JP4092380B2 - Perfume composition containing nerolide-loxide and method for producing the same - Google Patents

Description

The present invention relates to a fragrance composition containing nerolide-oxide (hereinafter referred to as Compound 1), and a method for producing Compound 1.

Nellolide-oxide represented by Formula 1 has already been reported as a volatile component such as a Labiatae plant (Non-Patent Document 1, Non-Patent Document 2). There are also reports on synthesis methods, for example, the method of epoxidizing the double bond at the 6,7-position of nerolidol and then cyclizing with an acid (Non-patent Document 3), or the synthesis shown in the following process diagram Law (Patent Document 1) and the like have been reported.

However, there is no description about fragrance in these reports, and furthermore, it is not used at all as a fragrance material. As for the synthesis method, regioselective monoepoxidation of nerolidol is difficult, and purification after cyclization is not sufficient by distillation alone, and purification by silica gel column chromatography (SCC) is necessary. . Further, in the method shown in the above process diagram, it is difficult to efficiently obtain both the ketone represented by Formula 4 and the halide used as the raw material for the Grignard reagent represented by Formula 5 in a short process. For example, in order to obtain a ketone represented by formula 4, the isopropenyl moiety of 2-methyl-2-vinyl-5-isopropenyltetrahydrofuran can be synthesized in one step by oxidation with ozone, permanganate, or the like. The regioselectivity of the reaction is low and the yield is poor. In addition, in order to obtain a good yield of a halide as a raw material for the Grignard reagent represented by Formula 5, for example, synthesis is performed in two steps by using a cyclopropylmethyl ketone as a substrate and a Grignard reaction and a reaction with hydrohalic acid Although it can be said that it is not an inexpensive raw material system, these methods are not necessarily excellent from the viewpoint of economic efficiency and industrial development.
Prior art documents relating to the invention of the present application include the following.

Biochem. Syst. Ecol. (1996), 24 (6), 571-575

J. Essent. Oil Res. (1999), 11 (3), 317-320 Bull. Soc. Chim. France (1965), (2), 484-486 Japanese Unexamined Patent Publication No. 55-40675

Blended fragrances are indispensable for the purpose of differentiating foods and beverages, cosmetics, etc. and increasing the commercial value. With regard to natural essential oils and synthetic fragrances as materials, new ones are constantly being developed to provide a rich fragrance variation in daily life. However, in recent years, consumers have attracted attention to the safety of fragrances. On the other hand, development of a perfume material that has a strong character derived from nature and produces a desirable natural feeling has been a concern.

As a result of scrutinizing the aroma component of strawberry jam, the present inventors synthesized Compound 1 represented by Formula 1 as an estimated component. As a result, the compound 1 has a transparent fruity and floral flavor characteristic like a strawberry or milk, which is preferable, for example, by adding and using it in a food fragrance or a cosmetic fragrance. We found that transparency and sweetness were added.
Furthermore, as a result of intensive investigations on the production method of Compound 1, the present invention was completed by finding an advantageous method in both economical efficiency and industrialization, with a low number of steps and a high yield.

The present invention is represented by the formula 1

The fragrance | flavor composition characterized by containing the nerolide-oxide represented by these. A process for producing nerolide-oxide, comprising reacting an epoxide represented by formula 2 with an anion equivalent represented by formula 3 derived from prenyl halide in the presence of copper (I) It is.
Compound 1 can be synthesized, for example, by the method shown in the following process diagram.

That is, by reacting an epoxide represented by Formula 2 and an anion equivalent represented by Formula 3 derived from prenyl halide in the presence of copper (I), Compound 1 represented by Formula 1 is obtained. obtain.

Epoxide represented by Formula 2 can be easily synthesized by a conventionally known method. For example, commercially available 2-methyl-2-vinyl-5-isopropenyltetrahydrofuran is epoxidized with a peracid such as peracetic acid. Can be obtained.

Anion equivalents represented by Formula 3 include, for example, Grignard reagent (M = MgX, where X represents halogen), organolithium reagent (M = Li), organozinc reagent (M = ZnX), organic A cerium reagent (M = Cex ₂ ) and the like can be mentioned, but a Grignard reagent is preferred from the viewpoint of economy and operability. The amount used can generally range from about 0.7 to about 10 moles with respect to 1 mole of epoxide represented by Formula 2, but can preferably be used in the range of about 1 to about 5 moles. In addition, as a raw material of the organometallic reagent quoted here, prenyl chloride, prenyl bromide, etc. are mentioned, for example, These are marketed.

In the above step, the copper (I) used includes, for example, cuprous iodide, cuprous bromide and cuprous chloride, and the amount used is 1 mol of epoxide represented by Formula 2. In general, a range of about 0.001 to about 10 mol can be mentioned, but a range of about 0.01 to about 1 mol can be preferably used.

Examples of the reaction solvent include ethers such as tetrahydrofuran (THF), diethyl ether, and 1,2-dimethoxyethane (DME). The reaction conditions generally include a temperature range of about −80 to 70 ° C. and a time period of about 2 to 6 hours.
Examples of the inert gas used in each step include argon, helium, and nitrogen.

Separation / purification methods in each step include, for example, atmospheric or reduced pressure distillation, normal phase or reverse phase column chromatography, normal phase or reverse phase high performance liquid chromatography (HPLC), gas chromatography (GC) using a nonpolar or polar column. Etc.

Compound 1 obtained by the above reaction has a transparent, fruity, floral flavor and flavor characteristic like strawberries and milk.
Compound 1 has its own unique fragrance as described above. By adding Compound 1 to a known fragrance composition, the fragrance composition produces the fragrance characteristics of Compound 1, and the fragrance It exhibits a very effective harmony with the fragrance of the composition itself and exhibits excellent effects in improving and enhancing the fragrance of each fragrance composition.

