JPH062701B2 - Cis-2,2,3-trimethyl-6-methylene-cyclohexane derivative and process for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention has the following formula (A), which is useful as a synthetic intermediate of (±) -cis-γ-iron, which is highly valuable as a flavoring substance having an iris odor. A novel compound 2,2,3-trimethyl-6-methylene-cyclohexane derivative represented by
The present invention also relates to a method for producing the compound and use thereof.

More specifically, the present invention provides the following formula (A) However, in the formula, R represents a CHO group or a CH ₂ OH group, and is represented by: 2,2,3-trimethyl-6-methylene-
It relates to a cyclohexane derivative. The compound of the above formula (A) has an aroma and flavor of green, citrus, pine needle, fruit, and excellent durability, and includes an aroma and flavor imparting or modulating agent (improving agent and reinforcing agent of various flavor compositions. Food and drink (including favorite items), cosmetics,
It is useful in a wide range of applications such as health, hygiene, and pharmaceuticals, and the present invention also relates to such use, and further, the present invention relates to production of the compound of the above formula (A).

(b) Conventional Technology The compound of formula (A) of the present invention can be synthesized as an intermediate (±)
-Cis-γ-iron is not known to exist in iris oil, which is highly valuable as a natural flavor. The applicant is
First, a method for selectively producing only a cis-form without generation of a trans-form was established, and the compound has odor characteristics comparable to natural iris oil and a trans-form. It has been clarified that it has a much more excellent odor, and it has already been proposed in Japanese Patent Application No. 59-65094.

As described above, the above formula (A) useful as a synthetic intermediate of (±) -cis-γ-iron having high fragrance value is represented by the following formula (A) -1 Cis-γ-methylcyclocitral represented by the following formula and the following formula (A) -2 Cis-γ-methylcyclogeraniol represented by Examples of the compounds similar in structure to the compounds of the present invention include, for example, Helv, Chim. Acta, Voluman XLI, Fascicu
The following formulas (a) and (b) described in lus V (1958) No. 149, P1368. The γ-methylcyclocitral and γ-methylcyclogeraniol represented by can be mentioned, and in the known literature, these compounds of formulas (a) and (b) are d, l-γ- It has been shown to be used as a synthetic intermediate for iron. In the above process drawings, it is clarified which of the cis type and trans type compounds derived from the cyclohexane ring of the compound of formula (a), the compound of formula (b) and d, l-γ-iron. Absent.

The present inventors have described the formula (a), (b) by the method described in the literature.
As a result of synthesizing d and l-γ-iron and examining the stereoisomerism thereof, both were found to be trans-type. Further, the odor characteristics of the formulas (a) and (b) compounds have not been clarified in the document, and according to the studies by the present inventors, both the compounds of the formulas (a) and (b) It turns out that it is of no value as a fragrance substance. Further, there is no known example of using the compound of formula (a) or formula (b) as a fragrance.

(c) Problems to be Solved by the Invention From the trans-type of the above formula (a) γ-methylcyclocitral and the above formula (b) γ-methylcyclogeraniol obtained according to the disclosure of the above conventional proposal, a fragrance Only thin trans-type (±) -γ-iron can be obtained.

(d) Means for Solving Problems The present invention provides a method for synthesizing cis-type (±) -γ-iron having a high perfume value, particularly γ-methylcyclo that can be used as a synthetic intermediate for the compound. We have conducted intensive studies on a method capable of selectively synthesizing cis-forms of citral and γ-methylcyclogeraniol.

