JP2000034243A - Optically active 1- (p-mentha-3'-yl) ethanol and fragrance containing it as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optically active 1-(p-menth-3'-yl)ethanol having a unique citrus aroma making users remember a grapefruit, a muscat or a litchi, high in tastefulness and useful as various kinds of cosmetics by making the compound represented by a specific chemical structural formula. SOLUTION: This (1R, 1'S, 3'S, 4'R)-1-(p-menth-3'-yl)ethanol is represented by the formula. A perfume is preferably prepared by including >=5 wt.% of the compound. A perfume composition containing 0.01-50 wt.% of the above compound is useful as a citrus perfume composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fragrance containing optically active 1- (p-mentha-3'-yl) ethanol having a citrus-like odor. In particular, the present invention relates to a fragrance containing optically active 1- (p-mentha-3′-yl) ethanol having a citrus-like odor used for flavoring of cosmetics.

[0002]

2. Description of the Related Art In recent years, along with the diversification of various cosmetics and health and hygiene materials, there has been an increasing demand for new fragrances used in these fragrances. Development is being demanded. In particular, development of a new fragrance material is desired for citrus-based fragrances, which are one of the most in demand fragrances. Also,
Citrus-based synthetic fragrances represented by citral, citronellal, limonene, etc. are all particularly unstable to chlorine-based bleaches. Therefore, development of citrus-based fragrances having excellent stability is strongly desired. I have.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a compound having a citrus scent that satisfies the above demand and a fragrance containing the compound as an active ingredient.

[0004]

[Means for Solving the Problems] In such a situation,
The present inventors have synthesized various optical isomers of 1- (p-mentha-3′-yl) ethanol and studied their fragrances, their potential as compounding materials, and the like. )

Embedded image (1R, 1'S, 3'S, 4'R) -1-
(P-mentha-3'-yl) ethanol was found to have a unique citrus-like aroma with high palatability, reminiscent of grapefruit, muscat, or lychee that other isomers do not have, and completed the present invention. did.

According to the present invention, (1)
R, 1'S, 3'S, 4'R) -1- (p-mentor
3'-yl) ethanol.

The present invention also comprises (1R, 1'S, 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol represented by the formula (1) as an active ingredient. Perfume. The present invention also provides (1R, 1'S, 3'S,
The present invention relates to a fragrance comprising 1- (p-mentha-3'-yl) ethanol containing 4% by weight or more of 4'R) -1- (p-mentha-3'-yl) ethanol. The present invention also provides
1- which contains 5% by weight or more of (1R, 1'S, 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol.
(P-mentha-3′-yl) ethanol in an amount of 0.01 to 5
It relates to a perfume composition containing 0% by weight. The present invention also provides
1- which contains 5% by weight or more of (1R, 1'S, 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol.
(P-mentha-3′-yl) ethanol in an amount of 0.01 to 5
It relates to a citrus-based fragrance composition containing 0% by weight.

[0007]

DETAILED DESCRIPTION OF THE INVENTION 1- (p-mentha-3'-yl)
Ethanol is a compound obtained by reduction of p-menth-3-ylmethylketone, and is known as a physiological cooling agent acting on mucous membranes such as skin and oral cavity (UK Patent No. 1,315,626). Specification). However, 1
It is reported that the odor of-(p-mentha-3'-yl) ethanol itself is almost odorless. Also,
There is no description about the stereochemistry, purity, and physical properties of 1- (p-mentha-3′-yl) ethanol. Since 1- (p-mentha-3′-yl) ethanol has four asymmetric carbons in the molecule, there are a total of 16 isomers including optical isomers. There is no report of the isolation of any of these, and their flavors are not known. Furthermore, there is no report that these optically active substances were individually synthesized, and of course, there is no report that they are used as a fragrance.

The (1R, 1'S, 3'S, 4 ') of the present invention
The reaction for producing (R) -1- (p-mentha-3′-yl) ethanol is as follows. That is, (1S, 3S, 4R) -menthol (hereinafter referred to as d-menthol) represented by the formula (2) is halogenated using a zinc halide and a mineral acid, and is represented by the formula (3). (1
S, 3S, 4R) -3-halogeno-p-menthane, and then a carbon-carbon bond reaction with acetaldehyde represented by the formula (1) (1R, 1 ′S,
3 ′S, 4′R) -1- (p-mentha-3′-yl) ethanol is produced.

