JPS603308B2 - Acetyl cyclohexenone ketals, their production and use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to acetylcyclohexenone ketals represented by the following formula: [11] where R represents a hydrogen atom or a methyl group, and their production and utilization.

Furthermore, it relates to a method for producing the compound of formula {1} above and its use. 4-Hydroxy-B-damascone and 8-damanocenone, represented by the following formula, [4-hydroxy-6-damascone] [8-damascenone], are known aromatic compounds isolated and collected from natural tobacco leaves and naturally sourced Bulgarian rose oil, respectively. It is an ingredient.

The present inventors have conducted research on the synthesis of the above-mentioned natural aroma components and their related compounds. As a result, it was discovered that acetylcyclohexenone ketals represented by the formula m above can be easily synthesized from inexpensive and easily available raw materials.

Furthermore, the acetylcyclohexenone ketals represented by the formula [1-], which have not been described in any prior literature, are useful as intermediates for synthesizing the above-mentioned 4-hydroxy-8-damascone, 3-damascenone, and their analogues (desmethyl derivatives). discovered that it is an extremely unique and long-lasting fragrance ingredient with a floral aroma. Thus, the formula '11 acetylcyclohexenone ketals have shown remarkable usefulness as excellent long-lasting fragrance imparting agents or modulators, and have been used in a wide range of fields such as perfumery products, cosmetics, and health/hygiene/pharmaceuticals. It was found to be useful as a persistent aroma imparting or modulating agent. Accordingly, it is an object of the present invention to provide acetylcyclohexenone ketals of the formula m, their preparation and use.

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

The compounds of the formula m of the present invention have the following formulas '1'' and '1r.
Compounds included. (1-acetyl-6,6-dimethyl-4,4-echo-ethylenedioxy-1-cyclohexene) (1-acetyl-2,6,6-trimethyl-4,4
-ethylenedioxy-1-cyclohexene) above formula (U
'The compound has the following formula '21, where R' is C, ~C5
The heated reaction product of 2-trimethylsilyloxy-4-alkoxy-1,3-butadiene, which represents an alkyl group, and methyl oxide, which is represented by the following formula It can be produced industrially advantageously by reacting with glycol.

Further, the above formula {1}'' compound is a compound of the formula [11', 1-acetyl-6,6-dimethyl-4,
It can be easily obtained by treating 4-ethylenedioxy-1-cyclohexene with a methylating agent and then reacting with a halogen, followed by a dehydrohalogenation reaction in the presence of a base. The above reaction can be illustrated as follows in a process diagram. The above formula '2) compound is, for example, J. Am. Chem. SM907808 (1974)
It can be manufactured according to the method described in .

For example, in a mixture of triethylamine and a catalytic amount of zinc chloride in an inert solvent according to the following formula:
2-trimethylsilyloxy-4-methoxy-1,3-butadiene can be produced by addition-reacting 4-methoxy-3-buten-2-one and trimethylsilyl chloride.

The formation of 1-acetyl-6,6-dimethyl-4,4-ethylenedioxy-1-cyclohexene of formula '1' from a compound of formula ■ and a compound of formula '3} is a heating reaction product of a compound of formula ■ and a compound of formula '1'. By reacting with ethylene glycol in the presence of an acid catalyst, it can be carried out selectively and in good yield by an industrially easy means.

