JP4950633B2 - Process for producing camphorenylcyclohexenol compound - Google Patents

Description

  The present invention relates to a method for producing a campforenyl cyclohexenol compound, a campforenyl cyclohexenol compound, a campforenyl cyclohexenone compound, and a fragrance composition containing these compounds.

  Conventionally, as a method for synthesizing a camphorenylcyclohexenol compound having a sandalwood fragrance, as described in Patent Document 1, a starting material camphorenal is reacted with piperidine under an acid catalyst. There has been proposed a method in which enamination is carried out, followed by reaction with an alkyl vinyl ketone under an acid catalyst, followed by an intramolecular aldol reaction under an acid catalyst to form a campforenyl cyclohexenone compound, and finally reduction with a reducing agent.

US Pat. No. 5,189,003

However, the method for synthesizing the camphorenylcyclohexenol compound described in Patent Document 1 has drawbacks such as a large number of reaction steps, an unstable alkyl vinyl ketone as a raw material on the way, and easy polymerization. There is a problem that it is difficult to use industrially.
With the diversification of demands for flavoring products such as various cosmetics, cleaning agents, and fragrances in recent years, it is extremely important to find new fragrance materials. The fragrance of a fragrance material is generally greatly different depending on the slight difference in the structure of the compound. In order to obtain a new fragrance having various fragrances, various compounds having slightly different structures are synthesized, and It is extremely important to consider the aroma. The various camphorenylcyclohexenol compounds disclosed in Patent Document 1 are insufficient to develop the characteristics of natural sandalwood, and the development of compounds with a higher texture of naturalness is desired.

The present invention is intended to solve the above-described problems of the prior art, an industrial production method of a campforenyl cyclohexenol compound, a campforenyl cyclohexenol compound and a campforenyl cyclohexenone compound, It is another object of the present invention to provide a fragrance composition containing them, particularly a fragrance composition that expresses the characteristics of sandalwood with a high natural texture.
As a result of intensive studies, the present inventors have made a camphorenyl cyclohexenol compound react with a β-ketoester that is industrially available as a raw material on the way and an α, β-unsaturated aldehyde in the presence of a base catalyst, It has been found that since the campforenylcyclohexenone compound derived thereby can be reduced, it can be produced easily and stably, and industrial production becomes possible.
That is, the present invention relates to a β-ketoester represented by the following general formula (1) (hereinafter referred to as β-ketoester (1)) and an α, β-unsaturated aldehyde represented by the following general formula (2). (Hereinafter referred to as α, β-unsaturated aldehyde (2)) in the presence of a basic compound, and a camphorenyl cyclohexenone compound (hereinafter referred to as camphorene) represented by the following general formula (3). Nylcyclohexenone compound (3)), and a camphorenylcyclohexenol compound (hereinafter, camphorenyl) represented by the following general formula (4) obtained by reducing the compound in the presence of a reducing agent. A method for producing a cyclohexenol compound (4)) is provided.

(Wherein R ¹ and R ² each independently represents hydrogen, a linear or branched alkyl group, an alkenyl group or an alkynyl group, and R ³ represents a linear or branched alkyl group, alkenyl group or Represents an alkynyl group.)

In addition, the present inventors synthesized various compounds and examined the effects of the fragrance and the blended fragrance, and that the specific camphorenylcyclohexenol compound has an excellent natural sandalwood fragrance, And certain camphorenylcyclohexenone compounds have been found to have an excellent cumin oil-like aroma.
That is, the present invention relates to a campforenyl cyclohexenol compound represented by the general formula (6) (hereinafter referred to as campforenyl cyclohexenol compound (6)) and a campforenyl cyclohexenone compound (hereinafter referred to as campfore). Nylcyclohexenone compound (5)), and a fragrance composition containing these compounds alone or in combination of two or more.

(In the formula, R ⁴ represents a linear or branched alkyl group, alkenyl group or alkynyl group, and R ⁵ represents hydrogen or a substituent represented by R ^4. )

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method applicable industrially can be provided by manufacturing a camphorenyl cyclohexenol compound and a camphorenyl cyclohexenone compound easily and stably. Further, a fragrance composition using a campforenyl cyclohexenol compound alone or in combination of two or more can exhibit the characteristics of sandalwood with a high natural texture, and a campforenyl cyclohexenone compound alone or 2 A perfume composition using more than one species can provide a cumin oil-like aroma.