[0009]

Embedded image (In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom.)

In the above reaction formula, d-menthol represented by the formula (2) is halogenated using a zinc halide and a mineral acid to form a (1S, 3S, 4R)-
Examples of the zinc halide used in the reaction for producing 3-halogeno-p-menthane include zinc chloride, zinc bromide, and zinc iodide. Examples of the mineral acid include hydrochloric acid, hydrobromic acid, and hydroiodic acid. The concentration of the mineral acid used is about 20 to 50% when using hydrochloric acid, about 20 to 60% when using hydrobromic acid, and about 20 to 70% when using hydroiodic acid. As a combination of a zinc halide and a mineral acid, it is particularly preferable to use zinc chloride and concentrated hydrochloric acid.

The zinc halide is used in an amount of 1 to 10 times, preferably 2 to 5 times the mole of the compound of the formula (2). The mineral acid varies depending on the concentration of the mineral acid used. ), Preferably 1 to 10 times, preferably 2
It is used up to 5 times in mole. The reaction temperature is 0-100 ° C., preferably 10-50 ° C., and the reaction time is 1-10 hours. Purification of the reaction product is performed, for example, by extracting with a solvent of hydrocarbons (for example, hexane, heptane, toluene, etc.) after the reaction, distilling off the solvent, and then distilling.

In the preparation of the Grignard reagent for carrying out the reaction for obtaining the compound of the formula (1) by carbon-carbon bonding of acetaldehyde to the compound of the formula (3), magnesium is added to the compound of the formula (3) by 1 It is preferable to use 1.5 to 1.5 moles. In preparing the Grignard reagent, iodine, ethyl bromide, dibromoethane or the like may be used as a reaction initiator, and it is preferable to use 0.0001 to 0.01 mol% based on the compound of the formula (3). The reaction temperature is 0 to 100 ° C, preferably 20 to 70 ° C,
The reaction time is preferably 1 to 20 hours.

The reaction is carried out by using one or two or more solvents such as diethyl ether, diisopropyl ether, dimethoxyethane, dimethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and the like.
The reaction can be carried out by appropriately mixing species or more, and tetrahydrofuran is preferably used. Although the amount of the solvent is not particularly limited, it is preferable to use 1 to 10 times (volume) the compound of the formula (3).

In the carbon-carbon bonding reaction between the resulting Grignard reagent and acetaldehyde, the acetaldehyde is preferably used in a molar amount of 1 to 1.5 times the amount of the compound of the formula (3). When acetaldehyde is charged, the reaction temperature is -70 to 70 ° C, preferably -20 to 30 ° C,
It is good to carry out the charging in minutes to 10 hours, preferably 5 minutes to 3 hours. After the charging, the reaction temperature is further -70 to 70 ° C, preferably -20 to 30 ° C, and 3 minutes to 10 hours, preferably The aging reaction is preferably performed in 5 minutes to 3 hours.

(1R, 1'S, 3'S, 4'R) -1-
(P-mentha-3'-yl) ethanol is obtained by reacting the compound of formula (3) with magnesium to give a Grignard reagent and reacting with acetaldehyde (1R, 1'S, 3'S, 4). 'R) -1- (p-mentha-3'-yl) ethanol and (1S, 1'S, 3'
It is obtained by purifying a mixture with (S, 4′R) -1- (p-mentha-3′-yl) ethanol. For purification, for example, after the reaction, dilute hydrochloric acid (1 N) is added, and if necessary, the solvent is distilled off. Then, ethers (diethyl ether, diisopropyl ether, etc.) and hydrocarbons (hexane, heptane, toluene, etc.) are added. Extract with solvent,
After distilling off the solvent, it is obtained by distillation (1
R, 1'S, 3'S, 4'R) -1- (p-mentor
3′-yl) ethanol and (1S, 1 ′S, 3 ′S,
It is carried out by separating a mixture with 4′R) -1- (p-mentha-3′-yl) ethanol by silica gel column chromatography or the like.

