JP3427866B2 - Trans-3-acetoxy-1,8-cineole and fragrance composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has spice-like, tree-like, fruit-like, flower-like aroma and flavor characteristics with a cool sensation and is useful as a fragrance compound. A) -1

[0002]

[Chemical 3]

In the formula, Ac represents an acetyl group, and relates to trans-3-acetoxy-1,8-cineole.

Further, the present invention has the above-mentioned formula (A) -1 compound and the following formula (A) -2 which has aroma and flavor characteristics similar to those of the compound and is useful as a perfume compound.

[0005]

[Chemical 4]

In the formula, Ac represents an acetyl group, cis-3-acetoxy-1,8-cineole represented by the following formula (A) -3

[0007]

[Chemical 5]

Trans-3-hydroxy-represented by
1,8-Cineol and the following formula (A) -4

[0009]

[Chemical 6]

Cis-3-hydroxy-1,8 represented by
-The following formula (A) including cineole

[0011]

[Chemical 7]

In the formula, R represents a hydrogen atom or an acetyl group, and also relates to a novel fragrance composition containing a 3-hydroxy-1,8-cineole derivative represented by

[0013]

2. Description of the Related Art The present inventors have found that Galanga [Al, which belongs to the tropical genus Galanga genus plant belonging to Nepal, is the origin of the plant.
pinia galanga (L.) Willd.] I have continued to study the aroma and flavor components of essential oils. As a result, it was determined that the compound of the above formula (A) was a key flavor component of the aroma or flavor of galanga essential oil, and it was successfully extracted and separated from the galanga essential oil, and these were easily synthesized. I found that. Furthermore, the compound of the above formula (A) is a spice-like, tree-like, fruit-like, which has a long-lasting and refreshing feeling,
A perfume composition having a flower-like aroma and flavor property and containing the compound is used in a wide range of applications such as foods and drinks (including luxury items), soaps / detergents, cosmetics, health / hygiene products, pharmaceuticals, etc. The present invention was completed by discovering that it is useful as an excellent persistent aroma and flavor imparting agent.

Of the compounds included in the above formula (A),
The trans-form compound represented by the above formula (A) -1 is not described in conventional literatures, and is a novel compound created by the present inventors for the first time. On the other hand, the above formula (A)-
The compounds of 2, (A) -3 and (A) -4 are described in the prior art, for example, the compound of formula (A) -2 is
It has been reported that it can be obtained by oxidizing 1,8-cineole with chromyl acetate (J. Org. Chem. 198).
7, 52, 1505-1511) and the compound of formula (A) -3 is reported to be obtained by oxidizing 1,8-cineole with metachlorobenzoic acid or treating it with a microorganism of the genus Aspergillus. (Phytochemistry, 198
8, 27, 3861-3869; Agric. Biol. Chem. 1982, 46, 26
01 ~ 2604). Furthermore, the compound of formula (A) -4 is 1,8-
It has been reported that cineole can also be obtained by oxidation with the above-mentioned chromyl acetate or microorganisms of the genus Aspergillus (J. Org. Chem. 1987, 52, 1505).
~ 1511; Agric. Biol. Chem. 1982, 46, 2601-2604).

[0015] However, although the above-mentioned conventional documents describe the method for producing the compounds of formula (A) -2 to formula (A) -4 and the identification data, these compounds are spice-like, There is no description or suggestion that it has aroma and flavor characteristics such as woody, fruity, and flower-like, and the persistence of these characteristics, and that it is useful as a blended flavor material.

[0016]

Recently, with the diversification of consumers' taste, it is desired to develop various kinds of products. This tendency is particularly strong in the food and drink / cosmetics industry, and there is a strong demand for the development of foods and drinks and cosmetics that are rich in variety that suits the tastes of consumers. In order to meet these demands, the fragrance, which is one of the raw materials for foods and beverages and cosmetics, cannot be sufficiently dealt with by only the fragrance compound that has been conventionally proposed, and has a unique aroma and flavor characteristic which has never been achieved. The development of perfume compounds with excellent sustainability has become an urgent issue.

Accordingly, the inventors of the present invention have made intensive studies in order to solve the above-mentioned problems, and as a result, the novel formula described above was found by the present inventors for the first time in galanga essential oil and successfully isolated. The compound of the formula (A), which includes the compound of (A) -1, is a spice-like, tree-like, and
The present invention has been completed by discovering that it has an aroma and flavor such as fruit and flower, is excellent in the persistence of aroma and flavor characteristics, and is extremely useful as a flavoring substance.

