JPH0380151B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to dimethyl or trimethylcyclohexyl derivatives, which are new compounds useful as perfume materials. The invention also relates to a method for making the compound and its use. More specifically, the present invention relates to the following formula (A) However, in the formula, X represents a hydrogen atom or a group Z, and Y represents a group Z when X is a hydrogen atom, and
indicates a methyl group, where the group Z is

【formula】

【formula】

【formula】

[Formula] and

It relates to a dimethyl or trimethylcyclohexyl derivative represented by the following formula, which represents a group selected from the group consisting of: Furthermore, the present invention also relates to a persistent aroma and flavor imparting or modulating agent characterized by containing the above-mentioned compound of formula (A) as an active ingredient, and also relates to a method for producing these compounds of formula (A). In recent years, preferences for food, drink, and cosmetics have been diversifying, and in line with this trend, there has been a demand for the development of a variety of new aroma and flavor materials that are rich in variety that did not previously exist. In view of the above circumstances, the present inventors have conducted research and development on dimethyl or trimethylcyclohexyl derivatives useful as aroma and flavor materials. As a result, we discovered that it was possible to synthesize a dimethyl or trimethylcyclohexyl derivative represented by the above formula (A), which had not been previously described in any literature, and succeeded in its synthesis. Furthermore, the present inventors have found that the compound of formula (A) has a floral aroma such as citrus, fruity, spicy, melancholy, earthy, tobacco-like, fatsy, camphor-like, and is industrially easy and easy to use. It has been discovered that it can be produced at low cost and is useful as a long-lasting aroma imparting or improving reinforcing agent for various fragrance compositions. The compound of the above formula (A) of the present invention is a compound of the formula (A) below, which is conventionally known as a fragrance substance, for example, the following formula (A) having a violet-like odor and the following formula (B) having a rose-like odor.

【formula】

The α-ionone formula (a) and the indamascone formula (b) represented by [formula] have some structural similarities, but surprisingly have completely different nuances and have excellent long-lasting aromas and flavors. It turned out that there was. Furthermore, the above formula (A) compound can be used in various flavor compositions, such as fruit-based, roasted nut-based, spice-based, citrus-based, roast beef-based, mill-based, fat-based, Western liquor-based, tobacco-based, flower-based, green-based, It is a useful compound that can be incorporated into various fragrance compositions such as musk-based and wood-based fragrance compositions, and used as a long-lasting aromatic flavor imparting agent or as an improving reinforcing agent. It was found that this is a new compound that is also useful as an intermediate. Therefore, an object of the present invention is to provide the compound of formula (A), 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 long-lasting aroma and flavor imparting or improving reinforcing agent, which is characterized by containing the compound of formula (A) as an active ingredient. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The following formula (A)-1 included in the formula (A) of the present invention However, in the formula, Z has the same meaning as mentioned above. To synthesize the dimethylcyclohexyl derivative represented by For example, 4,4-dimethylcyclohexanone represented by is reacted in the presence of dimethylformamide and phosphorus oxytrichloride to form the following formula (2). 2-chloro-5,5-dimethyl-6 represented by
-hexene-1-carbaldehyde is formed, and then the compound of formula (2) is subjected to a catalytic reduction reaction in the presence of triethylamine and Lindlar's catalyst to form the following formula:
(3) 3,3-dimethylcyclohexane-1-carbaldehyde is formed and then the compound of formula (3) is converted to e.g.

By contacting with [formula], the following formula (4) included in formula (A)-1 of the present invention can be obtained. 1-(3,3-dimethylcyclohexan-1-yl)-3-buten-1-ol represented by the formula can be synthesized. Furthermore, by oxidizing the above formula (4) compound with Jone's reagent in acetone, for example, the following formula (5) included in formula (1)-A of the present invention can be obtained. 1-(3,3-dimethylcyclohexan-1-yl)-3-buten-1-one represented by the formula can be synthesized. Further, by isomerizing the compound of formula (5) above in the presence of an acid catalyst in an organic solvent, for example, the compound of formula (6) below included in formula (A)-1 of the present invention can be obtained. 1-(3,3-dimethylcyclohexan-1-yl)-2-buten-1-one represented by the formula can be synthesized. Also, the formula (3) obtained above
By condensing the compound with, for example, acetone or methyl ethyl ketone in an organic solvent in the presence of an alkali catalyst, the following formula (7) included in the formula (A)-1 of the present invention or the following formula (8) can be obtained. 1-(3,3-dimethyl-cyclohexan-1-yl)-1-buten-3-one (7) or 1-(3,3-dimethyl-cyclohexane-1) represented by
-yl)-2-methyl-1-buten-3-one (8)
can be synthesized. The above reaction can be shown in a process diagram as follows. In addition, the following formula (A)-2 included in formula (A) of the present invention

