JPS6045545A - Trans-gamma-dihydroirone and its preparation - Google Patents

Abstract

NEW MATERIAL:The trans-gamma-dihydroirone of formula I . USE:An agent for imparting or modifying lasting perfume. It has stronger violet fragrance than cis-gamma-dihydroirone which is an isomer of the objective compound, and has excellent lasting property. It can be used as an additive for perfumery composition having green note, flowery note, woody note, etc. It is useful also in wide fields such as foods, drinks, cosmetics, health and sanitary goods, pharmaceuticals, etc., synthetic intermediate of other perfumes, pharmaceuticals, and various other organic syntheses. PREPARATION:The compound of formula I can be prepared easily by reacting the compound of formula III with the compound of formula IV (R is lower alkyl; X is halogen) in the presence of a base, hydrolyzing the resultant novel trans- alkyl 4-( 2-methylene-5,6,6-trimethylcyclohexyl )-2-methyl-2,3-epoxybutyrate of formula II with an alkali, and thermally decarbonating the product under neutral or acidic condition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound, trans-r-sohydroilone, which has not been previously described in the literature, a method for producing the compound, and its use.

More specifically, the present invention provides the following formula fil It relates to trans-γ-sohydroilone represented by

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

The present invention also relates to a persistent aroma and flavor imparting or modulating agent characterized by containing the compound of formula (1) above as an effective IJIZ component.

Hitherto, cis-γ-dihydroilone represented by the following formula (1)', which corresponds to an isomer of the above-mentioned formula (1) compound, has been isolated and identified from natural orris rhizome oil and is known. Furthermore, it is also known that the chain formula (1)' cis-γ-duhydroirone is a compound having a violet-like odor.

However, the formula (1) of the present invention corresponding to the trans isomer
) for trans-γ-dihydroilone.

Its existence, both in natural products and synthetically, was previously completely unknown.

The present inventors have discovered a known compound trans-2-methylene-5 represented by the following formula (3),
We have been conducting research on the synthesis of derivatives of 6,6-trimethylcyclohexylacetaldehyde.

As a result, the above formula fl, the existence of which was previously completely unknown, was found.
) can be synthesized, and trans-γ-dihydroin of the chain formula (1) can still be obtained in good yield from the above-mentioned compound of the known formula (3).

It was discovered that it can be easily synthesized industrially with intermediate purity.

Furthermore, trans-γ-dihydroilone of the chain formula (1) has a much stronger violet-like odor and has excellent persistence compared to its isomer, the formula (1)′ cis-γ-sohydroilone. It was discovered that it is a fragrant substance that has all kinds of aromas.

According to the research of the present inventor, the above formula (1) trans-γ
- Dihydroilone is a useful compound that can be added to various fragrance compositions, such as green, flower, and woody fragrance compositions, and used as a long-lasting aroma and flavor imparting or modulating agent.

It has also been found that the compound of formula (1) above is useful as a synthetic intermediate for other fragrances, pharmaceuticals, and other organic threat intermediates.

Furthermore, the compound of chain formula (1) has excellent sustainability and exhibits remarkable properties as a persistent aroma and flavor imparting or modulating agent, and is useful in food and beverages, cosmetics, health/hygiene/pharmaceuticals, etc. It has been found that it is useful as an excellent long-lasting aroma or preparation in a wide range of fields.

Therefore, the object of the present invention is to solve the above formula (1), which has not been described in the literature so far.
An object of the present invention is to provide a trans-r-dihydride ion and a method for producing the same.

Another object of the present invention is to provide a long-lasting aroma and flavor imparting or modulating agent containing the compound of formula (1) above as an effective R content.

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

The above formula (1) compound of the present invention is, for example, the following formula (3
) trans-2-methylene-5,6゜6-drimethylcyclohexylacetaldehyde represented by the following formula (3)')'C00R(3)' where R represents a lower alkyl group in the presence of a base. , X represents a halogen atom.

The following formula +21 can be obtained by condensation reaction with argyl 2-halopropionate represented by
represents a lower alkyl group.

trans-alkyl 4-(2-methylene-
Easily synthesized by hydrolyzing 5,6,6-)limethylcyclohexyl)-2-methyl-2,3-epoxybutyrate with an alkali and decarboxylating it by heating under neutral to acidic conditions. I can do it.

The embodiment of the above-mentioned formula (1) compound 9 of the present invention can be shown as shown in the reaction process diagram below.

(3) (3)'(2) (1) In the example of the above process diagram, the known compound formula (3) trans-
From 2-methylene-5,6,6-drimethylcyclohexylaldehyde, the above formula (2) trans-alkyl 4-(2-methylene-5゜6.6-drimethylcyclohexyl)-2-methyl- K for synthesizing 2,3-epoxybutyrates is a compound of the above formula (3) with a C0OR alkyl 2-halopropionate represented by the above formula (3)', preferably in an organic solvent in the presence of a base. It can be easily synthesized by carrying out a condensation reaction.

