JPS6241715B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention discloses 2,4-dihydroxy-7-isopropyl-2,4-dihydroxy-7-isopropyl-, a novel compound which has not been described in the literature and is useful as an intermediate for the synthesis of known flavor substances isolated from shifu tobacco, and also as a flavoring substance itself. 4-Methyl-10-ethylenedioxy-5(E)
-Relating to undecen-1-ol. The invention also relates to the preparation and use of said compounds. More specifically, the present invention is based on the following formula (B) 2 of the new compound not described in the conventional literature represented by
4-dihydroxy-7-isopropyl-4-methyl-10-ethylenedioxy-5(E)-undecene-
Regarding 1-ol. Furthermore, the present invention also relates to a persistent aroma and flavor imparting or modulating agent characterized by containing the compound of formula (B) as an active ingredient, and also relates to a method for producing these. The present inventors discovered that the following formula (1), which is a known flavor substance isolated from Suifu tobacco, 1,4-epoxy-2,10-dihydroxy-7-isopropyl-4-methyl-5(E)-
Research was conducted to develop a new synthesis method for undecene. As a result, a novel compound 2,4-dihydroxy-7-
It was discovered that isopropyl-4-methyl-10-ethylenedioxy-5(E)-undecen-1-ol could be synthesized, and the synthesis was successfully carried out. Furthermore, it has been found that the compound of formula (B) is useful as a synthetic intermediate for the compound of formula (1) above. Furthermore, the present inventors have discovered that the compound of formula (B) has an aroma reminiscent of hay with a weak green odor, has excellent retention properties, and can be easily and inexpensively produced industrially. that it can be manufactured, and that the formula
It has been discovered that the compound (B) is useful as a long-lasting aroma imparting or flavor modulating agent for various fragrance compositions. The above formula (B) compound of the present invention can be incorporated into various flavor compositions, such as roasted nut-based, wood-based, green-based, flower-based, tobacco-based, Western liquor-based, roast beef-based, and spice-based fragrance compositions. The compound of formula (B) above is a useful compound that can be used as a long-lasting aroma and flavor imparting or modulating agent. 1) It was found that this is a new compound that is also useful as an intermediate for the synthesis of compounds. Therefore, an object of the present invention is to provide the compound of formula (B), which has not been described in any literature, and a method for producing the same. Another object of the present invention is to provide a persistent aroma and flavor imparting or modulating agent characterized by containing the compound of formula (B) as an active ingredient, as well as a synthetic intermediate for the compound of formula (1). The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The following formula (B) of the present invention 2,4-dihydroxy-7-isopropyl-4-methyl-10-ethylenedioxy-5 represented by
(E)-Undecen-1-ol can be synthesized, for example, as follows. 5-isopropyl-3,8-nonadiene-2,
The following formula (4) can be easily synthesized from 8-dione 5-isopropyl-8-ethylenedioxy-3-nonen-2-one represented by

[Formula] (wherein, X represents a halogen atom) When contacted with magnesium allyl halide represented by the following formula (3) A novel compound represented by 4-hydroxy-7-isopropyl-4-methyl-10- which has not been described in any prior literature.
Ethylenedioxy-1,5(E)-undecadiene is formed. The compound of formula (3) can then be easily synthesized by oxidizing it with an oxidizing agent in an organic solvent, for example, in the presence of water and osminium tetroxide. The 1,4-epoxy compound of the formula (1), which is known as a flavor substance isolated from Shufu tobacco, using the novel compound of the formula (B), which has not been described in the conventional literature of the present invention.
2,10-dihydroxy-7-isopropyl-4-
To synthesize methyl-5(E)-undecene, for example, the compound of formula (B) is brought into contact with an acid catalyst in an organic solvent to cause a ring-closing reaction, and then hydrogenated in an organic solvent in the presence of a reducing reagent. It can be easily synthesized by A method for synthesizing the compound of formula (1), which is known as a flavor substance isolated from watermelon tobacco, has not been previously known, and the present inventors were the first to successfully synthesize it. The process diagram including the production example of the compound of formula (B) of the present invention and the production example of the above formula (1) can be expressed as follows. According to the invention, said formula (B) 2,4dihydroxy-7-isopropyl-4-methyl-10-ethylenedioxy-5(E)-undecen-1-ol is, for example, Helv.Chim.acta. 1867 (1975), using the formula (4) 5-isopropyl-8-ethylene-dioxy-3-nonen-2-one as a starting material. In the process diagram above, from the formula (4) to the formula (3)4
-Hydroxy-7-isopropyl-4-methyl-
To synthesize 10-ethylenedioxy-1,5(E)-undecadiene, the compound of formula (4) is converted into, for example,
in organic solvent,

This can be easily carried out by contacting with allyl magnesium halide represented by the formula. Preferred examples of the allyl magnesium halide used in the above reaction include allyl magnesium bromide, allyl magnesium chloride, and allyl magnesium iodide. The amount of these allyl magnesium halides to be used is, for example, about 1 to about 5
The amount used may be in the molar range.
