JP2013001820A - Perfume composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a perfume improving agent which has high aromatic characteristics and retention characteristics such as fragrance and persistence without changing the perfume blending of a perfume composition as a base, a perfume composition containing the same, various products including the perfume composition, and a new compound included in general formula (1).SOLUTION: The perfume composition contains an alcohol derivative represented by general formula (1), wherein Ris a 1-6C hydrocarbon group, and Ris a 1-4C hydrocarbon group, hydroxy group or a 1-4C alkoxy group.

Description

  The present invention relates to a fragrance composition, and more specifically, a fragrance composition excellent in fragrance characteristics such as fragrance and residual fragrance and retention effect, and a cosmetic, toiletry product, bathing agent, quasi-drug containing the same. Or it relates to various products such as pharmaceuticals.

  Conventionally, when a fragrant substance is scented and an excellent fragrance composition is prepared, in order to maintain a desired fragrance, various suspending agents or fragrance improving agents that adjust the fragrance characteristics and retention of the fragrant substance are fragrances. It is blended. Specifically, dipropylene glycol, triethyl citrate, benzyl benzoate, benzyl salicylate, diethyl phthalate, isopropyl myristate, and the like have been proposed and used as such retention agents or fragrance improving agents. Of these, benzyl salicylate has been reported to induce delayed contact dermatitis (Non-patent Document 1), which is not preferable in terms of safety. In addition, diethyl phthalate is not preferable because its use as an endocrine disrupting substance has been restrained. Other retention agents may also have a low residual fragrance imparting effect, or the fragrance of the retention agent itself may modulate the fragrance of the fragrance composition in an undesirable direction, thus imparting excellent fragrance persistence. Therefore, it is desired to develop an odorless fragrance improving agent that can control the fragrance of a fragrance composition.

  Under such circumstances, various retention agents and fragrance improving agents have been proposed in order to satisfy such demands. For example, p-menthane-3,8-diol (patent document 1), 2-hydroxymethyl-cycloalkanol derivative (patent document 2), specific biphenyl compound and the like (patent document 3), glyceryl ether derivative (patent document 4) , Diacetyl rhododendrol (Patent Document 5) is proposed as a retention agent. However, these compounds are also difficult to satisfy conditions such as versatility and retention effect as a retention agent.

  In addition, as for the above-mentioned retention agent and fragrance improving agent, although the effect by sensory evaluation on odor paper as a blended fragrance is described, it is effective in products obtained by adding the blended fragrance. Is not mentioned at all, and it is desired to develop a blended fragrance reflecting the excellent fragrance improving effect in the product form and the fragrance improving agent.

JP-A-4-337395 Japanese Patent Laid-Open No. 5-295388 JP-A-7-62383 JP 2003-238985 A JP 2010-90259 A

“Skin”, Vol. 23, No. 4, 421-441

  An object of this invention is to provide the products which reflected the improvement effect while improving the fragrance characteristic and residual fragrance property of a fragrance | flavor composition. That is, more specifically, without changing the fragrance of the base fragrance composition, the fragrance properties such as fragrance and sustainability, a fragrance improving agent with high retention characteristics, and a fragrance composition containing the same, Furthermore, the fragrance composition is blended, and an object is to provide various products having good fragrance characteristics such as fragrance and sustainability, and retention characteristics.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the alcohol derivative represented by the following general formula (1) significantly enhances the fragrance and the residual fragrance of the fragrance composition. It came to be completed. The present invention relates to the following inventions (1) to (9).

（式中、Ｒ_１は炭素数１〜６の炭化水素基であり、Ｒ_２は炭素数１〜４の炭化水素基、水酸基又は炭素数１〜４のアルコキシ基である。）
で表されるアルコール誘導体を配合してなることを特徴とする香料組成物。 (1) General formula (1)

(In the formula, R ₁ is a hydrocarbon group having 1 to 6 carbon atoms, and R ₂ is a hydrocarbon group having 1 to 4 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.)
The fragrance | flavor composition formed by mix | blending the alcohol derivative represented by these.