[Formula] However, in order to synthesize the trimethylcyclohexyl derivative in which Z is represented by the same meaning as above, commercially available products such as the following formula can be used.
(1)′ Using 3,5,5-trimethylcyclohexan-1-one represented by as a starting material, the above formula (A)
It can be easily synthesized by the same method used to synthesize -1. The process diagram of this reaction can be shown as follows. Specific examples of compounds included in the compound of formula (A) of the present invention and characteristics of the gradient are shown below.

[Table] Formula (8)

[Table] Equation (8)′
Formula (A)-1 included in formula (A) of the present invention [formula (4), formula
(5), Equation (6), Equation (7), Equation (8)] and Equation (A)-2 [Equation (4)',
formula
(5)′, Formula (6)′, Formula (7)′, Formula (8)′] will be described in detail below according to the example of the process diagram described above. To synthesize the compound of formula (4) included in formula (A)-1 of the present invention, for example, which is easily available on the market,
It can be easily synthesized in three steps using 4,4-dimethylcyclohexanone formula (1) as a starting material. In order to obtain 3,3-dimethyl-6-chloro-6-hexene-1-carbaldehyde of formula (2), the compound of formula (1) is heated, for example, in the presence of dimethyl formaldehyde and phosphorus oxytrichloride at a reaction temperature. For example, it can be easily synthesized by reacting (Vilsmeir) at a temperature of about -30°C to about 100°C for about 0.5 to about 24 hours. The amount of dimethyl formaldehyde used in the above reaction is, for example, approximately
The amount used may range from about 1.0 to about 10 moles. The amount of phosphorus oxytrichloride to be used is, for example, about 1 to about 10 moles based on the compound of formula (1). After the reaction is completed, the compound of formula (2) can be easily obtained by post-treatment according to a conventional method. 3,3-dimethylcyclohexane of the above formula (3)
In order to synthesize 1-carbaldehyde, the compound of formula (3) can be easily synthesized by subjecting the compound of formula (2), which can be obtained as described above, to catalytic hydrogen reduction in the presence of, for example, triethylamine and Lindlar's catalyst. can be converted into. In this case, it is convenient to use organic solvents, such as methanol. The reaction can be easily carried out, for example, at a hydrogen pressure of 1 to 50 kg/cm ² and a reaction temperature of about 10° to about 40°C. After the reaction is complete, process according to the usual method to obtain the formula
(3) The compound can be easily obtained. The compound of formula (4) of the present invention can be prepared by separately preparing the compound of formula (3), which can be obtained as described above, in an organic solvent such as ether, and then preparing an allylmagnesium halide.

