JPH0259564A - Production of (r)-(-)-2-decen-5-olide - Google Patents

Abstract

PURPOSE:To advantageously obtain the subject compound from a readily available raw material by successively passing (+)-1,2-epoxyheptane through respective steps for reaction with a vinylmagnesium halide, epoxidizing agent and cyanogen compound and a thermal reaction step in the presence of an acid. CONSTITUTION:(+)-1,2-Epoxyheptane expressed by formula 5 is reacted with a vinylmagnesium halide to provide (+)-4-hydroxy-1-nonene expressed by formula 4, which is then reacted with an epoxidizing agent to afford (-)-4-hydroxy-1,2- epoxynonane expressed by formula 3. The resultant compound expressed by formula 3 is subsequently reacted with NaCN, KCN or HCN to provide (-)-2,4- dihydroxynonylnitrile expressed by formula 2, which is then thermally reacted in the presence of an acid to industrially afford the objective compound, expressed by formula 1, having persistent, natural mild and sweet lactone-like flavor and aroma and characteristics of enhancing fatty, buttery or milky flavor and aroma in high purity at a low cost in a few steps by simple operation.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a novel method for producing (R)-(-)-2-decene-5-olide represented by the following formula (1), and a method for using the compound of the formula as an active ingredient. It relates to a long-lasting fragrance composition containing as.

More specifically, the present invention relates to a method for synthesizing the target compound of formula (1) in a short process using (+)-1,2-epoxyheptane as a starting material.

Furthermore, the present invention has a long-lasting, mild, natural sweet lactone-like aroma and flavor, and further has the property of enhancing the 7-acutey-like, butter-like, and milk-like aromas. The present invention relates to a fragrance composition containing the following (R)-(-)-2-decene-5-olide as an active ingredient.

This time, the compound of the above formula (1) has an excellent long-lasting aroma and flavor, and can be used as a long-lasting aroma and flavor imparting or modulating agent for various fragrance compositions, food and beverages (including luxury goods), cosmetics, etc. It has been discovered that it is useful in a wide range of fields such as medicine, health care, and pharmaceuticals.

Therefore, the object of the present invention is to provide (R)-(-
)-2-Decene-5-olide, and to provide a fragrance composition that can be used in various fields and contains a compound of formula (1) as an active ingredient.

(Prior art) Optically active (R) represented by the above formula (1) of the present invention
-(-)-2-Decene-5-olide was isolated and identified as an aroma component contained in sugarcane molasses, and is known to have a sugar-like aroma [Agr, Bio
1. Chem, 32 (10).

1306-1309 (1968)].

On the other hand, optically inactive 2-decene-5-olide is known to have a butter-like aroma (Japanese Patent Publication No. 4
6-41183). The present applicant has previously proposed an improved manufacturing method (Japanese Unexamined Patent Publication No. 63-57
Publication No. 583). According to this proposal, optically inactive 4-hydroxy-1-nonene is reacted with an epoxidizing agent to synthesize optically inactive 4-hydroxy-1,2-epoxynonane, and then , the epoxide is reacted with sodium cyanide to form optically inactive 2°4-dihydroxynonylnitrile, and the nitrile is further treated with acid to form optically inactive 2-decene-5- Synthesizing oride.

(Problems to be Solved by the Invention) In the above-mentioned conventional proposal, the compound of formula (1) of the present invention was isolated and identified as an aroma component of sugarcane molasses, and it was found that it has a sugar-like aroma. However, there is no description or suggestion of the usefulness of the compound or its use as a flavoring agent. Furthermore, the manufacturing method previously proposed by the applicant is a method for synthesizing optically inactive 2-decene-5-olide, and the method for manufacturing the optically active compound of formula (1) of the present invention is Yes, it has not been proposed yet.

As a result of intensive research, the present inventors have now selected (10)-1,2-epoxyethane, which is easily available on the market, as a raw material to achieve high purity with a small number of steps and without by-products. It has been discovered that the compound of formula (1) can be synthesized. Furthermore, when used as an aroma flavoring agent in a perfume composition, the aroma properties of the optically active compound of formula (1) produced by the method of the present invention are superior to those of the conventional optically inactive 2-decene- We discovered that compared to the aroma characteristics of 5-olide, it has a long-lasting, mild natural sweetness, and is also excellent in enhancing fanty-like, butter-like, and milk-like aromas. The present invention was completed.