The production of the thermal reaction product by the thermal Diels-Alder reaction can be carried out by bringing both reaction components into contact under heated conditions in the presence or absence of an inert organic solvent. The heating condition is, for example, about 50o.
For example, the temperature is about 300 qo to about 300 qo, more preferably about 800 to about 250°C. The reaction can be carried out under atmospheric pressure conditions or under pressurized conditions, for example, under atmospheric pressure conditions to
A condition of about 50k9/enemy can be exemplified. Although the reaction time may be changed appropriately depending on the reaction temperature, pressure conditions, etc. employed, the reaction time can be, for example, about 1 hour to about 10 hours. During the reaction, there are no particular restrictions on the amount of compound of formula 1 to be used, but compounds of formula 1
An example of the amount used is about 0.5 to about 20 moles, and more preferably about 1 to about 10 moles.
Further, in the above reaction, when an inert organic solvent is used, aromatic hydrocarbon solvents such as benzene, toluene, and xylene can be used, for example. These solvents can be used alone or in the form of a mixture of two or more, and the amount used may be selected as appropriate. For example, the expression {2) and the expression (
3} Based on the total weight of the compound, the amount used may be up to about 10 times the weight of blood, more preferably up to about 5 times the weight of blood. As an example of the above formula ■ raw material compound,
4-methoxy form, 4-ethoxy form, 4-n-propoxy form, 4-iso-propoxy form, 4-n-butoxy form,
Examples include 4-iso-butoxy, 4-n-amyloxy, and 4-iso-amyloxy. The heated reaction product of the compound of formula {2) and the compound of formula '3', which can be formed as described above, is reacted with ethylene glycol in the presence of an acid catalyst to form the compound of formula [1}
1-acetyl6 of the formula {1}' where R is a hydrogen atom
- Can be easily converted to 6-dimethyl-4,4-ethylenedioxy-1-cyclohexene.

The reaction can be carried out using the above-mentioned thermal reaction product system as it is, or it can also be carried out using the residue obtained by removing the solvent and/or low-boiling point components from the reaction product system. . The ketalization reaction between the heated reaction product and ethylene glycol can be carried out over a wide temperature range, for example, from room temperature to about 150°C, and it is more preferable to employ heating conditions of about 80°C to about 11°C.

The reaction time varies depending on the solvent used, the reaction temperature, the type of acid catalyst, etc., but is usually about 1 minute to about 1q hour. The reaction molar ratio can also be selected appropriately, for example, the formula '
For example, the amount of ethylene glycol used is about 0.5 to about 10 moles per mole of 3' methyl oxide.
A more preferred example is an amount of about 1 to about 3 moles. Examples of Shun catalysts used in the reaction include benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid,
Examples include sulfonic acids such as methanesulfonic acid and mineral acids such as sulfuric acid and phosphoric acid. These acid catalysts are added to the weight of the heated reaction product, for example, about 0.5
Amounts on the order of from about 4% by weight may be used, and amounts on the order of from about 1 to about 2% by weight are more preferably utilized. The reaction is preferably carried out in the presence of an inert organic solvent, examples of which include aromatic hydrocarbons such as benzene, toluene, xylene, etc., and halogenated aliphatic hydrocarbons such as methylene chloride. I can give it to you. These solvents can be used alone or in a mixture of two or more. There is no particular limit to the amount of solvent used, but based on the weight of the heated reaction product from the Diels-Alder reaction, it is, for example, about 2 to about 10 times the amount of solvent, more preferably about 5 to about 5 times the amount of solvent. It is about twice the weight of After the completion of the above ketalization reaction,
The resulting reaction product is poured into water and extracted with a suitable solvent such as hexane, benzane, benzene, toluene, enal, ethyl acetate, chloroform, methylene chloride, carbon tetrachloride, etc. Neutralize the phase, e.g.
By washing with water, drying and concentrating, in the formula '1}, R
1-acetyl-6,6-dimethyl-4,4-ethylenedioxy-1-cyclohexene of the formula [1}' in which is a hydrogen atom can be obtained in high yield and with bridge purity.

If desired, further vacuum distillation, column chromatography,
Further purification can also be carried out using other known means.