Using d-menthol (2) as a raw material, (1)
R, 1'S, 3'S, 4'R) -1- (p-mentor
3′-yl) ethanol and (1S, 1 ′S, 3 ′S,
By the same method as that for obtaining a mixture with (4'R) -1- (p-mentha-3'-yl) ethanol, (1R, 3
(1S, 1'R, 3'R, 4'S)-using R, 4S) -menthol (hereinafter referred to as l-menthol) as a raw material.
It is an epimer of 1- (p-mentha-3'-yl) ethanol and its hydroxyl group (1R, 1'R, 3'R, 4'S).
-1- (p-mentha-3'-yl) ethanol can be obtained.

However, among the four optically active 1- (p-mentha-3'-yl) ethanols thus obtained, (1R, 1'S, 3'S, 4'R ) -1- (p-mentha-3′-yl) ethanol has a particularly refreshing grapefruit-like, muscat-like and litchi-like highly citrus-like aroma, whereas its enantiomer (1S, 1'R, 3'R, 4'S) -1- (p
-Mentha-3'-yl) ethanol is almost odorless and poor in odor value, and is not suitable for use as a fragrance. In addition, hydroxyl groups differ in stereochemistry (1S, 1'S, 3'S,
4′R) -1- (p-mentha-3′-yl) ethanol was also almost odorless and poor in odor value, and was not suitable for use as a fragrance. Furthermore, (1R, 1′R, 3′R, 4 ′S) -1- (p-mentha-3′-yl) ethanol having different stereochemistry of the hydroxyl group of the enantiomer is almost odorless, has poor odor value, and has a fragrance. (See Tables 1 and 2).

The (1R, 1'S, 3'S, 4 ') of the present invention
R) -1- (p-mentha-3′-yl) ethanol is
Even when added to the chlorine-based bleaching agent, the color and flavor are not changed at all, and therefore, the (1R, 1'S, 3 ')
(S, 4'R) -1- (p-mentha-3'-yl) ethanol is a fragrance that is stable to chlorine bleach base materials.
The (1R, 1'S, 3'S, 4'R) -1- (p
-Mentha-3'-yl) ethanol is citrus-like, reminiscent of grapefruit, muscat or lychee, is fresher, has a higher palatability and is more effective in imparting fragrance, and has a base odor of soap and the like and a bleach odor. Or it has a strong ozone odor masking power and is a very useful fragrance material.By blending it, it has a good diffusibility and stability and a strong retention property. A perfume composition can be provided.

The (1R, 1'S, 3'S, 4 ') of the present invention
R) -1- (p-mentha-3′-yl) ethanol is
Since it has a citrus-like fragrance with high palatability and can be a useful fragrance substance, it may be used as a single fragrance component. In the present invention, (1R, 1 ′S,
3 ′S, 4′R) -1- (p-mentha-3′-yl) ethanol is substituted with the other stereoisomer 1- (p-mentha) described above.
Those containing 3′-yl) ethanol may be used as the fragrance component. In that case, (1R, 1'S,
It is preferable that 3 ′S, 4′R) -1- (p-mentha-3′-yl) ethanol is contained in an amount of 5% by weight or more.

Furthermore, in the present invention, (1R, 1'S, 3 '
S, 4'R) -1- (p-mentha-3'-yl) ethanol alone or another stereoisomer 1- (p-mentha-
A perfume composition in which a commonly used perfume component is further added to a coexistence of 3'-yl) ethanols can also be used as the perfume component. As other fragrances that can be added and used, citrus-based fragrance compositions are particularly preferable. , “Per
fume and Flavor Chemical
s ", published by the author
r, Montclair, N .; J. (U.S.A.) 1
A wide range of perfume ingredients, such as those described in 969, can be used. Representative examples include α-pinene, limonene, cis-3-hexenol, phenylethyl alcohol, styryl acetate, eugenol, rose oxide, linalool, benzaldehyde, and muscone.

The (1R, 1'S, 3'S, 4 ') of the present invention
The amount of R) -1- (p-mentha-3′-yl) ethanol in the flavor composition varies depending on the type and purpose of the prepared flavor, but is 0.01 to 50% by weight in the composition. In particular, a blending amount of 0.1 to 20% by weight is preferable.