[Method for producing camphorenylcyclohexenol compound]
The campforenyl cyclohexenol compound (4) is obtained, for example, by reacting a β-ketoester (1) with an α, β-unsaturated aldehyde (2) in the presence of a basic compound, and the resulting camphorenylcyclohexenone. It can be produced by reducing the compound (3) in the presence of a reducing agent.

Here, in the formula, R ¹ and R ² each independently represent hydrogen, a linear or branched alkyl group, an alkenyl group, or an alkynyl group. Among them, R ¹ represents a linear or branched alkyl group, alkenyl. Group or alkynyl group is preferable, methyl group, ethyl group, or propyl group is more preferable, and methyl group is particularly preferable. R ² is preferably hydrogen or a substituent represented by R ¹ , more preferably hydrogen, a methyl group, an ethyl group, or a propyl group, and particularly preferably hydrogen. R ¹ and R ² may be the same or different. R ³ represents a linear or branched alkyl group, alkenyl group or alkynyl group, preferably a methyl group, an ethyl group or a propyl group.
More specifically, the production method of the camphorenylcyclohexenol compound (4) of the present invention can be represented by the following reaction formula.

  First, a β-keto ester (1) and an α, β-unsaturated aldehyde (2) are reacted in the presence of a basic compound to obtain a camphorenyl cyclohexenone compound (3). As a method for allowing a basic compound to act on β-ketoester (1) and α, β-unsaturated aldehyde (2), β-ketoester (1) and α, β-unsaturated aldehyde (2) are previously dissolved in a solvent. The method of adding a basic compound to the reaction solution obtained by making it carry out is mentioned.

The charging ratio of β-ketoester (1) and α, β-unsaturated aldehyde (2) (β-ketoester (1) / α, β-unsaturated aldehyde (2), molar ratio) improves the yield, From the viewpoint of increasing the reactivity, it is preferably 1 to 3, and more preferably 1 to 1.5.
As the solvent, an alcohol-based solvent is preferable from the viewpoint of increasing the reactivity. Examples of alcohol solvents include methanol, ethanol, propanol, butanol, pentanol, hexanol and the like.

The concentration of the reaction solution (the number of moles of β-ketoester (1) relative to 1 liter of solvent) is preferably 0.1 to 2 in order to improve the yield and increase the reactivity, and 0.5 to 1 More preferably, it is .5.
The reaction temperature is −10 to 10 ° C., preferably −5 to 5 ° C. from the viewpoint of suppressing the formation of by-products and increasing the reaction rate, and it is preferable to raise the temperature to the reflux temperature after the addition is completed.

  Examples of basic compounds include metal alkoxides. Among the metal alkoxides, one or more selected from the group consisting of sodium methoxide, sodium ethoxide and potassium tertiary butoxide are preferable. The addition amount of the basic compound is preferably 10 to 50 mol%, more preferably 20 to 30 mol%, relative to 1 mol of the β-ketoester (1).

  The camphorenylcyclohexenone compound (3) produced by the above reaction is neutralized by adding an acid such as hydrochloric acid, sulfuric acid or nitric acid to the reaction solution after the reaction, and then purified by silica gel column chromatography or distillation. And can be isolated. The reaction can be terminated at the time when the α, β-unsaturated aldehyde (2) disappears by gas chromatography, thin layer liquid chromatography, or the like.

Next, the camphorenylcyclohexenol compound (4) is obtained by reducing the obtained camphorenylcyclohexenone compound (3) in the presence of a reducing agent.
The reduction reaction can be performed using a known method without any particular limitation. Examples of the reducing agent include metal hydride compounds, among which lithium alumina hydride, sodium borohydride, and the like can be suitably used.

[Camphorenyl cyclohexenone compound and camphorenyl cyclohexenol compound]
The camphorenylcyclohexenone compound of the present invention is represented by the following general formula (5), and the camphorenylcyclohexenol compound of the present invention is represented by the following general formula (6).

In the formula, R ⁴ represents a linear or branched alkyl group, alkenyl group or alkynyl group, and from the viewpoint of fragrance, a methyl group, an ethyl group or a propyl group is preferable, and a methyl group is more preferable. R ⁵ represents hydrogen or a substituent represented by R ⁴ , preferably hydrogen, methyl group, ethyl group, or propyl group, more preferably hydrogen.