  For example, by adding and using Compound 1 to a floral blended fragrance, effects such as increased transparency, volume, and mild sweetness can be obtained. In addition, for example, by adding and using it in a fruit-based blended fragrance, effects such as increased ripeness, sweetness, and natural feeling can be obtained. In addition to these, for example, by adding to and using a blended fragrance such as vanilla, milk, woody, citrus, etc., the body feeling and the natural feeling are improved, and each character is enhanced.

That is, the fragrance composition of the present invention is a fragrance composition containing Compound 1. The content thereof is generally in the range of about 0.001 to about 20% by weight, preferably about 0.1 to about 10% by weight, based on the total weight of the fragrance composition, but is not limited thereto. The content can be appropriately adjusted depending on the kind of the product.

When preparing a fragrance composition using Compound 1, other fragrance compounds used include, for example, various hydrocarbons such as limonene, caryophyllene, and pinene; various types such as acetaldehyde, α-hexylcinnamaldehyde, and citral. Aldehydes: various ketones such as maltol, benzylacetone, damacenone; various alcohols such as butanol, benzyl alcohol, linalol; geranyl ethyl ether, rose oxide, furfura Various ether oxides such as ethyl acetate; various esters such as ethyl acetate, benzyl acetate and linalyl acetate; various lactones such as γ-decalactone, coumarin and sclareolide; Various hetero compounds such as isopropyl-4-methylthiazol and phenylacetonitrile Substances: Various natural materials such as jasmine absolute, fern wood oil, oris concrete. Examples of the solvent to be used include ethanol, dipropylene glycol (DPG), benzyl benzoate (BB), water, triacetin, triethyl citrate (TEC) and the like.

The fragrance composition of the present invention is used in the following food and drink products and cosmetics, thereby imparting its characteristic fragrance or fragrance flavor property to the product, and satisfying the needs of consumers and unique. Products can be provided.
Examples of the foods and beverages include various beverages such as alcoholic beverages, citrus beverages, fruit beverages, milk beverages, carbonated beverages, tea beverages; Various kinds of luxury products such as tobacco, chewing gum, candy, pudding and jelly; various dairy products such as cheese and yoghurt; various types of sports such as Japanese style and western styles; Examples include instant foods, snack foods, animal and plant extracts.

  Examples of cosmetics include perfume such as parfum, eau de parfum and eau de toilette; various toiletry products such as shampoos, rinses, treatments, soaps and body shampoos; Fragrances such as candles, kneading fragrances; hair dyes such as hair dyes, bleaching agents and hair tonics; various cosmetics such as foundations, lotions, emulsions, creams and lipsticks Examples: Various fragrances such as indoor fragrances and car fragrances; various detergents such as dish detergents, laundry detergents and softeners.

The nerolide oxide provided by the present invention has a transparent fruity and floral flavor characteristic like strawberry and milk, and is a useful preparation material in a fragrance composition.

  In addition, the fragrance composition of the present invention has excellent fragrance characteristics that are improved and enhanced, such as imparting transparency and sweetness, while producing the fragrance characteristics of Compound 1.

  Furthermore, the production method of the present invention has a short number of steps, is inexpensive and has a high yield, and is advantageous in both economic efficiency and industrial development.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this.
Example 1: Synthesis of Compound 1 Under an argon atmosphere, a suspension of epoxide (12.7 g, 0.075 mol), cuprous iodide (1.52 g, 0.008 mol), and THF (100 mL) represented by Formula 2 is − The mixture was cooled to 30 ° C., and a 0.5 M THF solution (300 mL, 0.15 mol) of prenyl magnesium chloride separately prepared was dropped therein over 1 hour, followed by stirring at −30 ° C. for 3 hours. The reaction mixture was poured into ice-cooled saturated aqueous ammonium chloride solution, extracted twice with toluene (200 mL), and the combined organic layer was washed with saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 16.7 g of a crude product. This was subjected to vacuum distillation to obtain 15.8 g of a fraction having a boiling point of 114 to 130 ° C./2 mmHg as Compound 1 (yield 87.8%). As a result of GC analysis (Hewlett Packard 5890, DB-1, 60 m × 0.25 mm, 0.25 μm), the chemical purity of the isomer mixture of Compound 1 was 99.0%. The individual mass spectra of the obtained isomers were almost the same.
Mass spectrum of Compound 1
EI-MS (m / z): 238 (M ⁺ ), 155, 138, 109, 93, 69, 55, 43.
Example 2: Preparation of a loose type fragrance Each component (part by weight) shown in Table 1 below was mixed as a loose type fragrance composition.

About the above-mentioned fragrance composition, when compared with 10 well-trained professional panelists, all of Example 2 were recognized to have a sweeter volume feel, and the effect of a transparent red luscious aroma was effective. It is said that it expresses.

Example 3 Preparation of Strawberry Type Fragrance Each component (part by weight) shown in Table 2 below was mixed as a strawberry type fragrance composition.

As for the above fragrance composition, when compared with 10 well-trained professional panelists, all were more mature in Example 3, and the succulent sweet flesh texture was effectively enhanced. did.

Claims (2)

Formula 1

The fragrance | flavor composition characterized by containing the nerolide-oxide represented by these. Formula 2

Formula 3 derived from epoxide and prenyl halide represented by

The anion equivalent represented by the formula (M in the formula represents a metal atom or a metal salt) is reacted in the presence of copper (I). Manufacturing method.