohols such as Santarex, terpineol, tetrahydrolinalol, benzyl alcohol, phenylethyl alcohol, phenylethyldimethylcarbinol, hydroxycitronellal; higher alcohols such as oleyl alcohol, stearyl alcohol, octyldodecanol; ethylene glycol, propylene glycol , glycerin, polyhydric alcohols such as 1,3-butanediol; indole, 5-methyl-3-heptanone oxime, limonenethiol, 1-p-mentene-8-thiol, butyl anthranilate, cis-3 anthranilate - Nitrogen- and/or sulfur-containing compounds such as hexenyl, phenylethyl anthranilate, cinnamyl anthranilate, dimethylsulfide, 8-mercaptomenthone; anionic surfactants such as sulfosuccinic acid esters and sodium polyoxyethylene alkylsulfate; amphoteric surfactants such as betaine salts; cationic surfactants such as dialkylammonium salts; ionic surfactants; thickeners/gelling agents; antioxidants; ultraviolet absorbers; coloring agents; preservatives;

In addition to these, other perfume components listed in the above section (Fragrance Composition/Method for Improving Flavor of Fragrance Composition) can also be used as other additives in cosmetics. The other additives may be used singly or in combination of two or more.

The fragrance tone of the cosmetics is not particularly limited, and may be any fragrance tone that can be imparted by a flavor imparting agent comprising a hydroxyaldehyde compound represented by Formula 1 or a fragrance composition containing the same. , citrus tone, floral tone, fougere tone, fruity tone, green tone, woody tone, moss tone, tropical flower tone, lily of the valley tone, oriental tone, chypre tone and the like. More specific examples include, but are not limited to, lemon, orange, grapefruit, lime, yuzu, kabosu, rose, geranium, jasmine, lily of the valley, hyacinth, lilac, plumeria, pineapple, mango, and peach. For example, it can be preferably used in cosmetics exhibiting floral, lily of the valley, citrus, fougere, or woody fragrances, and particularly preferably in cosmetics exhibiting floral or lily of the valley fragrances.

In the present invention, the concentration in the cosmetics can be arbitrarily determined according to the fragrance of these products, the degree of desired effects, and the like.

For example, the concentration of the flavor imparting agent comprising the hydroxyaldehyde compound represented by Formula 1 is, for example, 10 ppb to 10%, preferably 1 ppm to 5%, more preferably 100 ppm (0.01%), based on the total weight of the cosmetic product. ) to 3%, particularly preferably 0.05% to 2%. More specifically, the lower limit is 10 ppb, 100 ppb, 1 ppm, 5 ppm, 10 ppm, 100 ppm, 0.05%, 0.1%, 1%, 5%, and the upper limit is 10%, 5%, 4 %, 3%, 2%, 1%, 0.1%, 100 ppm, 10 ppm, 5 ppm, 1 ppm, 100 ppb, including within any combination of these lower and upper limits, including but not limited to: Not limited. Examples of preferred concentrations include 5 ppm to 4%, or 5 ppm to 2% as the concentration of the flavor imparting agent comprising the hydroxyaldehyde compound represented by Formula 1, relative to the total weight of the cosmetic. However, it is not limited to these. Although it depends on the type and fragrance of the cosmetic product, when the concentration of the flavor imparting agent composed of the hydroxyaldehyde compound represented by Formula 1 in the cosmetic product is 10 ppb or more, a high blending effect is felt, and 10% If it is below, it is possible to suppress excessive imparting of the fragrance derived from the flavor imparting agent to the cosmetic product to be blended. However, depending on the fragrance of cosmetics, the concentration may be lower than the lower limit or higher than the upper limit.

By blending a flavor-imparting agent comprising a hydroxyaldehyde compound represented by Formula 1 or a fragrance composition containing the same into a cosmetic product as described above, it is possible, for example, to improve the lingering, long-lasting and/or Improving diffusibility, imparting lily of the valley, floral, and/or citrus fragrances, imparting freshness, freshness, greenness, naturalness, transparency, volume, etc., masking offensive odors of cosmetics materials themselves, etc. It is possible to obtain a perfuming effect including at least one of the effects of.

Examples of food and drink as consumer goods include, but are not limited to, various citrus flavors such as lemon, orange, grapefruit, lime, mandarin, mandarin orange, kabosu, sudachi, hassaku, iyokan, yuzu, shikuwasa, and kumquat. various fruit flavors such as strawberry, blueberry, raspberry, apple, cherry, plum, apricot, peach, pineapple, banana, melon, mango, papaya, kiwi, pear, grape, muscat grape, kyoho; milk such as milk, yogurt and butter Flavor: Vanilla flavor; various tea flavors such as green tea, black tea, oolong tea, herbal tea; coffee flavor; cola flavor; cacao flavor; cocoa flavor; various mint flavors such as spearmint and peppermint; , cloves, pepper, coriander, Japanese pepper, perilla, ginger, star anise, thyme, capsicum, nutmeg, basil, marjoram, rosemary, laurel, garlic, wasabi; Various nut flavors; alcoholic beverage flavors such as wine, brandy, whiskey, rum, gin, liqueur, sake, shochu, and beer; vegetable flavors such as onions, celery, carrots, tomatoes, and cucumbers; chicken, duck, pork, beef, Various livestock meat flavors such as mutton and horse meat; red fish such as tuna; white fish such as mackerel, sea bream, salmon and horse mackerel; freshwater fish such as sweetfish, trout and carp; Various crustaceans such as seaweed, various seaweeds such as wakame, kelp, and other seafood and seaweed flavors; various grain flavors such as rice, barley, wheat, and malt; Food and drink having one or more flavors such as various fats and oils such as oils and fats and various fish oils. In particular, it can be suitably used for citrus-flavored, black tea, and muscat-flavored foods and drinks. In addition, the flavor of the food and drink may be a food and drink that makes you feel only one of the above flavors, a food and drink that makes you feel two or more flavors, and the plurality of flavors may be the same or different. Examples of the former include fruit flavors that make you feel multiple fruit flavors such as banana, peach and apple flavors (so-called mixed fruit flavors), and examples of the latter include citrus flavors such as lemon and milk flavors. (citrus-flavored lactic acid bacteria drink, etc.), mint-flavored, citrus-flavored, and cola-flavored (mint- or lemon-flavored cola drinks, etc.).

More specific examples of food and drink include senbei, arare rice crackers, rice cakes, rice cakes, steamed buns, uiro, red bean paste, yokan, mizu yokan, kingyoku, jelly, castella, hard candy, biscuits, crackers, potato chips, cookies, Confectionery such as pie, pudding, butter cream, custard cream, cream puff, waffle, sponge cake, donut, chocolate, chewing gum, caramel, candy, paste such as peanut paste; bread, udon, ramen, Chinese noodles, sushi, Gomoku rice, fried rice, pilaf, gyoza skin, shumai skin, okonomiyaki, takoyaki, and other breads, noodles, rice; Pickles such as those pickle bases; Fish such as mackerel, sardines, saury, salmon, tuna, bonito, whale, flatfish, sand eel, sweetfish, squid such as flying squid, spear squid, crest squid, firefly squid, common octopus, Octopus such as octopus, prawns such as tiger prawns, botan prawns, spiny lobsters and black tigers, crabs such as king crabs, snow crabs, blue crabs and horse crabs, shellfish such as clams, clams, scallops, oysters and mussels; Processed seafood foods such as canned foods, boiled fish, tsukudani, surimi, fish paste products (chikuwa, kamaboko, fried kamaboko, crab leg kamaboko, etc.), fried foods, tempura; chicken, pork, beef, mutton, horse meat, etc. Meat: Curry, stew, beef stew, hayashi rice sauce, meat sauce, mapo tofu, hamburg steak, dumplings, kamameshi mix, soups (corn soup, tomato soup, consommé soup, etc.), meatballs, braised cubes, canned meat, etc. Processed foods and drinks using livestock meat; Table salt, Seasoning salt, Soy sauce, Powdered soy sauce, Miso, Powdered miso, Moromi, Hishio, Furikake, Ochazuke mix, Margarine, Mayonnaise, Dressing, Vinegar, Sanbaizu, Powdered sushi vinegar, Chinese food Nomoto, tempura sauce, noodle soup (kelp or bonito stock, etc.), sauce (chuno sauce, tomato sauce, etc.), ketchup, yakiniku sauce, curry roux, stew mix, soup stock, dashi stock (kelp or bonito stock) Dashi, etc.), compound seasonings, hon mirin, new mirin (boiled mirin), seasonings such as mixed flour such as fried chicken powder and takoyaki powder, and animal or vegetable seasonings added with these seasonings Dairy products such as cheese, yogurt, and butter; Various yeasts such as brewer's yeast and baker's yeast; various microbial fermented products such as lactic acid bacteria; Ingredients and side dishes: fruit juice drinks and juice-containing soft drinks such as apples, grapes, and citrus fruits (grapefruit, orange, lemon, etc.), fruit pulp drinks and fruit drinks containing fruit; tomatoes, green peppers, celery, gourd, bitter gourd , vegetables such as carrots, potatoes, asparagus, bracken, and fern, vegetable-based beverages containing these vegetables, vegetable-containing foods and drinks such as vegetable soup; coffee, cocoa, green tea, black tea, oolong tea, soft drinks, cola drinks, Carbonated beverages (such as cider with various flavors such as citrus), lactic acid beverages, and other beverages; beverages containing herbal medicines and herbs; Functional drinks such as beer-taste drinks, sports drinks, honey drinks, vitamin supplement drinks, mineral supplement drinks, nutrition drinks, nutrition drinks, lactic acid drinks; Non-alcoholic beverages such as beverages; wine, shochu, awamori, refined sake, beer, chuhai, cocktail drinks, low-malt beer, fruit wine, condiments, and other brewed liquor (sparkling) such as the so-called "third beer" or liqueurs (effervescent), or alcoholic beverages containing these;

