JPH07109253A - Production of 4-(6,6-dimethyl-2-methylenecyclohexyl)-2-methyl-2-butenal and perfume composition - Google Patents

Abstract

PURPOSE:To obtain the compound useful as a perfume by reaction of readily available or producible theta-cyclohomogeranial as starting material with a propanal alkylimine in the presence of a base followed by hydrolysis with an acid. CONSTITUTION:y-Cyclohomogeranial of formula 3 is reacted with a propanal alkylimine of formula 2 (R is 1-6C alkyl or alicyclic group) in the presence of a base in an organic solvent followed by hydrolysis in the presence of an acid to obtain the objective compound, 4-(6,6-dimethyl-2-methylenecyclohexyl)-2- methyl-2 butenal of formula 1. The compound of the formula 1 presents amberlike, woody, iononelike, irislike, fruity or floral scent. The other objective sustainable perfume composition contains this compound of the formula 1 as active ingredient. The above production method is an industrially advantageous one because the aimed compound can be obtained only in a single step. By this method, the objective compound can be easily synthesized in a high yield and purity.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has a persistent aroma and flavor such as amber-like, wood-like, ionone-like, iris-like, fruity-like, floral-like and is useful as a fragrance.
-(6,6-Dimethyl-2-methylenecyclohexyl)
The present invention relates to a method for producing 2-methyl-2-butenal and a fragrance composition containing the compound as an active ingredient. More specifically, the present invention is constituted by the inventions (A) and (B) described below. That is,

Invention (A): The following formula (3)

[0003]

[Chemical 5]

Γ-Cyclohomogeneal represented by the following formula (2) in the presence of a base in an organic solvent

[0005]

[Chemical 6]

[In the formula, R represents a C _{1 to} C ₆ linear or branched lower alkyl group or an alicyclic group. ] It reacts with the propanal alkyl imine represented by these, Then, the following formula (1) characterized by hydrolyzing a reaction product in presence of an acid

[0007]

[Chemical 7]

4- (6,6-dimethyl-2-) represented by
It relates to a method for producing methylenecyclohexyl) -2-methyl-2-butenal.

The present invention also includes (B) invention: the following formula (1)

[0010]

[Chemical 8]

4- (6,6-dimethyl-2-) represented by
It relates to a fragrance composition containing methylenecyclohexyl) -2-methyl-2-butenal as an active ingredient.

[0012]

2. Description of the Related Art There are several known methods for producing the compound of the above formula (1). For example, (±) -γ-ionone is reacted with ethyl chloroacetate to obtain (± ) -Glycidic ester, a method of synthesizing the compound of the formula (1) by hydrolyzing the ester by heating for decarboxylation in the presence of a base, and reporting the reaction [N]
ouv.J.Chim., 2 (4) 427 ■ 430 (1978)] and [J.Chem.Soc., 72
7 ■ 733 (1942)]. The presence of the compound of formula (1) has been confirmed in a mixture of several isomers obtained from dehydroabietic acid in 12 steps [Helv. Chim. Acta., 64 (5) 1257.
■ 1287 (1981)].

On the other hand, although no proposal has been made so far regarding the use of the compound of formula (1) as a fragrance, 4- (6,6-dimethyl-2-methylenecyclohexyl) -2, which has a structure similar to that of the compound of formula (1), has been reported. -Methylenebutanal (hereinafter, referred to as γ-coronal) is reported to be present in the volatile components of Ambergris tincture, and further, the compound is reported to have a scent of seashore, marine products, and marine notes. [7th International Essential Oil Congress Proceedings, No 136,479
■ 482 (1977)].

Furthermore, in recent years, consumers' tastes have diversified,
Along with that, cosmetics, foods and drinks, etc. having various flavors are produced. Against these diversification,
The conventionally known fragrance compounds alone cannot meet the demand for fragrances for cosmetics and foods and drinks having various flavors, and there is a strong demand for a new type of unique fragrance material that has never existed before.

[0015]

However, the above-mentioned conventional method for producing the compound of the formula (1) is not limited to the starting material γ.
-Ionone is not satisfactory because it is difficult to obtain it with high purity and high yield, and it is difficult to obtain it.
In addition, γ-coronal, which has a structure similar to that of the compound of formula (1), has a marine note-like fragrance, but lacks the persistence of aroma and flavor, and has not hitherto been able to satisfy the diversified consumer preference. There was a problem to be solved, such as being insufficient as a unique type of fragrance material.

[0016]

Under such circumstances, as a result of intensive studies, the present inventors have found that γ-cyclohomogeneranial, which is easy to obtain or easy to manufacture, is selected as a starting material. It was discovered that the compound of formula (1) can be produced by the process, and further, the compound of formula (1) has an aroma like amber, wood, ionone, iris, fruity, floral, etc. The present invention was completed by discovering that it is also excellent and useful as a new type of unique fragrance material.

