JPH02337B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides 2-methyl-5-
Isopropenyl-2-cyclohexene derivative, its use as a persistent aroma and flavor imparting or modulating agent;
Furthermore, it relates to its manufacturing method. More specifically, the present invention is based on the following formula (1) However, in the formula, R may have a hydrogen atom, a _C1 - _C6 alkyl group, a _C2 - _C6 alkenyl group, or a substituent selected from the group consisting of hydroxy, lower alkyl, and lower alkoxy. 2-methyl-5-isopropenyl-2, which represents a phenyl lower alkyl group, and in the formula, when the bond represented by 〓 represents a double bond, R represents a hydrogen atom.
-Relating to cyclohexenone derivatives. Furthermore, the present invention relates to a long-lasting aroma and flavor imparting or modulating agent characterized by containing the above compound of formula (1) as an active ingredient, and also relates to a method for producing the compound of formula (1). The present inventors have conducted research on cyclohexenones. As a result, the 2-methyl-5-isopropenyl-2-cyclohexenone derivative represented by the formula (1) is a compound that has not been previously described in the literature, and the compound of formula (1) can be easily obtained in good yield. Furthermore, the compound of formula (1) has an excellent fruit-like, grass-like, wood-like, and flower-like aroma and flavor, and has an excellent long-lasting aroma. We have discovered that this is a unique compound that is extremely effective as an imparting or modulating agent. Furthermore, the compound of formula (1) is useful as an excellent long-lasting aroma and flavor imparting or flavor modulating agent in a wide range of fields, including food and beverages (including luxury goods), cosmetics, health care, etc.
It has been discovered that this compound is extremely useful as an excellent long-lasting aroma and flavor imparting or flavor modulating agent in a wide range of fields such as hygiene and medicine. Furthermore, the inventors have also discovered that the compound of formula (1) is useful as a synthetic intermediate for other fragrance compounds and pharmaceuticals. Therefore, an object of the present invention is to provide the compound of formula (1), 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 modulating agent containing the above-mentioned compound of formula (1) 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. In the compound of the above formula (1) of the present invention, R has a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, and a substituent selected from hydroxy, lower alkyl, and lower alkoxy; Examples of compounds representing a group selected from the group consisting of phenyl lower alkyl groups include the following formula (5): After isomerizing the carvone represented by, a silylation reaction is performed to obtain the following formula (4) 5-isopropenyl-2-methyl-
1-trimethylsiloxy-1,3-cyclohexadiene is formed, and then the compound of formula (4) is converted into the following formula (4)' R ¹ -CHO (4)' where R ¹ is a hydrogen atom C ₁ -C ₆ alkyl group,
Condensed with aldehydes represented by C ₂ -C ₆ alkenyl, and a group selected from the group consisting of phenyl lower alkyl groups optionally having a substituent selected from hydroxy, lower alkyl, and lower alkoxy. It can be easily produced by reaction. The compound of formula (1) that can be produced in this way has the following formula in formula (1):
It can be expressed as (1)-1. However, in the formula, R ₁ has the same meaning as above. In addition, the following formula (1)-2 when the broken line included in the compound of formula (1) is a double bond and R is a hydrogen atom 2-Methyl-5-isopropenyl-
In order to produce a 2-cyclohexenone derivative, for example, 5-isopropenyl-2-methyl-1-trimethylsiloxy-1,3 represented by the above formula (4)
- Condensation reaction of cyclohexadiene with alkyl orthoformate produces the following formula (3) However, in the formula, R ² may be the same or different at the same time.
4-dialkoxymethyl-5-isopropenyl-2-methyl-2-cyclocenone, which represents a _C1 to _C5 alkyl group, is formed, and then the compound of formula (3) is hydrolyzed to form the following formula: (2) It can be easily synthesized by forming 3-methyl-4-oxo-6-isopropenyl-2-cyclohexene-1-carbaldehyde represented by and further isomerizing the compound of formula (2). The above embodiment of forming the above formula (1)-1 and the above formula (1)-2 compounds included in the above formula (1) from the above formula (5) compound can be schematically represented as follows. Can be done. In the formula, R ¹ and R ² have the same meanings as described above. The known compound of formula (5) used in the above production mode can be easily produced by various methods known per se, and can also be inexpensively and easily obtained on the market.