In the present invention, the concentration of the flavor-imparting agent comprising the hydroxyaldehyde compound represented by formula 1 in the food or drink can be arbitrarily determined according to the flavor of the food or drink, the degree of desired effect, and the like.

As an example of the concentration, the concentration of the flavor imparting agent comprising the hydroxyaldehyde compound represented by Formula 1 is, for example, 10 ppt to 10 ppm, more preferably 100 ppt to 10 ppm, relative to the total weight of the food and drink. More specifically, the lower limit is any one of 1 ppt, 10 ppt, 100 ppt, 1 ppb, 10 ppb, 100 ppb, and 1 ppm, and the upper limit is any of 10 ppm, 1 ppm, 100 ppb, 10 ppb, 1 ppb, and 100 ppt. Ranges within any combination of values include, but are not limited to. Examples of preferred concentrations include, for example, 100 ppt to 1 ppm or 1 ppb to 100 ppb as the concentration of the flavor-imparting agent comprising the hydroxyaldehyde compound represented by Formula 1 with respect to the total mass of the food and drink. However, it is not limited to these. Although it depends on the type and flavor of the food and drink, when the concentration of the flavor-imparting agent composed of the hydroxyaldehyde compound represented by Formula 1 in the food and drink is 10 ppt or more, a high blending effect is felt, and 10 ppm or less. As a result, it is possible to prevent the aroma of the flavor-imparting agent itself composed of the hydroxyaldehyde compound represented by Formula 1 from protruding and undesirably altering the flavor of the food or drink to be blended. However, depending on the flavor of food and drink, the concentration may be lower than the lower limit or higher than the upper limit.

As described above, by blending the flavor-imparting agent comprising the hydroxyaldehyde compound represented by Formula 1 or the flavoring composition containing the same into the food or drink, for example, the flavor of the food or drink is enhanced, the bitterness such as the feeling of pericarp is imparted, It is possible to obtain an aroma imparting effect including at least one of giving an oily feeling like pericarp wax, giving a feeling of volume, giving a feeling of citrus fruit, and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to these.

[Example 1] Synthesis of hydroxyaldehyde compound represented by formula 1 As an example of the hydroxyaldehyde compound represented by formula 1, the hydroxyaldehyde compounds represented by formulas 1-1 to 1-7 are described below (1) to Synthesized according to the procedure of (7). Among them, the hydroxyaldehyde compounds represented by formulas 1-3 to 1-7 synthesized in (3) to (7) are also hydroxyaldehyde compounds represented by formula 1'.

(1) Synthesis of compound of formula 1-1 (8-hydroxy-4,8-dimethyl-4,9-decadienal)

(i) Synthesis of Compound 1b 2.22 g (9.98 mmol) of compound 1a (mixture of E and Z isomers) was dissolved in dichloromethane (70 mL), cooled to 0° C., and the cooled solution was added with metachloroperbenzoic acid ( mCPBA) (70%) 2.96 g (12.0 mmol) was gradually added over 2.5 hours, and the mixture was further stirred at 0°C for 1 hour. Then, a saturated aqueous sodium sulfite solution was added to decompose excess oxidant, ether (150 mL) was added, and the organic layer was separated. The organic layer was washed successively with saturated aqueous sodium sulfite solution, saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to obtain 2.51 g of a colorless oily substance. This was purified with a silica gel column (33 mm id x 36 cm L, n-hexane:ethyl acetate = 5:1), first recovering 0.41 g (1.8 mmol) of colorless oily starting compound 1a, then 1.43 g (6.00 mmol) of colorless oily compound 1b was obtained.

(ii) Synthesis of compound 1c 0.70 g of compound 1b (2.94 mmol) was suspended in a mixture of tetrahydrofuran (THF) and water (THF:water=1:1) (15.5 mL), followed by 3% filtration. 1.7 mL (ca. 0.51 mmol) of chloric acid aqueous solution was added, and the mixture was stirred at room temperature for 3 hours. After adding saturated saline and ether to the obtained reaction solution, the organic layer was separated. The organic layer was washed successively with a saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to obtain 0.73 g of a colorless oily substance. This was purified with a silica gel column (33 mm id x 10 cm L, toluene:acetone = 5:1) to obtain 0.41 g (1.6 mmol) of colorless oily compound 1c.

(iii) Synthesis of compound of formula 1-1 0.36 g of compound 1c (1.4 mmol) was dissolved in a mixture of tetrahydrofuran (THF) and water (THF: water = 1:1) (15 mL) to obtain 0.37 g (1.7 mmol) of sodium periodate was gradually added to the resulting solution over 2 hours, and the mixture was further stirred at room temperature for 4 hours. Sodium chloride, water and ether were added to the obtained reaction solution, and the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to obtain 0.27 g of a colorless oily substance. This was purified with a silica gel column (33 mm id x 5.5 cm L, n-hexane:ethyl acetate = 10:1) to obtain 0.25 g (1.3 mmol) of the compound of formula 1-1 as a colorless oil. rice field. This was a mixture of E and Z isomers (4E:4Z = about 1:1). Isomer ratios were calculated by separation by gas chromatography (GC). GC conditions are described below;
GC device: GC-2025 (manufactured by Shimadzu Corporation)
Column: TC-1, 0.53 mm I.D. D. × 30 m L, df 1.50 μm (manufactured by GL Sciences Inc.)
Detector: Flame Ionization Detector (FID)
Injection temperature: 300°C
Detector temperature: 300°C
Temperature rise conditions: 100°C → 300°C (20°C rise per minute)
Linear velocity: 60.0 cm/S
The retention time of GC was measured, and the ratio of the respective peak areas was obtained to obtain the isomer ratio. In the following examples as well, the isomer ratio of the isomer mixture was measured under the above GC conditions.

