JP2002187886A - 4-Methyl-3- (Z-2-pentenyl) -2 (5H) -furanone and fragrance composition containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new jasmine floral-like perfumery material having unique and characteristic jasmine-like fragrance and excellent secondary characteristics comprising high retention of fragrance and provide a perfumery composition containing the material. SOLUTION: The new perfumery material is 4-methyl-3-(Z-2-pentenyl)-2(5H)- furanone expressed by formula 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to novel compounds. This compound is particularly useful as a fragrance, more particularly as a jasmine-like fragrance, and is mainly used in cosmetics. Furthermore, the present invention relates to a fragrance composition containing the novel compound.

[0002]

2. Description of the Related Art Floral, green, citrus, fruity, spicy, and the like are known as basic fragrances of fragrances, and typical floral fragrances include rose-like fragrance, jasmine-like fragrance, and mugue-like fragrance. . As jasmine-like flavors, for example, the following compounds are known. First, methyldihydrojasmonate (1) is widely used as a general-purpose fragrance. This seems to be due to the low price. Also, cis jasmon (2), which is one of the trace key aroma components of jasmine flowers, is known. Since this compound has a stronger characteristic odor, it has been studied in various ways, and an industrial synthetic method has been established and is now widely used.

[0003]

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Further, recently, 4-methyl-3-pentyl-2 (5H) -furanone (4) has been reported in Japanese Patent Application Laid-Open No. Hei 4-257572. Although this compound satisfies the criteria in terms of odor characteristics, the odor intensity is not so high,
There is room for research.

[0005]

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[0006]

In recent years, with the diversification of cosmetics, it has been desired to develop new perfume materials having unique and excellent aroma characteristics. The same is true in the field of jasmine-like fragrances, and the emergence of an excellent fragrance material having a particularly characteristic jasmine-like fragrance and exhibiting high residual scent has been awaited. Since the appearance of a characteristic fragrance material is likely to lead to the provision of a more individualized fragrance, there has been a particularly strong demand from perfumers to develop new fragrances having the above characteristics. An object of the present invention is to provide a novel and unique jasmine floral-like fragrance material and a fragrance composition containing the same.

[0007]

Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive studies and as a result, have found that 4-methyl-3-
The inventors have found that (Z-2-pentenyl) -2 (5H) -furanone (3) is a jasmine floral-like fragrance material having high palatability, and further studied to complete the present invention. Equation-1

That is, the above compound (3) is a tuberose,
It shows a unique and excellent jasmine-like floral aroma with narcissus, tobacco, lactone, and fermented odorous side notes, and has a very excellent residual scent compared to conventionally known jasmine-based flavors. . By using this compound, it was possible to create a fragrance with high palatability and excellent lingering scent.

The present invention is a novel compound which has not been described in the literature.
An object of the present invention is to provide 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3) and a fragrance composition containing the same.
Further, the present invention provides 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3), which is a novel, unique and excellent jasmine floral-like fragrance material, and contains the same. It is also to provide a fragrance composition.

The details of the present invention are described below. Of the compound of the present invention
4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3) is represented by the above formula-1, and the unsaturated bond of the pentenyl group in the side chain is a cis bond.

This compound can be produced, for example, by the method shown in Reaction Scheme-1. Reaction formula-1

Embedded image Ph represents phenyl, Et represents ethyl, TES represents trimethylsiloxy, and TMS represents trimethylsilyl.

The production method will be described in more detail. To a methylene chloride solution of phenyl Z-4-heptenoate (5), a titanium tetrachloride solution and a triethylamine solution are sequentially dropped at a low temperature (for example, -78 ° C.), and then triethylsiloxyacetone is dropped. By reaction, the addition product phenyl 2-
(1-hydroxy-1-methyl-2-triethylsiloxyethyl)
Z-4-heptenate (6) is obtained. Next, the obtained (6) is cyclized with trifluoroacetic acid to give 4-hydroxy
-4-methyl-3- (Z-2-pentenyl) tetrahydrofuran-2-
ON (7) can be synthesized. By dehydrating this (7) with a dehydrating agent, the target product, 4-methyl-3- (Z-
2-pentenyl) -2 (5H) -furanone (3) can be produced. By employing this method, the target compound can be produced in only three steps. The starting material phenyl Z-4-heptenate (5) may be a commercially available product or may be prepared by a known method. Any known dehydrating agent can be used.