It can be easily synthesized by contacting with [Formula]. The above reaction can be easily carried out by reacting for about 1 to about 5 hours at a reaction temperature of, for example, about 10°C to about 50°C, usually under water cooling. The amount of allylmagnesium to be used is, for example, about 1 to about 5 mol based on the compound of formula (3) above. The amount of organic solvent used includes
There are no particular restrictions and it can be selected as appropriate, but for example, about 2 to about 20
A range of about twice the weight can be mentioned. After the reaction is completed, the above compound of formula (4) can be easily obtained by processing according to a conventional method. The compound of formula (5) of the present invention can be synthesized by oxidizing the compound of formula (4), which can be obtained as described above, with Jone's reagent, which is easily available on the market, in an organic solvent, for example. Can be easily synthesized. The oxidation reaction can be carried out, for example, at a temperature in the range of about 10° to about 50° C. while dropping the Jone's reagent. The reaction time can be, for example, about 0.5 to about 24 hours. The amount of Jone's reagent to be used is, for example, about 2/3 of the compound of formula (4).
A range of about 3 moles may be mentioned. Examples of organic solvents include acetone. The amount of acetone to be used may be appropriately selected, and can be exemplified in a range of about 3 to about 50 times the weight of the compound of formula (4). After the reaction is completed, the compound of formula (5) can be easily obtained by treatment according to a conventional method. The compound of formula (6) of the present invention can be easily synthesized by isomerizing the compound of formula (5), which can be obtained as described above, in an organic solvent in the presence of an acid catalyst. I can do it. The isomerization reaction is carried out at a temperature of about 0.5 to about -10℃ to about 150℃, for example.
This can be easily carried out by reacting for 24 hours. As the acid catalyst, for example, acids such as para-toluenesulfonic acid, sulfuric acid, phosphoric acid, and hydrochloric acid can be used. The amount of these acids to be used can be selected as appropriate, but for example, for the compound of formula (5), approximately
Ranges of the order of 0.1 to about 10% by weight may be mentioned. Examples of organic solvents include toluene, xylene, benzene, ether, THF, and hexane. The amount of these organic solvents to be used is, for example, about 0.5 to about 100 times the weight of the compound of formula (5). After the reaction is completed, the compound of formula (6) can be easily obtained by processing according to a conventional method. In order to obtain the compound of formula (7) of the present invention, the compound of formula (7) is easily synthesized by condensing the compound of formula (3) obtained above with acetone, for example, in the presence of an alkali catalyst. be able to. The reaction can be easily carried out under refluxing acetone for, for example, about 0.5 to about 24 hours. Examples of the alkali catalyst used in the condensation reaction include sodium hydroxide,
Examples include potassium hydroxide, barium hydroxide, and lithium hydroxide. The amount of these alkali catalysts to be used may be appropriately selected depending on the catalyst used, and may be, for example, in the range of about 0.01 to about 20% by weight based on the compound of formula (3). After the reaction is completed, the compound of formula (7) can be easily obtained by treatment according to conventional methods. In order to obtain the compound of formula (8) of the present invention, the compound of formula (8) can be obtained by the same method as the above-mentioned method for synthesizing the compound of formula (7), except that methyl ethyl ketone is used instead of acetone. can be easily synthesized. Next, formula (A)-2 (formula
(4)′, Formula (5)′, Formula (6)′, Formula (7)′, Formula (8)′) will be explained below according to the above-mentioned process diagram. Formula (A)-2 of the present invention (Formula (4)', Formula (5)', Formula (6)', Formula
(7)′, formula (8)′), in the method for synthesizing the above formula (A)-1, 4, 4 of the above formula (1) as a starting material.
-Formula (1)′ above instead of dimethylcyclohexanone