It can also be easily isolated and obtained from natural sources. The compound of formula (1) of the present invention can be synthesized, for example, using the compound of formula (5) that can be obtained as described above as a starting material. Formula (5) used in the present invention
Any of the (+), (-), and (±) optical isomers of the compound can be employed as a raw material. In the above manufacturing embodiment of the compound of formula (1)-1 included in the compound of formula (1) of the present invention, from the compound of formula (5) to the compound of formula (4)
The compound can be produced by, for example, isomerizing the carvone of formula (5) by contacting it with an alkylmagnesium halide in the presence of a Lewis acid, and then contacting it with trimethylhalosilane, such as trimethylchlorosilane, in the presence of a tertiary amine. This can be easily carried out by a silylation reaction. When carrying out this reaction, for example, in the presence of a Lewis acid, preferably in an ethereal organic solvent, about -80
℃ to about 50℃, more preferably about -10℃ to about 10℃, for about 1 to about 3 hours, the carvone of formula (5) and the alkylmagnesium halide are brought into contact, and further under similar conditions. This can be carried out by adding a tertiary amine, trimethylchlorosilane and an aprotic polar solvent and allowing them to contact each other for about 5 to about 48 hours. The amount of alkylmagnesium halide and trimethychlorosilane to be used relative to the carvone can be selected as appropriate, but it is approximately 1 per mole of carvone.
A preferable example is an amount of about 2 mol to about 2 mol.
Further, the amount of the tertiary amine to be used can be selected as appropriate, and a preferable example is about 0.1 to about 1 mole per mole of carvone. Furthermore, the amount of the Lewis acid to be used is preferably about 0.01 to about 0.5 mol per 1 mol of carvone. Examples of the ether organic solvent used in the reaction include diethyl ether, dipropyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, and any combination thereof. Examples of the alkylmagnesium halides include methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride,
Examples include ethylmagnesium bromide. Further, as an example of the Lewis acid, ferric chloride can be exemplified. Furthermore, examples of the above-mentioned tertiary amines include trimethylamine,
Examples include tripropylamine, tributylamine, pyridine, N,N-dimethylaniline, etc. Examples of the aprotic polar solvents include N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and hexamethyl. Examples include phosphoric acid triamide. For example, the compound of formula (4), which is an oily substance with a boiling point of about 111 to 112°C/17 mmHg and not described in any prior literature, which can be formed as described above, can be formed by condensation reaction with aldehydes of formula (4)'. 4(1-hydroxy-alkyl or alkenyl or aralkyl)-5- of the above formula (1)-1 can be easily obtained by
It can be converted to isopropenyl-2-methyl-2-cyclohexenone. This reaction is carried out, for example, in the presence of a Lewis acid, preferably in a halogenated organic solvent, for example about -
80° to about 50°C, more preferably about -60° to about -40°C
This can be carried out by bringing the compound of formula (4) and the compound of formula (4)' into contact under low-temperature conditions such as. The reaction time can be selected as appropriate, for example, from about 10 minutes to about
An example of a contact time is 10 hours, more preferably about 1 to 2 hours. Furthermore, the amount of the compound of formula (4)′ to be used relative to the compound of formula (4) can be selected as appropriate;
For example, about 1 to about 5 per mole of the compound of formula (4)
For example, the amount used is about 1 to about 1.5 moles, preferably about 1 to about 1.5 moles. Furthermore, the amount of the Lewis acid used can be selected as appropriate, and the compound 1 of formula (4)