Allyl magnesium halide can be easily prepared by, for example, reacting allyl halide with magnesium metal in an organic solvent such as ether or tetrahydrofuran according to a conventional method. Examples of the organic solvent used in the above reaction include tetrahydrofuran, dimethyl ether, diethyl ether, benzene, and toluene. The amount of these organic solvents to be used can be selected as appropriate, and can be exemplified in a range of about 0.5 to about 10 times the weight of the compound of formula (4). The temperature and time of the above reaction can also be selected appropriately, for example, the reaction can be easily carried out at a temperature in the range of about 20° to about 70°C and for a time in the range of about 1 to about 50 hours. After the reaction is completed, the compound of formula (3) can be easily obtained by, for example, pouring the reaction solution into a saturated aqueous ammonium chloride solution, extracting with an organic solvent, washing the organic solvent layer with brine, drying, and concentrating. Can be synthesized. The formula (B) 2,4-dihydroxy-7-isopropyl-4-methyl-10-ethylenedioxy-5(E)-undecene of the present invention is obtained from the formula (3) compound that can be obtained as described above. -1-ol can be obtained by oxidizing the compound of formula (3) with an oxidizing agent in the presence of water and a catalytic amount of osminium tetroxide, for example. For example, the reaction takes place at a temperature range of about 10 to about 30°C and a temperature of about 20 to about 200°C.
Can be done subject to time conditions. Examples of the oxidizing agent used in this reaction include trimethylamine-N-oxide and N-methylmorpholine N-oxide. The amount of these oxidizing agents to be used can be selected as appropriate, and may range from about 0.5 to about 2 moles based on the compound of formula (3). Further, the amount of osminium tetroxide used in this reaction is, for example, about 1/1000 to about 1/1/1000 to about 1/1000, based on the compound of formula (3).
An example is a range of about 10% by weight. Examples of the organic solvent to be used include acetone, methyl ethyl ketone, methanol, ethanol, t-butanol, and sec-butanol. The amount of these organic solvents to be used can be selected as appropriate, and for example, may be in the range of about 0.5 to about 50 times the weight of the compound of formula (3). There are no particular restrictions on the amount of water used, but it is preferably in a range of about 0.5 to about 5 times the weight of the compound of formula (3). After the reaction is completed, an organic solvent such as dichloromethane is injected into the reaction solution for extraction, and the organic layer is washed with water, dried over magnesium sulfate, and concentrated to obtain the compound of formula (B). The compound of formula (2) can be obtained by mixing the compound of formula (B), which can be obtained as described above, in an organic solvent.
It can be easily obtained by carrying out a ring-closing reaction in the presence of an acid catalyst. The ring-closing reaction is performed, for example, from about 0 to
This can be carried out at a temperature of about 40° C. for about 2 to about 20 hours. Examples of the acid catalyst used in the reaction include sulfuric acid, hydrochloric acid, and phosphoric acid. The amount of these acid catalysts to be used can be selected, but for example, about 1 to about
A range of about 50% by weight can be exemplified.