As a result, the above formula (A) -1 included in the above formula (A).
Cis-γ-methylcyclocitral represented by the following formula (3) However, in the formula, R ′ and R ″ each represent a lower alkyl group, or R ′ and R ″ together represent a lower alkylene group, and cis-2- (2-methylene-5,6) , 6-
It has been discovered that trimethylcyclohexan-1-yl) -N, N-dialkyl or -alkyleneacetonitrile can be easily and selectively synthesized by contacting it with silver nitrate in an organic solvent. And, the compound of the formula (3) is, for example, the following formula (1) 1- (3,3,4-trimethyl-1-cyclohexen-1-yl) methyl alcohol, which is easy to synthesize by itself, is added to a halogenating agent, mesylating agent or tosyl in the presence of a base in an organic solvent. Formula (2) below that can be formed by reacting with an agent In the formula, X is halogen such as Br, Cl, I, mesyloxy group (OM _S ) or tosyloxy group (O
1- (3,3,4-trimethyl-1-cyclohexen-1-yl) methylene halide or mesylate or tosylate represented by the formula (1), which represents T _S ), in an organic solvent in the presence of a base, N, N- Di-lower alkyl or lower alkylene-
It has been found that it can be easily obtained by reacting with aminoacetonitrile.

Further, cis-γ-methylcyclogeraniol represented by the above formula (A)-(2) included in the above formula (A) has the following formula (2) ′. 1- (3,3,4-trimethyl-1-cyclohexen-1-yl) methyleneoxymethylene-1-
It has been discovered that tributyltin can be easily and selectively synthesized by contacting butyllithium in an organic solvent. Then, the compound of the formula (2) ′ has, for example, the following formula (1) similar to that described above. It has been found that the compound can be easily obtained by reacting it with methylenetributyltin iodide (ICH ₂ SnBu ₃ ) in the presence of sodium hydride in an organic solvent.

Furthermore, according to the studies by the present inventors, for example, the compound of the formula (A) which can be produced as described above is
Not only are they new synthetic intermediates useful for the synthesis of (±) -cis-γ-iron, but these compounds themselves have green, citrus, pine needle, fruity aroma and flavor characteristics and excellent persistence. The compound of the formula (A) is used in various flavor compositions such as fruit-based, vegetable-based, citrus-based, spice-based, liquor-based, roast nut-based, roast beef-based, tobacco-based, flower-based, green-based, wood It has been found that the compound is a useful compound which can be incorporated into various flavoring compositions such as a milk-based flavoring composition, a milk-based flavoring composition, a fat-based flavoring composition, and the like, and can be used for producing various new flavoring compositions.

Therefore, an object of the present invention is to provide a novel synthetic intermediate of (±) -cis-γ-iron, a process for producing the same, and various novel fragrance compositions containing the compound of the formula (A) as an active ingredient. It is in.

These and many other objects and advantages of the present invention will become more apparent from the description below. An aspect of a synthesis example of the compound of formula (A) -1 and the compound of formula (A) -2 can be represented as follows when shown in a process diagram.

Formula (A) -1 Formula (A) -2 The synthesis of the compounds of formula (A) -1 and formula (A) -2 will be described in more detail by taking the above-mentioned embodiment as an example.

Synthesis Example of Formula (A) -1 Compound Synthesis of 1- (3,3,4-trimethyl-1-cyclohexen-1-yl) -methylene halide of the above formula (2) is as follows.
The above formula (1) 1- (3,3,4-trimethyl-1-cyclohexen-1-yl) -methyl alcohol is preferably halogenated, mesylated or tosylated in an organic solvent in the presence of a base. It can be easily performed by reacting with an agent.

The reaction can be preferably carried out, for example, under a temperature condition of about -78 ° to about + 150 ° C, for example, within a reaction time of about 1 to about 5 hours.

Specific examples of the organic solvent used in the reaction include ethers such as ether tetrahydrofuran. The amount of these organic solvents to be used is not particularly limited and may be appropriately selected. For example, the amount used is preferably about 1 to about 10 times by weight the amount of the compound of the formula (1). . In addition, examples of the halogenating agent, mesylating agent, and tosylating agent used in the reaction include phosphorus tribromide, phosphorus trichloride, methanesulfonyl chloride, p-toluenesulfonyl chloride, and the like.
In the example of the above process chart, an example using phosphorus tribromide as the halogenating agent is shown. The amount of these agents used can be appropriately selected and changed, but for example, the amount used in the range of about 1 to about 3 mol can be preferably exemplified with respect to the above formula (1). Furthermore, examples of the base include organic bases such as pyridine and triethylamine.
In the example of the above process diagram, an example using pyridine is shown. The amount of these bases to be used may be appropriately selected and, for example, the amount of use in the range of about 0.1 to about 2 moles relative to the compound of the formula (1) can be preferably mentioned. After the final amount of the reaction, for example, the organic layer is subjected to post-treatment such as washing with water and neutralization, and the solvent is distilled off, followed by purification using a means such as distillation or column chromatography to easily obtain the compound of the formula (2). be able to.