The physical properties of the obtained compound of formula 1-1 were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) ppm: 1.25 (s, 3H, C8-CH ₃ ), 1.5-1.6 (m, 2H, 7-H ₂ ), 1.58 (br. s, E-C4-CH ₃ )/1.65 (br. s, Z-C4-CH ₃ )(3H), 1.93-2.08 (m, 2H, 6-H ₂ ), 2.28 (t, J=7.2 Hz, E-3-H ₂ )/2.32 (t, J=7.2 Hz, Z-3-H ₂ ) (2H), 2.45 to 2.50 (m, 2H, 2-H ₂ ), 5.03 (br.d, J=10.4 Hz, 1H, 10-cis-H), 5.13 (br.t, J=7.6 Hz, 1H, 5-H ), 5.18 (br.d, J=17.2 Hz, 1H, 10-trans-H), 5.88 (dd, J=10.4, 17.2 Hz, 1H, 9-H), 9. 72 (t, J = 1.8 Hz) / 9.74 (t, J = 1.8 Hz) (1H, E/Z-CHO)
¹³ C-NMR (100 MHz, CDCl ₃ ) ppm: 16.06 (E-C4-CH ₃ ), 22.47/22.62 (E/Z-C6), 23.03 (Z-C4-CH ₃ ) , 24.21 (Z-C3), 27.86/27.91 (E/Z-C8-CH ₃ ), 31.74 (E-C3), 41.86/42.04/42.08/42 .15 (E/Z-C2, E/Z-C7), 73.25/73.31 (E/Z-C8), 111.74/111.82 (E/Z-C10), 125.33 ( E-C5), 126.46 (Z-C5), 133.18 (Z-C4), 133.32 (E-C4), 144.86/144.89 (E/Z-C9), 202.30 (Z-C1), 202.61 (E-C1)
IR (neat) cm ⁻¹ : 3700 to 3110 (br), 2970, 2930, 2872, 1720, 1452, 1412, 1374, 1110, 996, 920
The scent of the obtained compound of formula 1-1 (mixture of isomers) was a lily of the valley-like, rose-like, green, floral, and fruity scent with a light and soft impression.

(2) Synthesis of compound of formula 1-2 (10-hydroxy-4,8-dimethyl-4,8-decadienal)

(i) Synthesis of compound 2b 2.64 g (9.98 mmol) of compound 2a (mixture of E and Z isomers) was dissolved in dichloromethane (70 mL) and cooled to 0°C. 2.96 g (12.0 mmol) of mCPBA) (70%) was gradually added over 2 hours, and the mixture was further stirred at 0°C for 1.5 hours. Then, a saturated aqueous sodium sulfite solution was added to the solution to decompose excess oxidant, ether (180 mL) was added, and the organic layer was separated. The organic layer was washed successively with saturated aqueous sodium sulfite solution, saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to obtain 2.92 g of a colorless oily substance. This was purified with a silica gel column (33 mm id x 35 cm L, n-hexane:ethyl acetate = 15:1 to 1:1), and the raw material acetic 0.20 g (0.76 mmol) of farnesyl (compound 2a) was recovered, and a colorless oily compound 2b (10,11-epoxy) and a positional isomer (6 , 7-epoxy) (about 3:1) 1.58 g (5.63 mmol) was eluted.

(ii) Synthesis of compound 2c 1.57 g (5.60 mmol) of a mixture (about 3:1) of compound 2b (10,11-epoxy) and positional isomer (6,7-epoxy) of compound 2b was Suspend in a mixture of tetrahydrofuran (THF) and water (THF: water = 1:1) (29.5 mL), add 3.2 mL (ca. 0.96 mmol) of 3% perchloric acid aqueous solution, and stir at room temperature for 3 hours. Stirred for .5 hours. After stirring, the liquid was extracted with ether. The organic layer obtained by the ether extraction was washed successively with saturated aqueous sodium bicarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to give a colorless oil. 1.65 g of material were obtained. This was purified with a silica gel column (33 mm id x 22 cm L, toluene: acetone = 10: 1 to 9: 1), and 0.17 g ( 0.61 mmol) was recovered, followed by elution of 0.33 g (1.1 mmol) of the 6,7-dihydroxy compound as a colorless oily substance, followed by elution of compound 2c (10, 10, 11-dihydroxy compound) 1.04 g (3.49 mmol) was eluted.

(iii) Synthesis of compound 2d 1.00 g of compound 2c (3.35 mmol) was dissolved in a mixed solution of tetrahydrofuran (THF) and water (THF: water=1:1) (30 mL), and 0.5 mL of sodium periodate was added. 86 g (4.0 mmol) was added little by little over 2 hours, and the mixture was further stirred at room temperature for 4 hours. Then, water and ether were added to the reaction solution to dissolve the precipitate, and then the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to obtain 0.81 g of a colorless oily substance. This was purified with a silica gel column (33 mm id x 10 cm L, n-hexane-ethyl acetate = 20:1 to 5:1), and n-hexane-ethyl acetate = 20:1 gave compound 2d as a colorless oil. 0.61 g (2.6 mmol) eluted.

(iv) Synthesis of Compound of Formula 1-2 0.58 g of compound 2d (2.4 mmol) was dissolved in methanol (50 mL), 1.01 g (7.3 mmol) of potassium carbonate was added, and the mixture was stirred at room temperature for 1 hour. Then, water (30 mL) and sodium chloride were added to the reaction mixture, methanol was removed by an evaporator, and the mixture was extracted twice with ethyl acetate. After the organic layer obtained by extraction was dried over anhydrous magnesium sulfate, the solvent was removed by an evaporator to obtain 0.49 g of a colorless syrup-like substance. This was purified with a silica gel column (33 mm id x 8.5 cm L, toluene:acetone = 15:1 to 5:1) to obtain a colorless syrup-like compound of formula 1-2 with toluene:acetone = 10:1. 0.45 g (2.3 mmol) of was eluted. This was a mixture of four isomers (4E, 8E:4E, 8Z:4Z, 8E:4Z, 8Z = about 10:5:5:2).

The physical properties of the obtained compound of formula 1-2 were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) ppm: 1.56-1.71 (6H, C4-CH ₃ , C8-CH ₃ ), 2.0-2.1 (m, 4H, 6-H ₂ , 7-H ₂ ), 2.30 (m, 2H, 3-H ₂ ), 2.48 (m, 2H, 2-H ₂ ), 4.07 (br.d, J=7.2 Hz)/4 .12 (br.d, J = 7.2 Hz) (2H, 10-H ₂ ), 5.07-5.16 (m, 1H, 5-H), 5.30-5.45 (m, 1H , 9-H), 9.69-9.75 (m, 1H, CHO)
¹³ C-NMR (100 MHz, CDCl ₃ ) ppm: 16.06/16.10 (C4-CH ₃ ), 23.00/23.28 (C8-CH ₃ ), 25.90/26.12/26. 31 (C6), 24.30/31.69/31.88 (C3), 39.20/39.48 (C7), 42.11/44.29 (C2), 59.01/59.34 ( C10), 123.85/124.64/124.98/126.04 (C5, C9), 133.24 (C4), 138.97 (C8), 200.26/203.03 (C1)
IR (neat) cm ⁻¹ : 3700 to 3080 (br), 2960, 2930, 2858, 1720, 1665, 1445, 1380, 1112, 1010
The fragrance of the obtained compound of formula 1-2 (mixture of isomers) was a fruity, sweet and fresh fragrance, and a floral scent of fresh lily of the valley.

(3) Synthesis of compound of formula 1-3 (8-hydroxy-4,8-dimethyl-4-decenal)

(i) Synthesis of Compound 3b 3.25 g (134 mmol) of magnesium, 60 mL of ether, and a small amount of iodine and dibromoethane were added to a 500 mL four-necked flask, and 20.87 g (133.8 mmol) of ethyl iodide was added under a nitrogen atmosphere. A small amount of ether solution (90 mL) was added and heated with a dryer. After confirming the progress of the reaction, the rest of the ether solution was added dropwise over 70 minutes at such a speed that the ether was gently refluxed to prepare a Grignard reagent. After cooling for 30 minutes at room temperature with stirring, an ether solution (15-20 mL) of 20.00 g (102.9 mmol) of compound 3a (mixture of E and Z isomers) was added dropwise to the Grignard reagent over 45 minutes. and further stirred at room temperature for 30 minutes. Subsequently, the resulting reaction solution was poured into a cooled 1 to 2 mol/L hydrochloric acid aqueous solution to dissolve the precipitate, followed by extraction with ether. The ether layer was washed successively with water, saturated aqueous sodium hydrogencarbonate solution, 5% aqueous sodium thiosulfate solution and saturated brine, dried over anhydrous magnesium sulfate, and distilled to remove the solvent using an evaporator to obtain 22.59 g of an off-white oil. rice field. This was purified with a silica gel column (46 mm id x 40 cm L, n-hexane:ethyl acetate = 15:1) to obtain 20.05 g (89.36 mmol) of colorless oily compound 3b.