(2) The alcohol derivative of the general formula (1) is an alcohol derivative in which R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, and R ₂ is a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms. The fragrance composition according to item (1), wherein

（式中、Ｒ_１は炭素数２〜４のアルキル基及び炭素数２〜４のアルケニル基から選ばれる１種。）で表される４−（３−ヒドロキシ−３−置換）ブチルフェノールであることを特徴とする（１）項又は（２）項に記載の香料組成物。 (3) The alcohol derivative of the general formula (1) is represented by the general formula (2)

(Wherein R ₁ is one selected from an alkyl group having 2 to 4 carbon atoms and an alkenyl group having 2 to 4 carbon atoms), and is 4- (3-hydroxy-3-substituted) butylphenol. The fragrance composition according to item (1) or (2), wherein

(4) The alcohol derivative of the general formula (1) is 4- (3-hydroxy-3-methylpentyl) phenol, 4- (3-hydroxy-3-methyl-4-pentenyl) phenol and 4- (3- The fragrance composition according to any one of items (1) to (3), which is at least one selected from (hydroxy-3-methylhexyl) phenol.

(5) The alcohol derivative of the general formula (1) is contained in an amount of 1 to 90% by mass, preferably 5.0 to 30% by mass. The fragrance composition described.

(6) Cosmetics, toiletries, bathing agents, beverages, foods, quasi-drugs, characterized by comprising the fragrance composition according to any one of (1) to (5) above Goods or medicines.

(7) A method for enhancing the fragrance sustainability of a fragrance, which comprises adding the alcohol derivative of the general formula (1) to the fragrance composition.

（式中、Ｒ_１は炭素数２〜４の炭化水素基である。但し、Ｒ_１が１−プロペニル基である場合を除く。）
で表される４−（３−ヒドロキシ−３−置換）ブチルフェノール。 (8) General formula (2)

(In the formula, R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, except when R ₁ is a 1-propenyl group.)
4- (3-hydroxy-3-substituted) butylphenol represented by

(9) 4- (3-hydroxy-3-substituted) butylphenol of the general formula (2) is 4- (3-hydroxy-3-methylpentyl) phenol, 4- (3-hydroxy-3-methyl-4) The 4- (3-hydroxy-3-substituted) butylphenol according to the item (8), which is any one of -pentenyl) phenol and 4- (3-hydroxy-3-methylhexyl) phenol.

  According to the present invention comprising blending an alcohol derivative represented by the general formula (1) into a fragrance composition, a conventionally known retention agent and fragrance can be used without changing the fragrance of a known or known fragrance. Compared with the improving agent, it is possible to remarkably enhance the fragrance and the residual fragrance, and it is possible to obtain a fragrance composition having desired fragrance characteristics and remarkably high retention. In addition, the effect is the same in the product form containing the fragrance composition of the present invention, and has desired fragrance characteristics, fragrance, high residual fragrance cosmetics, toiletry products, bath agents, pharmaceuticals, etc. Products can be provided.

The present invention will be described in detail below.
In the alcohol derivative represented by the general formula (1) of the present invention, R ₁ is a hydrocarbon group having 1 to 6 carbon atoms, and R ₂ is a hydrocarbon group having 1 to 4 carbon atoms, a hydroxyl group, or 1 carbon atom. It is an alkoxy group of ~ 4.

Examples of the hydrocarbon group having 1 to 6 carbon atoms of R ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and 1,1-dimethylethyl. Group, pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, 2-ethylpropyl group, hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1 , 3-dimethylbutyl group, 2,3-dimethylbutyl group, 2,4-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, etc. Alkyl group; vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1-propenyl group, 1-pentenyl group, 2-pentenyl group Group, 3-pentenyl group, 4-pentenyl group, 2-penten-2-yl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 2-hexene- Examples thereof include alkenyl groups having 2 to 6 carbon atoms such as a 2-yl group.

Examples of the hydrocarbon group having 1 to 4 carbon atoms as R ₂ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and 1,1-dimethyl group. C1-C4 alkyl group such as ethyl group, vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1-propenyl Examples thereof include alkenyl groups having 2 to 4 carbon atoms such as groups.

Examples of the alkoxy group having ₂ to 4 carbon atoms as R ₂ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. Is mentioned.