Therefore, an object of the present invention is to provide a compound of the above formula (A) -1, which has not been described in the prior art, and a compound of the above formula (A) -1 to formula (A) -4. It is intended to provide a perfume composition containing the compound of the above formula (A) as an active ingredient.

[0019]

Means for Solving the Problems trans-3-acetoxy-1,8-cineole of formula (A) -1 and formula (A)-
The cis-3-acetoxy-1,8-cineole of 2 can be obtained by a conventionally known method or a production method developed by the present inventors using piperitenone as a starting material (hereinafter referred to as piperitenone method) ( A) -3 trans-3-hydroxy-1,8-cineole or cis-3-hydroxy-1,8-cineole of formula (A) -4 is acetylated by a commonly used method. (Hereinafter, referred to as acetylation method), it can be easily synthesized. Hereinafter, the method for synthesizing the compound of formula (A) -1 to formula (A) -4 of the present invention will be described in more detail.

[0020](A) -1 or formula by acetylation method
Synthesis of compound (A) -2 Acetylation reaction of compound of formula (A) -3 or formula (A) -4
The reaction is the condition of the usual acetylation reaction that is generally performed.
Can be carried out as is, for example
The compound of formula (A) -3 or formula (A) -4 as a raw material is pyridinium.
Amine, triethylamine, methylene chloride, chloroform,
Tetrahydrofuran, ether, toluene, benzene, etc.
After dissolving in 1 mol of the organic solvent,
About 1 to 1 of acetylating agents such as hydroacetic acid, acetyl chloride, and acetic acid
Add about 2 moles within a temperature range of about 0 ° C to about 100 ° C.
After reacting for about 0.1 to about 10 hours, the reaction is generated
Washing, extraction, drying, distillation, column chromatography
Purify by appropriately adopting ordinary separation means such as
Yields a compound of formula (A) -1 or formula (A) -2
It can be obtained with high efficiency and high purity.

[0021]Formula (A) -3 or formula by piperitenone method
Synthesis of compound (A) -4 The piperitenone method is based on piperitenone in the presence of acid.
By performing a hydrolysis and a cyclization reaction, 3-oxo-1,
First step of forming 8-cineole;
By treating with a reducing agent in a solvent, cis-3-hydr
Roxy-1,8-cineole [compound of formula (A) -4]
A second step of forming a compound of formula (A) -4
By the Mitsunobu inversion reaction that is generally performed, trans-
3-hydroxy-1,8-cineol [of the formula (A) -3
Compound] is formed. Below this
The peritenone method will be described in more detail for each step.
It (1) First step (combining 3-oxo-1,8-cineole)
Formed) Hydrolysis and cyclization of piperitenone in acidic aqueous solution
Thereby synthesizing 3-oxo-1,8-cineole
It For the reaction temperature and reaction time of this reaction, for example,
For example, at a temperature of about 0 ° C to about 100 ° C for about 1 to about 72 hours.
Can be adopted. Acids that can be used include sulfur
Ore of acid, hydrochloric acid, nitric acid, acetic acid, p-toluenesulfonic acid, etc.
An acid and an organic acid can be illustrated. Use of these acids
The dose varies depending on the type of acid, but it is usually piperite.
About 0.1 to about 100 moles per mole of non-, more preferred
Specifically, it may be in the range of about 1 mol to about 10 mol.
it can. Further, as the reaction solvent, for example, tetrahydr
Rofuran, methanol, ethanol, acetonitrile, etc.
The organic solvent can be used. Furthermore, it accelerates the reaction
If necessary, trioctyl ammonium chloride
Quaternary compounds such as chloride and tetrabutylammonium chloride
Phase transfer catalysts such as ammonium salts and boron trifluoride, salts
The reaction can also be carried out in the presence of a Lewis acid such as zinc oxide.
It After the reaction is completed, the reaction product is distilled, washed, extracted and dried.
Normal separation means such as drying and column chromatography
Good yield and good purity by adopting and purifying appropriately
To give 3-oxo-1,8-cineole
It

(2) Second step [of compound of formula (A) -4
[Synthesis] 3-oxo-1,8-cineole obtained in the first step is treated with a reducing agent in an organic solvent to give cis-3.
-Hydroxy-1,8-cineole [compound of formula (A) -4] can be easily produced. As the reaction temperature and reaction time of the reduction reaction, for example, a temperature of about −30 ° C. to about 100 ° C. and a period of about 0.1 hour to about 24 hours can be adopted. Examples of the reducing agent include metal hydrides such as lithium aluminum hydride and sodium borohydride, and the amount thereof is usually 1 mol of 3-oxo-1,8-cineole. About 0.25 mol or more, more preferably about 0.5 mol to about 1
It can be exemplified within the range of moles.