An example of the amount used is about 0.1 to about 3 moles, more preferably about 1 mole. Examples of the halogenated organic solvent used in the reaction include monochloromethane, dichloromethane, chloroform, carbon tetrachloride, monochloroethane, 1,2-dichloroethane, and mixtures thereof. Examples of Lewis acids include titanium tetrachloride, tin tetrachloride, aluminum chloride, zinc chloride, boron trifluoride diethyl ether complex, and boron trifluoride acetic acid complex. Examples of compounds of formula (4)' used in the reaction include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, isobutyraldehyde, acrylaldehyde, crotonaldehyde, trans-2-hexenal, benzaldehyde, phenyl. Examples include acetaldehyde and vanillin. After distilling off the solvent, the reaction product can be purified by vacuum distillation, column chromatography, or the like, if desired. For example, the above formula (1)-1, which can be obtained as described above and which has not been described in the conventional literature,
The 4-(1-hydroxy-alkyl or alkenyl or aralkyl)-5-isopropenyl-2-methyl-2-cyclohexenone can exist in two isomeric forms, cis and trans, which are exemplified above. It can be separated and purified by purification means such as. For example, as representative examples of the formula (1)-1 compound included in the formula (1) of the present invention that can be produced as described above, the following compounds can be exemplified. The physicochemical data of these compounds are shown in Example 3 below. (a) 4-hydroxymethyl-5-isopropenyl-2-methyl-2-cyclohexenone (b) 4-(1-hydroxyethyl)-5-isopropenyl-2-methyl-2-cyclohexenone (c) 4 -(1-Hydroxypropyl)-5-isopropenyl-2-methyl-2-cyclohexenone (d) 4-(1-hydroxybutyl)-5-isopropenyl-2-methyl-2-cyclohexenone (e) 4 -(1-hydroxypentyl)-5-isopropenyl-2-methyl-2-cyclohexenone (f) 4-(1-hydroxy-2-methylpropyl)-5-isopropenyl-2-methyl-2-
Cyclohexenone (g) 4-(1-hydroxy-2-propenyl)-
5-isopropenyl-2-methyl-2-cyclohexenone (h) 4-(1-hydroxy-2-butenyl)-5
-Isopropenyl-2-methyl-2-cyclohexenone(i) 4-(1-hydroxy-2-hexenyl)-
5-isopropenyl-2-methyl-2-cyclohexenone (j) 4-(α-hydroxybenzyl)-5-isopropenyl-2-methyl-2-cyclohexenone (k) 4-(1-hydroxy-2- phenylethyl)-5-isopropenyl-2-methyl-2-
Cyclohexenone (l) 4-(α-hydroxy-4-hydroxy-3
-Methoxybenzyl)-5-isopropenyl-
2-Methyl-2-cyclohexenone Also, formula (1)-2 included in the compound of formula (1) of the present invention
In the above production mode of the compound, the production of the compound of formula (3), a new substance not previously described in literature, from the compound of formula (4) is as follows:
For example, in the presence of a Lewis acid, preferably in a halogenated organic solvent, and under low temperature conditions such as about -80°C to about 50°C, more preferably about -60°C to about -40°C, the formula (4) This can be carried out by bringing the compound into contact with trialkyl orthoformate. The reaction time can be selected as appropriate; for example, a contact time of about 10 minutes to about 10 hours, more preferably about 1 to 2 hours, can be exemplified. Further, the amount of alkyl orthoformate to be used relative to the compound of formula (4) can be appropriately selected, for example, about 1 to 5 moles, more preferably about 1 to about 1.5 moles, per 1 mole of the compound of formula (4). The usage amount can be exemplified. Furthermore, the amount of Lewis acid to be used can be selected as appropriate, and may be about 0.1 to about 3 mol, more preferably about 1 mol, per 1 mol of the compound of formula (4). Preferred examples of the alkyl orthoformate include methyl orthoformate, ethyl orthoformate, and propyl orthoformate. Examples of the halogenated organic solvent used in the reaction include monochloromethane, dichloromethane, chloroform, carbon tetrachloride 1,2-dichloroethane, and mixtures thereof. Examples of Lewis acids include titanium tetrachloride, tin tetrachloride, aluminum chloride, zinc chloride, boron trifluoride diethyl ether complex, and boron trifluoride acetic acid complex. The reaction product can be purified by means such as vacuum distillation and column chromatography, if desired. For example, 4-dialkoxy-5-isopropenyl- of formula (3) which can be obtained as described above.