Specific examples of the alcohol derivative represented by the general formula (1) of the present invention include, for example.
4- (3-hydroxy-3-methylpentyl) phenol, 3- (3-hydroxy-3-methylpentyl) phenol, 2- (3-hydroxy-3-methylpentyl) phenol, 4- (3-hydroxy-3 -Methylhexyl) phenol, 3- (3-hydroxy-3-methylhexyl) phenol, 2- (3-hydroxy-3-methylhexyl) phenol, 4- (3-hydroxy-3-methylpentyl) phenol 3- (3-hydroxy-3-methylpentyl) phenol, 2- (3-hydroxy-3-methylpentyl) phenol, 4- (3-hydroxy-3,4-dimethylpentyl) phenol, 3- (3- Hydroxy-3,4-dimethylpentyl) phenol, 2- (3-hydroxy-3,4-dimethylpentyl) phenol, -(3-hydroxy-3,5-dimethylhexyl) phenol, 3- (3-hydroxy-3,5-dimethylhexyl) phenol, 2- (3-hydroxy-3,5-dimethylhexyl) phenol, 4- ( 3-hydroxy-3-methyl-4-pentenyl) phenol, 3- (3-hydroxy-3-methyl-4-pentenyl) phenol, 2- (3-hydroxy-3-methyl-4-pentenyl) phenol, 4- (3-hydroxy-3,4-dimethyl-4-pentenyl) phenol, 3- (3-hydroxy-3,4-dimethyl-4-pentenyl) phenol, 2- (3-hydroxy-3,4-dimethyl-4) -Pentenyl) phenol, 4- (3-hydroxy-3-methyl-5-hexenyl) phenol, 3- (3-hydroxy-3-methyl- - hexenyl) phenol, 2- (3-hydroxy-3-methyl-5-hexenyl) phenol.

  1- (4-methoxyphenyl) -3-methyl-3-pentanol, 1- (3-methoxyphenyl) -3-methyl-3-pentanol, 1- (2-methoxyphenyl) -3-methyl-3 -Pentanol, 1- (4-methoxyphenyl) -3-methyl-3-hexanol, 1- (3-methoxyphenyl) -3-methyl-3-hexanol, 1- (2-methoxyphenyl) -3-methyl -3-hexanol, 1- (4-methoxyphenyl) -3-methyl-3-heptanol, 1- (3-methoxyphenyl) -3-methyl-3-heptanol, 1- (2-methoxyphenyl) -3- Methyl-3-heptanol, 1- (4-methoxyphenyl) -3,4-dimethyl-3-pentanol, 1- (3-methoxyphenyl) -3,4-dimethyl-3-pentano 1- (2-methoxyphenyl) -3,4-dimethyl-3-pentanol, 1- (4-methoxyphenyl) -3,5-dimethyl-3-hexanol, 1- (3-methoxyphenyl)- 3,5-dimethyl-3-hexanol, 1- (2-methoxyphenyl) -3,5-dimethyl-3-hexanol.

  5- (4-methoxyphenyl) -3-methyl-1-penten-3-ol, 5- (3-methoxyphenyl) -3-methyl-1-penten-3-ol, 5- (2-methoxyphenyl) -3-Methyl-1-penten-3-ol, 5- (4-methoxyphenyl) -3,4-dimethyl-1-penten-3-ol, 5- (3-methoxyphenyl) -3,4-dimethyl -1-penten-3-ol, 5- (2-methoxyphenyl) -3,4-dimethyl-1-penten-3-ol, 1- (4-methoxyphenyl) -3-dimethyl-5-hexene-3 -Ol, 1- (3-methoxyphenyl) -3-dimethyl-5-hexen-3-ol, 1- (2-methoxyphenyl) -3-dimethyl-5-hexen-3-ol, 1- (4-ethoxy Phenyl)- -Methyl-3-pentanol, 1- (3-ethoxyphenyl) -3-methyl-3-pentanol, 1- (2-ethoxyphenyl) -3-methyl-3-pentanol, 1- (4-ethoxy Phenyl) -3-methyl-3-hexanol, 1- (3-ethoxyphenyl) -3-methyl-3-hexanol, 1- (2-ethoxyphenyl) -3-methyl-3-hexanol, 1- (4- Ethoxyphenyl) -3-methyl-3-heptanol, 1- (3-ethoxyphenyl) -3-methyl-3-heptanol, 1- (2-ethoxyphenyl) -3-methyl-3-heptanol, 1- (4 -Ethoxyphenyl) -3,4-dimethyl-3-pentanol, 1- (3-ethoxyphenyl) -3,4-dimethyl-3-pentanol, 1- (2-ethoxypheny) ) -3,4-dimethyl-3-pentanol, 1- (4-ethoxyphenyl) -3,5-dimethyl-3-hexanol, 1- (3-ethoxyphenyl) -3,5-dimethyl-3-hexanol 1- (2-ethoxyphenyl) -3,5-dimethyl-3-hexanol.

