JP2002114769A - 5-(3z-hexenyl)-4-methyl-4,5-dihydro-2(3h)-furanone and perfume composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aroma and flavor composition that includes the furanone cis-isomer having the smell of green, floral and fresh peach peel and the trans-isomer having butter, nuts, woody and powdery peach pulp and can be used as the components for flavor composition, further the flavor composition show these excellent flavor properties and can give improved and enhanced natural feeling and volume. SOLUTION: The objective flavor components are the cis-isomer or the trans- isomer of 5-(3Z-hexenyl)-4-methyl-4,5-dihydro-2(3H)-furanone, respectively and the flavor composition characteristically comprises one or two of the trans isomer and the cis-isomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cis-form and a trans-form of 5- (3Z-hexenyl) -4-methyl-4,5-dihydro-2 (3H) -furanone (also referred to as a compound of the formula 1). And a fragrance composition containing one or two of them.

[0002]

2. Description of the Related Art Lactones represented by formulas 2 and 3 are known as analogous compounds of the compound of formula 1.

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Embedded image The former has a fragrance of butter, nuts, fruity and floral, and the latter has a fragrance of green and jasmine, and is used as a compounded fragrance material ("Synthetic fragrance" by Motoichi Indo, Chemical Industry) Published by Nipposha, p555-557, 1996). Further, a lactone compound represented by the general formula 4 is isolated from peach fruit,
It is known to have green, nut, and milky flavors (Japanese Patent Application Laid-Open No. 9-87267).

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[0003]

In recent years, with the diversification of consumer needs, the development of more characteristic and unique foods and drinks or cosmetics has been required. With regard to the fragrance as one of these raw materials, the development of a compounded fragrance having a similarly strong character has been pending.

[0004] The present inventors have intensively studied for the invention of a lactone compound having an unprecedented character. As a result, the cis-form of the compound of the present invention, which is not described in the literature, is green, floral, and fresh peach-peel-like, and the trans-form is butter, nut, woody, and powdery peach-like pulp. It has been found to have aroma flavor properties. The present invention has been completed by finding that adding or using one or two of these to a food flavor or a cosmetic flavor imparts a favorable natural feeling and volume.

[0005]

SUMMARY OF THE INVENTION

Embedded image 5- (3Z-hexenyl) -4-methyl-4,5-
A fragrance composition comprising a cis form or a trans form of dihydro-2 (3H) -furanone, and one or two compounds thereof.

The compound of the present invention can be synthesized by the method shown in the following process diagram using 3Z-hexenyl chloride and ethyl 3-formylbutanoate obtained by a conventionally known method as starting materials.

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That is, a Grignard reagent represented by Formula 5 is added to tetrahydrofuran (THF) under an inert gas atmosphere.
A product obtained by reacting ethyl 3-formylbutanoate represented by the formula 6 is subjected to alkali hydrolysis, followed by dehydration and ring closure under hydrochloric acid to obtain a mixture of a cis-form and a trans-form of the compound 1 of the present invention. . This is separated and purified by a method such as high performance liquid chromatography (HPLC) to obtain a pure cis form and a trans form, respectively.

The reaction of a formyl ester with a Grignard reagent is generally known, and includes, for example, the reaction of an alkyl 3-formylpropanoate with 3Z-hexenylmagnesium halide (JP-A-7-188202).

The starting material for the Grignard reagent represented by Formula 5 is 3
Z-hexenyl chloride is, for example, 3Z-hexeno-
The starting material is easily obtained by reaction with a chlorinating agent such as thionyl chloride, oxalyl chloride or phosphorus trichloride. The compound represented by the formula 6 can be obtained, for example, by adding hydrogen bromide to a double bond of a crotonic acid ester, and then cyanating and reducing [Chem.
er. 1975, 108 (1), 208-214].

In the above Grignard reaction, the Grignard reagent is used, for example, in an amount of about 0.5 to about 1 mol of the compound represented by the formula 6.
A range of about 10 moles may be mentioned, but preferably about
It can be used in a ratio of about 0.9 to about 1.2 mol. The reaction conditions include a temperature of about -80 ° C to about 100 ° C for about 2 hours to about 10 hours.

As the solvent used in the above reaction, for example,
THF, diethyl ether, 1,2-dimethoxyethane, benzene, toluene, n-hexane and the like can be mentioned. In addition, examples of the inert gas include nitrogen, helium, and argon.

As a method for separating and purifying the cis form and the trans form, for example, normal pressure or reduced pressure distillation, normal phase or reverse phase column chromatography, normal phase or reverse phase HPLC, gas chromatography using a nonpolar or polar column ( GC) and the like.