For example, the above formula (2) that can be obtained as described above
2- (2-methylene-5,6,6-trimethylcyclohexan-1-yl) represented by the above formula (3) from a compound
To synthesize —N, N-dialkyl or alkyleneaminoacetonitrile, for example, the compound of formula (2) is added to an organic solvent in calcium carbonate, sodium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, water. In the presence of a base such as barium oxide, N, N-
It can be easily synthesized by reacting with di-lower alkyl or lower alkylene-aminoacetonitrile.

The reaction can be preferably carried out, for example, under a temperature condition of about −78 to about + 200 ° C. and for a reaction time of about 0.5 to about 48 hours.

The amount of N, N-dilower alkyl or lower alkylene-aminoacetonitrile used in the above reaction is preferably in the range of, for example, about 1 to about 2 mol relative to the compound of the above formula (2). Can be mentioned. As the amount of the base used, for example, the amount used in the range of about 0.1 to about 10 mol relative to the compound of the above formula (2) can be preferably mentioned. Further, as the organic solvent,
Examples include dimethylformamide, tetrahydrofuran, acetonitrile, dimethylsulfoxide, toluene, ether, dioxane and the like. There is no particular restriction on the amount of these organic solvents used, and it may be appropriately selected.
The amount of the compound (2) to be used is preferably in the range of, for example, about 1 to about 100 times by weight. After completion of the reaction, for example, the reaction product is extracted with an organic solvent such as hexane, ether, or toluene, washed with water, dried, and purified by means such as column chromatography or distillation to easily obtain the compound of formula (3). You can

The cis-γ-methylcyclocitral represented by the formula (A) -1 of the present invention is easily synthesized, for example, by bringing the compound of the formula (3) obtainable as described above into contact with silver nitrate in an organic solvent. can do.

The reaction is preferably carried out in an organic solvent, and organic solvents such as tetrahydrofuran and ether can be preferably used. The reaction temperature and the reaction time can be appropriately selected depending on the solvent used, but for example, about -20 to about +
A reaction temperature of about 50 and a reaction time of about 2 to about 48 hours can be exemplified. The amount of the organic solvent used is preferably, for example, about 1 to about 100 times by weight the amount of the compound of the formula (3).

The amount of silver nitrate used in the above reaction can be appropriately selected and changed, and for example, it can be exemplified in the range of about 0.1 to about 10 mol relative to the compound of the formula (3). After the reaction,
The compound of formula (A) -1 of the present invention can be easily obtained by removing the produced crystals, separating the organic layer, drying and purifying it by means such as distillation and column chromatography.

Synthesis Example of Compound of Formula (A) -2 In the above-mentioned process chart, from the compound of formula (1) to 1-of formula (2) ′
(3,3,4-trimethyl-1-cyclohexene-1-
The formation of (yl) -methyleneoxymethylene-1-tributyltin is carried out, for example, by adding sodium hydride in an organic solvent, then adding the compound of formula (1), reacting until the generation of hydrogen ceases, and then methylene iodide. Tributyltin (I
CH ₂ SnBu ₃ ) can be added and reacted. The reaction can be performed, for example, at about -78 to about + 50 ° C, for example, for about 0.5 to about 5 hours. The methylenetributyltin iodide used here is described in J. Orgmetal. Chem. , 30
151 to 166 (1971).