[0013] As a result of examination by three perfumers on the odor characteristics of the thus obtained 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3) in odor paper, it was found to be very excellent. It turned out to be a fragrance material. That is, Table 1 shows the comparison results of the odor characteristics of the following three compounds over time in odor paper. 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3) and a compound having a structure similar to this compound, and have a relatively low residual scent property among jasmine-based fragrance materials. Cis jasmon (2), which is considered to be high, and 4-methyl-3-pentyl-2 (5
H) -Furanone (4).

[0014]

[Table 1] 4-Methyl-3- (Z-2-pentenyl) -2 (5H) -f
Aroma characteristics of lanone (3) and related compounds From “Aroma” and “Relative intensity” in Table 1, it is possible to know the aroma and the change in the aroma intensity of the compounds described in the left column of Table 1 when 30 minutes or 24 hours have elapsed. Here, "30 minutes of odor paper" means that 30 minutes have passed after the compounds described in the left column of Table 1 were applied to odor paper. "Scented paper 24
"Time" means that the compound shown in the left column of Table 1
It means that 4 hours have passed. "Relative strength" in the column of "Scent paper 30 minutes" refers to the compound after 30 minutes.
The odor intensity of each compound is shown when the odor intensity of (2) is set to 10, and the “relative intensity” in the column of “scent paper 24 hours” is 2
The odor intensity of each compound is shown when the odor intensity of the compound (3) after 4 hours has elapsed is set to 10.

As can be easily understood from Table 1, first, regarding the change in relative odor intensity, in the initial stage (30 minutes after the perfume is applied to the odor paper), 4-methyl-3- (Z-2 -Pentenyl) -2 (5H) -furanone (3) has an aroma intensity of compound (4)
Although it was stronger than that of Compound (2), it was about half that of Compound (2). Surprisingly, however, the odor intensity of 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3) was 24 hours after the perfume was applied to the odor paper. The intensity is reversed as compared with the odor intensity of the fragrance. From this point, 4-methyl-3- (Z-2-pentenyl) -2 (5
It was revealed that H) -furanone (3) had a much better residual odor than the compound (2). Considering that the trend of blended fragrances in recent fragrance products is that there are many products that require a long scent, the conventional jasmine floral fragrance material has few excellent scents. Therefore, the high residual odor of 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3), which is the compound of the present invention, is remarkable. Furthermore, 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3)
Can be said to basically show jasmine floral incense, but it should be noted that as a side note, compound
(2) and (4) were found to have a very unique personality with a pleasant tubellose, tobacco-like, and lactone-like aroma that was not found in (2) and (4). Compounds (2) and (4)
Although it is effective for fragrance for women, it is the compound of the present invention 4-methyl-3- (Z-2-pentenyl) -2 (5H)
The fact that the furanone (3) has the above-mentioned aroma characteristics means that the compound (3) is extremely effectively used for fragrance creation of fragrance for men.

Next, a fragrance composition containing the compound (3) will be described. The fragrance composition of the present invention comprises a fragrance, a commonly used additive, and the like as constituent components. The fragrance herein is a novel 4-methyl-3- (Z-2-
Pentenyl) -2 (5H) -furanone (3) may be used alone, or may be used in combination with other known fragrances before the present application. That is, the compound (3) can be used as a fragrance enhancer.

[0017] The usual additives, which are the other components, refer to components necessary for preparing a fragrance composition. That is, since cosmetics, health and hygiene materials, pharmaceuticals, and the like are also perfume compositions, those necessary for preparing the cosmetics, health and hygiene materials, pharmaceuticals, and the like are referred to as ordinary additives. . That is, shampoos, body shampoos, rinses, perfumes, colons, hair tonics, hair creams, pomades, other hair-growing cosmetic bases, white powder, lipsticks, other cosmetic bases and cosmetic detergents, soaps, liquid soaps , Dishwashing detergents, laundry detergents, softeners, indoor air fresheners, furniture care, drifting agents, disinfectants, insecticides, repellents, various other types of health and safety detergents, toothpaste, mouthwash, toilet paper, and pharmaceuticals What is needed to prepare a perfume and the like to make it easy to take is called a usual additive.