(Means for solving the present invention) Thus, according to the present invention, (
-)-4-hydroxy-1,2-epoxynonane is formed, and then the compound of formula (3) is reacted with sodium cyanide, potassium cyanide or hydrogen cyanide to form (+)- (-)-2,4-dihydroxynonylnitrile represented by the following formula (4) is formed by reacting 1,2-epoxyheptane with vinylmagnesium halide, and further, by reacting 1,2-epoxyheptane with vinylmagnesium halide, There is provided a method for producing (+)-4-hydroxy-1-nonene represented by the following formula (1), which comprises subjecting a compound to a heating reaction in the presence of an acid.

According to the present invention, the compound of the above formula (4) is further reacted with an epoxidizing agent to form a (R)-
A method for producing (-)-2-decene-5-olide is provided.

According to the method of the present invention, the compound of formula (1) above can be produced industrially with high purity and at low cost through easy operations.

The method for producing the compound of formula (1) of the present invention is shown in the following process diagram.

m-CPBA: m-chloroperbenzoic acid The method for producing (R)-(-)-2-decene-5-olide of the present invention will be explained in more detail below according to the above process diagram.

To synthesize (+)-4-hydroxy-1-nonene of formula (4) above from (+)-1,2-epoxyheptane of formula (5) above, the compound of formula (5) is mixed in an organic solvent. , can be easily synthesized by reacting with vinyl magnesium halide in the presence of a metal halide.

The reaction is usually carried out at a temperature in the range of about -80°C to about 60°C, more preferably about -40°C to about 20°C, for example,
It can be carried out for about 0.5 hours to about 4 hours, more preferably about 1 hour to about 2 hours.

Specific examples of vinylmagnesium halides used in this reaction include vinylmagnesium chloride,
Preferred examples include vinylmagnesium bromide. The amount of vinyl manesium halide used is
Although not strictly limited, in general, formula (5)
A range of about 1.0 mol to about 10 mol, more preferably about 1 mol to about 2 mol, can be mentioned per 1 mol of the compound. Further, specific examples of metal halides include copper iodide, copper bromide, copper chloride, and the like. A catalytic amount of these metal halides is sufficient, but for example, compound 1 of formula (5)
Approximately 0.0% per mole. A range of about 1 mol to about 0.5 mol of O can be mentioned. Furthermore, examples of the organic solvent used in the above reaction include tetrahydrofuran, ether, and dioxane. The amount of these organic solvents to be used is not particularly limited, but a preferred range is about 2 to about 10 times the weight of the compound of formula (5).

After the reaction is completed, it is neutralized, washed with water, concentrated, and dried according to conventional methods, and if necessary, purified by means such as distillation to obtain the formula (
The compound 4) can be obtained with high purity.

(+)− of equation (4) that can be obtained as described above
(-) of the above formula (3) from 4-hydroxy-1-nonene
-4-hydroxy-1,2-epoxynonane can be easily synthesized by reacting the compound of formula (4) with an epoxidizing agent in an organic solvent.

The reaction is usually carried out at a temperature within the range of about 2 to about 10°C,
For example, the reaction time can be about 2 hours to about 48 hours.

Specific examples of the epoxidizing agent used in this reaction include m-chloroperbenzoic acid, perbenzoic acid, peracetic acid, performic acid, and the like.

The amount of these epoxidizing agents used is not particularly limited, but
Generally, about 1 mol to 1 mol of the compound of formula (4)
A range of about 1.5 moles can be exemplified. Furthermore, examples of the organic solvent used in this reaction include methylene chloride, chloroform, carbon tetrachloride, toluene, and hexane. The amount of these organic solvents to be used is also not limited, but preferably ranges from about 1 to about 20 times the weight of the compound of formula (4).