Examples of organic solvents include acetone, methyl ethyl ketone, and tetrahydrofuran. These organic solvents can be used in an amount of about 1 to about 50 times the weight of the compound of formula (B). . After the reaction is complete, powder of sodium hydrogen carbonate, for example, is added to the reaction solution, extracted with ether, the ether layer is washed with saturated brine, dried over magnesium sulfate, concentrated, and the residue is purified by, for example, silica gel column chromatography ( The compound of formula (2) can be easily obtained with high purity by purification using hexane/ethyl acetate=6/4). For example, by using the compound of the formula (2) which can be obtained as described above, a known flavor substance of the formula (1) 1,4-epoxy-2,10-dihydroxy-7 isolated from Shufu tobacco can be obtained. -Isopropyl-4-methyl-5(E)-undecene can be synthesized by hydrogenating the compound of formula (2), which can be obtained as described above, in the presence of a ring reagent, for example, in an organic solvent. This can be done by The hydrogenation reaction can be easily carried out, for example, at a temperature of about 0 to about 40°C for about 0.5 to about 5 hours. As the reducing reagent, any reagent that can selectively reduce ketones can be used, and examples thereof include lithium aluminum hydride, sodium boron hydride, and the like. The amount of these reducing reagents to be used can be selected as appropriate, and may be, for example, in the range of about 50 to about 200 mol% relative to the compound of formula (2). Further, as the organic solvent, for example, tetrahydrofuran, dimethyl ether, diethyl ether, etc. can be used, and the amount of these organic solvents to be used can be appropriately selected. An example is a range of about 2 to 50 times the weight. After the reaction is completed, the compound of formula (1) can be easily obtained by processing according to a conventional method. New compound formula (B) 2 of the present invention not described in prior literature,
4-dihydroxy-7-isopropyl-4-methyl-10-ethylenedioxy-5(E)-undecene-
It has been discovered that 1-ol is useful not only as an intermediate in the synthesis of tobacco flavor components, as described above, but also as a persistent aroma flavoring or modulating agent in its own right. The compound of formula (B) is a new compound that has an aroma reminiscent of hay with a weak green odor, and has excellent retention properties, and is particularly useful in various foods and beverages, cosmetics, and health care products.・Has excellent persistence and unique aroma as a flavor imparting or modulating agent for hygiene and pharmaceutical products. More specifically, by blending the compound of formula (B) with, for example, one or more types of synthetic single flavoring agents, various new long-lasting aroma and flavor imparting or modulating agents can be prepared. For example, bergamot oil, lemon oil, geranium oil,
When blended with synthetic essential oils such as mandarin oil and lavender oil, it is possible to prepare a novel long-lasting aroma and flavor imparting or modulating agent that has the mild and rich flavor inherent in natural essential oils. Further examples include orange oil, lime oil, lemon oil, grapefruit oil, oakmoss oil, citronella oil, vetiver oil, cinnamon oil, pachyoli oil, thyme oil, clove oil, bergamot oil,
It is possible to prepare a novel long-lasting aroma and flavor imparting or modulating agent that is well compatible with natural essential oils such as rose oil and emphasizes the characteristics of the essential oil. Furthermore, among natural fragrances and synthetic single fragrances,
Compound fragrances made by blending two or more types, such as single florals (single floral scents) of rose, diasmine, lilac, osmanthus, carnation, and miyuge, combined floral bouquets of these, and green notes, spicy notes, or aldehyde notes. When added to fragrance compositions such as modern floral bouquets or oriental bouquets, or flavor compositions such as strawberry, lemon, orange, grapefruit, apple, pineapple, etc., it has a mild, rich, natural appearance and is long-lasting. It is possible to obtain a novel aroma and flavor imparting or modulating agent with enhanced The amount of the compound of formula (B) varies depending on the purpose and the aroma/flavor imparting or modulating agent, but
For example, a range of about 0.001 to about 50% by weight of the total can be exemplified. Thus, according to the present invention, it is possible to provide a long-lasting aroma and flavor imparting or improving reinforcing agent containing the compound of formula (B) as an active ingredient, and using this agent, the compound of formula (B) can be used as an aroma and flavor ingredient. Foods and drinks characterized by containing the compound, cosmetics and cosmetics characterized by containing the compound of formula (B) as an aroma component, and health/cosmetic products characterized by containing the compound of formula (B) as an aroma component. Hygiene/
Pharmaceuticals, etc. can be provided. For example, beverages such as fruit juice drinks, fruit alcoholic beverages, milk drinks, and carbonated drinks; frozen desserts such as ice creams, sherbets, and ice candy;
Japanese and Western sweets, jams, chewing gums, breads, coffee, cocoa, black tea, luxury goods such as tea; soups such as Japanese soups and Western soups; flavor seasonings, various instant drinks and foods, various It is possible to provide food and drink substances blended in appropriate amounts to impart unique aroma and flavor to snack foods and the like. For example, an appropriate amount that can impart a unique aroma to shampoos, hair creams, pomades, and other hair cosmetic bases; oshiroi, lipsticks, and other cosmetic bases and cosmetic detergent bases. We can provide cosmetics containing the following.