(ii) Synthesis of compound 3c 19.99 g of compound 3b (E/Z≈3:2) (89.09 mmol) was suspended in a mixed solvent of 1,2-dimethoxyethane (90 mL) and water (60 mL), followed by Under cooling, a solution of 16.97 g (95.35 mmol) of N-bromosuccinimide (NBS) in 1,2-dimethoxyethane (240 mL) was added dropwise over 40 minutes, followed by stirring at 0° C. for 4 hours. Subsequently, saturated saline (500 mL) was added to the obtained reaction solution, and ether (1 L) extraction was performed. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to obtain 30.42 g of pale yellow oily compound 3c, which was used in the next reaction without further purification. .

(iii) Synthesis of compound 3d 30.42 g of compound 3c was dissolved in methanol (400 mL), 39.03 g (282.4 mmol) of potassium carbonate was added to the resulting solution, and the mixture was stirred overnight (13 hours) at room temperature. Subsequently, the solid matter was removed by celite filtration, washed well with methanol, and the methanol and filtrate were combined and concentrated to about 1/2 using an evaporator. After adding saturated brine (300 mL), ether (700 mL) Extraction was performed. The organic layer was filtered once to remove colorless gelatinous matter, washed successively with water, saturated sodium bicarbonate solution and saturated brine, dried over potassium carbonate, and the solvent was distilled off using an evaporator to give a colorless oily substance. 23.97 g was obtained. This was purified with a silica gel column (46 mm id x 42.5 cm L, n-hexane:ethyl acetate = 15:1 to 4:1) and purified with n-hexane:ethyl acetate = 5:1 to 4:1. 3.77 g (15.7 mmol) of compound 3d (E/Z≈2:1) was eluted as a colorless oil.

(iv) Synthesis of compound of formula 1-3 3.77 g of compound 3d (E/Z ≈ 2:1) (15.7 mmol) was dissolved in ether (70 mL), and the solution was cooled with ice and treated with diperiodate. A solution of 4.02 g (17.6 mmol) of hydrate (HIO ₄ .2H ₂ O) in tetrahydrofuran (THF) (36 mL) was added dropwise over 40 minutes and stirred at 0° C. for 1 hour. Subsequently, water (75 mL) was added to the reaction solution, the organic layer was separated, and the aqueous layer was extracted with ether (350 mL). The separated organic layer and the organic layer obtained by ether extraction were combined, washed successively with water, saturated aqueous sodium bicarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and evaporated to remove the solvent using an evaporator to give a yellow oily substance. 3.50 g was obtained. This was purified with a silica gel column (46 mm i.d. x 18 cm L, n-hexane:ethyl acetate = 9:1 to 4:1) to obtain a slightly yellow oily substance with n-hexane:ethyl acetate = 4:1. 13 g was eluted. This was purified again with a silica gel column (33 mm id x 31 cm L, n-hexane:ethyl acetate = 5:1 to 3:1) to obtain 1.97 g (9 .93 mmol). This was a mixture of E and Z isomers (4E:4Z = about 3:2).

The physical properties of the obtained compound of formula 1-3 were as follows.
¹ H-NMR (400 MHz, C ₆ D ₆ ) ppm: 0.81 (t, J = 7.6 Hz, E-10-H ₃ ) / 0.82 (t, J = 7.6 Hz, Z-10- H ₃ )(3H), 0.99(s, E—C8—CH ₃ )/0.99(s, Z—C8—CH ₃ )(3H), 1.30-1.37 (m, 4H, 7-H ₂ , 9-H ₂ ), 1.42 (br.s, E-C4-CH ₃ )/1.49 (d, J=1.2 Hz Z-C4-CH ₃ ) (3H), 1. 93 ~ 2.05 (m, 4H, 2- _H2 , 6- _H2 ), 2.04 (t, J = 7.4Hz, E-3- _H2 ) / 2.15 (t, J = 7 .4 Hz, Z-3-H ₂ ) (2H), 5.07 (qt, J = 1.2, 7.2 Hz, E-5-H) / 5.13 (br.t, J = 7.2 Hz , Z-5-H) (1H), 9.31 (t, J = 1.6 Hz, Z-CHO) / 9.33 (t, J = 1.6 Hz, E-CHO) (1H)
¹³ C-NMR (100 MHz, C ₆ D ₆ ) ppm: 8.37 (C-10), 15.89 (E-C4-CH ₃ ), 22.64 (Z-C6), 22.79 (E- C6), 23.08 (Z-C4-CH ₃ ), 24.30 (Z-C3), 26.32 (Z-C8-CH ₃ ), 26.36 (E-C8-CH ₃ ), 31. 94 (E-C3), 34.69 (E-C9), 34.73 (Z-C9), 41.44 (E-C7), 41.74 (Z-C7), 42.08 (E-C2 ), 42.14 (Z-C2), 71.97 (Z-C8), 71.99 (E-C8), 125.91 (E-C5), 127.12 (Z-C5), 133.02 (Z-C4), 133.14 (E-C4), 200.43/200.48/200.61/200.64 (C1)
IR (neat) cm ⁻¹ : 3700 to 3100 (br), 2965, 2935, 2880, 1722, 1455, 1372, 1135, 1058
The resulting compound of formula 1-3 (mixture of isomers) had a fruity, sweet, green, floral, lily-of-the-valley-like, and powder-like scent, and had an elegant, soft, refreshing and fresh scent.

(4) Synthesis of compound of formula 1-4 (8-hydroxy-4,8-dimethyldecanal)

0.74 g (3.7 mmol) of the compound of formula 1-3 (8-hydroxy-4,8-dimethyl-4-decenal) was dissolved in ethyl acetate (30 mL) and 0.17 g of platinum (IV) oxide (PtO ₂ ). was added, and the mixture was stirred at room temperature for 20 hours under a hydrogen atmosphere. After completion of the reaction, the catalyst was filtered off and washed thoroughly with ethyl acetate. The filtrates were combined and the solvent was distilled off using an evaporator to obtain 0.72 g of an off-white oily substance. This was purified with a silica gel column (33 mm id x 10 cm L, n-hexane:ethyl acetate = 5:1) to obtain 452 mg (2.26 mmol) of compound 1-4 as a colorless oil.

The physical properties of the obtained compound of formula 1-4 were as follows.
¹ H-NMR (400 MHz, C ₆ D ₆ ) ppm: 0.69 (d, J = 6.4 Hz, 3H, C4-CH ₃ ), 0.83 (t, J = 7.4 Hz, 3H, 10- H ₃ ), 0.9-1.0 (m)/1.05-1.2 (m) (2H, 5-H ₂ ), 1.00 (s, 3H, C8-CH ₃ ), 1. 1 to 1.2 (m, 1H, 4-H), 1.1 to 1.2 (m) / 1.35 to 1.45 (m) (2H, 3-H ₂ ), 1.15 to 1 .4 (m, 4H, 6-H ₂ , 7-H ₂ ), 1.34 (q, J=7.4 Hz, 2H, 9-H ₂ ), 1.85 (m, 2H, 2-H ₂ ), 9.34 (t, J = 1.8Hz, 1H, CHO)
¹³ C-NMR (100 MHz, C ₆ D ₆ ) ppm: 8.39 (C10), 19.32 (C4-CH ₃ ), 21.38 (C6), 26.43/26.49 (C8-CH ₃ ), 28.96 (C3), 32.45 (C4), 34.64/34.72 (C9), 37.56 (C5), 41.58 (C2), 41.88 (C7), 72. 11 (C8), 200.94 (C1)
IR (neat) cm ⁻¹ : 3700 to 3130 (br), 2965, 2938, 2878, 1722, 1460, 1380, 1270, 1185, 1150
The fragrance of the obtained compound of Formula 1-4 was light and sweet, including floral, resin-like sweet fragrance, light fruity, rose-like, powder-like, and lily-of-the-valley-like scents.