The campforenyl cyclohexenone compound (5) represented by the general formula (5) is a compound included in the campforenyl cyclohexenone compound (3), and is represented by R ⁴ in the general formula (5). As mentioned above, it is a compound in which a substituent in which hydrogen is removed from R ¹ in the general formula (3) is introduced, has a cumin oil-like fragrance, and is used alone or in combination with other components. It can be used as a perfuming ingredient.

The campforenyl cyclohexenol compound (6) represented by the general formula (6) is a compound included in the campforenyl cyclohexenol compound (4), and R ⁵ in the general formula (6) As shown, it is a compound in which a substituent from which hydrogen has been removed is introduced into R ¹ in the general formula (4), and has a natural sandalwood fragrance that is not found in conventional synthetic products. The compound can be used alone or in combination with other ingredients as a perfuming ingredient for soaps, champignans, detergents, cosmetics, fragrances and the like.

  Furthermore, among the campforenyl cyclohexenol compound (6), a cis-isomer compound in which the camphorenyl group and the hydroxyl group represented by the following general formula (7) are in a cis conformational relationship is preferable from the viewpoint of fragrance.

In the formula, R ⁴ and R ⁵ are the same as described above.

[Perfume composition]
In the fragrance composition of the present invention, the campforenyl cyclohexenone compound (5) and the campforenyl cyclohexenol compound (6) are used alone or in combination with other commonly used fragrance ingredients or blended fragrances having a desired composition. It can be obtained by mixing and blending seeds or more. In particular, it is preferable from the point of fragrance to use the campforenyl cyclohexenol compound (6) alone. Furthermore, among the campforenyl cyclohexenol compound (6), a cis-isomer compound in which the camphorenyl group and the hydroxyl group represented by the general formula (7) are in a cis conformational relationship is preferable from the viewpoint of fragrance.
The amount of the camphorenylcyclohexenone compound (5) and the camphorenylcyclohexenol compound (6) in the fragrance composition of the present invention depends on the type of the blended fragrance, the type of the target fragrance, and the strength of the fragrance. Although different, 0.1-90 mass% is preferable and 1-40 mass% is more preferable. Examples of the fragrance component that can be used in combination with the camphorenylcyclohexenone compound (5) and the camphorenylcyclohexenol compound (6) of the present invention include hydrocarbons, alcohols, phenols, esters, Examples thereof include natural essential oils such as carbonates, aldehydes, ketones, acetals, ethers, nitriles, carboxylic acids, and lactones, natural extracts, and synthetic fragrances.

[Identification of sample]
The structure of the compound obtained in the example was identified by nuclear magnetic resonance spectrum ( ¹ H-NMR, ¹³ C-NMR). The nuclear magnetic resonance spectrum was measured by Mercury 400 manufactured by Varian, using chloroform-d as a solvent.

Example 1: Synthesis of 2-methyl-4- (2 ', 2', 3'-trimethyl-3'-cyclopenten-1'-yl) -2-cyclohexen-1-one Dimroth, thermometer, magnetic stir bar To a 1 L 4-neck flask equipped with 2- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-propenal (66.1 g, 363.3 mmol), propionyl Methyl acetate (48.2 g, 363.3 mmol) and 363 ml of ethanol were added. Under a nitrogen atmosphere, potassium tertiary butoxide (2.2 g, 18 mmol) was added while keeping the temperature in the tank at 0 ° C., and the mixture was stirred at 0 ° C. for 30 minutes. After stirring for 30 minutes, potassium tertiary butoxide (8.6 g, 72.0 mmol) was further added, the temperature in the tank was raised to 90 ° C., and the reaction was carried out for 7 hours under reflux. After completion of the reaction, the temperature in the tank was cooled to room temperature, and then the solvent was distilled off under reduced pressure. 150 ml of ether was added to the residue obtained by distilling off the solvent, neutralized with 100 ml of 1M hydrochloric acid, transferred to a separatory funnel, 3 times with 30 ml of 1M aqueous sodium hydroxide solution, and 2 times with 100 ml of saturated brine. Washed twice, separated into layers, and extracted. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain 86.9 g of a crude product. By purifying by simple distillation, 54.7 g of the desired product represented by the following chemical formula (I) could be obtained.