The obtained compound of formula [11'] is an oily compound not described in any literature, and its boiling point is 30-81°C/0.05 Hg. Further, the results of infrared, nuclear magnetic resonance, and mass spectra are shown in Examples below. Furthermore, it has been found that this compound of formula 01', which has not been described in any literature, has a unique aroma of floral steel and is a long-lasting aroma component. In the present invention, 1-acetyl-2,6,6-trimethyl-4,4-ethylenedioxy-1-cyclohexene of the formula '1r in which R is a methyl group is also a compound not described in the literature, For example, the compound of formula '1}' obtained as described above is treated with a methylating agent and then treated with a halogen to form 1-acetyl-1 of the formula '4'.
It can be obtained by forming -halo-2,6,6-trimethyl-4,4-ethylenedioxycyclohexane and then subjecting it to a dehydrohalogenation reaction in the presence of a base. The above formula (2) compound can be prepared by reacting the compound of formula (1'' with, for example, dimethylsteel lithium (Li(CH3)2Cu), or, for example, by reacting methylmagnesium halide (C ratio MgX... ...X can be formed by treating with a methylating agent and then reacting with a halogen such as CI2, Br, or 12.This methylation The reaction of treating with a halogen and then reacting with a halogen can be carried out, for example, in an inert organic solvent.
This can be carried out by adding a methylating agent as exemplified above to the above-mentioned compound of formula {1'', and then adding a halogen, and the compound of formula [41] can be formed in good yield and excellent selectivity. . The methylation reaction and halogenation reaction are preferably carried out at room temperature or as low a temperature as possible, for example, at a temperature of about 1,800 to about 180°C. It is more preferable to adopt a temperature condition of about 1,600 to about 110:00. Examples of the above-mentioned methylmagnesium halide include methylmagnesium chloride, methylmagnesium bromide, and methylmagnesium iodide. Further, examples of the above-mentioned halogenated first steel include cuprous chloride, cuprous bromide, and cuprous iodide. The amount of the methylating agent such as the above dimethyl steel lithium and methylmagnesium halide can be selected as appropriate, for example, about 1 to about 5 mol per 1 mol of the compound of formula [1'' More preferably, the amount used is about .2 to about 3 moles. Further, the amount of cuprous halide to be used can be appropriately selected. For example, about 0.01 to about 3 mol is sufficient per 1 mol of the compound of formula '1)', and more preferably about 0.01 to about 3 mol is sufficient. .1 to about 2
The amount used is on the order of moles. Further, the amount of halogen to be used after treatment with a methylating agent is sufficient to be used in an amount of about 1 to about 20 moles per mole of the above-mentioned methylating agent.
For example, a usage amount of about 2 to about 10 moles can be more preferably employed. The treatment with the above-mentioned chilling agent and halogen is
It is preferably carried out in the presence of an inert organic solvent, such as ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, benzene, toluene, n-hexane, and aliphatic or aromatic hydrocarbons. be able to.

These solvents can be used alone or in the form of a mixture of two or more. There is no particular restriction on the amount of these solvents used, but for example, the amount used may be about 2 to about 10 times the weight of the compound of formula '11', and about 5 times the weight of the compound of formula '11'.
An amount of about 5 to about 5 times the weight can be more preferably employed. In the present invention, 1-acetyl-1-halo-2,6,6-trimethyl-4 of formula '4} which can be formed as described above
- 4-ethylenedioxycyclohexane can be isolated if desired. For example, the reaction product reacted with the halogen is injected into water, and a suitable solvent such as n-hexane, benzene, toluene, ether,
By extracting with ethyl acetate, chloroform, methylene chloride, carbon tetrachloride, etc., and neutralizing, washing with water, drying and concentrating the solvent phase, the compound of formula (1) can be obtained in high yield and purity. If desired, further purification can be carried out using vacuum distillation, column chromatography, or other known means. In the present invention, for example,
1-acetyl-1-halo2,6,6-trimethyl-4,4-ethylenedioxycyclohexane of the formula '4} which can be obtained as described above is also an oily compound not described in the literature, for example 1 -The boiling point of the bromine body is Hg on the rudder ~ 9/0.08 side.

Its infrared and nuclear magnetic resonance spectra are shown in Examples below. In the present invention, a compound of formula [1r] in which R in formula '1' is a methyl group can be obtained by subjecting a compound of formula '41, which can be obtained as described above, to a dehydrohalogenation reaction in the presence of a base, for example. can be easily produced with high yield and high selectivity.