The compound can be easily synthesized in the same manner as the compound of formula (A)-1 except that 3,5,5-trimethylcyclohexanone is used. It has been discovered that the novel compound formula (A) dimethyl or trimethyl cyclohexyl derivatives of the present invention are useful as persistent aroma flavoring or improving enhancers. The compound of formula (A) is a novel compound having a citrus, fruity, spicy, usury, earthy, tobacco-like, fatsy, camphor-like floral aroma and flavor, and is particularly useful in various foods, drinks, and cosmetics. It has excellent durability and unique aroma as a flavor imparting or improving reinforcing agent for health, hygiene, pharmaceuticals, etc. The compound of formula (A) of the present invention blends 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 compound of formula (A). More specifically, the compound of formula (A) may be combined with, for example, bergamot oil, lemon oil, geranium oil,
When blended with synthetic essential oils such as lavender oil and mandarin oil, it is possible to impart to the synthetic essential oil a mild, rich, and long-lasting improvement effect on the aroma and flavor inherent in natural essential oils. Also, for example,
It blends well with citrus essential oils such as orange, lime, lemon, grapefruit, etc.; natural essential oils such as lavender oil, vetiver oil, cedar wood oil, citronella oil, geranium oil, lavandin oil, sandal oil, etc.; It is possible to prepare a novel fragrance composition that is mellow, full-bodied, 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 durability can be prepared. The amount of the above formula (A) compound varies depending on its purpose and the aroma and flavor composition to be blended, but for example, it is generally about 0.001 to about
A range of about 30% by weight 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 (A) as an active ingredient, and using this agent, the compound of formula (A) can be used as an aroma and flavor ingredient. food and beverages characterized by containing the compound of formula (A), cosmetics and cosmetics characterized by containing the compound of formula (A) as an aroma component, and health/cosmetic products characterized by containing the compound of formula (A) 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; Japanese seasonings, various instant drinks and foods, It is possible to provide food and drink containing various snack foods and the like in an appropriate amount that can impart the unique aroma and flavor. Also, for example, shampoos, hair creams, pomades, and other hair cosmetic base materials;
Cosmetics can be provided in which a suitable amount of the cosmetics, lipsticks, other cosmetic bases, cosmetic detergent bases, etc. can be blended to impart the unique fragrance. Furthermore, laundry detergents, disinfectant detergents, deodorant detergents,
Room air fresheners and various health and hygiene detergents: Various health and hygiene materials such as toothpaste, toilet paper, and toilet paper; Health, hygiene, and pharmaceuticals such as flavorings and flavoring agents to make it easier to take medicines. It is possible to provide health, sanitary, and pharmaceutical products containing or applying an appropriate amount of the same to give it its unique flavor. EXAMPLES Below, several embodiments of production and usage examples of the compound of formula (A) of the present invention will be explained in more detail with reference to Examples. Example 1 Synthesis of 2-chloro-5,5-dimethyl-1-cyclohexene-1-carbaldehyde formula (2). 1. Pour 70 g of DMF and 130 g of chloroform into a four-necked flask, cool in an ice water bath, and bring the internal temperature to 10℃.
Keep it. In this, 80g of phosphorus oxychloride (POCl ₃ )
(0.52 mole) slowly (dropping time 35
min, dropping reaction temperature 10-20). After the addition is complete, continue stirring for an additional 30 minutes. Next in this is Dimethyl Ketone.
(4) Add 60 g (0.476 mole) dropwise (dropping time 1.0 hour, dropping reaction temperature 10-40°C). After the dropwise addition is completed, the mixture is heated and reacted at 68°C for 3 hours at Reflux. Cool the reaction solution again, and add 142 g of sodium acetate and 357 g of water.
Add solution of g. By subsequently heating 1
The reaction is completed by refluxing for a period of time. Separate the oil layer,
The aqueous layer is extracted with methylene chloride and combined with the oil layer. The oil layer was washed with water, washed with soda ash, and dried with Na ₂ CO _3. The solvent was recovered. The remaining liquid was distilled under reduced pressure with 0.5 g of sodium acetate to obtain 2-chloro-5,5-dimethyl-1-cyclohexene-1-carbaldehyde. 50
(boiling point 70-75°C/3 mmHg, yield 61%).
Residue 11g. Example 2 Synthesis of 3,3-dimethyl-cyclohexane-1-carbaldehyde formula (3). 155g (0.9g) of formula (2) compound in 1 autoclave
mol), triethylamine 109 g (1.08 mol), Lindlar catalyst 7.5 g and methanol to a total volume of 500 g