The identification result of the obtained target product, 2-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-one, was as follows. It is as follows.
¹ H-NMR (CDCl ₃ ) δ 0.96 (s, 3 H, minor), 0.97 (s, 3 H, major), 1.09 (s, 3 H, minor), 1.11 (s, 3 H, major), 1.60 -1.62 (m), 1.77-1.79 (m), 5.22-5.25 (m), 6.70-6.72 (m, 1 H, minor), 6.88-6.89 (m, 1 H, major).
¹³ C-NMR (CDCl ₃ ) δ 13.02, 16.71, 16.76, 20.18, 20.45, 27.74, 28.04, 47.24, 47.67, 53.30, 53.80, 121.31, 121.47, 134.74, 135.34, 148.57, 148.69, 149.94, 150.09, 199.99, 200.05 .

Example 2: Synthesis of 2-methyl-4- (2 ', 2', 3'-trimethyl-3'-cyclopenten-1'-yl) -2-cyclohexen-1-ol Dimroth, thermometer, magnetic stir bar Then, lithium alumina hydride (2.7 g, 56.9 mmol) and 304 ml of ether were added to a 500 ml four-necked flask equipped with a dropping funnel, and the temperature in the tank was cooled to 0 ° C. 2-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-one while keeping the temperature in the bath at 0 ° C. in a nitrogen atmosphere A solution obtained by diluting (24.8 g, 113.7 mmol) in 50 ml of ether was gradually dropped from the dropping funnel into the tank over 40 minutes. After completion of the dropwise addition, the temperature was raised to 50 ° C., and the mixture was stirred for 1.5 hours under reflux. After completion of the reaction, the temperature in the tank was cooled to 0 ° C., 75 ml of 10% by mass sulfuric acid was dropped from the dropping funnel into the tank over 10 minutes to neutralize, and then the organic layer was extracted using a separatory funnel. The aqueous layer was extracted twice with 50 ml of ether, and the combined organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 27.8 g of a crude product. By fractionation by silica gel column chromatography (ethyl acetate: hexane = 1.5: 8.5 (volume ratio)), the following chemical formula, which is a cis-isomer compound in which the camphorenyl group and the hydroxyl group have a cis conformational relationship ( 6.78 g of the expected product represented by II) was obtained.

Identification of cis-form compound of 2-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-ol which is the obtained target product The results are as follows.
¹ H-NMR (CDCl ₃ ) δ 0.90 (s, 3 H, minor), 0.93 (s, 3 H, major) 1.08 (s, 3 H, minor), 1.13 (d, 3 H, major) 1.59-1.61 (m), 1.79-1.80 (m) 3.88-3.95 (m), 5.21 (bs), 5.52 (bs, 1 H, minor), 5.71 (bs, 1 H, major).
¹³ C-NMR (CDCl ₃ ) δ 13.04, 18.79, 19.99, 27.75, 33.74, 35.55, 54.63, 73.35, 121.27, 129.29, 134.14.

Example 3: Synthesis of 6-methyl-4- (2 ', 2', 3'-trimethyl-3'-cyclopenten-1'-yl) -2-cyclohexen-1-one Dimroth, thermometer, magnetic stir bar To a 300 ml four-necked flask equipped with 2- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-propenal (29.38 g, 167.2 mmol), 2 -Ethyl methylacetoacetate (25.10 g, 167.2 mmol) and 167 ml of ethanol were added. Under a nitrogen atmosphere, potassium tertiary butoxide (0.99 g, 8 mmol) was added while keeping the temperature in the tank at 0 ° C., and the mixture was stirred at 0 ° C. for 30 minutes. After stirring for 30 minutes, potassium tertiary butoxide (3.99 g, 33 mmol) was further added, the temperature in the tank was raised to 90 ° C., and the reaction was carried out for 7 hours under reflux. After completion of the reaction, the temperature in the tank was cooled to room temperature, and then the solvent was distilled off under reduced pressure. 150 ml of ether was added to the residue obtained by distilling off the solvent, neutralized with 100 ml of 1M hydrochloric acid, transferred to a separatory funnel, 3 times with 30 ml of 1M aqueous sodium hydroxide solution, and 2 times with 100 ml of saturated brine. Washed twice, separated into layers, and extracted. The organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain 40.96 g of a crude product. After purification by silica gel column chromatography (ethyl acetate: hexane = 1.5: 8.5 (volume ratio)), further purification by Kugel distillation (0.3 mmHg, 90 ° C. to 120 ° C.) 17.5 g of the desired product represented by the following chemical formula (III) could be obtained.