  5- (4-Ethoxyphenyl) -3-methyl-1-penten-3-ol, 5- (3-ethoxyphenyl) -3-methyl-1-penten-3-ol, 5- (2-ethoxyphenyl) -3-Methyl-1-penten-3-ol, 5- (4-ethoxyphenyl) -3,4-dimethyl-1-penten-3-ol, 5- (3-ethoxyphenyl) -3,4-dimethyl -1-penten-3-ol, 5- (2-ethoxyphenyl) -3,4-dimethyl-1-penten-3-ol, 1- (4-ethoxyphenyl) -3-dimethyl-5-hexene-3 -Ol, 1- (3-ethoxyphenyl) -3-dimethyl-5-hexen-3-ol, 1- (2-ethoxyphenyl) -3-dimethyl-5-hexen-3-ol.

  1- (4-Isopropoxyphenyl) -3-methyl-3-pentanol, 1- (3-Isopropoxyphenyl) -3-methyl-3-pentanol, 1- (2-Isopropoxyphenyl) -3- Methyl-3-pentanol, 1- (4-isopropoxyphenyl) -3-methyl-3-hexanol, 1- (3-isopropoxyphenyl) -3-methyl-3-hexanol, 1- (2-isopropoxy) Phenyl) -3-methyl-3-hexanol, 1- (4-isopropoxyphenyl) -3-methyl-3-heptanol, 1- (3-isopropoxyphenyl) -3-methyl-3-heptanol, 1- ( 2-isopropoxyphenyl) -3-methyl-3-heptanol, 1- (4-isopropoxyphenyl) -3,4-dimethyl-3-pentanol, -(3-Isopropoxyphenyl) -3,4-dimethyl-3-pentanol, 1- (2-Isopropoxyphenyl) -3,4-dimethyl-3-pentanol, 1- (4-Isopropoxyphenyl) -3,5-dimethyl-3-hexanol, 1- (3-isopropoxyphenyl) -3,5-dimethyl-3-hexanol, 1- (2-isopropoxyphenyl) -3,5-dimethyl-3-hexanol .

  5- (4-isopropoxyphenyl) -3-methyl-1-penten-3-ol, 5- (3-isopropoxyphenyl) -3-methyl-1-penten-3-ol, 5- (2-iso Propoxyphenyl) -3-methyl-1-penten-3-ol, 5- (4-isopropoxyphenyl) -3,4-dimethyl-1-penten-3-ol, 5- (3-isopropoxyphenyl)- 3,4-dimethyl-1-penten-3-ol, 5- (2-isopropoxyphenyl) -3,4-dimethyl-1-penten-3-ol, 1- (4-isopropoxyphenyl) -3- Dimethyl-5-hexen-3-ol, 1- (3-isopropoxyphenyl) -3-dimethyl-5-hexen-3-ol, 1- (2-isopropoxyphenyl) -3-dimethyl-5 Hexene-3-ol.

In the general formula (1), R ₂ is a para-hydroxyl group, and R ₁ is a hydrocarbon group having 2 to 4 carbon atoms (except when R ₁ is a 1-propenyl group). 4- (3-Hydroxy-3-substituted) butylphenol represented by the general formula (2) is a novel compound not conventionally known.

Specific examples of R ₁ in the general formula (2) having 2 to 4 carbon atoms (except when R ₁ is a 1-propenyl group) and 4- (3-hydroxy-3-substituted) ) Specific examples of the compound name of butylphenol include those similar to those mentioned for the general formula (1). In general formula (1), since the carbon atom having a hydroxyl group in the alkyl chain is an asymmetric carbon atom except when R ₁ is a methyl group, the alcohol derivative represented by general formula (1) is optically active. Or racemate can be formed. In the present invention, the alcohol derivative represented by the general formula (1) may be an optically active substance or a racemic substance, and includes any case.