Furthermore, laundry detergents, disinfectant detergents, deodorizing detergents, and various health and hygiene detergents: toothpaste,
Various health and hygiene materials such as toilet paper and toilet paper: Flavoring and flavoring agents to make medicines easier to take; We can provide applied health, hygiene, and pharmaceutical products. Compound (B) has desirable suitability as a tobacco flavor improver. In other words, when compound (B) was added to various tobacco raw materials that lacked aroma and taste and were irritating, and an evaluation test was conducted on the aroma and taste of these materials, it was found that compound (B) harmonized well with the original tobacco aroma and gave a rounded aroma. have
It has been found that it has many excellent effects, such as emphasizing the tobacco-like taste, suppressing irritation, and having long-lasting effects. (B) There are no particular restrictions on the timing or means of adding the compound to tobacco raw materials, and it can be used by dissolving it in an organic solvent such as ethanol and adding it to shredded tobacco, just like other commonly used flavorings. The effect of improving the flavor and aroma can also be achieved by incorporating it into other materials for manufacturing cigarettes, such as wrapping paper, glue, or filters. (B) There are no particular restrictions on the types of tobacco to which the compound can be applied; recycled tobacco manufactured from regular leaf tobacco, synthetic tobacco manufactured from natural fibers or plant tissue culture, etc. By adding the compound (B) during the manufacturing process or after the product is manufactured, the flavor and aroma of these products can be significantly improved. (B) The amount of the compound to be added can be very small, and a sufficient effect can be obtained by adding 0.00001 to 0.01% by weight, preferably 0.0001 to 0.001% by weight, to the tobacco or tobacco manufacturing materials, so it is economical. also has great advantages. EXAMPLES Below, several embodiments of production and usage examples of the compound of formula (B) of the present invention will be explained in more detail with reference to Examples. Reference Example 1 Synthesis of 4-hydroxy-7-isopropyl-4-methyl-10-ethylenedioxy-1,5(E)-undecadiene (3) 40 ml of tetrahydrofuran and 1.8 g (0.078 mol) of magnesium were placed in a flask. A mixed solution of 5.7 g (0.075 mol) of allyl chloride and 6 ml of tetrahydrofuran was added dropwise at a temperature of 20°C to 30°C over 1 hour. After stirring at room temperature (20℃) for 20 minutes, 12 g of 5-isopropyl-8-ethylene-dioxy-1,5(E)-undecadiene
A mixed solution of (0.05 mol) and 10 ml of tetrahydrofuran was added dropwise at 10°C over 1 hour. At room temperature after dropping
The mixture was stirred for 10 hours, and the reaction was further carried out at 50° to 60°C for 5 hours. After the reaction is completed, the reaction solution is cooled, poured into a saturated aqueous ammonium chloride solution, and extracted twice with ether. The ether layer was washed with a saline solution, dried over magnesium sulfate, concentrated, and distilled under reduced pressure to obtain a compound of formula (3) with a boiling point of 110° to 115°C/0.5 mmHg.
Obtained 10g. Yield 70.2%. NMR (ppm): 0.84 (3H), 0.93 (3H), 1.31
(3H), 1.33 (3H), 1.16~1.95 (6H), 2.32
(2H), 3.92 (4H), 4.90~6.28 (5H) IR (cm ^-1 ): 3460, 1620, 1057, 992, 989, 945,
916, 858 Example 1 2,4-dihydroxy-7-isopropyl-4
-Synthesis of methyl-10-ethylenedioxy-5(E)-undecen-1-ol (B) 4-hydroxy-7-isopropyl-4-methyl-10-ethylenedioxy-1,5
(E)-undecadiene (3) 2.8 g (5.92 mmol), N
- 865 mg of methylmorpholine N-oxide, 10 ml of acetone, and 800 μl of a 1% butanol solution of osminium tetroxide are combined and stirred at room temperature (25° C.) for 7 days. After that, add 0.1 sodium bisulfite to the reaction system.