Prepare to make ml. The reaction is carried out under the conditions of a hydrogen pressure of 1 to 30 kg/cm ² and a reaction temperature of 25° + 3° C. until no hydrogen absorption is observed. After completing the reaction and confirming that unreacted substances have disappeared, the catalyst is separated by filtration, the reaction product is poured into 1 liter of water, and extracted with ether (500 ml x 2). The extract is sequentially washed with dilute hydrochloric acid (500 ml x 2), saline solution, and sodium bicarbonate aqueous solution. The residue was then dried over magnesium sulfate, the solvent was distilled off, and then distilled under reduced pressure to obtain 98 g (Y=78%) of the compound of formula (3) having a boiling point of 78-80°C/20 mmHg. Example 3 1-(3,3,-dimethylcyclohexane-1-
Synthesis of yl)-3-buten-1-ol formula (4). Charge 7.2 g of metallic magnesium and 100 ml of dry ether into a 500 ml flask and stir vigorously. A solution of 19.2 g (0.25 mol) of allyl chloride and 150 ml of dry ether is added dropwise into the solution to prepare a Grignard reagent. Next, in this, 28g of formula (3) compound
A solution of (0.2 mol) and 100 ml of dry ether was added dropwise under cooling with water (28° to 30°C, 1 hour). After the dropwise addition, stirring was continued for 30 minutes to complete the reaction. The reaction solution is poured into an aqueous ammonium chloride solution. The ether layer is separated, washed with brine, and then dried with magnesium sulfate. After collecting the ether, the remaining liquid is distilled under reduced pressure to a boiling point of 80° to 85°C (3 mmHg).
22 g (Y=60%) of the compound of formula (4) having the formula (4) was obtained. Example 4 1-(3,3-dimethylcyclohexane-1-
Synthesis of yl)-3-buten-1-one formula (5). 21 g (0.115 mol) of formula (4) compound in a 500 ml flask,
Add 175g of acetone. Add 67 g of Johns reagent (15 g of CrO ₃ , 27 g of H ₂ O, 25 g of H ₂ SO ₄ ) to this.
Add dropwise at a reaction temperature of 15° to 20°C. After completion of the reaction, confirm that unreacted substances have disappeared, and reduce excess Cr() by adding isopropyl alcohol. After that, the solid matter was removed, sodium carbonate was added to the acetone solution for neutralization, and after distilling off the acetone, it was distilled under reduced pressure to obtain 18.5g of the compound of formula (5) having a boiling point of 77-79℃/2mmHg ( Y=88%) was obtained. Example 5 1-(3,3-dimethylcyclohexane-1-
Synthesis of yl)-2-buten-1-one formula (6). 18 g of the compound of formula (5), 150 g of toluene, and 0.5 g of para-toluenesulfonic acid are placed in a flask and an isomerization reaction is carried out at 95° C. for 3 hours. After completion, cool and neutralize with aqueous sodium hydrogen carbonate solution. After distilling off toluene, the residue was distilled under reduced pressure to obtain 15 g (Y=73%) of the compound of formula (6) having a boiling point of 78° to 80°C/2 mmHg. Example 6 1-(3,3-dimethylcyclohexane-1-
yl)-1-buten-3-one formula (7). 100 g (1.72 mol) of acetone and 12 g of a 3% barium hydroxide aqueous solution were placed in a flask, and 28 g (0.2 mol) of the compound of formula (3) was added into the flask while refluxing the acetone.
A mixed solution of 28 g (0.48 mol) of acetone and 28 g (0.48 mol) of acetone was added dropwise and reacted (for 1 hour). After the dropwise addition, the reaction is further carried out at 60° to 62°C for 5 hours to complete the reaction. After completion, add 50% sulfuric acid aqueous solution to neutralize. After distilling off the acetone, 100 g of toluene is added to the remaining liquid and washing is performed with water. 1 g of para-toluenesulfonic acid was added to the toluene layer and refluxed for 1 hour to dehydrate the aldol compound. After completion of the process, the compound of formula (7) having a boiling point of 90° to 91°C (2 mmHg) is obtained by neutralizing and washing with an aqueous sodium carbonate solution, distilling off toluene, and distilling it under reduced pressure.
22g (Y=60%) was obtained. Example 7 1-(3,3-dimethylcyclohexane-1-
yl)-2-methyl-1-buten-3-one formula (8)
synthesis of. Formula (7) compound 56g, methyl ethyl ketone 150g,
By carrying out the same operation as for the synthesis of the compound of formula (7) in Example 6 using 18 g of barium hydroxide aqueous solution and 1 g of para-toluenesulfonic acid, the boiling point was 94° to 95°C (2
59 g (Y=78%) of the compound of formula (8) having a compound of formula (8) having a molecular weight (mmHg) were obtained. Example 8 Synthesis of 2-chloro-4,4,6-trimethyl-1-cyclohexene-1-carbaldehyde formula (2)'. In Example 1, 4,4- used as a raw material
Dimethylcyclohexan-1-one Instead of formula (1), 2-chloro-4,4,6-trimethyl-1-
Using cyclohexene-1-carbaldehyde,
By performing the same operation as in Example 1, the boiling point was 69°~
58 g of formula (2)′ compound with 71°C/2 mmHg (Y=63
%) was obtained. Example 9 2,4,4-trimethyl-cyclohexane-1