Examples of the organic solvent used in the reduction reaction include diethyl ether, tetrahydrofuran, diglyme, dimethoxyethane and the like. Although the amount of these solvents used is not strictly limited, it is usually appropriate to use about 1 to about 100 parts by weight per 1 part by weight of 3-oxo-1,8-cineole. After completion of the reaction, the reaction product is distilled, washed, extracted,
The compound of formula (A) -4 can be obtained in good yield and good purity by appropriately adopting and purifying an ordinary separation means such as drying or column chromatography.

(3) Third step [of compound of formula (A) -3
Synthesis] By subjecting the compound of formula (A) -4 obtained in the second step to Mitsunobu inversion reaction, trans-3-hydroxy-1,
8-Cineol [compound of formula (A) -3] can be easily produced. For this reaction, the conditions of the usual Mitsunobu inversion reaction that is generally performed can be directly adopted, and for example, the compound of the formula (A) -4 can be prepared in an organic solvent such as tetrahydrofuran or diethyl ether. Reaction with 5-dinitrobenzoic acid, triphenylphosphine and diethyl azodicarboxylate to form the 3,5-dinitrobenzoic acid ester of the compound of formula (A) -3. The amount of each of 3,5-dinitrobenzoic acid, triphenylphosphine and diethyl azodicarboxylate used is within the range of about 1 to about 1.5 mol per 1 mol of the compound of the formula (A) -4. Can be illustrated. The reaction temperature and reaction time of this reaction are, for example, about -30 ° C to
A temperature of about 70 ° C. for about 1 hour to about 24 hours can be employed. After completion of the reaction, the reaction product is purified by appropriately adopting usual separation means such as distillation, washing, extraction, drying and column chromatography to obtain a compound of the formula (A) -3 in good yield and good purity. The 3,5-dinitrobenzoic acid ester of the compound can be obtained.

The 3,5-dinitrobenzoic acid ester of the compound of formula (A) -3 thus obtained is hydrolyzed or alcoholysed in the presence of a base in water or an organic solvent to give Trans-3-hydroxy-
1,8-Cineol [compound of formula (A) -3] can be easily produced. As the reaction temperature and reaction time of this reaction, for example, a temperature of about 0 ° C. to about 100 ° C. and about 0.5 to about 10 hours can be adopted.
Examples of the organic solvent that can be used include methanol, ethanol, isopropanol, propanol, tetrahydrofuran, ether, and the like. The amount used is not particularly limited, but usually 3,5-dinitrobenzoic acid ester 1 A preferred range is from about 5 to about 100 parts by weight relative to parts by weight. Examples of the base that can be used include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, and the like. The amount of the base used is, for example, 1 mol of 3,5-dinitrobenzoic acid ester. And can be in the range of about 0.05 to about 1 mole. After the completion of the reaction, the reaction product is purified by appropriately adopting an ordinary separation means such as distillation, washing, extraction, drying, and column chromatography to obtain a compound of formula (A) -3 in good yield and purity. The compound can be obtained.

The compound of the formula (A) which can be obtained as described above has a refreshing spice-like, tree-like, fruit-like, flower-like aroma and flavor characteristics, and further these The compound possesses an extremely excellent persistence of the properties and can be used by adding it to various perfume compositions. When the compound of formula (A) -1 to formula (A) -4, that is, the compound of formula (A) is used in the fragrance composition, the addition amount thereof varies depending on the purpose or the type of the fragrance composition. Generally, from about 0.001 of the total amount of perfume composition
It can be exemplified in the range of about 30% by weight, preferably about 0.01 to about 20% by weight.

Thus, according to the present invention, the above formula (A)
An aroma and flavor imparting composition containing the compound of claim 1 as an active ingredient can be provided, and the composition is used to further contain the compound of formula (A) as an aroma and flavor ingredient. Cosmetics characterized by containing the compound of (A) as an aroma component, and health care characterized by containing the compound of formula (A) as an aroma-flavor component.
We can provide hygiene and medicine.