The reaction may be carried out by bringing the compound of formula '41 Ihi into contact with a base in the presence or absence of a solvent. The reaction can be carried out, for example, at room temperature to about 200 pm, and at room temperature to about 150 pm.
A temperature condition of about 0.degree. C. can be more preferably employed. The reaction time can also be selected appropriately depending on the base used, reaction temperature, etc.
For example, it can be carried out for about 1 to about 150 hours.
As the base used in the reaction, lithium carbonate-lithium halide, aniline or its derivatives, pyridine or its derivatives, diazabicyclo derivatives, etc. can be used. Specific examples of these include salts such as lithium carbonate-lithium chloride and lithium carbonate-lithium bromide; aniline such as aniline, N.N-dimethylaniline, N.N-diethylaniline, N-methylaniline, and N-ethylaniline; Its derivatives: DBU (1,8-diazapicyclo[5,3,0]-7-undecene), DBN (1,
5-diazabicyclo[4.3.0]-5-nonene), D
Examples include diazapicyclo conductors such as B○ (1.4-diazabicyclo[2.2.2]octane). The amount of these bases to be used is, for example, about 1 to about 50 mol per 1 mol of the compound of formula '4-, which is sufficient,
About 2 to about 20 moles can be more preferably employed. or,
Examples of solvents when performing the above dehydrohalogenation reaction in the presence of a solvent include dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, benzene,
Examples include toluene. These can be used alone or in the form of a mixture of multiple types. There is no particular restriction on the amount of the solvent to be used, but for example, an amount of about 1 to about 100 times the weight of the compound of formula '4} can be exemplified, and about 5 to about 5 times the weight of the compound. can be more preferably employed. Compounds of formula [1}'' that can be formed in this way can be prepared, for example, by injecting the dehydrohalogenation reaction product into water and using a suitable solvent such as n-hexane, benzene, toluene, ether, ethyl acetate, chloroform, It can be extracted with a solvent such as methylene chloride and carbon tetrachloride, and the solvent phase can be isolated, for example, by washing with hydrochloric acid, neutralizing, washing with water, drying and concentrating.

If desired, further purification can be carried out using, for example, vacuum distillation, column chromatography, or other known purification means. In the present invention, the compound 1- of formula {1}'' obtained as described above, in which R is a methyl group,
Acetyl-2,6,6-trimethyl-4,4-ethylenedioxy-1-cyclohexene is also an oily compound described at the end of the literature, and its boiling point is 82-83°C/0.05 Hg.

Its infrared, nuclear magnetic resonance and mass spectra are shown in Examples below. Furthermore, formula '11'' which is not described in this document
It was found that the compound has a unique floral aroma and is a long-lasting aroma component. According to the present invention, for example, an acetylcyclohexenone ketal represented by the above formula 'U obtained as described above, in which R represents a hydrogen atom or a methyl group, is contained as an active ingredient. A characteristic long-lasting aroma imparting or modulating agent can be provided.

The compound of formula [1} is unique as a long-lasting aroma imparting or modulating agent capable of imparting a long-lasting floral aroma in a wide range of fields such as cosmetics, cosmetics, and health/hygiene/pharmaceuticals. It was found that it has certain characteristics. Thus, for example, fragrances, tobacco, various cosmetic creams, tonics, lotions, hair and hair nourishing products, soaps and detergents, toiletries, dust paper, antiperspirants, depilatory products and other health products.・It is useful as a unique long-lasting aroma imparting or modulating agent in a wide range of fields such as hygiene and pharmaceuticals.

Hereinafter, several aspects of the present invention will be explained in more detail with reference to Reference Examples and Examples. Reference Example 1 Production of 2-trimethylsilyloxy-4-methoxy-1,3-butadiene 250 ml of triethylamine and 2 ml of zinc chloride
At room temperature, 225 ml of trimethylsilyl chloride and 1 ml of 4-methoxy-3-buten-2-one were added to a suspension of 5 ml of trimethylsilyl chloride at room temperature.
A solution of 600 ml of benzene was added dropwise in 1 hour.