The amount of sodium hydride used in the above reaction can be, for example, in the range of about 1 to about 2 mol based on the compound of the formula (1). The amount of methylenetributyltin iodide used may be, for example, in the range of about 1 to 2 mol based on the compound of the formula (1). Further, examples of the organic solvent used in the reaction include solvents such as tetrahydrofuran and ether. The amount of these organic solvents used can be appropriately selected and changed, but is, for example, about 1 to about 20 relative to the compound of the formula (1).
The amount used may be, for example, about twice the weight. After completion of the reaction, the obtained compound of the formula (2) 'can be used for the next reaction without usually isolating.

For example, the formation of the compound of formula (A) -2 of the present invention from the compound of formula (2) ′ obtained as described above is facilitated by contacting the compound of formula (2) with butyllithium in an organic solvent. Can be done. The reaction is, for example, about -78 to +3.
It can be easily carried out by reacting within a temperature range of about 0 ° C. for about 0.5 to about 5 hours.
The amount of butyllithium used in the reaction is preferably in the range of about 1 to about 2 mol based on the compound of the formula (2) '. Further, examples of the organic solvent include solvents such as ether and tetrahydrofuran. The amount of these solvents to be used may be appropriately selected and may be, for example, about 1 to about 20 times by weight the amount of the compound of the formula (2) ′. After completion of the reaction, the reaction solution is poured into an aqueous solution of ammonium chloride, extracted with, for example, hexane, washed with water, dried, and then purified by a means such as column chromatography or distillation to obtain pure formula (A) -2. The compound can be obtained.

The compound of formula (1) used in the above-mentioned production method of the compound of formula (A) of the present invention is a compound described in JP-A-57-134428 of the same applicant, which is disclosed in JP-A-57-134428. Although it can be produced by the method disclosed in JP-A-134428, it can be produced more advantageously by the improved method (Japanese Patent Application No. 60-) related to the application of the same applicant as the present application, which is preferable.

According to the improved method, 3,3,4-trimethyl-1-cyclohexene represented by the formula (b) shown in the following process diagram is used.
By hydrogenating 1-carbaldehyde, the above formula
(1) The compound can be easily produced. A process chart including the production mode of the compound of the formula (b) is shown below.

The method for synthesizing the compound of formula (1) will be described in more detail below with reference to the above process chart.

In the above process diagram, the formula (d) 2,2,3-trimethyl-
6-Hydroxymethylenecyclohexanone is commercially available or easily synthesized 2,3-dimethylcyclohexanone, for example, methylated with methyl bromide in the presence of sodium hydride and then ethyl formate in the presence of sodium methoxide. It can be easily synthesized by reacting.

From the compound of formula (d), from formula (c) 2,2,3-trimethyl-6-
To obtain (1-ethoxyethoxymethylene) cyclohexanone, the compound of formula (d) can be easily synthesized by reacting it with ethyl vinyl ether in the presence of an acid. Examples of the acid used in this reaction include phosphoric acid,
Sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, etc. can be mentioned. The amount of these acids to be used varies depending on the kind of the acid, but is, for example, about 0.5 to 5 relative to the compound of the formula (d).
A range of about 10% can be preferably exemplified.
The amount of ethyl vinyl ether used can be appropriately selected. For example, the amount is about 1 to about 1 relative to the compound of formula (d).
A range of about 0 mol can be mentioned. The reaction can be easily performed under a temperature condition of, for example, about 0 ° to about 50 ° C., for example, for about 1 to about 5 hours. After completion of the reaction, for example, it was poured into an aqueous solution of sodium bicarbonate, dried over magnesium sulfate, and concentrated to obtain a compound of formula (c).

In order to synthesize the above formula (b) 3,3,4-trimethyl-1-cyclohexene-1-carbaldehyde, for example, the compound of formula (c) which can be synthesized as described above is present in a solvent in the presence of a reducing reagent. It can be easily synthesized by hydrogenating below. Although the reaction temperature and the reaction time can be appropriately selected, for example, about 0 to about 50 ° C., about 1 to about 5 hours can be exemplified. Examples of the solvent include ethanol, water, isopropyl alcohol, ether, TH
F can be mentioned. The amount of these organic solvents used can be appropriately selected, but for example, about 0.5 to
A range of about 5% by weight can be exemplified. Examples of the reducing reagent include sodium borohydride, lithium aluminum hydride and the like. The amount of these reducing reagents used can be, for example, in the range of about 1/4 to about 2 mol relative to the compound of the formula (c). After completion of the reaction, the post treatment is carried out according to the usual method
(b) The compound can be easily synthesized.