  The alcohol derivative represented by the general formula (1) including the general formula (2) can be synthesized, for example, according to the following reaction formula.

（式中、Ｒ_１及びＲ_２の定義は前記と同様であり、Ｘはハロゲン原子を表す。）

(Wherein, R ₁ and R ₂ are as defined above, and X represents a halogen atom.)

The alcohol derivative of the general formula (1) can be easily produced by reacting the ketone derivative represented by the general formula (3) with the Grineer reagent (4). When R ₂ is a hydroxyl group, the hydrogen of the hydroxyl group may be anionized with a base in advance.
Examples of the halogen atom in the Grineer reagent of the general formula (4) used in the above synthesis method include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The above reaction can be carried out in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as hexane, heptane and octane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, diethyl And ethers such as ether, diisopropyl ether, tetrahydrofuran and dioxolane. These may be used singly or as a mixed solution of two or more. As the solvent, ethers are preferable, and among them, diethyl ether, diisopropyl ether, tetrahydrofuran and the like are more preferable because of their versatility and high reaction selectivity and yield.

  The amount of these solvents to be used is not particularly limited, but is about 0.1 to 30 times, preferably about 0.5 to 5 times the volume of the raw material compound (substrate). The amount of the acidic substance used in this reaction is preferably about 0.1 to 10 parts by mass, more preferably about 0.5 to 5 parts by mass with respect to 1 part by mass of the raw material compound (substrate). Although used, it is not limited to this range. The reaction temperature is in the range of about -20 to 200 ° C, preferably -5 ° C to the boiling point of the solvent used. Thus, the reaction can be performed smoothly. From the reaction solution obtained by the reaction, after completion of the reaction, the solvent is distilled off under reduced pressure. The alcohol derivative of the present invention can be produced by subjecting the obtained residue to distillation under reduced pressure.

The alcohol derivative of the present invention represented by the general formula (1) thus obtained has a fruity, anisic, sweet, slightly sugary, slightly cresolic, jasmine-like floral fragrance, and is blended with this. By this, the perfume composition with high palatability can be provided.
Furthermore, by blending the alcohol derivative of the general formula (1) of the present invention, the desired fragrance persistence and residual fragrance use effect, that is, the fragrance persistence of the fragrance is enhanced.

  The fragrance composition of the present invention contains an alicol derivative represented by the general formula (1) as an essential component, but is also known or known as a fragrance component, such as ketones, aldehydes, esters, alcohols, ethers. Terpenes, natural essential oils, synthetic musks and the like are blended alone or in appropriate combination to form a fragrance composition.

  Examples of the fragrance composition in which the alcohol derivative represented by the general formula (1) is blended include, for example, cosmetics, quasi-drugs and external preparations such as pharmaceuticals, body and clothing cleaning agents, bleaching agents and softening agents. Fragrances ordinarily used in various products such as bathing agents.

  The blending amount of the alcohol derivative represented by the general formula (1) into the fragrance composition is an appropriate amount depending on the fragrance composition to be applied, or depending on the form of the product to which the fragrance composition is further applied, the usage mode, and the like. However, generally 1.0 to 90 mass% is preferable with respect to the total amount of the fragrance composition including the applied alcohol derivative, and more preferably 5.0 to 30 mass%. Moreover, the compounding quantity and application method to a product of the fragrance | flavor composition obtained by this invention can be suitably changed with the kind of product, a use purpose, etc. Usually, the compounding quantity of the fragrance | flavor composition to a product is 0.01-50 mass% in a final product composition, Preferably it is 0.05-30 mass%.

  Products to which the fragrance composition of the present invention is applied include, for example, skin cosmetics, shampoos, rinses, conditioners, hair cosmetics such as hair arts, hair creams, perfumes, colons, soaps, indoor fragrances, Examples include cosmetics such as toothpaste, toiletries such as detergents and softeners, quasi-drugs such as bath preparations, poultices, and ointments, and pharmaceuticals. However, products to which the fragrance composition of the present invention can be applied are not limited to those described above.