After that, it reacts for 2 feedings at 60k0. After completion of the reaction, the reactants were poured into 6 ether bottles and placed in a Celite furnace. By concentrating the furnace liquid and distilling the resulting iso clear water under reduced pressure,
Pure 2-trimethylsilyloxy-4-methoxy-11
131 g (76%) of 3-butadiene are obtained. Boiling point: 43
〜44oo/3佽Hg Nuclear magnetic resonance spectrum (CC14): 60.20 (group,
s), 3.54 (3 days, s), 3.97 (2 days, bro
ad s), 5.22 (IH, d, J=1 is Z), 6.
74 (IH, d, J = 12 Hz) Example 1 Preparation of 1-acetyl-6,6-dimethyl-4,4-ethylenedioxy-1-cyclohexene In a 300' autoclave, 2-trimethylsilyloxy-4-methoxy 1 - Charge 100 m of 3-butadiene and 20 m of mesityl oxide, and react at 18,000 mC for 2 hours.

After cooling, the reactant was added to a mixture of 18.0 m of ethylene glycol, 1.0 m of p-toluenesulfonic acid and 500 M of benzene, and reacted for 30 minutes by azeotropic method at 80 mm. After the reaction is completed, the reaction product is washed with sodium carbonate water. The benzene layer is washed with water, M is 04, dried and concentrated, and the resulting residue is distilled under reduced pressure to obtain pure 1-acetyl-6,6-dimethyl-4,4-ethylenedioxy-1-cyclohexene at 28. Get 0 nights (67%). Boiling point: 80-81q0
/0.05 Hg Rf (Si02): 0.27 (n-hexane/ethyl acetate = 3/1) Infrared absorption spectrum (liquid film): 1665,
1620, 1090 skin-I nuclear magnetic resonance spectrum (CD
C13): 61.26 (bait, s), 1.68 (ga, s)
, 2.27 (phantom, s), 2.50 (2 days, d, J=Niji Se), 3.95 (grind, s), 6.67 (IH, t, J=4
Hz) Mass spectrum: m/e210 (M+), 195
, 167, 10 ku 107, 87, 86 81, 4 & 4
2,41 legs A solution consisting of 30 minutes of 2-trimethylsilyloxy-4-methoxy-1,3-butadiene, 10 hours of mesityl oxide, and 100 minutes of xylene was reacted at 150 hours for 15 hours.

After the reaction is completed, the reaction product is concentrated, and to the resulting residue are added 8 parts of ethylene glycol, 0.5 parts of p-toluenesulfonic acid, and 100 parts of benzene, and the mixture is reacted for 1 hour under refluxing benzene. After cooling, the reaction product is washed with sodium carbonate water and the benzene layer is separated. The benzene layer was washed with water, dried with M-04, concentrated, and the resulting residue was distilled under reduced pressure to obtain a pure product.
-Acetyl-6,6-dimethyl-4,4-ethylenedioxy-1-cyclohexene was obtained in an amount of 11.0 min (52%). Example 2 Production process of 1-acetyl-1-promo-2,6,6-trimethyl-4,4-ethylenedioxycyclohexane In a suspension of 15.0% cuprous chloride and 200% diethyl ether under a nitrogen atmosphere. While cooling at 0°C, an ether solution of methyllithium (1.0 mmol/) 150' was added, and the mixture was reacted at the same temperature for 30 minutes.

