JPS61140518A - Durative perfume or perfume modifier - Google Patents

Abstract

PURPOSE:The titled perfume substance that contains 1-methyl-4-isopropyl-1,2:3,4- diepoxy-cyclohexane as an active ingredient, thus having a fresh camphor-like smell with soft and sweet green tone. CONSTITUTION:The objective substance contains, as an active ingredient, 1- methyl-4-isopropyl-1,2:3,4-diepoxy-cyclohexane. The compound of the formula well harmonizes with a variety of synthetic perfumes, natural essence oils and citrus oil and can prepare a durative perfume composition with mild, good-body smell just like natural perfume. It can be applied to beverage, cosmetics, further in the fields of health, hygiene and medicine. The compound of the formula is extracted from citron peels.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of l-methyl-4-isopropyl-1,2:3,4-jepoxy-cyclohexane useful as a perfume material and to a process for its preparation.

More specifically, the present invention provides l represented by the following formula (1).
-Methyl-4-isopropyl- also relates to a persistent aroma and flavor imparting or improving reinforcing agent characterized by containing 2:3,4-jepoxy-cyclohexane as an active ingredient.

The present invention also relates to a method for producing the compound of formula (1) above.

BACKGROUND ART In recent years, preferences for food, drink, and cosmetics have tended to become more diverse, and as a result, there has been a demand for the development of a wide variety of new aroma and flavor materials that were not previously available.

The present inventors are currently analyzing volatile flavoring substances in the peel of yuzu, and have discovered the presence of the above compound of formula (1), whose existence was previously unknown in the peel of yuzu. and succeeded in isolating the compound of formula (1) from the peel of yuzu.

Furthermore, the present inventors have found that the compound of formula (1) has a fresh, camphor-like aroma with a soft, sweet green feel, and has excellent persistence, and has a long lasting effect on various fragrance compositions. It has been discovered that there are many useful compounds that can be used as aroma and flavor imparting or improving reinforcement agents.

According to the research of the present inventors, the compound of formula (1) can be used in various fragrance compositions, such as fruit-based, roasted nut-based, spice-based, Western liquor-based, tobacco-based, flower-based, green-based, musk-based, It has been found that it is a useful compound that can be incorporated into flavor compositions such as vegetable, beef, wood, and marine products, and used as a long-lasting aromatic flavor imparting or improving reinforcement agent.

The compound of formula (1) above is derived from henobodicum oil (henopodicum oil).
It is known to be produced by thermal rearrangement of ascaridol (AscaridoL: used medically as a powerful anthelmintic drug) expressed by the following formula (J, 0.C,.

33(11), 4285-4.286 (1968))
.

This document reports on a kinetic study of ascaridol by thermal rearrangement. However, this report does not mention anything about the aroma and flavor properties of the compound of formula TI) or its persistence, and naturally, it does not mention anything about its usefulness in the field of fragrances.

As mentioned above, the present inventors have discovered that the compound of formula (1) has excellent aroma and flavor characteristics and excellent sustainability, and is a compound that deserves attention as a persistent aroma and flavor imparting or improving reinforcing agent. Ta. Therefore, an object of the present invention is to provide a novel persistent aroma/flavor imparting or improving reinforcing agent containing the compound of formula (1) as an active ingredient.

The above objects as well as many other objects and advantages of the present invention will become more apparent from the following description.

The compound of the formula (1) of the present invention can be extracted from the fruit of a yuzu plant. For example, crushed or crushed yuzu peel can be extracted from the fruit of a yuzu plant. An extract can be obtained by adding an organic solvent such as and standing still or stirring. In this case, for example, about so@
Preferably, the extraction is carried out at a temperature below C°, especially below room temperature. Yuzu oil can be obtained by distilling off the organic solvent from the extract. For example, apply this yuzu oil to a pressure of 1.7
Molecular distillation is carried out under the conditions of x 10 Torr and a temperature of 5 G' to 90° C., and the distillate is adsorbed on a silica gel column, for example, and developed with an organic solvent such as pentane to elute hydrocarbon components. For example, the oxygen-containing component containing the compound of formula (1) is eluted by developing with an organic solvent such as ethyl ether.

The solvent is distilled off from this oxygen-containing component, and the residue is adsorbed onto a silica gel column, first developed with a solvent such as pentane, then developed with a mixed solvent of pentane-ethyl ether, and the concentration of ethyl ether is determined. Raise the volume and elute. In this way, it is possible to divide the developing solution into two parts of appropriate amounts, collect the fractions containing the above formula (1) compound of the present invention, and distill off the solvent to obtain the above formula (1) compound. can.

Furthermore, if necessary, the compound of formula (1) obtained as described above may be purified, for example, by means such as precision distillation.