After the reaction is completed, the compound of formula (3) can be obtained in high purity by washing with water and concentrating according to a conventional method, and then purifying, for example, by means such as distillation, if necessary.

Next, in order to synthesize the (-)-2,4-dihydroxynonylnitrile of the above formula (2) from the compound of the formula (3) that can be obtained as described above, for example, the compound of the formula (3)
This can be easily carried out by reacting the compound with a cyanide such as potassium cyanide, sodium cyanide or hydrogen cyanide. This reaction is suitably carried out, usually in a solvent such as water, methanol, ethanol, or tetrahydro7rane, in the presence of an acid such as acetic acid, propionic acid, magnesium sulfate, or ammonium chloride.

The reaction temperature and reaction time of the above reaction can be appropriately selected and carried out, for example, at a reaction temperature in the range of about 0°C to about 100°C, and a reaction time of about 1 hour to about 10 hours. can be exemplified preferably. The amount of cyanide used in this reaction is usually preferably about 1 mol to about 2 mol per 1 mol of the compound of formula (3). Further, the amount of the solvent used as described above is not particularly limited and can be selected as appropriate, but for example, about 2 to about 2
It can be used within a range of about 0 times the weight.

Further, the amount of the above-mentioned acid used is not particularly limited, but is generally about 1 to 1 to 1 mole of the compound of formula (3).
A preferable example is a range of about 2 moles.

After the reaction is completed, the compound of formula (2) can be easily obtained by performing treatments such as extraction, water washing, drying, and concentration.

From the compound of formula (2) obtained as described above, the desired compound of formula (1) (R) -(-), -2-decene-5-
Olide can be easily synthesized, for example, by subjecting the compound of formula (2) to a heating reaction in the presence of an acid.

The above reaction can be carried out, for example, at a reaction temperature of about 0° C. to about 100° C. and a reaction time of about 0.5 hour to about 10 hours.

Examples of acids that can be used in this reaction include hydrochloric acid, sulfuric acid, and phosphoric acid. There are no special restrictions on the amount of these acids used, and they can be selected as appropriate.
For example, an amount of about 1 mol to about 10 mol can be preferably mentioned per 1 mol of the compound of formula (2).

After completion of the reaction, the target compound (R)-(-)-2-decene-5-olide of formula (1) can be obtained by performing treatments such as extraction, washing, and concentration.

The obtained compound of formula (1) can be further purified by means such as distillation, if necessary.

The compound of formula (1), which can be synthesized as described above, has a long-lasting, mild and natural sweet lactone-like aroma and flavor, and also has a 7-starchy, butter-like,
It has the property of enhancing the milk-like aroma and flavor, and has the property of harmonizing well with various synthetic fragrances, natural essential oils, etc. Therefore, if the compound of formula (1) is used, various new fragrance compositions can be created. can prepare things. The amount of the compound represented by formula (1) in the fragrance composition varies depending on the type and use of the fragrance composition, but generally it is about 0.001 to about 30% by weight of the total. I can list a range.

Thus, the present invention provides a fragrance composition containing the compound of formula (1) as an active ingredient, and the composition can be used to contain the compound of formula (1) as an aromatic flavor ingredient. Food and drink products characterized by; Tobacco products characterized by containing the compound of formula (1) as a flavor component; Cosmetics characterized by containing the compound of formula (1) as a flavor component; Formula (1) ) Compounds can be provided as health, hygiene, pharmaceuticals, etc., which are characterized by containing the compound as an aromatic flavor component. More specifically, for example, dairy products such as butter milk; beverages such as fruit juice drinks, fruit alcoholic beverages, milk drinks, and carbonated drinks; frozen desserts such as ice creams, sherbet, and popsicles; Japanese and Western sweets. luxury goods such as jams, chewing gums, breads, coffee, cocoa, black tea, green tea, and tobacco; soups such as Japanese soups and Western soups - flavor seasonings, various instant beverages or foods, various It is possible to provide food and drink products with aroma and flavor by adding an appropriate amount to snack foods and the like. For example, fragrance can be added to shampoos, hair creams, pomades, and other hair cosmetic bases; by adding an appropriate amount to shampoos, hair creams, pomades, and other hair cosmetic bases; Cosmetics can be provided. Furthermore, cleaning detergents, disinfectant detergents, deodorizing detergents, indoor air fresheners and other various health and hygiene detergents; various health and hygiene materials such as toothpaste, tissues and toilet paper; and pharmaceuticals. It is also possible to provide health, hygiene, and pharmaceutical products that have been blended with appropriate amounts of flavoring and flavoring agents to make them easier to take.