  When the blending amount of the fragrance composition into the product is shown for each product as the amount of the alcohol derivative represented by the general formula (1), skin cosmetics, shampoos, rinses, conditioners, hair arts, hair creams, etc. For cosmetics such as hair cosmetics, perfumes, colons, soaps, bathing agents, etc., usually 0.01 to 30% by weight, especially 0.05 to 10% by weight, based on the total composition of the product. It is preferable to use at a concentration of In addition, the blending amount of the alcohol derivative in toiletries such as detergents and softeners is usually 0.01 to 1% by mass, particularly 0.05 to 0.3% by mass with respect to the total composition of the product. The concentration is preferably used.

In addition, the products to be applied are appropriately blended with optional ingredients according to the intended use of each product, such as cosmetics, toiletries, bathing agents, insurance hygiene materials, quasi drugs, pharmaceuticals, etc. Provided as final product.
Moreover, when the alcohol derivative represented by the general formula (1) is blended in a state of being contained in a fragrance composition when blended in a product, the alcohol derivative and the fragrance composition are separately blended. Compared with the case where it is blended as a component, it is possible to obtain a product that is remarkably superior in fragrance characteristics, fragrance characteristics such as residual fragrance properties, and residual characteristics. For this reason, the fragrance | flavor composition of this invention is especially preferable as a fragrance | flavor composition mix | blended with a final product.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to synthesis examples of alcohol derivatives of the general formula (1) and use test examples thereof as examples, but the present invention is not limited thereto.
In addition, the measurement of the product in a synthesis example was performed using the following apparatus apparatus.
Nuclear magnetic resonance spectrum: ¹ H-NMR: AVANCE III 500 (500 MHz) (manufactured by Bruker))
External reference material: Tetramethylsilane

Example 1
<Synthesis of 4- (3-hydroxy-3-methylpentyl) phenol>

Under a nitrogen atmosphere, 16.42 g (0.100 mol) of 4- (4-hydroxyphenyl) butan-2-one was dissolved in 50 ml of dehydrated THF, cooled to 2 ° C., and 4.20 g (0 .105 mol) was added over 10 minutes and stirred for 30 minutes. At the same temperature, 35 ml (0.105 mol) of ethyl magnesium bromide 39% ethyl ether solution was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 1 hour. The reaction solution was cooled to 2 ° C., and 200 ml of 1N hydrochloric acid was added dropwise. After recovering the organic solvent with an evaporator, the aqueous layer was extracted with toluene, and the organic layer was washed with water and concentrated to obtain 14.97 g of a crude product.
The resulting crude product was purified by silica gel chromatography (developing solvent; toluene: ethyl acetate = 5: 1), and 9.74 g (0.050 mol, 50) of 4- (3-hydroxy-3-methylpentyl) phenol. 0.0% yield).

¹ H-NMR (500 MHz, CDCl ₃ ): σ 0.93 (t, 3H, J = 7.5), 1.20 (s, 3H), 1.56 (q, 2H, J = 7.5), 1.73 (t, 2H, J = 7.0), 2.60 (q, 2H, J = 6.4), 5.06 (s, 1H), 6.75 (d, 2H, J = 4) .3), 7.06 (d, 2H, J = 4.4)

Example 2
<Synthesis of 4- (3-hydroxy-3-methyl-4-pentenyl) phenol>

Under nitrogen atmosphere, 16.42 g (0.100 mol) of 4- (4-hydroxyphenyl) butan-2-one was dissolved in 50 ml of dehydrated THF, cooled to 2 ° C., and 4.20 g (0.105 mol) of sodium hydride. ) Was added over 10 minutes and stirred for 30 minutes. At the same temperature, 53 ml (0.105 mol) of a 28% THF solution of vinylmagnesium bromide was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 1 hour. The reaction solution was cooled to 2 ° C., and 200 ml of 1N aqueous hydrochloric acid was added dropwise. After recovering the organic solvent with an evaporator, the aqueous layer was extracted with toluene, and the organic layer was washed with water and concentrated to obtain 15.37 g of a crude product.
The obtained crude product was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 5: 1), and 9.04 g (0.047 mol, 47) of 4- (3-hydroxy-3-methylpentyl) phenol. 0.0% yield).