The amount of the fragrance added to the fragrance composition is in a wide range and it is difficult to define the amount. However, usually, the amount of the fragrance added is about 0.01 to 20% by weight based on the whole fragrance composition. This makes it possible to effectively express the aroma characteristics of the compound (3) of the present invention. In the fragrance composition of the present invention, components other than the above components may be added and blended.

[0019]

The compound (3) of the present invention has a strong residual scent and is useful as a fragrance having a high palatability. Therefore, a unique fragrance imparting agent or a fragrance improving reinforcing agent can be provided. In addition, by containing the compound (3) of the present invention as a fragrance component, it is possible to provide cosmetics, health and hygiene materials, pharmaceuticals and the like having high palatability. That is, shampoos, body shampoos, rinses, perfumes, colons, hair tonics, hair creams, pomades, other hair-growing cosmetic bases, white powder, lipsticks, other cosmetic bases and cosmetic detergents, soaps, liquid soaps , Dishwashing detergents, laundry detergents, softeners, indoor air fresheners, furniture care, drifting agents, disinfectants, insecticides, repellents, various other types of health and safety detergents, toothpaste, mouthwash, toilet paper, and pharmaceuticals The commercial value can be enhanced by blending an appropriate amount capable of imparting a unique fragrance to a perfume or the like for easy taking.

[0020]

The present invention will be described in more detail with reference to the following examples and prescription examples, but the present invention is not limited to these examples. The analytical instruments used are as follows. NMR: Varian Unity 1-plus 300 IR: JASCO FT / IR-8000

[0021]

Example 1 Synthesis of phenyl 2- (1-hydroxy-1-methyl-2-triethylsiloxyethyl) -Z-4-heptenate (6) Under an argon atmosphere, phenyl Z-4-heptenate (5) (2.04
g, 10 mmol) in methylene chloride (20 ml) at −78 ° C. at room temperature with titanium tetrachloride (1.0 methylene chloride solution; 12 ml) and triethylamine (1.42 g; 14 mmol) in methylene chloride (5 ml).
The solution was sequentially added dropwise and stirred for 30 minutes. Then, a solution of triethylsiloxyacetone (2.07 g, 11 mmol) in methylene chloride (5 ml) was added dropwise, and the mixture was stirred for 1.5 hours. The reaction mixture was poured into cold water, extracted with ether, and the organic layer was washed with water, washed with saturated saline, and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the crude product was subjected to silica gel column chromatography (hexane / ether = 40/1 to 20).
/ 1), and the desired product, colorless and transparent phenyl 2-
(1-hydroxy-1-methyl-2-triethylsiloxyethyl)
-Z-4-heptenate (6) (2.58 g, yield 66% Th) was obtained. The spectrum data of the obtained phenyl 2- (1-hydroxy-1-methyl-2-triethylsiloxyethyl) -Z-4-heptenate (6) showed the following values.

[0022] IR (film); 1755, 1651 cm -1 1 HNMR [300 MHz; δ (CDCl 3)]; 0.60-0.68 (6H, m), 0.96
(3H, t, J = 7.5Hz), 0.95-1.00 (9H, m), 1.28 (1.6H,
s), 1.33 (1.4Hs) 2.04-2.29 (3H, m), 2.44-2.71 (2H,
m), 2.93-3.03 (1H, m) 3.46-3.67 (2H, m), 5.35-5.56 (2H, m
m) 7.01-7.40 (5H, m)

[0023]