The cis-form of the compound of the present invention obtained by the above reaction is green, floral and fresh peach-peel-like, and the trans-form is butter, nut, woody and powdery peach-like pulp. It has an aroma and flavor characteristics. As described above, the compound of the present invention itself has a unique fragrance.However, by including one or two kinds of the compound of the present invention in a known fragrance composition, the fragrance composition becomes the respective compound. While exhibiting a very effective harmony with the fragrance of the fragrance composition itself, and exhibiting excellent effects of improving and enhancing the fragrance of each fragrance composition. For example, by adding and using a cis-form in a floral-based compounded flavor, a gorgeous and diffusible top note is imparted, and a volume and a natural feeling are imparted. In addition, for example, by adding and using a trans-form to a fruit-based mixed flavor, a mild sweetness with spreading is imparted, and a feeling of fruit juice and flesh is enhanced to give a united and natural feeling. Also,
For example, vanilla, milk,
By adding to and using woody, citrus-based blended fragrances, the body feel and natural feel are improved,
Each character is enhanced.

That is, the fragrance composition of the present invention is a fragrance composition containing the cis-form, trans-form of the compound of the present invention, or a mixture thereof. Its content generally ranges from about 0.001 to about 20% by weight of the total weight of the perfume composition, preferably from about 0.1 to about 10% by weight, but is not limited thereto, and the perfume composition of interest The content can be appropriately adjusted depending on the type of the product. The mixing ratio in the mixture of the cis-form and the trans-form is not particularly limited, and an effect according to the respective mixing ratio is exhibited, but generally, 20:80 to 80:20 can be mentioned.

When a fragrance composition is prepared using the compound of the present invention, other fragrance compounds to be used include, for example, various hydrocarbons such as limonene, caryophyllene and pinene; acetaldehyde, a-hexylcinnamaldehyde, citrate Various aldehydes such as toluene; maltole,
Various ketones such as benzylacetone and damacenone; various alcohols such as butanol, benzyl alcohol and linalool; various ethers such as geranyl ethyl ether, rosoxide and furfural. -Oxides; various esters such as ethyl acetate, benzyl acetate and linalyl acetate; various lactones such as g-decalactone, coumarin and sclareolide; indole, 2-isopropyl-4-methylthiazo-
And various hetero compounds such as phenylacetonitrile; jasmine absolute, fern-wood oil,
Various natural materials such as Oris concrete. Examples of the solvent to be used include ethanol, dipropylene glycol, water, triacetin, triethyl citrate and the like.

The fragrance composition of the present invention imparts its characteristic fragrance or fragrance and flavor characteristics to products by using it in the following foods and beverages and cosmetics, and is suitable for consumers' needs. In addition, unique products can be provided. As foods and drinks, for example, various drinks such as alcoholic beverages, citrus drinks, fruit drinks, milk drinks, carbonated drinks, and tea drinks;
Various frozen desserts such as ice cream, ice sorbet, popsicles; various favorite items such as tobacco, chewing gum, candy, pudding, jelly;
And various kinds of soups such as Western soups; instant foods, snack foods, and animal and plant extracts. Examples of the cosmetics include perfumes such as parfum, odeparfum and odetoile; shampoos, rinses, treatments, soaps and body shampoos.
Toiletry products such as scents; various incense such as incense sticks, candles, pastes, etc .; various hair products such as hair dyes, bleaches, hair tonics; foundations, lotions, lipsticks And various kinds of fragrances such as indoor fragrances and car fragrances; and various kinds of detergents such as dishwashing detergents, laundry detergents and softeners.

[0017]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. Example 1: Synthesis of 5- (3Z-hexenyl) -4-methyl 4,5-dihydro-2 (3H) -furanone Ethyl 3-formylbutanoate (33.8 g, 0.2 mol)
Prepared separately in a THF (200 mL) solution under an argon atmosphere 3
A 1 M THF solution of Z-hexenylmagnesium chloride (220 mL, 0.22 mol) was added dropwise at -65 to -60 ° C over 1 hour. After the completion of the dropwise addition, the reaction temperature was returned to room temperature over 1 hour. The reaction mixture was poured into an ice-cooled aqueous solution of ammonium chloride to stop the reaction, and once subjected to liquid separation treatment, the aqueous layer was extracted once with methyl t-butyl ether (MTBE).
The organic layers were combined and washed once with a saturated saline solution. After drying this over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 42.2 g of a crude product. This was mixed with 120 g (0.3 mol) of 10% sodium hydroxide and methanol (40 mL) without purification, and heated under reflux for 1 hour. The reaction mixture was cooled to room temperature and extracted with MTBE three times. The pH of the aqueous layer is adjusted to 1 or less with hydrochloric acid, salted out with sodium chloride, and then MTB.
The organic layer extracted twice with E was washed once with a saturated saline solution. This was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
19.2 g of a cis / trans mixture of the stereochemistry of the 4- and 5-position side chains of the compound 1 of the present invention at ~ 130 ° C (3 mmHg) was obtained (yield 50.2%). GC analysis (Hewlett Packard 5890, DB-1,
As a result, the chemical purity was 95.1%, and the ratio of cis-form: trans-form was 33:67. 41 mg of the obtained distillation fraction was subjected to reverse phase HPLC (Shimazu LC-10, ODS 5 mm, 2
0 × 250mm, mobile phase: acetonitrile / water = 47.5 / 52.5)
Separation and purification were performed using cis form 7 mg, trans form 13 m
g were each isolated. The IR, ¹ H NMR and MS spectrum data are shown below.