¹ H-NMR (500 MHz, CDCl ₃ ): σ 1.38 (s, 3H), 1.81 (t, 2H, J = 7.0), 2.58 (t, 2H, J = 7.0), 4.82 (s, 1H), 5.10 (d, 1H, J = 10.8), 5.23 (d, 1H, J = 17.1), 5.97 (q, 1H, J = 10) .8, 17.4), 6.75 (d, 2H, J = 4.3), 7.06 (d, 2H, J = 4.4)

Example 3
<Evaluation of aroma quality>
The alcohol derivative obtained in Example 1 or Example 2 was attached to a bottle mouth and a filter paper, and sensory evaluation was performed by a perfumer having experience of 5 years or more. As a result, the alcohol derivative obtained in Example 1 had a floral fragrance such as fruity, anisic, sweet, slightly sugary, slightly cresolic, and jasmine.
On the other hand, the alcohol derivative obtained in Example 2 had fruity, anisic, sweet, slightly sugary, slightly cresolic, jasmine-like floral, and slightly waxy fragrance.

Example 4
Test Example 1: <Perfume Composition Fragrance and Residual Fragrance Test>
In accordance with the formulation of Table 1, a fragrance composition was prepared, and a fragrance standing and a residual fragrance property test were performed. As a method, about 10.0 mg was weighed on a filter paper laid on the bottom of a wide-mouth bottle having a diameter of 40 mm and a height of 50 mm, and the lid was closed and left for 30 minutes to prepare an evaluation sample. The fragrance immediately after opening the lid and the residual fragrance after about 5 hours in an open system were evaluated.
The evaluation was repeated 3 times by 11 panelists specializing in incense for 5 years or more (total of 33), and the strength against the comparative prescription (Comparative Example 3) was evaluated.

(1) Results of scenting test Table 2 shows the results of the number of people who felt that the scenting was the highest for the comparative formulation (Comparative Example 3).

(2) Residual fragrance test results Table 3 shows the results of the number of persons who felt that the residual fragrance was strongest for the comparative formulation (Comparative Example 3).

  As is clear from the evaluation of the fragrance composition of Example 4 in Test Example 1, the alcohol derivative of the present invention (Example 1) gave a fragrance to the above prepared fragrance and showed excellent results in both the remaining fragrance properties.

Example 5
Test Example 2: Effect test with bathing agent 100 g of each of the bathing agents in Table 4 with 1.0% of the blended fragrances of Example 2 and Comparative Example 2 were prepared, and 20 g was added to 180 liters of 40-42 ° C. hot water. It melt | dissolved, and the fragrance intensity | strength immediately after and the fragrance intensity | strength after 30 minutes were compared and evaluated by the expert panel.

(1) Results of fragrance test Table 5 shows the results of the number of people who felt that fragrance was high.
(2) Residual fragrance test results Table 6 shows the results of the number of people who felt that the residual fragrance properties were strong.

  As apparent from the evaluation of the bathing agent of Example 5 in Test Example 2, the bathing agent containing the blended fragrance of the present invention is more fragrant and has a longer scent than the bathing agent of Comparative Example 4 containing triethyl citrate. Excellent results were shown.

<Example 6>
Test Example 3: Effect test with eau de cologne A fragrance composition was prepared according to the formulation of Table 7.

100 g of eau de cologne (95% ethanol solution) in which 5% of the fragrance composition of Example 6 and Comparative Example 5 was added was prepared, and an appropriate amount of each was applied to the inside of the left and right forearms to spray the fragrance immediately after, Residual fragrance property was evaluated after 4 hours.
Evaluation was carried out by 13 panelists specializing in incense that had been experienced for more than 5 years.

(1) Scent Standing Test Results Table 8 shows the results of the number of people who felt that the scent standing was high.
(2) Residual Aroma Test Results Table 9 shows the results of the number of people who felt that the residual aroma was strong.

  As apparent from Test Example 3, the eau de cologne containing the blended fragrance of the present invention showed a particularly superior residual scent compared to the cologne containing p-menthane-3,8-diol.

<Example 7>
Test Example 4: Effect test with shampoo and conditioner According to the formulation of Table 10, the fragrance compositions shown in Example 7 and Comparative Example 6 were prepared.