Synthesis of carbaldehyde formula (3)′. By carrying out the same operation as in Example 2 using the compound of formula (2)', 108 g (Y=85%) of the compound of formula (3)' having a boiling point of 78° to 80°C/20 mmHg was obtained. Example 10 1-(2,4,4-trimethylcyclohexan-1-yl)-1-hydroxy-3-butene formula
(4) Synthesis of ′. By carrying out the same operation as in Example 3 using the compound of formula (3)', 32 g (Y=82%) of the compound of formula (4)' having a boiling point of 78° to 80°C/2 mmHg was obtained. Example 11 Synthesis of 1-(2,4,4-trimethylcyclohexan-1-yl)-3-buten-1-one formula (5)'. Using the compound of formula (4)', the same procedure as in Example 4 was carried out to obtain 19 g (Y=83%) of the compound of formula (5)' having a boiling point of 73° to 74°C/1.5 mmHg. Example 12 Synthesis of 1-(2,4,4-trimethylcyclohexan-1-yl)-2-buten-1-one formula (6)'. By carrying out the same operation as in Example 5 using the formula (5)' compound, 15 g (Y=78%) of the formula (6)' compound having a boiling point of 74° to 75°C/1.5 mmHg was obtained. Example 13 Synthesis of 1-(2,4,4-trimethylcyclohexan-1-yl)-1-buten-3-one formula (7)'. Using the compound of formula (6)', the same procedure as in Example 6 was carried out to obtain 25 g (Y=65%) of the compound of formula (7)' having a boiling point of 94° to 95°C/2 mmHg. Example 14 Synthesis of 1-(2,4,4-trimethylcyclohexan-1-yl)-2-methyl-1-buten-3-one formula (8)'. Using the compound of formula (7)', the same procedure as in Example 7 was carried out to obtain 32 g (Y=77%) of the compound of formula (8)' having a boiling point of 92° to 93°C/1 mmHg. Example 15 A Lira type fragrance composition was produced by mixing the following components (parts by weight). Phenylethyl acetate 10 Cinnamic alcohol 40 Terpineol 130 Cyclamenaldehyde 10 Heliotropin 50 Cinnamyl acetate 10 Carnation 20 Linalool 30 Indole 2 Stylacus resinoid 30 Ylang ylang 10 Hydroxycitronellal 290 Benzyl acetate 20 Anisaldehyde 20 Absolute Toji Yasmin 20 Phenylethyl alcohol 278 Anis alcohol 30 1000 A fragrance composition was prepared by mixing 8 g of 1-(3,3-dimethylcyclohexan-1-yl)-3-buten-1-ol formula (4) with 100 g of the above composition. was manufactured. The aroma of this product was a novel lira-type aroma that was not seen before and had a sweet, greenish feel with an emphasis on it. Instead of the above formula (4), 1-(3,3-
dimethylcyclohexan-1-yl)-2-buten-1-one formula (6), 1-(3,3-dimethylcyclohexan-1-yl)-1-buten-3-one formula (7), 1-( A fragrance composition was prepared by mixing 10 g of each of 2,4,4-trimethylcyclohexane-1yl)-3-buten-1-one formula (5)' with 100 g of the above composition. All of the fragrance compositions had an emphasized dullness, but the composition containing formula (6) had a somewhat citrusy feeling, and the composition containing formula (7) had a somewhat heavy feeling. , and in the case of equation (5)′,
The emphasis was on freshness. All of them had a novel lira-type fragrance that had never existed before. Example 16 A hyacinth-based fragrance composition was produced by mixing the following components (parts by weight). Phenylacetaldehyde 100 Cinnamic alcohol 150 Hyacinth absolute 20 Phenylethyl alcohol 100 α-ionone 30 Benzyl propionate 70 Ylang-ylang oil 20 Amyl cinnamic aldehyde 50 Isoeugenol 40 Benzyl alcohol 100 Dimethylbenzyl carbinol 30 Galbanum resinoid 50 Phenylacetaldehyde dimethyl acetal 80 Lauryl alcohol 20 Nerol 80 Heliotropin 60 1000 100 g of the above composition was mixed with 5 g of 1-(3,3-dimethylcyclohexan-1-yl)-3-buten-1-one formula (5). A fragrance composition was produced. The aroma of this product was a novel, unprecedented Lira-type aroma composition with an emphasized green feel.
To the above formula (5) glue, 1-(2,4,4-trimethylcyclohexan-1-yl)-3-butene-1-
On formula (4)', 1-(2,4,4-trimethylcyclohexan-1-yl)-2-buten-1-one formula
(6)' and 1-(2,4,4-trimethylcyclohexan-1-yl)-1-buten-3-one formula (7)' A fragrance composition was produced in the same manner as above. . The top notes of these fragrances were very fresh, and all of them were new compositions having a novel lira-type fragrance that had never existed before. Example 17 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 Isoamyl alcohol 35 Diethyl malonate 30 Citral 15 Linalool 5 Maltol 20 1000 Composition By adding 20g of 1-(3,3-dimethylcyclohexan-1-yl)-2-methyl-1-buten-3-one to 1000g of pineapple, a novel and unprecedented product reminiscent of natural pineapple is produced. A pineapple aroma flavor composition was obtained.

Claims (1)

[Claims] 1. The following formula (A) However, in the formula, X represents a hydrogen atom or a group Z, and Y represents a group Z when X is a hydrogen atom, and
represents a methyl group, where the group Z represents a group selected from the group consisting of [Formula] [Formula] [Formula] [Formula] and [Formula], a dimethyl or trimethylcyclohexyl derivative represented by .