The object of the present invention is therefore to provide an industrially advantageous process in which the compound of the formula (1) can be produced in only one step, and to obtain amber-like, wood-like, ionone-like,
The present invention provides a long-lasting fragrance composition containing as an active ingredient a compound of formula (1) having an iris-like, fruity-like, floral-like odor. Hereinafter, the present invention will be described in detail.

According to the present invention, the compound of formula (1) can be synthesized by the following reaction formula.

[0019]

[Chemical 9]

[In the formula, R represents a C _{1 to} C ₆ linear or branched lower alkyl group or an alicyclic group. ]

The starting material γ-cyclohomogenerial [compound of formula (3)] is an alkyl 4- (2-methylene-6,6-dimethylcyclohexyl) -2-methyl-2 compound proposed by the present inventors. , 3-epoxy butyrate [Japanese Patent Publication No. 2-16305]. According to the production method, 2-hydroxymethylene-5,
Condensation reaction of 5-dimethylcyclohexanone with ethyl vinyl ether in the presence of acid to form 2- (1-ethoxyethyloxymethylene) -6,6-dimethyl-cyclohexanone, the formed product in the presence of a reducing reagent, It is reduced and then brought into contact with an inorganic acid to simultaneously carry out hydrolysis and dehydration reactions to form 3,3-dimethyl-1-cyclohexenemethanol. The product in the presence of mercury acetate,
Γ-Homocyclogeranial can be easily obtained by contacting with vinyl ether to form 1,1-dimethyl-1-cyclohexene vinyl methyl ether, and subjecting the formed product to a heat rearrangement reaction.

According to the present invention, a compound of formula (3), obtainable as described above, is reacted with a compound of formula (2), propanalalkylimine, in the presence of a base in an organic solvent, and then the product Is hydrolyzed in the presence of an acid to give 4- (6,6-dimethyl-2-
Methylenecyclohexyl) -2-methyl-2-butenal can be easily synthesized with high yield and high purity.

The reaction temperature in the reaction between the compound of formula (3) and the compound of formula (2) is, for example, about -80 ° C to about 30 ° C, more preferably about -50 ° C to about 20 ° C. , The reaction time can be appropriately selected, but for example, about 2
Time to about 10 hours is adopted. Examples of the kind of the alkyl group or the alicyclic group of the propanalalkylimine that is the compound (2) used include methyl,
Examples thereof include alkyl groups such as ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl and hexyl, and alicyclic groups such as cyclopentyl and cyclohexyl. Specific preferred examples of the compound of the formula (2) include propanal t-butylimine and propanal cyclohexylimine.
The amount of the compound of the formula (2) used can be, for example, equimolar or more, more preferably about 1.0 mol to about 1.2 mol, relative to 1 mol of the compound of the formula (3).

The type of base used in the above reaction is, for example, lithium diisopropylamide (hereinafter referred to as LD
Called A. ) And the like, and the amount used is represented by the formula (3)
About 1.0 mol to about 1.2 mol can be employed with respect to 1 mol of the compound. In addition, examples of the organic solvent used in this reaction include dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, and tetrahydrofuran. The amount of these organic solvents used can be, for example, in the range of about 5 to about 50 parts by weight with respect to 1 part by weight of the compound of the formula (3). After completion of the reaction, the condensation product crude product of the compounds of the formulas (3) and (2) is isolated, purified by appropriately adopting separation means such as distillation, column chromatography and the like after washing, extraction and drying. However, the following hydrolysis reaction is usually carried out using an acid without isolation / purification.

The reaction temperature of the hydrolysis reaction is, for example, about 0.
C. to about 100.degree. C., more preferably about 15.degree. C. to about 30.degree. C., and the reaction time is, for example, about 0.5 hour to.
It can be easily performed by contacting for about 10 hours.
Examples of the acid used in this reaction include oxalic acid, citric acid,
Sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, acetic acid and the like can be mentioned, and the amount used can be appropriately selected, but for example, from about 1 mol to about 1 mol relative to 1 mol of the compound of the formula (3). The amount can be about 50 mol. Such an acid is preferably diluted with water and used at a concentration of, for example, about 5 to 20% by weight. After completion of the reaction, the crude product of the hydrolysis reaction can be washed, extracted, dried, and then subjected to appropriate separation means such as distillation or column chromatography to obtain the compound of formula (1) in good yield and high purity. .

The 4- (6,6-dimethyl-2-methylenecyclohexyl) -2-methyl-2-butenal of the formula (1) of the present invention, which can be obtained as described above, is amber-like, wood-like, It possesses aroma and flavor characteristics such as ionone-like, iris-like, fruity-like, and floral-like, and has extremely excellent persistence, and can be used by adding it to various flavor compositions. The addition amount of the compound of the formula (1) varies depending on its purpose or the kind of the fragrance composition, but is generally about 0.0 of the total amount.
A range of about 01 to about 30% by weight can be exemplified.