Hereinafter, the present invention will be explained in more detail by giving examples.

(Example) Example 1 + -4-Hydroxy-1-nonene 4±
A 11-bed flask was charged with 1.17 g (48.8 mmol) of magnesium and 5 ml of tetrahydrofuran, and to this was added a solution of 5.63 g of vinyl bromide in tetrahydrofuran 2.
Drop 0ml in 1 hour. After the dropwise addition was completed, the solution was further stirred for 1.5 hours, and a catalytic amount of copper iodide was added to this solution, and after stirring for 1 hour, (+)-1,2-epoxyheptane 4. O
30 ml of a solution of Og (35° 1 mmol) in tetrahydrofuran are added dropwise. After dropping, 1. at a temperature of 0°C.
Stir and react for 5 hours. After the reaction was completed, the reaction solution was poured into an aqueous ammonium chloride solution, extracted with ether, and the extract was washed, dried, concentrated, and then distilled under reduced pressure to obtain 4.12 g of the compound of formula (4) (yield: 82.7 %) was obtained.

Point: 47℃~48℃/2.0mmHg Optical rotation: [,]
]'Otori-7.95' (c-1,56: ethanol) Example 2 -4-Hydroxy-1,2-epoxynonane Formula (3 compounds) In a synthesis flask, add 30ml of dichloromethane and 1% m-chloroperbenzoic acid 2. 68 g (15,5 mmol), (+)-4-
2.00 g (14.1 mmol) of hydroxy-1-nonene was charged and stirred for 8 hours.

After stirring, 1.34 g of m-chloroperbenzoic acid was added, and 8
Stir for some time to react. After the reaction is complete, filter the reaction solution.
Washing with water, drying, concentrating, and further silica gel column chromatography (n-hexane: vinegar g1 ml = 3:1
1.76 g of pure compound of formula (3) purified by (
A yield of near 9% is obtained.

Optical rotation ゛ [“]b′″″−9・60° (°″″l・
25・Ethanol) Example 3 0.37 g of sodium cyanide (7°12
mmol), 1.5 ml of water, ethanol/l.

5 ml, (-)-4-hydroxy-1,2-epoxynonane O-9 g (5.7 mmol), and acetic acid 0.43 g were charged. The temperature is brought to 55°C and the reaction is allowed to proceed for 4 hours with stirring. After the reaction was completed, extraction was performed with dichloromethane, and the extracted layer was washed with water, dried, and concentrated to obtain 0.97 g of the compound of formula (2) (
Yield: 92%).

Example 4 0.97 g (-)-2,4-dihydroxynonylnitrile (5.2 mmol) and 0.62 g of concentrated hydrochloric acid were placed in a flask.
was charged, heated to 100°C, and reacted for 3 hours. After the reaction is complete, extract with ether, wash the extract with water, dry and concentrate. Further, the product was purified by silica gel column chromatography (hexane:ethyl acetate) to obtain 0.42 g (yield: 43.8%) of the pure compound of formula (1).

Optical rotation: EaE'=-112,2@(C-2,
52CHCl3) Example 5 The following components (parts by weight) were mixed to obtain a butter-like blended fragrance composition.

ethyl acetate 3 ethyl butyrate 2 acetoin
13 diacetyl
82-hebutanone 32-nonanone 92-undecanone
4 butyric acid
432-tridecanone 6-caproic acid 18δ-octalactone 3-caprylic acid
31δ-decalactone 10δ-
undecalactone 5-capric acid
6δ-dodecalactone
36 vegetable oil 800 total 1000 (R)-(-)-2-decene-5- to 98g of the above composition
A new butter-like blended fragrance composition was prepared by mixing 2 g of Oride. Regarding this new blended fragrance composition and the above blended fragrance composition to which the compound is not added, expert panel 1
Comparison was made by 0 people.