By simultaneously performing a hydrolysis reaction and an isomerization reaction of 2-methyl-2-cyclohexenone, a new compound of the formula (1)-2 4-hydroxymethylidene-5-isopropenyl-2-methyl, which has not been previously described in any literature, can be obtained. -2-Cyclohexenone can be obtained easily and in high yield. In the above reaction, if desired, after hydrolyzing the compound of formula (3), the compound of formula (2) may be isolated and then subjected to an isomerization reaction. The hydrolysis reaction is carried out, for example, by treating the compound of formula (3) in an aqueous solution or in a mixed solution of water and an organic solvent at a temperature of about 0°C to about 50°C, more preferably about 20° to about 30°C. , for example, by contacting with an acid for a period of time, such as from about 1 hour to about 48 hours. Examples of organic solvents used in reactions are:
Examples include alcohol organic solvents such as methanol and ethanol, and ether organic solvents such as diethyl ether, tetrahydrofuran and dioxane. Further, the mixing ratio of the organic solvent to water can be selected as appropriate, and may be about 1/10 to about 10 times the weight of 1 part water. Further, examples of acids to be used include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, P-toluenesulfonic acid, benzenesulfonic acid, and the like. The reaction product can be purified by means such as vacuum distillation and column chromatography, if desired. In the compound of formula (1) of the present invention that can be produced as described above, examples of the C ₁ -C ₆ alkyl group of R are:
Examples include straight chain or branched alkyl groups such as methyl, ethyl, propyl, methylpropyl, butyl, pentyl, hexyl and the like. Also, C ₂ of R
Examples of the -C ₆ alkenyl group include alkenyl groups such as ethynyl, propenyl, butenyl, hexenyl and the like. Examples of phenyl lower alkyl groups include aralkyl groups such as benzyl and phenethyl. Further, such an aralkyl group may have a substituent, and examples thereof include hydroxy, lower alkyl such as C ₁ -C ₃ alkyl, and lower alkoxy such as C ₁ -C ₃ alkoxy. It has been discovered that the compounds of formula (1) of the present invention are useful as persistent aroma flavor imparting or modulating agents. The compound of formula (1) exhibits fruit-like, grass-like, wood-like, and flower-like aromas and flavors, and has excellent persistence.Furthermore, it has a mild and rich naturalness, and is particularly useful in various foods and beverages. It has excellent durability and a unique aroma and flavor as an aroma or flavor component for products, cosmetics, health/hygiene/pharmaceuticals. More specifically, when the compound of formula (1) is blended into synthetic essential oils such as bergamot oil, lemon oil, geranium oil, lavender oil, and mandarin oil, it produces the mild, rich, and long-lasting aroma inherent to natural essential oils. Imparting or modulating agents can be adjusted. It also harmonizes well with oak citrus oil such as orange, lime, lemon, grapefruit, etc., and can emphasize the characteristics of the essential oil, imparting or modulating a persistent aroma with a fresh, refreshing, and more natural feel. agent can be adjusted. Furthermore, when it is blended into flavor compositions such as strawberry, lemon, orange, grapefruit, apple, pineapple, etc., it is possible to obtain an aroma and flavor imparting or modulating agent that has a mild, rich, natural appearance and is highly durable. . The above formula (1)
The amount of the compound to be blended varies depending on the purpose and the aroma/flavor imparting or modulating agent to be blended, but is generally in the range of about 0.001 to about 10% by weight of the total. Thus, the present invention is characterized in that it contains the compound of formula (1) as a flavor component by using a persistent aroma and flavor imparting or modulating agent or enhancer comprising the compound of formula (1) as an active ingredient. Food and drinks, formula
It is possible to provide cosmetics characterized by containing the compound (1) as an aroma component, and health, hygiene, pharmaceutical products, etc. characterized by containing the compound of formula (1) as an aroma component. 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; It is possible to provide snack foods and the like with foods and drinks containing an appropriate amount that can impart the unique aroma and flavor. Also, for example, shampoos, hair creams, pomades, and other hair cosmetic bases;
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, deodorizing detergents, and various other health and sanitary detergents; various health and hygiene products such as toothpaste, toilet paper, and toilet paper.
Hygiene materials: We can provide health, hygiene, and pharmaceutical products that have been blended or applied with appropriate amounts to give unique flavors to health, hygiene, and pharmaceutical products, such as flavoring agents and flavoring agents to make medicines easier to take. . 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 Synthesis of 5-isopropenyl-2-methyl-1-trimethylsiloxy-1,3-cyclohexadiene: - Magnesium 0.8 mol (19.5 g), methyl bromide 0.8
mole (76 g), and anhydrous diethyl ether 350
Prepare methylmagnesium bromide from -10℃
Then, 2.0 g of ferric chloride was added, and then a solution of 0.6 mol (90 g) of carvone and 70 g of anhydrous diethyl ether was added dropwise over 30 minutes, followed by stirring for 1 hour. At 0℃, 60ml of triethylamine, trimethylchlorosilane
100ml, and hexamethylphosphate triamide 60
ml and stir for an additional 24 hours. The reaction solution was poured into ice water and extracted with hexane. The organic layer is washed with a 5% aqueous potassium hydrogen sulfate solution and further with a 5% aqueous sodium hydrogen carbonate solution, and then dried over anhydrous magnesium sulfate. Collect the solvent, distill the residual liquid under reduced pressure, and reduce the boiling point to 111.