The temperature and time of the above condensation reaction are 1, for example, about -10
Examples include ambient temperatures of about 9 DEG to about 100 DEG C., more preferably about 5 DEG to about 30 DEG C., and reaction times of about 1 to about 24 hours, more preferably about 2 to about 6 hours. Specific examples of the alkyl 2-halopropionate of formula (3)' used in the above reaction include methyl 2-chlorozolobionate.

Ethyl 2-chloropropionate, propyl 2-chlorozolobionate, glyph 2-chloropropionate, pentyl 2-chloropropionate, methyl 2-10-propionate, ethyl 2-bromopropionate, propyl 2-bromo Preferred examples include propionate, butyl 2-bromopropionate, pentyl 2-10 muderopionate, and the like. The amount of the above formula (3)' compound to be used may be appropriately selected, and is, for example, about 1 to about 5 times the amount of the above formula (3) compound, preferably about 1.2 to about 2 times the amount of the compound of formula (3). For example, the usage amount can be in the range of about twice the molar range. The base used in the above-mentioned father compounding reaction is as follows:
Examples include sodium methylate, sodium ethylate, and potassium t-1 toxide. Such a base can be used to form a compound of formula (3), for example,
~about 1~about 5 moles, preferably about 1.2~about 2 times the mole. Examples include ether, hexane, benzene, toluene, methanol, ethanol, etc. The amount of the organic solvent to be used is, for example, about 1
An example of the usage amount of lees is approximately 1 to 100 oz.

Specific examples of the above formula (2) compound, which is a new compound that has not been previously described in any literature, obtained by the above condensation reaction are as follows.

For example, compounds such as primary compounds can be suppressed.

trans-methyl 4-(2-methylene-5,6゜6-trimethylcyclohexyl)-2-methyl-2,3-epoxygutylate, trans-ethyl 4-(2-methylene-5,6,6-trimethylcyclohexyl) )-2-methyl-2,3-epoxybutyrate, trans-glopyr 4-(2-methylene-5,6,6-trimethylcyclohexyl)-2-methyl-2,3-ethyl; 1? Gycyptylate, trans-butyl 4-(2-methylene-5,6,6
-trimethylcyclohexyl)-2-methyl-2゜3-
Epoxybutyrate, trans-pentyl 4-(2-methylene-6,6-dimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate.

According to the present invention, for example, the above formula (2) trans-alkyl 4-(2-methylene-5,,6,6-trimethylcyclohexyl)-2- which can be obtained as described above
By hydrolyzing methyl-2,3-epoxybutyrate fg and then decarboxylating it, the above formula (1) trans-γ-dihydroilone can be easily obtained in a high yield.

The above hydrolysis reaction is carried out using, for example, the compound of formula (2).

Preferably in an organic solvent, for example from about θ°C to about 110°C.
, more preferably at a temperature of about 158C to 30C, for example, for about 0.5 to about 24 hours.

This can be accomplished by contacting with an alkali, preferably for a period of time such as about 1 to about 3 hours.

In carrying out this hydrolysis reaction, the amount of alkali to be used can be selected as appropriate, and for example, about 1 to about 3 moles can be used per 1 mole of the compound of formula (2).

Examples of organic solvents when a solvent is used in the reaction include methanol, ethanol, acetone, ether, toluene, and the like. As an example of alkali,
Examples include sodium hydroxide, potassium hydroxide, sodium methylate, and sodium ethylate.

Among these alkalis, alkalis such as sodium hydroxide and potassium hydroxide are preferably used in the form of an aqueous solution.

The reaction product of formula (2) is, for example, 1 rare 1 se? , the pH of the system is made neutral to positive using a natural or organic acid such as hydrobromic acid, sulfuric acid, phosphoric acid, perchloric acid, P-toluenesulfonic acid, benzenesulfonic acid, etc., and a thermal decarboxylation reaction is performed. By doing this, it can be converted to the target product of formula fl). This decarboxylation reaction is carried out at temperatures ranging from about 1509°C to about 300°C.
, more preferably under temperature conditions such as about 170° to about 240°C, for example, about 3 to about 24 hours, more preferably about 2 to about 24 hours.
Bamboo can be made by heating and reacting for about 6 hours. The reaction product of formula (1) can be purified by means such as distillation under reduced pressure.

The compound of formula (1) of the present invention may be used with various synthetic fragrances, natural fragrances, natural coffin oil, natural citrus oil, etc.
1] Long-lasting aroma and flavor imparting or modification using the compound of formula (1) as an active ingredient 1i! For example, food and drink products including tobacco and other luxury goods characterized by containing the above formula (1) trans-γ-dihydroilone as an aromatic flavor ingredient using Agent I; the above formula +11 compound as an aromatic flavor ingredient; It is possible to provide soaps, detergents, cosmetics characterized by containing the above-mentioned formula fil compound; health/hygiene and pharmaceutical products characterized by containing the above-mentioned formula fil compound as an aromatic flavor component; and the like. For example, luxury goods such as cigarettes; juices,
Fruit alcoholic drinks, milk drinks; Cold dishes such as ice creams and popsicles; Japanese and Western sweets; Soyams; Bread; Chewing gum, coffee, cocoa, black tea, tea, etc.; It is possible to provide food products, instant beverages, food products, etc., which are formulated with an appropriate formula that can impart that unique aroma and flavor. In addition, for example, it is possible to provide cosmetics in which an appropriate amount of the same is blended to impart a unique fragrance to shampoos, hair rinses, hair creams, pomades, and other hair cosmetic bases; cosmetic soaps and other makeup/facial cleansing bases, etc. .