The (1R, 1'S, 3'S, 4 ') of the present invention
When R) -1- (p-mentha-3′-yl) ethanol alone or a fragrance composition containing the compound is added to a fragrance preparation such as shampoo or rinse, the diffusivity and retention properties are enhanced, and citrus-like A scent can be imparted, and a fresh, highly-preferred scent can be imparted. The fragrance or fragrance composition of the present invention can be suitably used as a fragrance component in cosmetics, health and hygiene materials, pharmaceuticals and the like. That is, shampoos, rinses, perfumes, colons, hair tonics, hair creams, pomades, cosmetic bases for hair, other cosmetic bases and cosmetic detergents, indoor air fresheners, soaps, dishwashing detergents, laundry detergents , Softeners, disinfecting detergents, deodorant detergents, furnichia care, disinfectants, bactericides, repellents, bleaching agents, various other sanitary detergents,
It is used as a fragrance or the like to make toothpaste, mouthwash, toilet paper, and medicine easy to take, and can enhance their commercial value.

[0023]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples and can be modified without departing from the scope of the present invention. In addition, the apparatus used for the measurement of the physical properties in each example is as follows.

Gas chromatography equipment: GC 353 (manufactured by GL Sciences) and H
EWLETT PACKARD 5890 (manufactured by Hewlett-Packard) Proton nuclear magnetic resonance spectrum ( ¹ H-NMR) Equipment: AMX-400 (400 MHz) (manufactured by Bruker) Internal standard substance: tetramethylsilane (in deuterated chloroform) ¹³ C nuclear magnetic field Resonance spectrum ( ^13C -NMR) Equipment: AMX-400 (100MHz) FT-NMR
Measuring device (manufactured by Bruker) Internal standard substance: tetramethylsilane (in deuterated chloroform) Infrared absorption spectrum (IR) Instrument: IR-810 (manufactured by JASCO Corporation) Measuring method: film optical rotation instrument: DIP -370 (manufactured by JASCO Corporation) Mass spectrometry spectrum Equipment: M-80B (manufactured by Hitachi, Ltd.)

Example 1 (1R, 1'S, 3'S, 4 'from d-menthol)
Production of (R) -1- (p-mentha-3′-yl) ethanol (1) Synthesis of (1S, 3S, 4R) -3-chloro-p-menthane Four 500 ml ports equipped with a thermometer and a stirrer A round bottom flask was charged with 36% hydrochloric acid (175 g, 1.55 mol), and zinc chloride (225 g, 1.65 mol) was added under ice cooling. Next, d-menthol (78.1 g, 0.5 mol)
l) [manufactured by Takasago International Corporation, [α] _D ²⁰ + 49 °, C =
1.07, EtOH] and stirred at 35 ° C. for 3 hours. After separating the upper and lower layers of the reaction solution, hexane 150 ml
The product was extracted three times from the lower layer using and then combined with the upper layer. This was washed twice with 300 ml of water and 50 ml of saturated saline, respectively, and then hexane was removed under reduced pressure.
g was obtained. This is distilled in a Claisen still (boiling point: 59
~ 61 ° C / 4mmHg) to give (1S,
77.3 g of 3S, 4R) -3-chloro-p-menthane
(88% yield). Gas chromatography [Column: CP-WAX 52CB, 25 mm x 0.25 mm
(ID) × 0.2 μm (manufactured by GL Sciences Inc.), measurement temperature: 60 to 120 ° C. (heated at 4 ° C./min)]
Was 85% when the chemical purity was measured by the analysis using.

(1S, 3S, 4R) -3-chloro-p-
Mentane spectral data [α] _D ²⁰ + 41.2 ° (neat) ¹ H-NMR (400 MHz, CDCl ₃ , δ):
3.78 (1H, dt, J = 4.2, 11.1 Hz),
2.34 (1H, m), 2.23 (1H, m), 1.7
2 (2H, br.d), 1.48 to 1.35 (3H,
m), 1.09 to 0.98 (1H, m), 0.97 to
0.88 (1H, m), 0.92 (6H, d, J = 7.
0 Hz), 0.78 (3H, d, J = 6.9 Hz)