96 g of oily 5-isopropenyl-2-methyl-1-trimethylsiloxy-1,3-cyclohexadiene (yield 72
%) was obtained. IR1670, 1640, 1585, 920, 890,
843cm ^-1 ; NMR (CDCl ₃ ) δ=0.20 (9H, s),
1.65 (3H, m), 1.76 (3H, m), 2.18 (1H, m),
2.36 (1H, m), 3.13 (1H, m), 4.80 (2H, m),
5.37 (1H, dd, J=9.5, 3.0Hz), 5.80 (1H, dd,
J=9.5, 2.4Hz); Example 1 4-(1-hydroxy-2-methylpropyl)
-Synthesis of 5-isopropenyl-2-methyl-2-cyclohexenone; 20 mmol (4.44 g) of 5-isopropenyl-2-methyl-1-trimethylsiloxy-1,3-cyclohexadiene obtained in Reference Example 1, 20 mmol (2.84 g) of boron trifluoride diethyl ether complex is added to a solution of 24 mmol (1.73 g) of isobutyraldehyde and 20 ml of dichloromethane at -60°C, and the mixture is stirred for 2 hours under the same conditions. Pour water into the mixture, separate the oil layer and wash once with water. The oil layer is further stirred with a 10% aqueous oxalic acid solution at room temperature for 24 hours, separated and washed with a 5% aqueous sodium bicarbonate solution. The oil layer is dried with anhydrous magnesium sulfate. Dichloromethane was collected, and the residual liquid was separated and purified by silica gel column chromatography (hexane-ether) to obtain 4-(1-hydroxy-2-methylpropyl)-5-isopropenyl-2-methyl-2-cyclohexenone. Two isomers 2.40
g (54%) and 0.40 g (9%). :IR3460, 1660, 895cm ^-1 ; NMR ( _CDCl3 )
δ=0.95 (3H, d, J=6.5Hz), 0.99 (3H, d,
J=6.5Hz), 1.76 (6H, m), 2.0-3.1 (6H, m),
3.55 (1H, m), 4.85 (2H, m), 6.73 (1H, m); :IR3500, 1660, 890cm ^-1 ;NMR (CDCl ₃ )
δ=0.96 (6H, d, J=6.5Hz), 1.76 (3H, m),
1.86 (3H, m), 2.2-3.1 (6H, m), 3.56 (1H,
m), 4.48 (2H, m), 6.65 (1H, m). Boiling point of mixture with 115℃/0.05mmHg Example 2 Synthesis of 4-(1-hydroxybenzyl)-5-isopropenyl-2-methyl-2-cyclohexenone: - Using benzaldehyde instead of isobutyraldehyde, etc. was carried out in the same manner as in Example 1,
4-(α-hydroxybenzyl)-5-isopropenyl-2-methyl-2-cyclohexenone isomers (56%) and (4%) were obtained. :IR3450, 1665, 895cm ^-1 :NMR( _CDCl3 )
δ=1.70 (3H, m), 1.77 (3H, m), 2.3-3.2
(5H, m), 4.85 (1H, m), 4.94 (2H, m), 6.53
(1H, m), 7.30 (5H, s); :IR3400, 1660, ^{900cm -1} :NMR (CDCl ₃ ) δ
=1.73 (6H, m), 2.2-3.1 (5H, m), 4.75-4.95
(3H, m), 6.82 (1H, m), 7.25 (5H, s). Boiling point of mixture with 155°C/0.06mmHg Example 3 Example 1 was prepared to obtain various compounds included in the above formula (1)-1 compound.

[Table] Senone

[Table] Xenon reference example 2 4-diethoxymethyl-5-isopropenyl-
Synthesis of 2-methyl-2-cyclohexenone: - 40 g of dichloromethane, 60 g of triethyl orthoformate
mmol (8.88 g), and 5-isopropenyl-2-methyl-1-trimethylsiloxy-1,3
-To a solution of 45 mmol (9.99 g) of cyclohexadiene at -60°C, 45 mmol (6.39 g) of boron trifluoride diethyl ether complex is added dropwise over 1 hour.