Further, the above formula (1) compound can be obtained by distilling henobodium oil under reduced pressure to separate ascaridol having a boiling point of 95° to 98°C/8smHQ, and then distilling this ascaridol in an inert organic solvent, for example. Approximately 100°~15G℃100
It can also be easily obtained by heating under temperature conditions.

The compound of formula (1) that can be obtained as described above is:
It is a useful compound that has a fresh, camphor-like aroma with a soft, sweet green feel, and has excellent persistence.

The above formula (1) compound harmonizes well with various synthetic fragrances, natural fragrances, natural essential oils, synthetic essential oils, citrus oils, etc., and novel fragrance compositions can be prepared using the formula (1) compound. For example, the compound of formula (1) may be added to bergamot oil,
When blended with synthetic essential oils such as lemon oil, geranium oil, lavender oil, and mandarin oil, it can impart a mild, rich, and long-lasting improvement effect to the aroma and flavor inherent in natural essential oils. Also, for example,
Blends well with citrus essential oils such as orange, lime, lemon, grapefruit etc; natural essential oils such as lavender oil, vetiver oil, cedarwood oil, citronella oil, geranium oil, lapandin oil, sandal oil etc.
It is possible to emphasize the characteristics of the essential oil, and to prepare a novel fragrance composition that is mellow, rich, natural-looking, and has excellent long-lasting properties. Furthermore, when incorporated into flavor compositions such as strawberry, lemon, orange, grapefruit, apple, pineapple, banana, melon, etc. prepared from various synthetic fragrances, natural fragrances, natural essential oils, citrus oils, etc., it becomes mild and rich. A fragrance composition with a certain naturalness and enhanced persistence can be prepared. The amount of the above formula (1) compound varies depending on its purpose and the aroma and flavor composition to be blended, but for example, it generally ranges from about α001 to
A range of about 30 weights can be exemplified.

Thus, according to the present invention, it is possible to provide a persistent aroma and flavor imparting or improving reinforcing agent containing the compound of formula (1) as an active ingredient, and by using the agent, the compound of formula (1) can be used as an aroma and flavor component. Foods and beverages characterized by containing the compound of formula (1) as an aroma component, cosmetics and cosmetics characterized by containing the compound of formula (1) as an aroma component, health care products characterized by containing the compound of formula (1) as an aroma component Sanitation, medicines, 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 cream, sherbet, and popsicles; Japanese and Western sweets, jams, chewing gums, breads, and coffee. , cocoa, black tea, tea, and other luxury goods such as Japanese-style soups and Western-style soups; flavor seasonings; various instant beverages and foods; various snack foods; It is possible to provide food and drinks containing the following. Also, for example, it can impart a unique aroma to shampoos, hair creams, pomades, and other hair cosmetic bases; as well as cosmetic bases, lipsticks, and other cosmetic bases and cosmetic detergent bases. Cosmetics containing appropriate amounts can be provided. Furthermore, laundry detergents, disinfectant detergents, deodorizing detergents, room air fresheners, and various health and hygiene detergents:
Various health and hygiene materials such as toothpaste, tissues, and toilet paper; a unique flavor that can be added to health, hygiene, and pharmaceutical products such as flavoring and flavoring agents to make it easier to take medicines; We can provide health, hygiene, and pharmaceutical products that are formulated or applied in appropriate amounts.

EXAMPLES Below, several embodiments of production and usage examples of the compound of formula (1) of the present invention will be explained in more detail with reference to Examples.

Reference Example 1 In a refrigerator (4°C), 349 kf of yuzu peel is immersed in ethyl ether 301 for 30 minutes, and the extract is separated. The extraction residue was further immersed in ethyl ether 304 for 30 minutes to separate the extract. This extraction residue is further immersed in ethyl ether 301 for 30 minutes, and the extract is separated. A total of three extracts were combined and ethyl ether was removed to obtain Yuzu Oil 3111. This yuzu oil 31411 was heated to a pressure of L7 x 10 Torr and a temperature of 56°~ using a molecular distillation device.
Distillation was performed at 80° C. to separate fraction 1 into 2745Ii, fraction 2 at 17.3N, and residues 2 & 711.

60 jl of fraction 1 of the above molecular distillation was applied to a silica gel column (4 mm φX 50 am) and eluted with 6 g of pentane, and then eluted with 61 g of ethyl ether. Ethyl ether was distilled off from the above ethyl ether layer under reduced pressure,
One bottle of concentrated liquid 11 was obtained. Next, 15 g of the above concentrated solution was applied to a silica gel column (1 (mlφ x 60 aL), and first eluted with pentane (1,351 CFr-1), then stubbornly eluted with 1 chetyl ether/pentane IJ (Fr-2).
, 3 thiethyl ether/pentane 11 (Fr-3), 3
Elute each 7 lactation with ts ethyl ether/pentane 11 (Fr-4), 7 ethyl ether/pentane 11 (FT-4), and 100 thiethyl ether 11 (Fday 5).