To synthesize the formula (1) 1- (3,3,4-trimethyl-1-cyclohexen-1-yl) -methyl alcohol,
For example, the compound of the formula (b) obtainable as described above can be easily synthesized by hydrogenating in the presence of a reducing reagent, for example, in an organic solvent. The reaction conditions and the reaction method are similar to those described for the method of synthesizing the compound of formula (b) from the compound of formula (c) described above, whereby the compound of formula (1) can be easily synthesized.

The aroma of the compound of the formula (A) -1 included in the formula (A) of the present invention had green, citrus, fruity and heavy aroma and flavor characteristics. In addition, the fragrance of the compound of formula (A) -2 had a fragrance and aroma characteristic having a light green, pine needle-like sweet sensation.

The compound of the formula (A) of the present invention is well harmonized with various synthetic flavors, natural flavors, natural essential oils, synthetic essential oils, citrus oils, etc.
A novel fragrance composition can be prepared using the compound of formula (A). More specifically, when the compound of the formula (A) is blended with synthetic essential oils such as bergamot oil, lemon oil, geranium oil, lavender oil and mandarin oil, the natural essential oil has a mild and rich aroma and flavor. Moreover, it is possible to impart a persistent improving effect to the synthetic essential oil. Also, for example, citrus essential oils such as orange, lime, lemon, grapefruit; natural essential oils such as lavender oil, vetiver oil, cedar wood oil, citronella oil, geranium oil, lavandin oil, sandal oil; And the characteristics of the essential oil can be emphasized,
It is possible to prepare a novel fragrance composition that is mellow, rich and natural, and has excellent durability. Furthermore, for example, various synthetic flavors, natural flavors, natural essential oils, prepared from citrus oil, for example, strawberry,
When blended with flavor compositions such as lemon, orange, grapefruit, apple, pineapple, banana, melon, etc., a mild, full-bodied, natural-like and long-lasting flavoring composition can be prepared. The compounding amount of the compound of the formula (A) varies depending on the purpose and the aroma and flavor composition to be compounded, but, for example, generally, the range of about 0.001 to about 30% by weight of the whole is exemplified. You can

Thus, according to the present invention, it is possible to provide a persistent aroma and flavor imparting or improving / reinforcing agent comprising the compound of the formula (A) as an active ingredient, and using the agent, the compound of the formula (A) as an aroma and flavor ingredient. Foods and drinks characterized by containing, cosmetics characterized by containing a compound of formula (A) as an aroma component, and health care characterized by containing a compound of formula (A) as an aroma and flavor component It is possible to provide hygiene and medicine.

For example, beverages such as fruit juice drinks, fruit liquors, milk drinks, carbonated drinks; ice creams, sherbets, frozen desserts such as ice candies; Japanese and Western confectioneries, jams, chewing gums, breads, Appropriate for imparting its unique aroma and flavor to luxury items such as coffee, cocoa, black tea, and tea; soups such as Japanese soups and western-style soups; flavor seasonings, instant drinks and foods, snack foods, etc. It is possible to provide beverages in which the amount is mixed. Further, for example, a suitable amount capable of imparting its unique aroma to shampoos, hair creams, pomades, other cosmetic bases for hair; oscilloscopes, lipsticks, other cosmetic bases and cosmetic detergent bases, etc. It is possible to provide cosmetics containing Furthermore, laundry detergents, disinfectant detergents, deodorant cleaners, indoor air fresheners and various other health and hygiene detergents:
Various kinds of health and hygiene materials such as toothpaste, tattoo shoes, toilet paper, etc .; appropriate amount that can impart unique flavor to health, hygiene and medicines such as corrigents and flavoring agents for facilitating taking medicines. We can provide health care, hygiene, and medicines that have been mixed or applied.