The target product obtained, 6-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-one, is cumin oil-like. Spicy green aroma. The identified results are as follows.
¹ H-NMR (CDCl ₃ ) δ 0.96 (s, 3 H, minor), 0.97 (s, 3 H, major), 1.09 (s, 3 H, minor), 1.11 (s, 3 H, major), 1.60 -1.62 (m), 1.77-1.79 (m), 5.22-5.25 (m), 6.70-6.72 (m, 1 H, minor), 6.88-6.89 (m, 1 H, major).
¹³ C-NMR (CDCl ₃ ) δ 13.02, 16.71, 16.76, 20.18, 20.45, 27.74, 28.04, 47.24, 47.67, 53.30, 53.80, 121.31, 121.47, 134.74, 135.34, 148.57, 148.69, 149.94, 150.09, 199.99, 200.05 .

Example 4: Synthesis of 6-methyl-4- (2 ', 2', 3'-trimethyl-3'-cyclopenten-1'-yl) -2-cyclohexen-1-ol Dimroth, thermometer, magnetic stir bar Then, lithium alumina hydride (0.87 g, 18.3 mmol) and 117 ml of ether were added to a 300 ml four-necked flask equipped with a dropping funnel, and the temperature in the tank was cooled to 0 ° C. 6-Methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-one while keeping the temperature in the bath at 0 ° C. in a nitrogen atmosphere A solution obtained by diluting (8 g, 36.6 mmol) in 17 ml of ether was gradually dropped from the dropping funnel into the tank over 40 minutes. After completion of dropping, the temperature was raised to 50 ° C., and the mixture was stirred for 2.5 hours under reflux. After completion of the reaction, the temperature in the tank was cooled to 0 ° C., 30 ml of 10% by mass sulfuric acid was dropped from the dropping funnel into the tank over 10 minutes to neutralize, and then the organic layer was extracted using a separatory funnel. The aqueous layer was extracted twice with 50 ml of ether, and the combined organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure to obtain 8.2 g of a crude product. By fractionation by silica gel column chromatography (ethyl acetate: hexane = 1.5: 8.5 (volume ratio)), the following chemical formula, which is a cis-isomer compound in which a camphorenyl group and a hydroxyl group have a cis conformational relationship ( 0.35 g of the expected product represented by IV) was obtained.

The obtained target product, 6-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-ol cis-form compound, It was a natural sandal-like sandal scent. The identified results are as follows.
¹ H-NMR (CDCl ₃ ) δ 0.92 (s, 3 H), 1.01 (d, 3 H, J = 6.8 Hz), 1.08 (s, 3 H), 1.58-1.59 (m, 3 H), 3.73 ( bs), 5.21 (bs), 5.63-5.67 (m, 1 H), 5.95-5.99 (m, 1 H).
¹³ C-NMR (CDCl ₃ ) δ 13.04, 18.79, 19.99, 27.75, 33.74, 35.55, 54.63, 73.35, 121.27, 129.29, 134.14.

Example 5: Formulation example using 6-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-one The following floral type fragrance To 990 parts by mass of the composition, 6-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-one obtained in Example 3 was used. By adding 10 parts by mass, a spicy-green feeling was imparted and a floral feeling was promoted.
Further, 2-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-one obtained in Example 1 was evaluated in the same manner. However, the effects shown above could not be confirmed.