(2) (1R, 1'S, 3S, 4R) -1
Synthesis of-(p-mentha-3′-yl) ethanol A 500 ml four-necked round-bottomed flask equipped with a thermometer and a stirrer was charged with magnesium (14.0 g, 0.575) under a nitrogen stream.
mol), 20 ml of tetrahydrofuran and iodine (0.
01g). Next, ethyl bromide (0.03 g) as a reaction initiator was added, and the mixture was heated to 40 ° C. and stirred. Next, it was dissolved in 150 ml of tetrahydrofuran (1S, 3
S, 4R) -3-Chloro-p-menthane (77.3 g,
(0.443 mol) over 5 hours, and the reaction was aged at 40 ° C. for 1.5 hours. Next, acetaldehyde (20.4 g, 0.463 mol) was added dropwise with stirring over 30 minutes under ice cooling. After aging for 30 minutes under ice-cooling, the mixture was transferred to another container, and 1N hydrochloric acid 6
The reaction was terminated by adding 00 ml, and the mixture was separated into an organic layer and an aqueous layer. The product was extracted from the aqueous layer three times with 600 ml of diethyl ether, combined with the organic layer, and washed with 200 ml of saturated sodium bicarbonate, 200 ml of water twice, and 200 ml of saturated saline, followed by diethyl ether. Was removed under reduced pressure to obtain 83.3 g of a concentrated liquid. This was distilled (boiling point: 64 to 66 ° C./3 mmHg) using a distillation apparatus (Helipack No. 2, 15 cm, manufactured by Tokyo Wire Mesh Co., Ltd.), followed by silica gel column chromatography (solvent: hexane: ethyl acetate = 1).
0: 1) and (1R, 1'S, 3'S, 4'R)-
1- (p-mentha-3'-yl) ethanol was 14.0
g, (1S, 1'S, 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol, 14.0 g, was obtained. Gas chromatography [Column: CP-WAX 52C
B, 25 m 0.25 mm (ID) × 0.2 um (manufactured by GL Sciences), measurement temperature: 60 to 160 ° C.
(The temperature was raised at a rate of 4 ° C./min.)].
The purity of (p-mentha-3'-yl) ethanol was 96.
At 8%, (1S, 1'S, 3'S, 4'R) -1- (p
-Mentha-3'-yl) ethanol is 96.0% pure
Met.

(1R, 1'S, 3'S, 4'R) -1-
Spectral data of (p-mentha-3'-yl) ethanol [α] _D ²⁰ + 50 ° (C = 1.05, MeOH) IR: 3350 cm ⁻¹ (OH) MS (EI) m / z: 166 (MH ₂ O, 12), 1
37 (13), 123, (33), 110 (33), 1
09 (32), 97 (42), 96 (27), 95 (3
6), 83 (78), 82 (23), 81 (61), 7
0 (32), 69 (69), 67 (23), 57 (2
9), 55 (100), 45 (39), 43 (42),
41 (47), 39 (12)

¹ H-NMR (400 MHz, CDC
l ₃ , δ): 4.11 (1H, dq, J = 3.9, 6.5)
Hz), 1.88-1.77 (2H, m), 1.73
(1H, m), 1.65 (1H, m), 1.52 (1H,
m), 1.33 (1H, m), 1.28 (1H, br.
s, OH), 1.07 (3H, d, J = 6.5 Hz),
1.03 to 0.93 (2H, m), 0.91 (3H,
d, J = 6.5 Hz), 0.88 (3H, d, J = 6.
9Hz), 0.87 (1H, m), 0.78 (3H,
d, J = 6.9 Hz), 0.71 (1H, q, J = 1)
2.2 Hz) ¹³ C-NMR (100 MHz, CDCl ₃ , δ): 66.
89 (d), 45.16 (d), 44.59 (d), 3
5. 31 (t), 32.82 (t), 32.51
(D), 26.12 (d), 24.35 (t), 22.
75 (q), 21. 41 (q), 16.53 (q), 1
5. 20 (q)

(1S, 1'S, 3'S, 4'R) -1-
Spectral data of (p-mentha-3'-yl) ethanol [α] _D ²⁰ + 26 ° (C = 1.02, MeOH)