Spectral data IR (film, cm ^-1 ) of compound 1 (cis form): 3000, 2950, 2930, 2860, 1780, 146
0, 1160, 940 ¹ H NMR (300 MHz, CDCl ₃ , d ppm): 0.96 (3H, t, J = 7.5H
z), 1.02 (3H, d, J = 6.8Hz), 1.50-1.74 (2H, m), 2.0
6 (2H, dq, J = 7.8 and 7.8Hz), 2.20 (3H, m), 2.58 (1
H, m), 2.70 (1H, dd, J = 7.8Hz and 16.8Hz), 4.45 (1
H, m), 5.31 (1H, m), 5.45 (1H, m) EI-MS (m / z, rel. Intensity): 182 (M ⁺ , 2), 164 (1),
122 (25), 99 (14), 95 (18), 93 (14), 68 (100), 55
(16), 41 (31)

Spectra of compound 1 (trans form)
IR (film, cm ^-1 ): 3000, 2950, 2930, 2860, 1780, 146
0, 1215, 1160, 1040, 940 ¹ H NMR (300 MHz, CDCl ₃ , d ppm): 0.96 (3H, t, J = 7.5H
z), 1.13 (3H, d, J = 6.3Hz), 1.68 (2H, m), 2.05 (2H,
dq, J = 7.5 and 7.5Hz), 2.22 (4H, m), 2.67 (1H, d,
J = 9.0Hz), 4.01 (1H, ddd, J = 4.0, 7.7 and 12.1Hz), 5.
30 (1H, m), 5.42 (1H, m) EI-MS (m / z, rel. Intensity): 182 (M ⁺ , 3), 164 (1),
122 (21), 99 (14), 95 (17), 93 (14), 68 (100), 55
(13), 41 (26) Using the obtained cis / trans mixture, cis-form and trans-form of Compound 1, the fragrance compositions of the following Examples were prepared.

Example 2 Preparation of Jasmine-Type Perfume Each component (parts by weight) shown in Table 1 below was mixed as a jasmine-type perfume composition.

[Table 1] A well-trained professional paneler for the fragrance composition
When compared by 10 persons, all of the examples showed that Example 2 had a fresher, more floral natural feeling, unity, gorgeousness, and volume.
It is said to be superior in terms of the effect of boosting the flavor and aroma, and to express the aroma of natural jasmine effectively.

Example 3 Preparation of Peach Type Fragrance Each of the components (parts by weight) shown in Table 2 below was mixed as a peach type fragrance composition.

[Table 2] A well-trained professional paneler for the fragrance composition
When compared by 10 persons, all of them found that Example 3 was superior in terms of natural flesh feeling, strength, volume, and weight of the bottom, effectively reducing the fragrance of natural peach. I was expressing it.

Example 4 Preparation of Apple Type Flavor Each component (parts by weight) shown in Table 3 below was mixed as an apple type flavor composition.

[Table 3] A well-trained professional paneler for the fragrance composition
A comparison among 10 persons showed that all of the persons in Example 4 had milder incense tone and emphasized the body feeling and the juice feeling peculiar to apple.

Example 5: Preparation of Strawberry-type fragrance Each component (parts by weight) shown in Table 4 below was mixed as a strawberry-type fragrance composition.

[Table 4] A well-trained professional paneler for the fragrance composition
As a result of a comparison among 10 persons, all of the persons in Example 5 recognized that the top notes were coherent and spread, and emphasized the fresh ripeness of the strawberries.

[0024]

The cis-form of 5- (3Z-hexenyl) -4-methyl-4,5-dihydro-2 (3H) -furanone provided by the present invention is green, floral, and fresh.
Chi-peel, butter-shaped butter, nuts, woody,
It has powdery flesh-like aroma and flavor characteristics, and can be used as a useful blending material in flavor compositions. In addition, the fragrance composition of the present invention has improved and enhanced excellent odor characteristics, such as imparting a natural feeling and volume while producing the odor characteristics of each compound.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinori Fujiwara 5-17-17 Shindaka, Yodogawa-ku, Osaka-shi, Osaka F-term in the Osaka factory of Shiono Incense Co., Ltd. 4C037 EA06 4H059 BA17 BB15 BB22 BB44 DA09

Claims (2)

[Claims] [Claim 1] Formula 1 5- (3Z-hexenyl) -4-methyl-4,5-
Cis form or trans form of dihydro-2 (3H) -furanone. 2. A fragrance composition comprising one or two of the compounds according to claim 1.