The above Fr-3 and F-Day 4 fractions were concentrated under reduced pressure to obtain 470 my of the above formula (1) compound (Formula (1) compound).

Reference example 2 Americana Calidol 200.9. 100 wIt of heptane was charged into a flask and reacted for 3 hours with stirring at a temperature of 100' to 110'C. After the reaction, the organic layer was washed twice with an aqueous solution containing sodium chloride, dried over magnesium sulfate, and distilled under reduced pressure to a boiling point of 9G' to 93°C, 75 m H.
100.9 g of a fraction (formula (1) compound) was obtained.

Example 1 Example of Persistent Aroma and Flavor Imparting or Modulating Agent The following components (by weight) were mixed as an aroma and flavor composition for plums.

Amyl Butyrate 2 Benzaldehyde 17.5 Butyl Fomate
1 citronellol
l ethyl butyrate 5
Ethyl valerate 1.5 Inamyl propionate 1r-notictone 5 orange essential oil t5r-undecalactone
3 Vanillin l total 100 By adding Compound 2II of formula (1) to 100 g of the above composition, a novel plum flavor composition with excellent freshness and excellent persistence was obtained.

Example 2 The following ingredients (weight) as apple aroma components
were mixed.

Ethyl acetate 5-ethyl propionate 2-ethyl butyrate
3 ethyl isovalerate
6-isoamyl acetate 3-butyl alcohol 15-amyl alcohol 5-butyl propionate
7 butyl butyrate
12-hexenol 102-hexenyl acetate 18-isobutyric acid
4 Wanirin
2Hexylbutyrate 1Ethyl alcohol/I/18 Total 100 By adding the compound of formula (1) to the above composition 1001, a novel apple flavor composition with a strong bluish tinge and excellent persistence was obtained. .

Example 3 The following components (by weight) were mixed as an aroma and flavor composition for apricots.

Allylcycloheyacilcaproate α2benzaldehyde IL5 amyl acetate7.
5 Amyl butyrate 7.5 Amyl formate 10.0 Amyl valerate 1 & 0 Cinnamic aldehyde α5 Ethyl acetate
145 ethyl butyrate
4.5 ethylhexanoate 1αO
Ethylpareleate 50.0 Geranium (L5α-ionone
9.5 Isoamyl phenyl acetate 0.1 Benzyl acetate 9.5 Lemon oil &O orange oil 1α5 Propyl cinnamate α2r-Undecalactone
2110 neroli oil
1&5 vanillin 840
Total Zoo (LO the above composition 10
By adding compound 511 of the formula (1) to 011, a novel apricot fragrance composition with an emphasized sweet green feeling and a fresh and long-lasting effect was obtained.

Example 4 The following components (by weight) were mixed as aroma and flavor components for pineapple.

Ethyl acetate 300 Ethyl butyrate 250 Isoamyl acetate)
10G Isoamylvalerate 55 Isobutyric acid 70 Inovaleric acid
30 Allyl caproate 35 Ethyl caproate 20 Nithyl caprylate 15 Ethyl caproate
20 isoamyl alcohol
35 Diethylmalonate 30 Citral 15 Linalool
5 maltol
20 total 100
0 By adding 15y of the compound of formula (1) to the above composition 10GIi, a new pineapple fragrance composition having excellent persistence equivalent to the aroma of natural pineapple was obtained.

Example 5 Soap Composition A fragrance composition of Nibouketaibu was produced by mixing the following components (parts by weight).

Bergamot Synthetic 4 Linalyl Acetate 3 Geranium
5β-ionone
10 Lavender 2 Geraniol 11 Heliod 4 bottles
8 Benzyl acetate
6 Phenylethyl alcohol 1
8 citronellol 5 cedar oil lO methanyl acetate lλ5 amyl salicylate
45 total 100 Compound 51 of formula (1) was mixed with 100N of the above composition to produce a fragrance composition. This product and the above composition to which the compound of formula (1) was not added were added in a ratio of 1 weight to an unscented soap paste to produce a soap.

The soaps to which the compound was added had an enhanced bouquet-like aroma and excellent longevity compared to soaps to which the compound was not added.

Claims (1)

[Claims] 1. 1-methyl-4-isopropyl-1,2 represented by the following formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼... (1):
A persistent aroma and flavor imparting or improving reinforcing agent characterized by containing 3,4-diepoxy-cyclohexane as an active ingredient.