After stirring for 2 hours under the same conditions, the mixture was poured into a cooled 5% aqueous sodium hydrogen carbonate solution. The aqueous layer is extracted with dichloromethane. The organic layer is dried over anhydrous magnesium sulfate. Dichloromethane was collected, and the remaining liquid was subjected to silica gel column chromatography (hexane-
ether) to obtain 6.58 g (58%) and 1.02 g (9%) of two isomers of 4-diethoxymethyl-5-isopropenyl-2-methyl-2-cyclohexenone. :IR1670, 1110, 1060, 895cm ^-1 ; NMR
(CDCl ₃ ) δ = 1.18 (3H, t, J = 7.0Hz), 1.25
(3H, t, J=7.0Hz), 1.76 (6H, m), 2.2-3.1
(4H, m), 3.3-4.0 (4H, m), 4.45 (1H, d, J
=3.0Hz), 4.85 (2H, m), 6.88 (1H, m); :IR1670, 1110, 1060, 895cm ^-1 ;NMR
(CDCl ₃ ) δ=1.17 (3H, t, J=7.0Hz), 1.22
(3H, t, J=7.0Hz), 1.80 (6H, m), 2.0-3.1
(4H, m), 3.2-4.0 (4H, m), 4.42 (1H, d, J
= 5.0Hz), 4.84 (2H, m), 6.80 (1H, m). Example 4 Synthesis of 4-hydroxymethylidene-5-isopropenyl-2-methyl-2-cyclohexenone:- 4-diethoxymethyl-5-isopropenyl-
7.9 mmol (2.00 g) of 2-methyl-2-cyclohexenone (a mixture of two isomers), 10 g of tetrahydrofuran, and 10 g of 2N hydrochloric acid were charged.
Stir at ℃ for 4 hours. After adding water, extraction is performed with diethyl ether, and the organic layer is neutralized with a 5% aqueous sodium bicarbonate solution and then dried over anhydrous magnesium sulfate. Diethyl ether was collected, the residual liquid was separated and purified by silica gel column chromatography (hexane-ether), and 5-isopropenyl-4-
1.13 g (80%) of hydroxymethylidene-2-methyl-2-cyclohexenone (1 peak in GCL) was obtained. IR3180, 1610, 1590, 1160cm ^-1 NMR ( _CDCl3 )
δ=1.73 (6H, broads), 2.64 (2H, d, J=5.0
Hz), 3.73 (1H, m), 4.74 (2H, m), 4.85 (1H,
m), 6.86 (1H, m), 7.03 (1H, m). Persistent Aroma and Flavor Imparting or Modulating Agent Example 5 The following components (by weight) were mixed as an aroma and flavor composition for apples. Ethyl acetate 50 Ethyl propionate 20 Ethyl butyrate 30 Ethyl isovalerate 60 Isoamyl acetate 30 Butyl alcohol 150 Amyl alcohol 50 Butyl propionate 70 Butyl butyrate 10 2-Hexenol 100 2-Hexenyl acetate 180 Isobutyric acid 40 Vanillin 20 Hexyl Butyrate 10 Ethyl alcohol 180 Total 1000 Add 1000g of the above composition to 4-(1-hydroxy-
2-methylpropyl)-5-isopropenyl-2
By adding 20 g of -methyl-2-cyclohexenone, a new composition with excellent persistence as an apple aroma and flavor component was obtained. Similar results were obtained using 4-(α-hydroxybenzyl)-5-isopropenyl-2- instead of 4-(1-hydroxy-2-methylpropyl)-5-isopropenyl-2-methyl-2-cyclohexenone.