Example 2 Synthesis of 4-hydroxy-4-methyl-3- (Z-2-pentenyl) tetrahydrofuran-2-one (7) Phenyl 2- (1-hydroxy-1-methyl-) synthesized in Example 1
2-triethylsiloxyethyl) -Z-4-heptenate (6)
To a solution of (2.40 g, 6.12 mmol) in tetrahydrofuran (6.4 ml) was added a mixed solution of acetic acid / water (2: 1, vol / vol) at room temperature, and then trifluoroacetic acid (140 ml, 1.84 mmol). Stirred overnight. Water was added to the reaction mixture, and the mixture was stirred and extracted with ether. The organic layer was washed with water, washed with saturated saline, and then dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the crude product was purified by silica gel column chromatography (hexane / ether = 2/1 to 1/1), and the target compound was colorless and transparent 4-hydroxy-4-methyl-3-. (Z-2-pentenyl)
Tetrahydrofuran-2-one (7) (928 mg, yield: 82% T)
h). The spectrum data of the obtained 4-hydroxy-4-methyl-3- (Z-2-pentenyl) tetrahydrofuran-2-one (7) showed the following values.

[0024] IR (film); 3447, 1757 , 1651 cm -1 1 HNMR [300 MHz; δ (CDCl 3)]; 1.00 (3H, q, J = 7.6Hz),
1.38 (2.5H, s), 1.46 (0.5H.s), 2.05-2.18 (2H, m),
2.31-2.68 (3H, m), 4.01-4.20 (2H, m), 5.35-5.56 (2H,
m), 5.40-5.58 (2H, m),

[0025]

Example 3 Synthesis of 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3) 4-hydroxy-4-methyl-3- (Z- 2-pentenyl) tetrahydrofuran-2-one (7) (928 mg, 5.0
To a solution of 4 mmol) in methanol (10.2 ml) was added trimethylsilyl chloride (21.6 ml), and the mixture was refluxed at 70 ° C. overnight. After the reaction solution was cooled to room temperature, water was added thereto, and the mixture was extracted with ether. The organic layer was washed with water, saturated brine, and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, the crude product was purified by silica gel chromatography (hexane / ether = 4/1) to give colorless and transparent 4-methyl-3- (Z-2-pentenyl) -2.
(5H) -furanone (3) (716 mg, 86% 86% Th) was obtained. The spectrum data of the obtained 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3) showed the following values.

IR (film); 1751 1678 1651 cm ^{−1 1} HNMR [300 MHz; δ (CDCl ₃ )]; 1.00 (3H, t, J = 7.5 Hz),
2.04 (3H, s), 2.11-2.21 (2H.m), 3.03 (2H, d, J = 7.2H
z), 4.60 (2H, s), 5.29-5.38 (1H, m), 5.42-5.52 (1H, m) ¹³ CNMR [75 MHz; δ (CDCl ₃ )]; 12.24 14.05 20.58 21.5
9 72.44 123.61 126.18133.46 156.45 174.70

[0027]

[Prescription Example-1] Jasmine Floral Fragrance A jasmine floral fragrance having the following formula having high palatability was prepared. Perfume name Formulation (parts by weight) 4-Methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3) synthesized in Example-3 55 Aldehyde C-14 5 Benzyl acetate 536 cis-3- Hexenyl benzoate 30 cresylacetate 2 eugenol 15 l dihydrofarnesol 40 geraniol 40 cis-3-hexenyl acetate 3 indole 15 linalool 90 methylanthranilate 3 methyldihydrojasmonate 120 phenylethyl acetate 3 vanillane 3 total 1000 ylang

[0028]

[Prescription example-2] Men's fragrance A men's fragrance having high palatability with the following prescription was prepared. Perfume name Formulation (parts by weight) 4-Methyl-3- (Z-2-pentenyl) -2 (5H) -furanone (3) synthesized in Example-3 100 Aldehyde C-11 2 Alomis oil 10 Basil oil 10 Bergamot oil 100 Cistus labdanum absolute 10 Clary sage oil 35 Dihydromyrcenol 250 Galvanum oil 3 Isobutylquinoline 5 Iso-E-SuperTM 130 Lavender oil 50 Lemon oil California 50 Bactanol TM 15 Ethylene brush rate 65 Patchouli oil 50 l-citronellol 30 Coriander oil Gamma-methylyonone 25 l-styraryl acetate 20 total 1000

Claims (2)

[Claims] 1. A 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone represented by the formula-1. Equation-1 2. A fragrance composition comprising the 4-methyl-3- (Z-2-pentenyl) -2 (5H) -furanone according to claim 1.