Reference Example 1 (1S, 1′R, 3′R, 4 ′) from l-menthol
Preparation of (S) -1- (p-mentha-3′-yl) ethanol (1) Synthesis of (1R, 3R, 4S) -3-chloro-p-menthane 500 ml of a thermometer and a stirrer were attached. A 4-neck round bottom flask was charged with 36% hydrochloric acid (175 g, 1.55 mol), and zinc chloride (225 g, 1.65 mol) was added under ice-cooling. Next, l-menthol (78.1 g, 0.5 mol)
l, manufactured by Takasago International Corporation, [α] _D ²⁰ −49 °, C = 1.
0, EtOH) and stirred at 35 ° C for 3 hours. After separating the upper and lower layers of the reaction solution, the product was extracted three times from the lower layer with 150 ml of hexane and combined with the upper layer. This was washed twice with 300 ml of water and 50 ml of saturated saline, respectively, and hexane was removed under reduced pressure to obtain 82.7 g of a concentrated solution.
This is distilled in a Claisen still (boiling point: 59 to 61 ° C /
(4 mmHg) to give 77.3 g of (1R, 3R, 4S) -3-chloro-p-menthane (yield 88%). Gas chromatography [column: CP-WAX52CB,
25m x 0.25mm (ID) x 0.2um (manufactured by GL Sciences Inc., measuring temperature: 60 to 160C (4C)
Per minute) and the chemical purity was measured to be 85%.

(1R, 3R, 4S) -3-chloro-p-
Mentane spectral data [α] _D ²⁰ -41 ° (neat)

(2) (1S, 1'R, 3R, 4S) -1
Synthesis of-(p-mentha-3'-yl) ethanol A 500 ml four-necked round-bottomed flask equipped with a thermometer and a stirrer was charged with magnesium (14.0 g, 0.575) under a nitrogen stream.
mol), 20 ml of tetrahydrofuran and iodine (0.
01g). Next, ethyl bromide (0.03 g) as a reaction initiator was added, and the mixture was heated to 40 ° C. and stirred. Next, it was dissolved in 150 ml of tetrahydrofuran (1R, 3
R, 4S) -3-chloro-p-menthane (77.3
g, 0.443 mol) over 5 hours.
For 1.5 hours. Next, acetaldehyde (20.4 g, 0.463 mol) was added dropwise with stirring over 30 minutes under ice-cooling, a ripening reaction was performed for 30 minutes under ice-cooling, and the mixture was transferred to another container and cooled with ice. 1N hydrochloric acid 6
The reaction was terminated by adding 00 ml, and the mixture was separated into an organic layer and an aqueous layer. The product was extracted three times from the aqueous layer with 600 ml of diethyl ether and combined with the organic layer. This was washed twice with 200 ml of saturated sodium bicarbonate, 200 ml of water, and 200 ml of saturated saline, and the diethyl ether was removed under reduced pressure to obtain 83.3 g of a concentrated solution. This was distilled (boiling point: 64 to 66 ° C./3 mmHg) using a distillation apparatus (manufactured by Tokyo Wire Mesh Co .; Helipack No. 2, 15 cm), and then subjected to silica gel column chromatography (solvent; hexane: ethyl acetate = 1).
0: 1) and (1S, 1'R, 3'R, 4'S)-
14 g of 1- (p-mentha-3′-yl) ethanol,
14 g of (1R, 1'R, 3'R, 4'S) -1- (p-mentha-3'-yl) ethanol was obtained. Gas chromatography [Column: CP-WAX52CB, 25mx
The chemical purity was measured by analysis using 0.25 mm (ID) × 0.2 μm (manufactured by GL Sciences Inc.) at a measurement temperature of 60 to 160 ° C. (heating at 4 ° C./min) (1S). , 1′R, 3′R, 4 ′S) -1- (p-mentha-3′-yl) ethanol had a purity of 96.0% and (1
R, 1'R, 3'R, 4'S) -1- (p-mentor
The purity of 3'-yl) ethanol was 96.0%.

(1S, 1'R, 3'R, 4'S) -1-
Spectral data of (p-mentha-3'-yl) ethanol [α] _D ²⁰ -44 ° (C = 1.01, MeOH) (1R, 1′R, 3′R, 4 ′S) Spectrum data of -1- (p-mentha-3'-yl) ethanol [α] _D ²⁰ -25 ° (C = 1.06, MeOH)

Example 2 (Evaluation of Aroma) Each of the optically active 1- (p-mentha-3′-yl) ethanols obtained in Example 1 and Reference Example 1 was evaluated for its aroma. went. Approximately 30 mg of the sample was applied to each odor paper, and the results of evaluation performed by seven specialized panelists are shown in Table 1.