(e) Examples and Reference Examples Reference Example Synthesis of N, N-dimethylacetonitrile To 90 g of a 50% aqueous solution of dimethylamine, 114 g of a 50% aqueous solution of glycononitrile was added under water cooling, and the mixture was stirred at room temperature for 3 hours. Ether is added and salting out is performed with sodium chloride, followed by extraction. The extract is dried over magnesium sulfate and then distilled to obtain the desired product. 67 g Boiling point 130-135 ° C / 760 mmHg Yield 80% Synthesis of formula (A) -1 cis-γ-methylcyclocitral (1) 1- (3,3,4-trimethyl-1-cyclohexen-1-yl) methylene Synthesis of bromide formula (2) 1- (3,4,4-trimethyl-1-cyclohexene-
1-yl) methyl alcohol formula (1) 15.4 g (0.1 mol)
Is charged with 1 g of pyridine in 100 m of dry ether. Keep the internal temperature of cooling at 10 ± 5 ° C with an ice-water bath. At the same temperature, 10.8 g (0.04 mol) of phosphorus tribromide is added dropwise. After completion of the dropping, stirring is continued for 1 hour and left overnight.

The reaction solution was poured into ice water, the ether layer was separated, washed with brine,
Neutralize with sodium bicarbonate water, dry with magnesium sulfate, and concentrate. Purify by silica gel column chromatography.

Rf = 0.731 (n-hexane / ethyl acetate = 3/1) 16g
Yield 70% (Wakogel C-200 150 g n-hexane / ethyl acetate = 9/1) (2) cis-2- (2-methylene-5,6,6-trimethylcyclohexan-1-yl) N, N-dimethyl Acetonitrile Synthesis of formula (3) Formula (2) 2.3 g (10 mmol), N, N-dimethylaminoacetonitrile 0.84 g (10 mmol) calcium carbonate
2.2 g (16 mmol) with DMF 12 m 50 m
The mixture is placed in a flask and reacted under stirring at room temperature for 24 hours under argon. After the completion, 100 m of n-hexane is added and washed with water. 1.8 g of the formula (3) having Rf = 0.602 (n-hexane / ethynyl acetate 3/1) was obtained by drying treatment with magnesium sulfate, concentration and silica gel column chromatography. Yield 8
2% (3) cis-γ-methylcyclocitral formula (A) -1
12g of the formula (3) was charged together with 0.5m silver nitrate 150m, terrahydrofuran 240m, ether 120m,
Stir at room temperature for 24 hours. The produced crystals are filtered and the resulting organic layer is separated and dried over magnesium sulfate (anhydrous). After concentrating with an evaporator, the residual liquid is rectified under reduced pressure to give a cis-having a boiling point of 54 to 56 ° C (2 mmHg).
γ-Methylcyclocitral formula (A) -15.3 g was obtained. Yield 58.8% IR: 3060, 1720, 1640, 895 cm ^-1 Formula (A) -2 Synthesis of cis-γ-methylcyclogeraniol (1) Synthesis of methylenetributyltin iodide Cupric acetate 0.2 m in a 500 m four-necked flask. g, and dissolved by heating in 20 m of glacial acetic acid. Add 13 g (0.2 mol) of sandy zinc and stir for 2 minutes. Decant and wash with 20 m acetic acid. Wash with ether 40m three times,
dry.

Add 35m of dry THF and keep under argon atmosphere.

While stirring, 54 g (0.2 mol) of diiodomethane was added to the T
HF 35m solution is added dropwise. (40 ± 3 ℃, 2 hours)
Next, add 30 m (0.11 mol) of tributyltin chloride,
React with stirring overnight at room temperature.

After completion, the reaction solution is poured into ice water and extracted with ether. The extract is washed with diluted hydrochloric acid. After magnesium sulfate drying treatment,
Boiling point 110-118 ℃ (1mmH
The target product having g) is obtained.