(5) Synthesis of compound of formula 1-5 (8-hydroxy-4,8-dimethyl-4-nonenal)

(i) Synthesis of Compound 5b 1.63 g (67.1 mmol) of magnesium was added to a 300 mL four-necked flask, and 30 mL of ether, a small amount of iodine and dibromoethane were added. Under a nitrogen atmosphere, add a small amount of an ether solution (45 mL) of 9.50 g (66.9 mmol) of methyl iodide and heat with a dryer to confirm the progress of the reaction. was added dropwise over 45 minutes to prepare a Grignard reagent. The mixture was cooled to room temperature while stirring for 30 minutes, then an ether solution (10 mL) of 10.0 g of compound 5a (51.5 mmol) was added dropwise to the Grignard reagent over 20 minutes, and the mixture was further stirred at room temperature for 1 hour. Subsequently, the obtained reaction liquid was poured into a cooled 1 mol/L hydrochloric acid aqueous solution (80 mL) to dissolve the precipitate, and then the obtained liquid was extracted with ether. The ether layer was washed successively with water, saturated aqueous sodium hydrogencarbonate solution, 5% aqueous sodium thiosulfate solution and saturated brine, dried over anhydrous magnesium sulfate, and distilled to remove the solvent using an evaporator to give 10.64 g of a slightly yellow oily substance. Obtained. This was purified with a silica gel column (48 mm id x 36 cm L, n-hexane:ethyl acetate = 15:1 to 10:1) to obtain 10.28 g (48.9 mmol) of colorless oily compound 5b.

(ii) Synthesis of compound 5c 8.41 g of compound 5b (E/Z≈3:2) (40.0 mmol) was dissolved in dichloromethane (160 mL), cooled to 0° C. and treated with meta-chloroperbenzoic acid (mCPBA) (70 %) 11.83 g (48.0 mmol) was added little by little over 3 hours, and the mixture was further stirred at 0° C. for 1 hour. A saturated aqueous sodium sulfite solution (30 mL) was added to the stirred reaction solution to decompose excess oxidizing agent, ether (200 mL) was added, and the organic layer was separated. The organic layer was washed successively with saturated aqueous sodium sulfite solution, saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to obtain 13.23 g of a colorless oily substance. This was purified with a silica gel column (48 mm id x 35 cm L, n-hexane:ethyl acetate = 5:1 to 3:1) to obtain 4.47 g (19.7 mmol) of compound 5c as a colorless oil.

(iii) Synthesis of Compound of Formula 1-5 2.05 g of compound 5c (9.06 mmol) was dissolved in ether (35 mL) and treated with periodate dihydrate (HIO _{4.2H 2} O) 2 under ice cooling. A solution of .31 g (10.1 mmol) of tetrahydrofuran (THF) (20 mL) was added dropwise over 40 minutes (colorless precipitate was formed with the addition) and stirred at 0° C. for 1 hour. Water was added to the stirred reaction mixture, the organic layer was separated, and the aqueous layer was extracted with ether (100-200 mL). The separated organic layer and the organic layer obtained by ether extraction were combined, washed successively with water, saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and evaporated to remove the solvent using an evaporator. 1.64 g of oil was obtained. This was purified with a silica gel column (33 mm id x 24 cm L, n-hexane:ethyl acetate = 5:1 to 4:1) to obtain 0.71 g (3.9 mmol) of the compound of formula 1-5 as a colorless oil. )Obtained. This was a mixture of E and Z isomers (4E/4Z = about 10:9).

The physical properties of the obtained compound of formula 1-5 were as follows.
¹ H-NMR (400 MHz, C ₆ D ₆ ) ppm: 1.06 (s)/1.07 (s) (6H, C8-CH ₃ , 9-H ₃ ), 1.37 (m, 2H, 7 -H ₂ ), 1.41 (br.s, E-C4-CH ₃ )/1.49 (d, J=0.8 Hz, Z-C4-CH ₃ ) (3H), 1.93-1. 99 (m, 2H, 2-H ₂ ), 2.0 to 2.1 (m, 2H, 6-H ₂ ), 2.03 (t, J = 6.8 Hz, E-3-H ₂ )/ 2.15 (t, J=7.6 Hz, Z-3-H ₂ ) (2H), 5.06 (br. t, J=7.0 Hz, E-5-H)/5.12 (br. t, J = 7.2 Hz, Z-5-H) (1H), 9.31 (t, J = 1.4 Hz, Z-CHO) / 9.32 (t, J = 1.6 Hz, E-CHO ) (1H)
¹³ C-NMR (100 MHz, C ₆ D ₆ ) ppm: 15.88 (E-C4-CH ₃ ), 23.07 (Z-C6), 23.09 (Z-C4-CH ₃ ), 23.21 (E-C6), 24.28 (Z-C3), 29.37/29.40 (C8-CH ₃ , C9), 31.92 (E-C3), 42.06 (Z-C2), 42 .10 (E-C2), 43.81 (E-C7), 44.09 (Z-C7), 70.00 (Z-C8), 70.05 (E-C8), 125.86 (E- C5), 127.08 (Z-C5), 133.00 (Z-C4), 133.12 (E-C4), 200.71 (Z-C1), 200.82 (E-C1)
IR (neat) cm ⁻¹ : 3700 to 3100 (br), 2970, 2930, 2860, 1720, 1448, 1378, 1200, 1150, 1122
The resulting compound of formula 1-5 (mixture of isomers) has a lily-of-the-valley-like, sour, creamy, floral, and watery scent, and also has a cooling sensation and a slightly spicy sensation. It was a scent that made you feel

(6) Synthesis of compound of formula 1-6 (8-hydroxy-4,8,9-trimethyl-4-decenal)

(i) Synthesis of Compound 6b 1.63 g (67.1 mmol) of magnesium was added to a 300 mL four-necked flask, and 30 mL of ether, a small amount of iodine and dibromoethane were added. Under a nitrogen atmosphere, add a small amount of an ether solution (45 mL) of 11.72 g (68.95 mmol) of isopropyl iodide (i-PrI) and heat with a dryer to confirm the progress of the reaction. was added dropwise over 45 minutes at such a speed that the ether was gently refluxed to prepare a Grignard reagent. Cool to room temperature while stirring for 30 minutes, then add dropwise an ether solution (10 mL) of 10.1 g of compound 6a (52.0 mmol) over 40 minutes to the Grignard reagent, and stir for 1 hour while cooling to room temperature. bottom. The resulting reaction solution was poured into a cooled 1 mol/L hydrochloric acid aqueous solution (70 mL) to dissolve the precipitate, and the resulting solution was extracted with ether (200 mL). The ether layer was washed successively with water, saturated aqueous sodium hydrogencarbonate solution, 5% aqueous sodium thiosulfate solution and saturated brine, dried over anhydrous magnesium sulfate, and distilled to remove the solvent using an evaporator to obtain 10.81 g of a slightly yellow oily substance. Obtained. This was purified with a silica gel column (48 mm id x 28 cm L, n-hexane:ethyl acetate = 15:1) to obtain 5.54 g (23.2 mmol) of slightly yellow oily compound 6b.

(ii) Synthesis of compound 6c 5.43 g of compound 6b (E/Z≈2:1) (22.8 mmol) was dissolved in dichloromethane (100 mL), cooled to 0° C. and the cooled solution was added with meta-chloroperbenzoic acid ( mCPBA) (70%) 6.74 g (27.3 mmol) was added portionwise over 2 hours, and the mixture was further stirred at 0°C for 1 hour. Subsequently, a saturated aqueous sodium sulfite solution was added to the stirred reaction solution to decompose excess oxidizing agent, ether (100 mL) was added, and the organic layer was separated. The organic layer was washed successively with saturated aqueous sodium sulfite solution, saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to obtain 6.07 g of a colorless oily substance. This was purified with a silica gel column (48 mm id x 27 cm L, n-hexane:ethyl acetate = 5:1) to obtain 2.46 g (9.67 mmol) of colorless oily compound 6c.

(iii) Synthesis of Compound of Formula 1-6 2.42 g of compound 6c (9.51 mmol) was dissolved in ether (40 mL) and treated with periodate dihydrate (HIO _{4.2H 2} O) 2 under ice cooling. A solution of .80 g (10.1 mmol) of tetrahydrofuran (THF) (24 mL) was added dropwise over a period of 1 hour (a colorless precipitate formed with the addition) and stirred at 0° C. for 1 hour. Ice water was then added to the resulting reaction solution, the organic layer was separated, and the aqueous layer was extracted with ether (100 mL). The separated organic layer and the organic layer obtained by ether extraction were combined, washed successively with water, saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and evaporated to remove the solvent using an evaporator. 2.24 g of oil were obtained. This was purified with a silica gel column (33 mm id x 32.5 cm L, n-hexane:ethyl acetate = 5:1) to give 0.67 g (3.2 mmol) of the compound of formula 1-6 as pale yellow oil. Obtained. This was a mixture of E and Z isomers (4E/4Z = about 5:4).