[0036]

[Table 1]

As shown in Table 1, (1R,
1'S, 3'S, 4'R) -1- (p-mentha-3'-
Il) Only ethanol was found to have a citrus-like aroma reminiscent of grapefruit, muscat or lychee. In comparison, (1S,
1'R, 3'R, 4'S) -1- (p-mentha-3'-
Il) ethanol was almost odorless and had significant odor differences between the enantiomers. Further, (1S, 1'S, 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol having different hydroxyl groups is almost odorless, and further, the hydroxyl group of an enantiomer is obtained. The three-dimensional (1R, 1'R,
3'R, 4'S) -1- (p-mentha-3'-yl) ethanol was almost odorless and poor in odor value, and was not suitable for use as a fragrance.

Example 3 (Abundance and flavor intensity) (1R, 1'S, 3 ') of the present invention
The relationship between the amount of (S, 4'R) -1- (p-mentha-3'-yl) ethanol in the stereoisomer mixture and the effective flavor intensity was evaluated by the same functionalities as in Example 2. The method was evaluated. (1R, 1'S, 3'S, 4'R) -1-
As a comparative control containing no (p-mentha-3'-yl) ethanol, three isomers other than the compound of the present invention synthesized in Example 1 and Reference Example 1 having a weight ratio of 1: 1: 1 1 A stereoisomeric mixture of-(p-mentha-3'-yl) ethanol was prepared. To this was added (1R, 1'S, 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol, the compound of the present invention, and 5% by weight and 1%.
Table 2 shows the results of preparing a sample containing 0% by weight and evaluating the abundance and flavor intensity. As a result, the grapefruit was obtained when the amount of (1R, 1'S, 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol in the stereoisomer mixture was 5% by weight or more. And citrus-like odor reminiscent of muscat or lychee, and a remarkable difference was observed at 10% by weight or more.

[0039]

[Table 2]

Evaluation Criteria ++: Seven out of the seven panelists recognized that they had fragrance value. +: 5 out of 7 panelists recognized that it had fragrance value. -: Neither of the seven panelists recognized the perfume value.

Example 4 Production of Muscat-like Fragrance Fragrance Composition 800 Fragrance Fragrance Composition 800 prepared according to the following formulation
In parts by weight, (1R, 1'S, 3 'obtained in Example 1)
10 parts by weight of S, 4'R) -1- (p-mentha-3'-yl) ethanol was added, and the effect was evaluated by seven expert panelists. As a result, all members (1R, 1'S,
By using 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol, it is possible to impart a fresh, highly-preferred, muscat-like fragrance full of natural sensation and excellent strength. Replied.

(Fragrance composition for fragrance) Ethyl 2-methylbutyrate 8 parts by weight Ethyl acetoacetate 12 parts by weight Ethyl carbitol 336 parts by weight 10% ethyl isovalerate DPG (dipropylene glycol) solution 0.5 parts by weight Propionic acid Ethyl 8 parts by weight Covanol (trade name, manufactured by Takasago International Corporation) 40 parts by weight DPG solution of 50% oransa (trade name, manufactured by Takasago International Corporation) 60 parts by weight cis-3-hexenol 24 parts by weight cis-3 -Hexenyl methyl carbonate 1.5 parts by weight Methyl dihydroabiate 150 parts by weight Musk T (trade name, manufactured by Takasago International Corporation) 150 parts by weight Orange essential oil 10 parts by weight (total) (800 parts by weight)

An optically active 1 in a Muscat-like perfume composition
-(P-mentha-3'-yl) ethanol in (1
R, 1'S, 3'S, 4'R) -1- (p-mentor
The use of 3'-yl) ethanol added a unique, deeper, more natural fragrance. (1R, 1'S, 3'S, 4'R) -1-
(P-mentha-3'-yl) ethanol is very useful as an accent material for Muscat-like fragrances. This fragrance composition could be used effectively as a toiletry and cosmetics accent.

Example 5 Production of a citrus-like fragrance perfume composition A fragrance perfume composition 800 prepared according to the following formulation
In parts by weight, (1R, 1'S, 3 'obtained in Example 1)
10 parts by weight of S, 4'R) -1- (p-mentha-3'-yl) ethanol was added, and the effect was evaluated by seven expert panelists. As a result, all members (1R, 1'S,
By using 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol, it is possible to impart a refreshing and grapefruit-like fragrance with a natural peel feeling and excellent strength. Replied.