  Subsequently, 100 g of each shampoo containing 0.5% of the fragrance composition of Example 7 and Comparative Example 6 was produced according to the formulation in Table 11. Similarly, 100 g of each conditioner was produced according to the formulation in Table 12.

(Evaluation method)
5g of frog (human hair) was treated with 2.5g of shampoo and 5ml of warm water (40 ° C) for 1 minute, rinsed with 1000ml of warm water (40 ° C), and then towel-dried and fixed on aluminum foil for evaluation. A sample was used. The fragrance immediately after fixation and the residual fragrance after about 5 hours at room temperature were evaluated.
The conditioner was evaluated in the same manner as the shampoo using 5.0 g of conditioner for 5 g of Kamoji.
The evaluation was repeated 3 times by 10 panelists specializing in incense which have been experienced for 5 years or more (total 30 persons).

(1) Results of shampoo scenting test Table 13 shows the results of the number of people who felt that scenting was high.
(2) Residual fragrance test results of shampoo Table 14 shows the results of the number of people who felt that the residual fragrance was strong.
(1) Conditioner scenting test results Table 15 shows the results of the number of people who felt that scenting was high.
(2) Result of conditioner residual scent test results Table 16 shows the results of the number of persons who felt that the residual scent was strong.

  As is clear from Test Example 4, the shampoo and conditioner containing the blended fragrance of the present invention showed excellent results in both fragrance and residual fragrance, and particularly had a remarkable effect on the residual fragrance.

  The alcohol derivative represented by the general formula (1) blended in the fragrance composition of the present invention has aroma characteristics such as fragrance and sustainability and retention characteristics without changing the fragrance of the fragrance composition as a base. Since it is a high-quality fragrance improving agent, cosmetics such as skin cosmetics, shampoos, rinses, conditioners, hair cosmetics such as hair arts and hair creams, perfumes, colons, soaps, indoor air fresheners, toothpastes, etc. Contributing to improving the quality of perfume compositions for various products that require blending of perfume, such as toiletries such as detergents, softeners, quasi-drugs such as bath preparations, poultices, ointments, or pharmaceuticals It is.

Claims (9)

General formula (1)

(In the formula, R ₁ is a hydrocarbon group having 1 to 6 carbon atoms, and R ₂ is a hydrocarbon group having 1 to 4 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.)
The fragrance | flavor composition formed by mix | blending the alcohol derivative represented by these. 2. The alcohol derivative, wherein R ₁ in the general formula (1) is a hydrocarbon group having 2 to 4 carbon atoms, and R ₂ is a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms. The fragrance composition described. The alcohol derivative is represented by the general formula (2)

(Wherein R ₁ is one selected from an alkyl group having 2 to 4 carbon atoms and an alkenyl group having 2 to 4 carbon atoms), and is 4- (3-hydroxy-3-substituted) butylphenol. The fragrance composition according to claim 1, wherein:   The alcohol derivative is selected from 4- (3-hydroxy-3-methylpentyl) phenol, 4- (3-hydroxy-3-methyl-4-pentenyl) phenol and 4- (3-hydroxy-3-methylhexyl) phenol. The fragrance composition according to any one of claims 1 to 3, wherein the fragrance composition is at least one selected.   5-90 mass% of alcohol derivatives of the said General formula (1) are contained, The fragrance | flavor composition of any one of Claims 1-4 characterized by the above-mentioned.   A cosmetic, toiletry product, bath preparation, beverage, food, quasi-drug or pharmaceutical comprising the fragrance composition according to any one of claims 1 to 5.   A method for enhancing the fragrance sustainability of a fragrance, which comprises adding an alcohol derivative of the general formula (1) to the fragrance composition. General formula (2)

(In the formula, R ₁ is a hydrocarbon group having 2 to 4 carbon atoms, except when R ₁ is a 1-propenyl group.)
4- (3-hydroxy-3-substituted) butylphenol represented by   4- (3-hydroxy-3-substituted) butylphenol represented by the general formula (2) is 4- (3-hydroxy-3-methylpentyl) phenol or 4- (3-hydroxy-3-methyl-4). The 4- (3-hydroxy-3-substituted) butylphenol according to claim 8, which is any one of -pentenyl) phenol and 4- (3-hydroxy-3-methylhexyl) phenol.