The physical properties of the obtained compound of formula 1-6 were as follows.
¹ H-NMR (400 MHz, C ₆ D ₆ ) ppm: 0.80 (d, J = 6.8 Hz) / 0.80 (d, J = 6.8 Hz) / 0.87 (d, J = 6.8 Hz) 8 Hz) / 0.87 (d, J = 6.8 Hz) (6H, C9-CH ₃ , 10-H ₃ ), 0.93 (s, E-C8-CH ₃ ) / 0.94 (s, Z —C8-CH ₃ )(3H), 1.3-1.4 (m, 2H, 7-H ₂ ), 1.43 (br.s, E-C4-CH ₃ )/1.50 (d, J = 1.2 Hz Z-C4-CH ₃ ) (3H), 1.5-1.7 (m, 1H, 9-H), 1.9-2.05 (m, 2H, 2-H ₂ ), 1.95 to 2.1 (m, 2H, 6-H ₂ ), 2.04 (br.t, J=7.0 Hz, E-3-H ₂ )/2.16 (br.t, J= 7.0 Hz, Z-3-H ₂ ) (2H), 5.07 (qt, J=1.2, 7.2 Hz, E-5-H)/5.13 (br.t, J=7. 2Hz, Z-5-H) (1H), 9.31 (t, J = 1.6Hz, Z-CHO) / 9.32 (t, J = 1.6Hz, E-CHO) (1H)
¹³ C-NMR (100 MHz, C ₆ D ₆ ) ppm: 15.92 (E-C4-CH ₃ ), 17.11/17.67 (C9-CH ₃ , C10), 22.24 (Z-C6) , 22.38 (E-C6), 23.02 (Z-C4-CH ₃ ), 23.10 (C8-CH ₃ ), 24.30 (Z-C3), 31.94 (E-C3), 37.18 (E-C9), 37.26 (Z-C9), 39.74 (E-C7), 40.00 (Z-C7), 42.08 (E-C2), 42.14 (Z -C2), 73.95 (C8), 126.00 (E-C5), 127.23 (Z-C5), 133.01 (Z-C4), 133.16 (E-C4), 200.53 /200.66 (C1)
IR (neat) cm ⁻¹ :=3700 to 3130 (br), 2965, 2939, 2878, 1722, 1450, 1382, 1090
The resulting compound of formula 1-6 (mixture of isomers) has a lily-of-the-valley-like, powder-like, slightly acidic odor, floral, and lyrial (3-(4-tert-butylphenyl)-2-methylpropanal). The scent contained freshness, cucumber-like, alcohol-like, woody, green, and ozone-like scents, and gave a feeling of freshness, coolness, and stimulation (reminiscent of hotness).

(7) Synthesis of compound of formula 1-7 (8-cyclopropyl-8-hydroxy-4-methyl-4-nonenal)

(i) Synthesis of Compound 7b 1.63 g (67.1 mmol) of magnesium was added to a 300 mL four-necked flask, and 30 mL of ether, a small amount of iodine and dibromoethane were added. Under a nitrogen atmosphere, add a small amount of an ether solution (45 mL) of 8.09 g (66.9 mmol) of bromocyclopropane and heat with a dryer to confirm the progress of the reaction. Ether was added dropwise over 45 minutes at a speed at which ether was refluxed to prepare a Grignard reagent. Cool to room temperature while stirring for 30 minutes, then add dropwise an ether solution (10 mL) of 10.00 g of compound 7a (51.5 mmol) over 40 minutes to the Grignard reagent, and further stir for 30 minutes while cooling to room temperature. bottom. The obtained reaction solution was poured into a cooled 2 mol/L hydrochloric acid aqueous solution to dissolve the precipitate, and then the obtained solution was extracted with ether (150 mL). The ether layer was washed successively with water, saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off using an evaporator to obtain 11.66 g of a yellow oily substance. This was purified with a silica gel column (48 mm id x 32 cm L, n-hexane:ethyl acetate = 15:1) to obtain 8.31 g (35.2 mmol) of slightly yellow oily compound 7b.

(ii) Synthesis of compound 7c 8.29 g of compound 7b (E/Z≈5:3) (35.1 mmol) was dissolved in dichloromethane (150 mL), cooled to 0° C. and treated with meta-chloroperbenzoic acid (mCPBA) (65 %) 11.17 g (42.1 mmol) was gradually added over 2.5 hours, and the mixture was further stirred at 0°C for 1 hour. A saturated aqueous sodium sulfite solution was added to the stirred reaction solution to decompose excess oxidizing agent, ether (150 mL) was added, and the organic layer was separated. The organic layer was washed successively with saturated aqueous sodium sulfite solution, saturated aqueous sodium hydrogencarbonate solution and saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was removed by an evaporator to obtain 9.90 g of a colorless oily substance. This was purified with a silica gel column (48 mm id x 41 cm L, n-hexane:ethyl acetate = 5:1) to obtain 4.39 g (17.4 mmol) of compound 7c as a colorless oil.

(iii) Synthesis of Compound of Formula 1-7 4.32 g of compound 7c (17.1 mmol) was dissolved in ether (74 mL) and treated with periodate dihydrate (HIO _{4.2H 2} O) 4 under ice cooling. A solution of .52 g (19.8 mmol) of tetrahydrofuran (THF) (40 mL) was added dropwise over 1 hour and stirred at 0° C. for 1 hour. Ice water was added to the stirred reaction mixture, the organic layer was separated, and the aqueous layer was extracted with ether (200 mL). The separated organic layer and the organic layer obtained by ether extraction were combined, washed successively with water, saturated aqueous sodium bicarbonate solution, and saturated brine, dried over anhydrous magnesium sulfate, and evaporated to remove the solvent using an evaporator. 4.02 g of an oily substance of This was purified with a silica gel column (48 mm id x 23 cm L, n-hexane:ethyl acetate = 5:1) to obtain 1.24 g (5.90 mmol) of the compound of formula 1-7 as pale yellow oil. Obtained. This was a mixture of E and Z isomers (4E/4Z = about 11:10).

The physical properties of the obtained compound of formula 1-7 were as follows.
¹ H-NMR (400 MHz, C ₆ D ₆ ) ppm: 0.21-0.25 (m, 2H) / 0.29-0.35 (m, 1H) / 0.39-0.47 (m, 1H) (2xcyclopropyl-CH ₂ ), 0.62-0.70 (m, 1H, cyclopropyl-CH), 1.02 (s, E-9-H ₃ )/1.03 (s, Z-9- H ₃ )(3H), 1.44(br.s, E-C4-CH ₃ )/1.50(br.s, Z-C4-CH ₃ )(3H), 1.4-1.55( m, 2H, 7-H ₂ ), 1.9 to 2.0 (m, 2H, 2-H ₂ ), 2.04 (br.t, J=7.0 Hz, E-3-H ₂ )/ 2.15 (br.t, J = 6.6Hz, Z-3- _H2 ) (2H), 2.05-2.2 (m, 2H, 6- _H2 ), 5.09 (qt, J = 1.2, 7.2 Hz, E-5-H) / 5.16 (br.t, J = 7.2 Hz, Z-5-H) (1H), 9.31 (t, J = 1. 6Hz, Z-CHO) / 9.32 (t, J = 1.6Hz, E-CHO) (1H)
¹³ C-NMR (100 MHz, C ₆ D ₆ ) ppm: 0.38/0.75 (2xcyclopropyl-CH ₂ ), 15.92 (E-C4-CH ₃ ), 21.24/21.31 cyclopropyl-CH) , 22.82 (Z-C6), 22.97 (E-C6), 23.11 (Z-C4-CH ₃ ), 24.29 (Z-C3), 26.75 (Z-C9), 26 .79 (E-C9), 31.93 (E-C3), 42.07 (E-C2), 42.14 (Z-C2), 43.37 (E-C7), 43.63 (Z- C7), 70.03/70.06 (C8), 126.02 (E-C5), 127.21 (Z-C5), 133.02 (Z-C4), 133.15 (E-C4), 200.74/200.88 (C1)
IR (neat) cm ⁻¹ : 3700 to 3140 (br), 3000, 2970, 2925, 2855, 1720, 1450, 1385, 1374, 1110, 1050, 1020
The resulting compound of formula 1-7 (mixture of isomers) has a floral, slightly sour, narcinth (dimethylbenzyl carbinol)-like green linalool-like, rosalina (also called lavender tea tree)-like scent. , lily-of-the-valley, green, woody and aldehyde-like scents, and a refreshing aftertaste.