As a result, all 10 expert panelists agreed that the newly formulated fragrance composition to which the compound was added had an emphasized butteriness, and was significantly superior in terms of natural feel and sustainability.

Example 6 The following components (by weight) were mixed as a pineapple-like flavor component.

Ethyl acetate 300 Ethyl butyrate 250 Isoamyl acetate 100 Isoamyl valerate
55 isobutyric acid
70 Isovaleric acid 3
0 Allyl caproate 35 Ethyl caproate 20 Ethyl caprylate 15 Ethyl caproate 20 total
1000 By adding 8 g of the compound of formula (1) to 100 g of the above composition, a novel pineapple fragrance composition having an excellent persistence equivalent to that of natural pineapple fragrance with an emphasis on mildness was obtained.

Example 7 The following ingredients were mixed as a bouquet type perfume.

Phenylethyl alcohol 180 Linalyl acetate 30 Bergamot oil
40 rhodinol
50 Benzyl acetate 40
Hes Othrobin 80 Geraniol 110 Inamyl Alcohol Diethyl Malonate Citral 1 Linalool Maltol Rose Absolute-1-10 β-Ionone 100 Lavender 20 Diasmine Absolute 1O Amyl Salicylate 45 Linalyl Acetate 135 Vetiver Acetate 100 Citronellol
50 total 1000 (R)-(-)-2-decene-5- to 98g of the above composition
By adding 2 g of Oride, a novel bouquet-like perfume composition with natural sweetness and floral persistence was obtained.

Example 8 Each of the following components (parts by weight) as a blended fragrance for 0-ztive
was prepared.

Phenylethyl alcohol 200 Geraniol 50 Heli, Otrobin
20 citronellol
10 nerol
100 Hydroxycitronellal 30 Methyl phenyl carbinyl acetate 5 Geranium oil
30 linalool
30 benzyl acetate
35 benzyl alcohol
20 rose phenone 10 rhodinol 280 rose oil
lOβ-ionone
50 benzyl salicylate
40 cyclobentadecaturide
30 Guaiyaud oil 50
Total 1000 By adding 3 g of (R)-(-)-2-decene-5-olide of formula (1) to 97 g of the above composition, a novel rose-like blended fragrance composition with emphasized naturalness was obtained. Ta. Ten expert panelists conducted a comparative study of a blended fragrance composition to which the product of the present invention was added and a blended fragrance composition to which it was not added.

As a result, all 10 expert panelists agreed that the perfume composition containing the product of the present invention was significantly superior in both the characteristics of natural rose and its sustainability.

Other names

Claims (1)

[Claims] 1. The invention is characterized by reacting (+)-1,2-epoxyheptane represented by the following formula (5) ▲Mathematical formula, chemical formula, table, etc.▼(5) with vinylmagnesium halide The method for producing (+)-4-hydroxy-1-nonene shown by the following formula (4) ▲Mathematical formulas, chemical formulas, tables, etc.▼(4). 2. The following formula (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) By reacting (+)-4-hydroxy-1-nonene shown with an epoxidizing agent, the following formula (3) ▲ Mathematical formula ,Chemical formula,
There are tables etc. ▼(3) Forming (-)-4-hydroxy-1,2-epoxynonane shown by formula (3), then reacting the compound of formula (3) with sodium cyanide, potassium cyanide or hydrogen cyanide. , the following formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) Forming (-)-2,4-dihydroxynonylnitrile, and further adding the compound of formula (2) in the presence of an acid. A method for producing (R)-(-)-2-decene-5-olide represented by the following formula (1) ▲Mathematical formulas, chemical formulas, tables, etc.▼(1) characterized by a heating reaction. 3. A fragrance characterized by containing (R)-(-)-2-decene-5-olide as an active ingredient represented by the following formula (1) ▲ Numerical formula, chemical formula, table, etc. ▼ (1) Composition.