g, and 0.5 g of trisilyloxymagnesium, and stir at room temperature (25°C) for 1 hour. After the reaction was completed, it was extracted twice with dichloromethane, and the organic layer was washed with water, dried over magnesium sulfate, and concentrated to obtain the formula
(2) 3g of the compound was obtained (yield). IR (cm ^-1 ): 3405, 1456, 1378, 1118, 1058,
980, 948, 855 Reference example 2 1,4-epoxy-2-hydroxy-7-isopropyl-4-methyl-5-(E)-undecene-
Synthesis of 10-one (2) 2,4-dihydroxy-7-isopropyl-4-methyl-10-ethylenedioxy-
Prepare 3 g of 5(E)-undecen-1-ol (B), 30 ml of acetone, and 10% aqueous hydrochloric acid solution, and mix at room temperature (25
℃) overnight, add 7 g of sodium bicarbonate powder to the reaction system, stir, and extract with ether. The organic layer was washed with a saline solution, dried over magnesium sulfate, and purified by silica gel column chromatography (hexane/ethyl acetate = 6/4) to obtain 847 mg (52.5%) of the compound of formula (2). IR (cm ^-1 ): 3445, 1712, 1368, 1167, 1042, 980 Reference row 3 1,4-epoxy-2,10-dihydroxy-7
-Synthesis of isopropyl-4-methyl-5(E)-undecene (1) 3 ml of tetrahydrofuran and 50 mg of lithium aluminum hydride were placed in a flask, and 1,4-epoxy-2-hydroxy-7-isopropyl-4
-Methyl-5(E)undecen-10-one (2) 210mg
A mixed solution of 1 ml of tetrahydrofuran and 1 ml of tetrahydrofuran was added dropwise to react at 25°C. After completion of the reaction, post-treatment was performed according to a conventional method, and the product was purified by silica gel column chromatography (hexane/ethyl acetate = 2/1) to obtain 185 mg (yield: 88%) of the compound of formula (1). IR (cm ^-1 ): 3995, 1459, 1382, 1370, 1100,
1162, 1140, 975, 845, 780 Example 2 The following components (parts by weight) were mixed as an orchid type blended fragrance composition. Cyclopentadecanolide 5 Coumarin 1 Heliotropin 3 Ylang Ylang oil 8 Methylionone 10 Neroli oil 3 Hydroxycitronellal 5 Linalolo 7 Isobutyl salicylate 11 5-Cyclohexadecenone 2 Amyl salicylate 14 Oakmoss absolute 3 Vanillin 7 Phenylacetaldehyde 2 Phenylethyl alcohol 20 Benzyl acetate 6 100 By adding 5 g of the compound of formula (B) to 95 g of the above composition, a new rasp-type blended fragrance composition that was more natural and had excellent persistence was obtained. Example 3 The following components (parts by weight) were mixed as a bouquet type perfume composition. Phenylethyl alcohol 18 Linalyl acetate 3 Bergamot oil 4 Geranium oil 5 Benzyl acetate 6 Heliotropin 8 Geraniol 11 Lavender oil 2 β-ionone 10 Amyl lysyllate 4.5 Turvinyl acetate 13.5 Cedar oil 10 Citronellol 5 100 98g of the above composition was added to the formula By adding 2 g of the compound (B), a novel bouquet-prepared fragrance composition that was natural and had excellent persistence was obtained. Example 4 The following components (parts by weight) were mixed as a gardenia type perfume composition. Benzyl acetate 10 Hydroxycitronellal 15 Coumarin 1 Diasmine absolute 3 Orange flower absolute 2 Phenylmethylcarbinyl acetate 3 Heliotropin 10 Bergamot oil 10 Linalool 10 Amylcinnamic aldehyde 4 Ylang-ylang oil 7 Galaxolide 3 α- Ionone 10 Truesinoid 2 Phenylacetaldehyde 1.5 Isoeugenyl acetate 3.5 Cybeth 10% alcohol 1 Octylaldehyde 10% alcohol 0.5 Decylaldehyde 10% alcohol 0.5 Cyclohexyl butyrate 3 100 Adding 8 g of the compound of formula (B) to 92 g of the above composition. As a result, a new gardenia blended fragrance composition which is natural and has excellent durability was obtained. Example 5 The following components (by weight) were mixed as pineapple-like aroma and flavor components. Ethyl acetate 300 Ethyl butyrate 250 Isoamyl acetate 100 Isoamyl valerate 55 Isobutyric acid 70 Isovaleric acid 30 Allyl caproate 35 Ethyl caproate 20 Ethyl caprylate 15 Ethyl caproate 20 Isoamyl alcohol 35 Diethyl malonate 30 Citral 15 Linalool 5 Maltol 20 total 1000 By adding 7 g of the compound of formula (B) to 100 g of the above composition, a new composition with excellent persistence as a pineapple aroma and flavor component was obtained. Example 6 A 0.01% by weight ethanol solution of compound (B) isolated by the above method was added to 50 g of shredded tobacco for Japan Monopoly Corporation's brand name "Thierry" just before rolling.
The amount of (B) compound relative to shredded tobacco is 0.0001% by weight
After adding it by spraying it, it was rolled up into paper, and the rolled product of the above shredded tobacco without the addition of (B) compound was used as a control product, and the odor and taste when smoking these were compared using a two-point discrimination method. In particular, the evaluations of the 20 training experts on the panel were as shown in Table 1.

【table】

[Table] From the above table, it was found that compound (B) had the effect of significantly improving the odor and taste of product cigarettes.

Claims (1)

[Claims] 1. The following formula (B) 2,4-dihydroxy-7-isopropyl-4-methyl-10-ethylenedioxy-5 represented by
(E)-Undecen-1-ol.