(Fragrance fragrance composition) α-pinene 15 parts by weight 1-decanal 4 parts by weight Citronellal 3 parts by weight Ethyl carbitol 200 parts by weight Fluoropearl (trade name, manufactured by Herman & Reimer Co., Ltd.) 5 parts by weight Grapefruit essential oil 220 Parts by weight 1-citronellyl acetate 8 parts by weight 1-citronellyl nitrile 8 parts by weight citral 6 parts by weight Linaxol (trade name, manufactured by Takasago International Corporation) 12 parts by weight Musk T (trade name, manufactured by Takasago International Corporation) 26 Parts by weight Orange navel essential oil 150 parts by weight Orange essential oil 77 parts by weight Lubafran (manufactured by Quest Co., Ltd., trade name) 6 parts by weight Stiralyl acetate 60 parts by weight (total) (800 parts by weight)

1-optically active citrus-like fragrance composition
In (p-mentha-3'-yl) ethanol, (1R,
1'S, 3'S, 4'R) -1- (p-mentha-3'-
Il) Ethanol added a refreshing scent with a natural peel. (1
R, 1'S, 3'S, 4'R) -1- (p-mentor
3'-yl) ethanol is very useful as a material for citrus-like perfumes. This fragrance composition could be used effectively as a fragrance for household goods.

Example 6 (Stability of the bleaching agent to the substrate) The following formula (1) was used as a chlorine bleaching substrate (pH 13) in the following formulation.
R, 1'S, 3'S, 4'R) -1- (p-mentor
After adding 0.3% by weight of 3′-yl) ethanol, distilled water was added to make a total of 100. The mixture was incubated at 20 ° C. in a dark place for 4 weeks, and the change in color and flavor and the residual chlorine ratio at that time were measured. I asked. As a result, there was no change in color and fragrance at all, and it was revealed that the product of the present invention was stable to the base material of the bleaching agent. Residual chlorine rate is (1R, 1'S, 3'S, 4'R)
It is 98 when the control to which -1- (p-mentha-3'-yl) ethanol is not added is 100, and there is a low risk of consuming the available chlorine of sodium hypochlorite indispensable for the bleaching agent. It is a fragrance. From the above results, (1R,
1'S, 3'S, 4'R) -1- (p-mentha-3'-
Il) ethanol was found to be highly stable in bleach bases.

(Prescription of chlorine-based bleaching agent base material) Sodium hypochlorite solution (effective chlorine concentration 10%) 50.0% by weight (effective chlorine amount conversion 5.0) Sodium hydroxide 1.0% by weight Surface activity Agent 3.0% by weight (1R, 1'S, 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol 0.3% by weight Distilled water remaining (total) ( 100.0% by weight)

[0049]

According to the present invention, (1R, 1'S, 3'S,
It is intended to provide a novel fragrance containing 4'R) -1- (p-mentha-3'-yl) ethanol as an active ingredient.
(1R, 1'S, 3'S, 4'R) -1- (p-mentha-3'-yl) ethanol is excellent in properties as a fragrance,
Thereby, (1R, 1'S, 3'S, 4'R) -1-
Fragrance compositions containing (p-mentha-3'-yl) ethanol as an active ingredient are used in a wide variety of fields such as various cosmetics, health and hygiene materials, and medicine.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuro Yamazaki 1-4-11, Nishi-Hachiman, Hiratsuka-shi, Kanagawa F-term in the Research Laboratory of Takasago International Co., Ltd. 4H006 AA01 AA03 AB14 FC22 FE11 4H059 BA14 BB13 BB45 BB55 BB60 BC10 CA44 CA99 DA09 EA35

Claims (5)

[Claims] (1) Formula (1) (1R, 1'S, 3'S, 4'R) -1-
(P-mentha-3'-yl) ethanol. 2. Formula (1) (1R, 1'S, 3'S, 4'R) -1-
A perfume containing (p-mentha-3'-yl) ethanol as an active ingredient. 3. (1R, 1'S, 3'S, 4'R) -1
-A fragrance comprising 1- (p-mentha-3'-yl) ethanol containing at least 5% by weight of (p-mentha-3'-yl) ethanol. 4. The 1- (p-mentor-3 ′) according to claim 2,
-Il) A perfume composition containing 0.01 to 50% by weight of ethanol. 5. The fragrance composition according to claim 4, wherein the fragrance composition is a citrus-based fragrance composition.