For example, beverages such as fruit juice drinks, fruit liquors, milk drinks, carbonated drinks; ice creams, sherbets, frozen desserts such as ice candy; Japanese and Western sweets, jams, chewing gums, breads Appropriate compounds of formula (A) for foods, coffee, cocoa, tea, tea and other luxury items; Japanese-style soups, western-style soups; flavor seasonings, instant drinks and foods, snack foods, etc. By adding the amount
It is possible to provide foods and drinks having the unique aroma and flavor. Also, for example, shampoos, hair creams, pomades, and other hair cosmetic bases;
By adding an appropriate amount of the compound of the formula (A) to oscilloire, lipstick, other cosmetics bases, cosmetics detergent bases, etc., it is possible to provide cosmetics having a unique aroma. Furthermore, laundry detergents, disinfecting detergents, indoor air fresheners and various other health and hygiene materials containing an appropriate amount of the compound of formula (A); Health, hygiene, and medicines such as fragrances can be provided.

Hereinafter, the present invention will be described more specifically with reference to Examples and Reference Examples.

[0030]

【Example】

Reference Example 1 Synthesis of 3-oxo-1,8-cineol (piperitenone
Method) Piperitenone (6) was added to 35% sulfuric acid aqueous solution (1690 g).
7.5 g) was added, and the mixture was stirred at room temperature for 48 hours. The reaction mixture was poured into ice water and extracted with diethyl ether, and the obtained diethyl ether layer was washed with saturated brine and saturated aqueous sodium hydrogen carbonate solution. After drying over sodium sulfate, concentration under reduced pressure, the obtained residue was distilled under reduced pressure, and purified by silica gel column chromatography,
7.6 g of the target 3-oxo-1,8-cineole was obtained.

Reference Example 2 cis-3-hydroxy-1,8-cineole [formula (A)]
Compound of -4] (piperitenone method ) A suspension of lithium aluminum hydride (0.51 g) in dry ether (23 ml) was added to 3-oxo-under cooling with ice water.
1,8-Cineol (2.26 g) in dry ether (2
(3 ml) solution was added dropwise at 3 to 8 ° C over 20 minutes, and the mixture was stirred at room temperature for 1.5 hours. Cool with ice water again, and add water (0.5 m
l), 15% aqueous sodium hydroxide solution (0.5 ml),
Further water (1.5 ml) was added, the insoluble material was filtered off, the mother liquor was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the desired cis-3-hydroxy-1. , 8-Cineol 2.32 g was obtained.

(Reference example 3)Trans-3-hydroxy-1,8-cineol [formula
(A) -3 compound] (piperitenone method) Cis-3-hydroxy-1,8-cineole (2.04
g), triphenylphosphine (3.14 g) and 3,
Dried tetrahydric acid of 5-dinitrobenzoic acid (2.54 g)
Rofuran (30 ml) solution, under ice-water cooling, Azodical
Dry tetrahydrofura of diethyl borate (2.09 g)
Solution (10 ml) was added dropwise at 5-10 ° C for 20 minutes.
It was After further stirring at room temperature for 20 hours, the reaction mixture was reduced.
It was concentrated under pressure. The residue obtained is ethyl acetate (52 m
l), hexane (104 ml) was added thereto,
The precipitated crystals were filtered off. Concentrate the obtained mother liquor under reduced pressure
And the residue is purified by silica gel column chromatography.
To give trans-3-hydroxy-1,8-
Crude of 3,5-dinitrobenzoic acid ester of cineol
3.82 g of the product was obtained.

The obtained crude ester (3.82 g) was dissolved in methanol (60 ml), potassium carbonate (0.20 g) was added thereto, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to give the desired trans-3-hydroxy-1,8-cineole 0.96 g.
Got

Reference Example 4 cis-3-acetoxy-1,8-cineole [formula (A)]
-2 compound] cis-3-hydroxy-1,8-cineole (170 m
g), acetic anhydride (204 mg) and dimethylaminopyridine (4 mg) were added to pyridine (3.4 ml), and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into 1N-hydrochloric acid and extracted with ether. The ether layer was washed with saturated brine, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate and concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give the desired product. Cis-3-acetoxy-1,
193 mg of 8-cineole was obtained.