It can also be obtained by using methyl-2-cyclohexenone and 4-(1-hydroxy-4-hydroxy-3-methoxybenzyl)-5-isopropenyl-2-methyl-2-cyclohexenone, respectively. Ta. Example 6 The following components (by weight) were mixed as aroma and flavor components for pineapple. Ethyl acetate 300 Ethyl butyrate 250 Isoamyl acerate 100 Isoamyl valerate 55 Isobutyric acid 70 Isovaleric acid 30 Allyl caproate 35 Ethyl caproate 20 Ethyl caprylate 15 Ethyl caprate 20 Isoamyl alcohol 35 Diethyl malonate 30 Citral 15 Linalool 5 Maltol 20 total 1000 4-hydroxymethyl-5 to 1000g of the above composition
By adding 15 g of -isopropenyl-2-methyl-2-cyclohexenone, a new composition with a natural pineapple-like aroma and flavor and very long-lasting properties was obtained. A similar result is 4-
Instead of hydroxymethyl-5-isopropenyl-2-methyl-2-cyclohexenone, 4-(1
-Hydroxypropyl)-5-isopropenyl-
2-methyl-2-cyclohexenone, 4-(1-
Hydroxybutyl)-5-isopropenyl-2-
Methyl-2-cyclohexenone and 4-(1-hydroxypentyl)-5-isopropenyl-2-
They were also obtained by using methyl-2-cyclohexenone, respectively. Example 7 The following components (by weight) were mixed as an aroma and flavor composition for grapes. Amyl isovalerate 8 Cinnamyl alcohol 5 Cinnamyl isovalerate 3 Cinnamyl propionate 3 Citral 1 Ethyl acetate 62 Ethyl benzoate 3 Ethyl butyrate 16 Ethyl caproate 3 Ethyl enanthate 8 Hydroxycitronellal 1 Methyl anthrani Rate 132 Methyl salicylate 12 Pettigrain 1 Terpinyl acetate 10 Ethanol 732 Total 1000 By adding 30 g of 4-(1-hydroxyethyl)-5-isopropenyl-2-methyl-2-cyclohexenone to 1000 g of the above composition, A new composition with a natural grape-like aroma and extremely long-lasting properties was obtained. Similar results were obtained for 4-(1-hydroxy-2-propenyl)-5-
Isopropenyl-2-methyl-2-cyclohexenone, 4-(1-hydroxy-2-butenyl)-
5-isopropenyl-2-methyl-2-cyclohexenone, 4-(1-hydroxy-2-hexenyl)-5-isopropenyl-2-methyl-2-cyclohexenone and 4-(1-hydroxy-2-
phenylethyl)-5-isopropenyl-2-methyl-2-cyclohexenone. Example 8 A fragrance composition for shampoo was produced by mixing each component (parts by weight). Linalool 5 Absolute diasmine 2 β-phenylethyl alcohol 15 Rhodinol 15 Absolute rose 1 Hydroxycitronellol 30 Indole 10% benzyl benzoate solution 2 Stylac oil 3 Hexyl cinnamic aldehyde 15 Cyclamen aldehyde 4 Sandalwood oil 5 Phenylacetaldehyde 3 total 1000 By adding 2 g of 4(1-hydroxy-2-methylpropyl)-5-isopropenyl-2-methyl-2-cyclohexenone to 98 g of the above composition, a product with fresh lily of the valley-like characteristics and A new long-lasting composition was obtained. Also, 4-(1-hydroxy-benzyl)-5-isopropenyl-2-methyl-2-cyclohexenone, 4-hydroxymethylidene-5-isopropenyl-2-methyl-2
Similar results were obtained by adding -cyclohexenone and 4-hydroxymethylidene-5-isopropenyl-2-methyl-2-cyclohexenone. Example 9 Composition Powder for Soap A Narcissus-like fragrance composition was produced by mixing the following components (parts by weight). Bergamot oil 17 Ylang-ylang oil 5 Linalool 20 Benzyl acetate 5 Benzyl alcohol 25 Terpineol 12 Paracresyl acetate 1 Cinnamic alcohol 5 Eugenol 4 Heliotropin 4 Absolute Diasmin 2 Total 1000 4 (1-Hydroxy) added to 95 g of the above composition A fragrance composition was prepared by mixing 5 g of -2-methylpropyl)-5-isopropenyl-2-methyl-2-cyclohexenone. This and 4-(1-hydroxy-2-methylpropyl)-5-isopropenyl-2-methyl-
A soap was produced by adding a composition to which no 2-cyclohexenone was added at a ratio of 1% by weight to an unscented soap paste and molding it. 4-(1-hydroxy-2-methylpropyl)
- Soaps containing 5-isopropenyl-2-methyl-2-cyclohexenone have a lower
A new composition with natural narcissus-like characteristics and long-lasting properties was obtained.

Claims (1)

[Claims] 1 The following formula (1) However, in the formula, R may have a hydrogen atom, a _C1 - _C6 alkyl group, a _C2 - _C6 alkenyl group, or a substituent selected from the group consisting of hydroxy, lower alkyl, and lower alkoxy. 2-methyl-5-isopropenyl-2, which represents a phenyl lower alkyl group, and in the formula, when the bond represented by 〓 represents a double bond, R represents a hydrogen atom.
- Cyclohexenone derivative.