In addition, we also produce laundry detergents, ginseng detergents, deodorizing washes, GIJ products; FM polishing products, tissues, toilet paper, and other health and hygiene materials and pharmaceuticals that can be given their unique aroma and flavor. We can provide health, hygiene, and pharmaceutical products that contain or use

Example 1 Synthesis of trans-ethyl 4-(2-methylene-5,6°6-drimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate in 100 m of toluene. % Sodium Hydride 4.
Sodium ethoxide was prepared from 8I and ethanol 6y, and trans-2-methylene-5+6t6-drimethylcyclohexylacetaldehyde 18J? (0
, 1 mol) ethyl α-10 propionate 21.59
(0.12 mol) was added at 5°C for 2 hours and stirred at room temperature for 3 hours.

The reaction bath fi was added to an acetic acid water bath, and the organic layer was washed with heavy sodium chloride, dried, the solvent was distilled off, and then distilled to give trans-ethyl 4-(2-methylene-5,6,6-drimethylcyclohexyl). -2-Methyl-2°3-epoxybutyrate 22. S' (yield 79%) was obtained at ft-0HD point 11 s
a-t I BoGlo, 2xmHg.

Example 2 Synthesis of trans-γ-sohydroilone trans-ethyl 4-(2-entylene-5,6°6-drimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate 14.9 (0.05 mol) was added to a bath solution containing 24 g of ethanol and 4.2.9 g (0,075 mol) of caustic potassium, and stirred for 2 hours at room temperature.

The reaction bath solution was neutralized with an aqueous hydrochloric acid solution, extracted with ether, washed with water, dried, the solvent was distilled off, and Sodium Sodium O and SG were added and heated under reduced pressure (3m rough HI) (1s 09-230°C).
Trans-γ-duhydroirone 7.31! (yield 70%
) will be mourned as the 7th anniversary of his death.

IR (liquid film) 1720, 1625, 895 crC
'.

N,M,RCCDCL,')δ=0.77 (3H,s
) = 0.88 (3H, d, J = 4Hz) - 0,94
(3H18), 2.09 (3H,s ), 4.50 (1
11, broad s), 4.69 (tH, broa
d8).

Example 3 A fragrance composition in 0-Z was produced by mixing the following components (parts).

hydroxycitronellal 20 nerol 30 rose oxide 20 raniol 100 phenylethylgropione) 30 phenylethyl alcohol 385 citronellol 100 cinnamic alcohol 30 musk ketone 10 rhodinol 85 methylionone 5 phenylethylmethyl carbinol 100 eugenol 5 r Nylacetate 80 000 Trans-γ-dihydroilone 5 to 100g of the above composition
By mixing I, a new fragrance composition with enhanced rose-like aroma and excellent persistence was obtained.

Example 4 A bouquet-type fragrance composition was produced by mixing the following components.

(parts) Phenylethyl alcohol 180 Linalyl acetate 30 Pergamotsynthetic 4° Geranium 50 Pendyl acetate 6° Heliotropin 8° Geraniol 110 Lavender 2° p-ionone 100 Amyl salicylate 45 Turbinyl acetate 135 Cedar oil 100 Cyto. Neil 50 1.000 Above composition 1oo#K) Lance-γ-dihydroirone 1
A new fragrance composition was prepared by mixing 0.9.

The aroma of this product had a strong soft flower-like aroma and excellent fragrance persistence.

Claims (1)

[Claims] 1. Trans-γ-dihydroilone represented by the following formula (1). 2 The following formula (2) However, in the formula, R represents lower alkyl. trans-alkyl 4-(2-methylene-
5y6+6-)-2-methylcyclohexyl)-2-methyl-2,3-evogycyptylate is hydrolyzed with an alkali and decarburized by heating under neutral to coordinative conditions.
A method for producing trans-γ-dihydroilone, which is expressed by the following formula (1) and is represented by g. 3. Trans-2-methylene-5,6°6-drimethylcyclohexylacetaldehyde represented by the following formula (3) is prepared by the following formula (3)' in the presence of a base, where R represents lower alkyl radical. X represents a halogen atom, a trans-alkyl 4- represented by the following formula (2) obtained by a condensation reaction with an alkyl 2-halophonate bionate represented by: where R represents a lower alkyl group
(2-Methylea5.6.6-h-limethylcyclohexyl)-2-methyl-2,3-epoxybutyrate is hydrolyzed with an alkali and decarboxylated by heating under neutral to acidic conditions. The manufacturing method according to claim 2.