Yield 93.6% (2) 1- (3,3,4-trimethyl-1-cyclohexen-1-yl) methyleneoxymethylene-1-tributyltin Synthesis of formula (2) ′ 60% Sodium hydride 3.9 g ( 97 mmol) n-
Wash with hexane. Dry THF10 under argon atmosphere
0 m was added, then 1- (3,3,4-trimethyl-
1-cyclohexen-1-yl) -methyl alcohol formula
(1) 10 g (65 mmol) is added dropwise at 10 ± 5 ° C.
Stir for an additional hour at room temperature until hydrogen evolution ceases. Further, 15 m (50 mmol) of methylenetributyltin iodide was added and the mixture was stirred for 48 hours at room temperature.

After completion of the reaction, the reaction solution is used as it is in the next reaction.

(3) cis-γ-methylcyclogeraniol formula (A)-
Synthesis of 2 (10 g (44 mmol) of formula (2) was placed in 500 m of dry THF under an atmosphere of argon, and the temperature was adjusted to -65 ° C. To this, 190 m (285 mmol) of 1.5 N-butyllithium was added dropwise over 10 minutes. After that, the temperature is slowly increased and the internal temperature is raised to stop the reaction at -10 ° C. (60 minutes) The reaction solution is poured into ammonium chloride water and extracted with ether. After washing with brine, it is dried over magnesium sulfate and concentrated. The residue was distilled under reduced pressure to give 6.3 g of formula (A) -2 having a boiling point of 68 ° -69 ° C / 2 mmHg. Yield 85% Production of fragrance composition (1) A hyacinth fragrance composition was prepared by mixing the following components (parts by weight).

Phenylacetaldehyde 100 Cinnamic Alcohol 150 Hyacinth Busolute 20 Phenylethyl Alcohol 100 α-Ionone 30 Benzylpropionate 70 Ylang Ylang Oil 20 Amylcinnamic Aldehyde 50 Isoeugenol 40 Benzyl Alcohol 100 Dimethylbenzyl Carbinol 30 Galbanum Resinoid 50 Enylacetaldehyde dimethyl acetal 80 Lauryl alcohol 20 Nellore 80 Heliotropin 60 1000 A novel perfume composition was prepared by mixing 100 g of the above composition with 27 g of cis-γ-methylcyclogeraniol formula (A) of the present invention. The fragrance of this product has a fragrance that emphasizes the aroma of natural hyacinth, and a new hyacinth-based compounded fragrance having excellent durability was obtained.

(2) The following components (by weight) were mixed as the aroma and flavor components for pineapple.

Ethyl acetate 300 ethyl butyrate 250 isoamyl acetate 100 isoamyl valerate 55 isobutyric 70 isovaleric 30 ants Luke caproate 35 ethyl caproate 20 ethyl caprylate 15 isoamyl alcohol 35 diethyl malonate 30 citral 15 linalool 5 maltol 20 1000 the A novel perfume composition was produced by mixing 1000 g of the composition with 120 g of cis-γ-methylcyclocitral formula (A) -1 of the present invention. The fragrance of this product had a novel pineapple-like fragrance aroma that topnote (prior fragrance) was fresh and had no sweetness. It also had excellent durability.

(f) Effects According to the present invention, a novel synthetic intermediate which is extremely advantageous for synthesizing (±) -cis-γ-iron having high perfume value having a natural iris-like odor, and a novel production method thereof are provided. Can be provided.

The synthesis examples of (±) -cis-γ-iron from formula (A) -1 and formula (A) -2 of the present invention can be represented as follows.

Further, the formula (A) -1 and the formula (A) -2 can be used as a modulator, an improving agent, and a reinforcing agent for various fragrance compositions, and various new fragrance compositions can be provided.

Claims (2)

[Claims] 1. The following formula (A) -1. Cis-γ-methylcyclocitral represented by 2. The following formula (3) In the formula, R ′ and R ″ each represent a lower alkyl group, or R ′ and R ″ together represent a lower alkylene group, and cis-2- (2-methylene-5,6,6) 6-
Trimethylcyclohexan-1-yl) -N, N-dialkyl or -alkyleneacetonitrile is brought into contact with silver nitrate in an organic solvent, the following formula (A) -1: A method for producing cis-γ-methylcyclocitral represented by