Thus, according to the present invention, the above formula (1)
It is possible to provide a novel fragrance composition which imparts a persistent aroma and flavor characteristic using the compound of claim 1 as an active ingredient, and the compound (1) is contained as a persistent aroma and flavor ingredient using the composition. Foods and drinks containing the compound of the formula (1) as an aroma component, cosmetics characterized by containing the compound of the formula (1) as an aroma component, and health, hygiene and pharmaceutical products containing a compound of the formula (1) as an aroma and flavor component. Can be provided.

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 , Coffee, cocoa, tea, tea, etc .; Japanese soups, western soups; soups; flavors, instant drinks and foods, snack foods, etc. It is possible to provide food and drink with an appropriate amount added. In addition, for example, shampoos, hair creams, pomades, and other cosmetic bases for hair; oscilloscope, lipstick, other cosmetic bases and cosmetic detergent bases can be imparted with their unique aroma. It is possible to provide cosmetics with an added amount. Furthermore, it is possible to provide laundry detergents, disinfecting detergents, indoor air fresheners and various other health and hygiene materials; health and hygiene and pharmaceuticals such as corrigents and flavoring agents for facilitating the taking of medicines. .

Hereinafter, the present invention will be described in more detail with reference to examples.

[0030]

【Example】

Example 1 Synthesis of 4- (6,6-dimethyl-2-methylenecyclohexyl) -2-methyl-2-butenal (1) 10 ml dry ether in a 100 ml flask, 15% n
-Butyllithium in hexane 6 ml (9.36 x 1
(0 ^-3 mol) is added, 1.0 g (9.90 x 10 ^-3 mol) of diisopropylamine is added at -15 ° C, and the mixture is stirred for 1 hour while warming to 0 ° C to prepare LDA. Again-
Cool to 15 ° C. and propanal-t-butylimine 1.
1 g (9.73 × 10 ⁻³ mol) was added over 10 minutes,
Stir for 30 minutes while warming up to. The reaction solution was cooled again, and at -50 ° C γ-cyclohomogeneranial 1.5 g
(9.03 × 10 ⁻³ mol) was added over 30 minutes, and the reaction was stirred for 2 hours while gradually raising the temperature to room temperature. Then, the reaction solution is poured into 50 ml of a 15% aqueous solution of oxalic acid and stirred at room temperature for 2 hours. Then, the mixture was extracted with ether, and the ether layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine,
Dry over anhydrous magnesium sulfate. After recovering the ether, the obtained 1.8 g of crude oil was purified by silica gel column chromatography (hexane: esal acetate = 50: 1) to obtain 1.5 g of the compound of the formula (1) (yield: 80
%).

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

3 g of the compound of formula (1) was added to 97 g of the above composition.
A new blended fragrance composition was prepared by mixing. 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 10 professional panelists added the compound emphasized the iris-like and ionon-like odors accompanied by a fresh fresh green feeling, and was characterized by the natural lira's characteristic and sustainability. However, he said that he was significantly better.

Example 3 (Pineapple-like fragrance composition) The following components (weight) were mixed as a pineapple-like mixed fragrance composition.

4 g of the compound of formula (1) was added to 96 g of the above composition.
A new pineapple-like formulated fragrance composition was prepared by mixing. 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 added the compound was excellent in the sustainability by catching the characteristics of the natural pineapple in which the fresh fruity aroma was emphasized. .

[0035]

INDUSTRIAL APPLICABILITY According to the present invention, 4- (6,6) is useful as a fragrance having a persistent aroma of amber-like, wood-like, ionone-like, iris-like, fruity-like and floral-like.
-A novel method for producing dimethyl-2-methylenecyclohexyl) -2-methyl-2-butenal and a fragrance composition containing the compound are provided. The above-mentioned compound, which can be synthesized in a good yield and high purity in a short process by this production method, has a characteristic aroma and flavor, and can be used in a wide variety of fields as an aroma and flavor component for foods, cosmetics, various beverages and other pharmaceuticals.

Claims (2)

[Claims] 1. The following formula (3): In the organic solvent, γ-cyclohomogeneranial represented by
In the presence of a base, the following formula (2): [In the formula, R represents a C _{1 to} C ₆ linear or branched lower alkyl group or an alicyclic group. ] It reacts with the propanal alkyl imines represented by these, Then, the reaction product is hydrolyzed in presence of an acid, The following Formula (1): A method for producing 4- (6,6-dimethyl-2-methylenecyclohexyl) -2-methyl-2-butenal represented by 2. The following formula (1): A perfume composition comprising 4- (6,6-dimethyl-2-methylenecyclohexyl) -2-methyl-2-butenal represented by as an active ingredient.