Composition of floral green type fragrance composition (parts by mass)
Bergamot Oil Italy BGF 70
Dihydromyrsenol 65
Geraniol 45
Phenylethyl alcohol 175
Phenylhexanol 120
Hexylcinnamic aldehyde 110
Benzyl acetate 30
Methyl dihydrojasmonate 90
Acetyl cedrene 120
Sandal Mysore Core (registered trademark) 20
Hexamethylhexahydrocyclopentabenzopyran 110
Heliotropin 35
Total 990

Example 6: Formulation example using 6-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-ol Floral having the following composition 6-Methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexene obtained in Example 4 was added to 955 parts by mass of a fragrance composition of woody type. By adding 45 parts by mass of a -1-ol cis-isomer compound, a new floral woody-type fragrance composition in which natural sandal feeling, sweetness, softness, warmth and volume feeling are emphasized was obtained.
A similar evaluation of 2-methyl-4- (2 ′, 2 ′, 3′-trimethyl-3′-cyclopenten-1′-yl) -2-cyclohexen-1-ol obtained in Example 2 was made. Although it performed using the cis-isomer compound, the effect shown above was not able to be confirmed.

Composition of floral woody type fragrance composition (parts by mass)
Orange oil 20
Dihydromyrsenol 30
Geraniol 85
Phenylethyl alcohol 175
Phenylhexanol 120
Hexylcinnamic aldehyde 110
Methyl dihydrojasmonate 90
Acetyl cedrene 170
Methylhexahydrocyclopentabenzopyran 120
Heliotropin 35
Total 955

  From the results of Examples 1 to 4, it was found that the camphorenylcyclohexenol compound and the camphorenylcyclohexenone compound can be industrially produced by the production method of the present invention. In addition, from the results of Examples 3 and 4, the campforenyl cyclohexenol compound or camphorenyl cyclohexenone compound of the present invention has a sandalwood fragrance or cumin oil-like fragrance having a high naturalness texture, respectively. The results of Examples 5 and 6 showed that these compounds are very useful as a flavoring component.

  According to the production method of the present invention, a camphorenylcyclohexenol compound and a camphorenylcyclohexenone compound can be easily and stably produced, and thus industrial production is possible. Further, the fragrance composition using the campforenyl cyclohexenol compound obtained by the production method of the present invention alone or in combination of two or more can express the characteristics of sandalwood having a high natural texture, A fragrance composition using a nylcyclohexenone compound alone or in combination of two or more can provide a cumin oil-like fragrance.

Claims (10)

Β-ketoester represented by the general formula (1):

And an α, β-unsaturated aldehyde represented by the general formula (2):

Are reacted in the presence of a basic compound, and a camphorenylcyclohexenone compound represented by the general formula (3):

And a camphorenylcyclohexenol compound represented by the general formula (4) obtained by reducing the compound in the presence of a reducing agent:

Manufacturing method.
(Wherein R ¹ and R ² each independently represents hydrogen, a linear or branched alkyl group, an alkenyl group or an alkynyl group, and R ³ represents a linear or branched alkyl group, alkenyl group or Represents an alkynyl group.) The method for producing a camphorenylcyclohexenol-based compound according to claim 1, wherein R ¹ is a methyl group, an ethyl group, or a propyl group.   The method for producing a camphorenylcyclohexenol compound according to claim 1 or 2, wherein the basic compound is a metal alkoxide.   The manufacturing method according to claim 3, wherein the metal alkoxide is one or more selected from the group consisting of sodium methoxide, sodium ethoxide, and potassium tertiary butoxide. A campforenyl cyclohexenone compound represented by the general formula (5).

(In the formula, R ⁴ represents a linear or branched alkyl group, alkenyl group or alkynyl group, and R ⁵ represents hydrogen or a substituent represented by R ^4. ) The camphorenylcyclohexenone compound according to claim 5, wherein R ⁴ is a methyl group, an ethyl group or a propyl group. A campforenyl cyclohexenol compound represented by the general formula (6).

(In the formula, R ⁴ represents a linear or branched alkyl group, alkenyl group or alkynyl group, and R ⁵ represents hydrogen or a substituent represented by R ^4. ) The camphorenylcyclohexenol compound according to claim 7, wherein R ⁴ is a methyl group, an ethyl group or a propyl group. The camphorenyl cyclohexenol compound according to claim 7 or 8, which is a cis-isomer compound represented by the general formula (7) in which a camphorenyl group and a hydroxyl group have a cis conformational relationship.

(In the formula, R ⁴ represents a linear or branched alkyl group, alkenyl group or alkynyl group, and R ⁵ represents hydrogen or a substituent represented by R ^4. )   The fragrance | flavor composition which contains the campforenyl cyclohexenone compound or camphorenyl cyclohexenol compound of Claims 5-9 individually or in combination of 2 or more types.