(Example 1)Trans-3-acetoxy-1,8-cineole [formula
(A) -1 compound] Trans-3-hydroxy-1,8-cineole (34
0 mg), acetic anhydride (410 mg) and dimethylamino
Pyridine (7 mg) was added to pyridine (7 ml) at room temperature
The mixture was stirred below for 2 hours. Pour the reaction mixture into 1N-hydrochloric acid
And extracted with ether. Saturate the ether layer with saturated saline
Washed with aqueous sodium hydrogen carbonate solution and saturated saline
Then, dried over magnesium sulfate and concentrated under reduced pressure to obtain
The residue is purified by silica gel column chromatography.
The target trans-3-acetoxy-
403 mg of 1,8-cineole was obtained.

IR ν = 2980 cm ⁻¹ (m), 176
0 (m), 1370 (w), 1235 (s), 984
(W).

Example 2 The following components (parts by weight) were mixed as a lira-type compounded fragrance composition.

[0038] Trans-3-acetoxy-1,8 was added to 97 g of the above composition.
-A new formulated perfume composition was prepared by mixing 3 g of cineole. This newly prepared fragrance composition and the above-mentioned lyre-type fragrance composition containing no compound were compared by 10 expert panelists. As a result, the new compounded fragrance composition in which all of the 10 professional panelists added the compound emphasized the refreshing, flower-like aroma and flavor characteristics with a refreshing cleanness, and well characterized the natural lira. I was trying to catch it.

Trans-3-acetoxy-of Example 2
Cis-3-acetoxy-instead of 1,8-cineole
1,8-cineole, trans-3-hydroxy-1,
8-Cineol and cis-3-hydroxy-1,8-cineole were separately mixed in the same amount to prepare a novel blended fragrance composition. This newly prepared fragrance composition and the above-mentioned lyre-type fragrance composition containing no compound were compared by 10 expert panelists. As a result, as in the case of trans-3-acetoxy-1,8-cineole, the newly prepared fragrance composition in which all 10 professional panelists added the compound was a refreshing flower having a clean and clean feeling. It is said that the aroma and flavor characteristics are emphasized and the characteristics of natural lira are well captured.

Example 3 The following components (parts by weight) were mixed as a pineapple-like mixed flavor composition.

[0041] 6 g of cis-3-hydroxy-1,8-cineole was mixed with 94 g of the above composition to prepare a novel fragrance composition. This newly prepared fragrance composition was compared with the above-mentioned pineapple-like prepared fragrance composition in which the compound was not added, by 10 expert panelists. As a result, all of the 10 expert panelists said that the newly prepared fragrance composition containing the compound emphasized the characteristics of fresh pineapple-like fruit with a fresh refreshing sensation and captured the characteristics of natural pineapple well. did.

Cis-3-Hydroxy-1,8 of Example 3
-Trans-3-hydroxy-in place of cineole
1,8-cineole, cis-3-acetoxy-1,8-
Cineol and trans-3-acetoxy-1,8-cineole were separately mixed in the same amount to prepare a novel blended fragrance composition. This newly prepared fragrance composition was compared with the above-mentioned pineapple-like prepared fragrance composition in which the compound was not added, by 10 expert panelists. As a result, as in the case of cis-3-hydroxy-1,8-cineole, the newly prepared fragrance composition in which all 10 professional panelists added the compound was a fruity and sweet pineapple-like product with a fresh refreshing feeling. It is said that the characteristic of natural pineapple is well understood by emphasizing the characteristics of.

[0043]

INDUSTRIAL APPLICABILITY The present invention provides trans-3-acetoxy-1, represented by the above formula (A) -1, which has not been described in conventional literatures.
Provision of 8-cineole and compounds of formula (A) -1 as well as compounds of formulas (A) -2, (A) -3 and (A) -4 previously known but not known for use in perfumes 3-hydroxy-1,8 represented by formula (A) including
-To provide a fragrance composition containing a cineole derivative as an active ingredient. The compound of formula (A) has a long-lasting, refreshing, spice-like, woody, fruity, flower-like aroma and flavor characteristics, is useful as a perfume substance, and has a long-lasting flavor composition. It can be used as a compounding material.

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Claims (2)

(57) [Claims] 1. The following formula (A) -1: In the formula, Ac represents an acetyl group, represented by trans-
3-acetoxy-1,8-cineole. 2. The following formula (A): In the formula, R represents a hydrogen atom or an acetyl group, and contains a 3-hydroxy-1,8-cineole derivative represented by as an active ingredient.