[Example 2] Separation of E-isomer and Z-isomer and each aroma Therefore, these mixtures were subjected to separation of E and Z isomers under the following high performance liquid chromatography (HPLC) conditions;
Column: Inertsil diol (250 mm L.×4.6 mm I.D., 5 μm)
Mobile phase: hexane/ethanol = 95/5
Flow rate: 1mL/min
Detection: UV205nm
The results and the aroma of each isomer obtained were as follows.

(Compound of Formula 1-1)
(4E)-8-hydroxy-4, 8-dimethyl-4,9-decadienal (also called 4E form) and (4Z)-8-hydroxy-4,8-dimethyl-4,9-decadienal (also called 4Z form) were separated.

The 4E isomer and the 4Z isomer, like the mixture of the 4E isomer and the 4Z isomer obtained in Example 1(1), had scents containing lily of the valley, rose, green, fruity and the like. Therefore, each of the 4E isomer and 4Z isomer can be used alone as a flavor imparting agent. The 4E isomer alone has a fragrance that makes one feel fresh flowers of lily of the valley, and has a stronger fragrance than the 4Z isomer, and is considered to be particularly useful as a flavor imparting agent.

(Compound of formula 1-2)
From the isomer mixture of 10-hydroxy-4,8-dimethyl-4,8-decadienal of formula 1-2 obtained in Example 1(2) under the above HPLC conditions, (4E,8E)-10-hydroxy -4,8-dimethyl-4,8-decadienal (also referred to as 4E,8E form), (4E,8Z)-10-hydroxy-4,8-dimethyl-4,8-decadienal (also referred to as 4E,8Z form) , (4Z,8E)-10-hydroxy-4,8-dimethyl-4,8-decadienal (also referred to as 4Z,8E form), (4Z,8Z)-10-hydroxy-4,8-dimethyl-4,8 - isomers of decadienal (also called 4Z, 8Z isomers) were separated.

All of these four isomers, like the isomer mixture obtained in Example 1(2), gave an aroma containing lily of the valley, floral, freshness, fruitiness, sweetness, and the like. Therefore, each of these four isomers can be used alone as a flavoring agent. Among the four isomers, the "4E, 8E isomer" alone exhibited a fragrance reminiscent of fresh flowers of the lily of the valley. On the other hand, the other three isomers (i.e., "4E,8Z form", "4Z,8E form", and "4Z,8Z form") exhibit the scent of fresh lily of the valley, but also contain a gourd-like scent. It was thought that a flavor similar to that of "4E, 8E form" or a flavor containing a different scent could be imparted to various articles. In addition, the "4E,8E form" has a stronger aroma than the other three isomers, and was considered to be particularly useful as a flavor imparting agent.

(Compound of Formula 1-3)
From the isomer mixture of 8-hydroxy-4,8-dimethyl-4-decenal of formula 1-3 obtained in Example 1(3), (4E)-8-hydroxy-4,8 was obtained under the above HPLC conditions. -dimethyl-4-decenal (also called 4E form) and (4Z)-8-hydroxy-4,8-dimethyl-4-decenal (also called 4Z form) were separated.

The 4E isomer and the 4Z isomer, like the mixture of the 4E isomer and the 4Z isomer obtained in Example 1(3), have scents such as lily of the valley, floral, green, fruity, sweet, and powdery. there were. Therefore, each of the 4E isomer and 4Z isomer can be used alone as a flavor imparting agent. The 4E isomer has a stronger fragrance than the 4Z isomer, giving a scent closer to that of fresh flowers of the lily of the valley, and the 4E isomer was thought to be particularly useful as a flavor imparting agent.

(Compound of formula 1-5)
From the isomer mixture of 8-hydroxy-4,8-dimethyl-4-nonenal of formula 1-5 obtained in Example 1 (5), under the above HPLC conditions, (4E)-8-hydroxy-4,8 -dimethyl-4-nonenal (also referred to as 4E form) and (4Z)-8-hydroxy-4,8-dimethyl-4-nonenal (also referred to as 4Z form) were separated.

The 4E isomer and 4Z isomer, like the mixture of the 4E isomer and the 4Z isomer obtained in Example 1(5), gave a scent containing lily of the valley, floral, sour, creamy, watery, etc. . Therefore, each of the 4E isomer and 4Z isomer can be used alone as a flavor imparting agent. Compared to the 4Z form, the 4E form had an aroma closer to that of fresh Lily of the valley and had a stronger aroma. The 4E form was thought to be particularly useful as a flavoring agent.

(Compounds of formula 1-6)
From the isomer mixture of 8-hydroxy-4,8,9-trimethyl-4-decenal of formula 1-6 obtained in Example 1 (6), under the above HPLC conditions, (4E)-8-hydroxy-4 ,8,9-trimethyl-4-decenal (also called 4E form) and (4Z)-8-hydroxy-4,8,9-trimethyl-4-decenal (also called 4Z form) were separated.

The 4E and 4Z isomers, like the mixture of the 4E and 4Z isomers obtained in Example 1(6), have lily-of-the-valley-like, powder-like, sour, floral, cucumber-like, alcohol-like, woody, green, and ozone-like properties. It was something that made you feel the scent including. Therefore, each of the 4E isomer and 4Z isomer can be used alone as a flavor imparting agent. Compared to the 4Z form, the 4E form had an aroma closer to that of fresh Lily of the valley and had a stronger aroma. The 4E form was thought to be particularly useful as a flavoring agent.

(Compounds of Formula 1-7)
From the isomer mixture of 8-cyclopropyl-8-hydroxy-4-methyl-4-nonenal of formula 1-7 obtained in Example 1 (7), under the above HPLC conditions, (4E)-8-cyclopropyl -8-hydroxy-4-methyl-4-nonenal (also referred to as 4E form) and (4Z)-8-cyclopropyl-8-hydroxy-4-methyl-4-nonenal (also referred to as 4Z form) were separated.

Similar to the mixture of 4E and 4Z isomers obtained in Example 1 (7), the 4E isomer and 4Z isomer have scents containing lily of the valley, floral, sour, green, rosalina-like, woody, and aldehyde-like. It was something that made Therefore, each of the 4E isomer and 4Z isomer can be used alone as a flavor imparting agent. Compared to the 4Z form, the 4E form had an aroma closer to that of fresh Lily of the valley and had a stronger aroma. The 4E form was thought to be particularly useful as a flavoring agent.

[Example 3] Aroma Evaluation of Hydroxyaldehyde Compound Represented by Formula 1 As shown in Table 1 below, a lily of the valley-like basic blended fragrance composition was prepared.

Then, the hydroxyaldehyde compounds of formulas 1-1 to 1-7 obtained in Examples 1 (1) to (7) were added to the lily of the valley-like basic blended fragrance composition as the flavor imparting agent of the present invention, as shown in Table 2 below. A perfume composition of the present invention was prepared by blending as described, and its effect was confirmed by sensory evaluation. In the sensory evaluation, scented paper was impregnated with the perfume composition of the present invention, and 14 well-trained perfumers with 10 years or more of experience evaluated the scent. They were asked to score based on the following evaluation criteria and to comment on the quality of the scent.
(Evaluation criteria)
4 points: The fresh scent of fresh lily of the valley was greatly enhanced 3 points: The refreshing scent of fresh lily of the valley was enhanced 2 points: The refreshing scent of fresh lily of the valley was slightly enhanced 1 point: The fresh scent of lily of the valley was enhanced Slightly enhanced scent 0 points: Smells different from lily of the valley

Thus, all of the hydroxyaldehyde compounds of formulas 1-1 to 1-7 are excellent flavor imparting agents capable of imparting an excellent characteristic fragrance to the lily-of-the-valley-like fragrance, and capable of creating a high-quality fragrance reminiscent of fresh flowers. It was confirmed that it is effective.