Next, a solution of 40 ether of 1-acetyl-6,6-dimethyl-4,4-ethylenedioxy-1-cyclohexene (10.5%) was added to the above solution at 0°C, and the mixture was reacted at the same temperature for 4 hours. . Furthermore, a solution of 40% of benzene and 24% of bromine was added to the above solution while cooling at -60°C, and the mixture was reacted at 0°C for 3 minutes. After the reaction is completed, the reactant is poured into heavy sodium water,
After washing, separate the ether layer. The ether layer is washed with Hypo water, washed with heavy sodium chloride, washed with water, dried with MgSO4, and then concentrated. By distilling the obtained residual bamboo under reduced pressure, pure product 1
-acetyl-1-bromo-2,6,6-trimethyl-4
・4-ethylenedioxycyclohexane for 13.4 nights (
88%). Boiling point: 92-9yo/0.03 skin Hg Rr (Si02): 0.41 (n-hexane/ethyl acetate = 8/1) Infrared absorption spectrum (liquid film): 16901
090ka-1 nuclear magnetic resonance spectrum (CDC13): 6
1.06 (ga, s), 1.22 (thin, d, J=7HZ)
, 1.47 (group, s), 1,3-2.7 (group), 2.7
1 (shine, s), 3.85 (calm, s) [B' Under a nitrogen atmosphere, in a mixture of 0.36 m of metallic magnesium and 40 ether of methyl iodide at room temperature, [Methylmagnesium iodide is prepared by dropping the solution and then reacting for 3 minutes.

To this Grignard reagent solution, 1.0 mol of cuprous iodide was added, and then, under cooling at 0°C, 2.1 mol of 1-acetyl-6,6-dimethyl-4,4-ethylenedioxy-1-cyclohexene was added. 50 [solution was added dropwise over 1 hour.
After further reaction at the same temperature for 4 hours, the reaction solution was cooled to -40 qo, a benzene low' solution containing 4.0 bromine was added, and 0
Incubate at ℃ for 3 minutes. After the reaction is completed, the reactant is poured into sodium hydroxide solution, washed, and the ether layer is separated. After washing the ether layer with water, washing with heavy water, washing with water, and drying with M-04,
Concentrate. The obtained residue was subjected to silica gel chromatography (100
Evening) By purifying with [n-hexane/ethyl acetate = 6/1], pure 1-acetyl-1-from-2 was obtained.
- Obtain 2.9 g (82%) of 6,6-trimethyl-4,4-ethylenedioxycyclohexane. Example 3 Production wind of 1-acetyl 2,6,6-trimethyl-4,4-ethylenedioxy-1-cyclohexene 1-acetyl-1-from 2,6,6-trimethyl-4,4-ethylenedioxycyclohexane 12.2 A mixture of 4.2 liters of lithium chloride, 7.4 liters of lithium carbonate and DMFIOO was reacted at 100° C. for 2 hours.

After cooling, 200 g of ether was added to the reaction mixture and filtered. Add water to the furnace solution and separate the ether layer. The ether layer is washed with water, dried with M Trout 04, and then concentrated. The resulting residue was distilled under reduced pressure to obtain 7.0 units (78%) of pure 1-acetyl-1-from-2,6,6-trimethyl-4,4-ethylenedioxy-1-cyclohexene.
Boiling point: 82-83 o/0.05 Hg Rf (Si02): 0.28 (n-hexane/ethyl acetate: 3/1) Infrared absorption spectrum (liquid film): 169u
lo90-1 nuclear magnetic resonance spectrum (CDC13):
61.16 (thin, s), 1.63 (3 days, s), 1.6
7 (2 days, s), 2.26 (2 days, s), 2.32 (chichi, s), 4.96 (4 days, S) Mass spectrum: m/
e224 (M 10), 209, 181, 130123 9
F 87, 80 43 42, 41 (B' 1-acetyl-1-from-2,6,6-trimethyl-4,4-ethylenedioxycyclohexane 3.0 yen, DBU (1.
8-diazabicyclo[5.3.0]-7-undecene)
7.5 minutes and a solution consisting of 20 pieces of toluene at 100°C.
React for 2 hours.