[Example 4] Fragrance evaluation of geometric isomers Each of the hydroxyaldehyde compounds of the present invention shown in Table 3 below was added to the lily of the valley-like basic blend perfume composition prepared in Example 3 at a concentration of 1% (relative to the basic lily of the valley blend). A lily of the valley-like fragrance composition of the present invention was prepared by blending so as to be the total amount of the fragrance composition), and sensory evaluation was performed. In the sensory evaluation, odor paper was impregnated with the perfume composition of the present invention, and 7 well-trained perfumers with 10 years or more of experience scored the quality of the lily of the valley-like scent in the same manner as in Example 3. let me The average results of sensory evaluation are shown in Table 3 below.

As shown in Table 3, the compound of formula 1-1 and the compound of formula 1-2 have the effect of imparting an excellent fragrance even in a mixture of the E isomer and the Z isomer (see also Example 3). It was confirmed that the 4E isomer of -1 and the 4E and 8E isomers of formula 1-2 exhibit particularly excellent effects.

[Example 5] Formulation example 1 for cosmetics
Each of the hydroxyaldehyde compounds of formulas 1-1 to 1-7 obtained in Examples 1 (1) to (7) was added as the flavor imparting agent of the present invention to a commercially available hand soap with a lily of the valley scent at 50 ppm and 0.5 ppm. The hand soap of the present invention was prepared by blending so as to have a concentration of 1%, 1% (with respect to the total amount of hand soap), and packed in a commercially available empty push-type hand soap bottle. Then, five well-trained perfumers with more than 10 years of experience wash their hands in lukewarm water (about 35 ° C) using one push of a hand soap bottle (about 1 mL) in a closed laboratory. They were asked to perform a sensory evaluation of the scent in the laboratory and the scent of their hands after washing their hands. In the sensory evaluation, the natural feeling of the lily of the valley scent, the diffusibility of the scent in the laboratory space, and the lingering scent on the skin compared to the above-mentioned commercially available hand soap that does not contain the flavor imparting agent of the present invention. Scoring was performed according to the following criteria: improved to 4 points, improved to 3 points, slightly improved to 2 points, no change to 1 point, and deteriorated to 0 points. The natural scent of the lily of the valley means that the scent has a slightly greenish, refreshing scent reminiscent of fresh flowers of the lily of the valley. Table 4 shows the average scores of five perfumers.

Thus, each of the hydroxyaldehyde compounds of formulas 1-1 to 1-7, when used as a flavor-imparting agent, has an excellent effect capable of improving not only the quality of fragrance such as natural feeling but also diffusibility and lingering fragrance. It was confirmed that it works.

[Example 6] Formulation example 2 for cosmetics
The hydroxyaldehyde compounds of formulas 1-1 to 1-7 obtained in Examples 1 (1) to (7) were used as the flavor imparting agent of the present invention to prepare commercially available lemon-tone perfumes, mango-tone perfumes, ozone A cosmetic product of the present invention was obtained by blending with a men's perfume of the present invention at a concentration of 300 ppm with respect to the total weight of the perfume. Then, sensory evaluation was performed on the cosmetic product of the present invention by seven well-trained perfumers with 10 years or more of experience. In the sensory evaluation, each of the above-mentioned commercially available perfumes not containing the flavor imparting agent of the present invention was used as a control product, and the change in fragrance due to the blending of the flavor imparting agent of the present invention was evaluated. Compared to the control product, the fruity and voluminous feeling of the mango perfume, and the ozone and voluminous feeling of the ozonized perfume were greatly increased = 4 points, increased = 3 points, and slightly increased = 2 points. , no change = 1 point, deteriorated = 0 point. Here, the voluminousness means a scent that is coherent and strong, and that the scent can be felt for a long time. The average results of 7 panelists are shown in Table 5 below.

Thus, it was confirmed that the hydroxyaldehyde compounds of formulas 1-1 to 1-7 can significantly improve various aromas as flavor imparting agents.

[Example 7] Formulation example for food and drink Each of the hydroxyaldehyde compounds of formulas 1-1 to 1-7 obtained in Examples 1 (1) to (7) was commercially available as the flavoring agent of the present invention. The beverage of the present invention was prepared by blending with lemonade containing 50% of fruit juice of the present invention so as to have a concentration of 1 ppb (relative to the total amount of lemonade). Five panelists with 10 or more years of experience were then asked to comment on the flavor of the beverage of the present invention compared to the commercial lemonade without the flavor imparting agent of the present invention. As a result, all five panelists found that each of the hydroxyaldehyde compounds of formulas 1-1 to 1-7 enhances the lemon-like peel and juice feeling compared to the commercially available lemonade, which is the control product, and squeezes the fruit. He commented that it had a fresh, juicy and voluminous flavor.

Thus, it was confirmed that the flavor imparting agent of the present invention can impart a characteristic flavor to food and drink, and is also useful as a flavoring compound for food and drink.

This application is based on Japanese Patent Application No. 2020-028029 filed on February 21, 2020, the disclosure of which is incorporated herein by reference.

Claims (11)

A flavor imparting agent comprising at least one hydroxyaldehyde compound represented by the following formula 1.

[Wherein, the dashed lines at the C4 and C8 positions each independently represent a single bond or a double bond, and in the case of a double bond, a cis-type or a trans-type, or a cis-type and a trans-type Represents a mixture of arbitrary proportions,
When the C8 position is a single bond, R ₁ is an OH group, and R ₂ and R ₃ are each independently hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms; ₂ and R ₃ form a three-membered ring together with the carbon atom at the C9 position; or R ₂ and R ₃ together form a methylidene group having a double bond with the carbon atom at the C9 position. is either
When the C8 position is a double bond, R ₁ is absent, R ₂ is hydrogen or a linear or branched alkyl group having 1 to 3 carbon atoms, and R ₃ is an OH group or a CH ₂ OH group. be. ] 2. The flavor imparting agent according to claim 1, comprising at least one hydroxyaldehyde compound represented by the following formulas 1-1 to 1-7.

[In the formula, the wavy line represents a cis-type, a trans-type, or a mixture of the cis-type and the trans-type at any ratio. ] 3. The flavor imparting agent according to claim 1 or 2, wherein a double bond is present between C4 and C5 positions of said hydroxyaldehyde compound. 4. The flavor imparting agent according to claim 3, wherein the double bond between the C4 and C5 positions of said hydroxyaldehyde compound takes the E form. Any one of claims 1 to 4, comprising at least one of a hydroxyaldehyde compound represented by the following formula 1-1-1(4E) and a hydroxyaldehyde compound represented by formulas 1-2-1(4E, 8E). 1. The flavor-imparting agent according to 1.
A fragrance composition containing the flavor-imparting agent according to any one of claims 1 to 5. A consumer product comprising the flavor imparting agent according to any one of claims 1 to 5 or the perfume composition according to claim 6. A method for improving the flavor of a flavor composition, comprising blending the flavor-imparting agent according to any one of claims 1 to 5 into the flavor composition. A method of flavoring a consumer product, comprising incorporating the flavoring agent of any one of claims 1 to 5 or the flavoring composition of claim 6 into the consumer product. A hydroxyaldehyde compound represented by the following formula 1'.

[In the formula, the dashed line represents a single bond or a double bond, and in the case of a double bond, it represents a cis-type or a trans-type, or a mixture of the cis-type and the trans-type in an arbitrary ratio. , R ₂ ' and R ₃ ' are each independently hydrogen or a _linear or branched alkyl group having 1 to ₃ carbon atoms; Forms a three-membered ring. (Excluding the case where the dashed line is a single bond and R ₂ ' and R ₃ ' are hydrogen.)] The hydroxyaldehyde compound according to claim 10, represented by the following formulas 1-3 to 1-7.

[In the formula, the wavy line represents a cis-type, a trans-type, or a mixture of the cis-type and the trans-type at any ratio. ]