After the reaction is completed, the reaction mass is washed with cold INHCI water and the toluene layer is separated. The toluene layer is washed with heavy sodium chloride, washed with water, dried in M bag 04, and then concentrated. The obtained residue was subjected to silica gel column chromatography (100 min) [n-hexane/ethyl acetate=
6/1], pure 1-acetyl-
1.5 hours (68%) of 2,6,6-trimethyl-4,4-ethylenedioxy-1-cyclohexene are obtained. Example 4, Usage Example (Part 1) Manufacturing Prescription of Floral Note Fragrance Composition Example Weight (of linalool)
75 linalyl acetate
60 phenylethyl alcohol
150 10% Aldehyde C-10 (diethyl phthalate) 25 10% Aldehyde C-11 undecylenic (diethyl phthalate)
60 pendyl acetate
250 citronellol
60 nerol
25 Geraniol 45
Phenylethyl acetate 35 Citronellyl acetate 25 Dimethylbenzyl carbinyl acetate 15 Hydroxycitronellal 45 Lilial
15 Absolute diasmine 10 Hexyl cinnamic aldehyde 75 Sandalwad oil
10 musk ketones
20 total 1000 Composition 1 mixed according to the above prescription example
The composition obtained by adding 000 1-acetyl-6,6-dimethyl-4,4-ethylenedioxy-1-cyclohexene has a modified floral note, especially a rose fragrance, from the original composition. It lifts the fragrance, adds honey-like sweetness to the entire fragrance composition, and enhances the bouquet effect.

In this example, 1-acetyl-6,6-dimethyl-4,
When 4-ethylenedioxy-1-cyclohexene is replaced by 1-acetyl-2,6,6-trimethyl-4,4-ethylenedioxy-1-cyclohexene, the composition is also modified and improved from the original composition. Lifts up floral notes. (Part 2) Manufacturing recipe for tobacco flavor composition Example Weight (1-acetyl-2,6,6-trimethyl-4,4-ethylenedioxy-1-cyclohexene 1.0 fusel wine oil 1.0 cis-3-hexenol 1.0p-methyl-acetophenone 1.010% 8-ionone (ethanol) 0.55% 8-ionone (ethanol) 0.5 rum
5.0 eta/r
990 total 1000 According to the above prescription example, 10 parts of the mixed composition was added to 100 parts of the mixed composition.
Cigarettes are prepared using flavored tobacco.

The taste of the resulting cigarette is reminiscent of a weak caramel and malt-like odor and a persistent chigusa-like aroma. In this example, 1-acetyl-2,6,6-trimethyl-4,4
-ethylenedioxy-1-cyclohexene to 1-acetyl-6,6-dimethyl-4,4-ethylenedioxy-1
- Substituting cyclohexene also has the same effect.

Claims (1)

[Claims] 1 Acetyl cyclohexenone ketals represented by the following formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ However, in the formula, R represents a hydrogen atom or a methyl group. 2 1-acetyl-6,6-dimethyl-4,4 represented by the following formula (1)' ▲There are mathematical formulas, chemical formulas, tables, etc.▼
-Ethylenedioxy-1-cyclohexene is treated with a methylating agent, then reacted with a halogen, and then subjected to a dehydrohalogenation reaction in the presence of a base. 1-acetyl-2,6,6-trimethyl- represented by ▼
Method for producing 4,4-ethylenedioxy-1-cyclohexene. 3 Formula (2) below ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, in the formula, R' represents an alkyl group of C_1 to C_5,
The heated reaction product of 2-trimethylsilyloxy-4-alkoxy-1,3-butadiene represented by the following formula (3), ▲mathematical formula, chemical formula, table, etc. is available. 1-Acetyl-6,6-dimethyl-4,4 is reacted with ethylene glyco in the presence of a catalyst, resulting in the following formula (1)' ▲ Numerical formula, chemical formula, table, etc. ▼
-Ethylenedioxy-1-cyclohexene is treated with a methylating agent, then reacted with a halogen, and then subjected to a dehydrohalogenation reaction in the presence of a base. 1-acetyl-2,6,6-trimethyl- represented by ▼
Method for producing 4,4-ethylenedioxy-1-cyclohexene. 4 Formula (1) below ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, in the formula, R represents a hydrogen atom or a methyl group. Sexual aroma imparting or modulating agent.