JPS6251662A - 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-2-or-3-butene derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X represents=0 or -OH; dotted line indicates that either one is double bond provided that, when X is -OH, the double fond is located in the 3-position). EXAMPLE:1-(4,4-Dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-ol. USE:A perfume and an intermediate for synthesis of other perfume compounds, having a lasting floral, fruity and grassy fragrance and flavor with a rosy basic tone and useful as a flavoring agent and modifier for various foods and drinks, cosmetic, healthy goods, sanitary goods, drugs, etc. PREPARATION:Novel gamma-cycloavandulal expressed by formula II is reacted with an allylmagnesium halide in an organic solvent, oxidized and further isomerized to obtain the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Application Field The present invention relates to a novel compound which has not been described in any prior literature and is expected to be useful as a fragrance itself or as an intermediate for the synthesis of other perfumed metal products. . The invention also relates to a method for producing the compound and its use.

Specifically, the present invention is based on the following formula (1), where -X represents ;0 or -OH, a dotted line indicates the presence of a double bond in either one, and when -X is 10H indicates the presence of a double bond at the 3-position between the 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-2- or -3-butene derivatives represented by .

More specifically, the following formula (
1) 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-2-buten-1-one (hereinafter referred to as γ-isodamascone) represented by -1 has a sweet flower-like color with a rose tone. , also relates to a persistent aroma and flavor imparting or modulating agent characterized by having a fruit-like, slightly grass-like aroma and flavor and containing a compound of linear formula (1)-1 as an active ingredient;
It also relates to a method for producing a compound of linear formula (1)-1.

The present invention also provides 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-butene-1 represented by the following formula (1) -2 included in the compound of formula (1) above. -ol and 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-one represented by the following formula (1) -3,
It is an intermediate useful for the synthesis of the above formula (1)-1, and the linear formulas (1)-2 and (1)-3 have a flower-like aroma and flavor, and the formula (1)-2 or The present invention also relates to a persistent aroma and flavor imparting or modulating agent characterized by containing Formula Cl-3 as an active ingredient, and also relates to a linear manufacturing method.

(B) Prior Art As a compound having a structure similar to the above formula (1), for example, α-isodamascone represented by the following formula (A) is known. The above formula (A> compound is, for example, Dragoco Rep
ort, January issue, pages 17-20.

1979, but the odor properties of the compound are not described. According to the findings of the present inventors, it has a floral aroma with a rose tone as its base, but lacks sweetness and subtlety, and has a strong green feel.

(C) Problems to be solved by the invention In recent years, with the diversification of various foods, beverages, and cosmetics, there has been an increasing need for new, unprecedented aromas for the flavors of various foods, beverages, and fragrances for cosmetics. In particular, there is a desire to develop a fragrance substance that is mild, rich, fresh, and long-lasting.

For this reason, various known fragrance materials are suitably mixed and their blending amounts are adjusted to make the composition as natural as possible. Conventionally, there are few materials that are mild, rich, fresh, and natural-looking, and can also be long-lasting.In particular, there is a shortage of materials that have the above-mentioned properties that can be easily and inexpensively made by hand.

(D) Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive research on the isomer of α-isodamascone of the above formula (A), which is known as a fragrance compound.

As a result, γ of the formula (1)-1 included in the above formula (1)
- Isodamascone has a sweet floral, fruit-like, and slightly grass-like aroma with a rose tone that is superior in sweetness and richness to the aroma of the conventionally known compound of formula (A) above. and has excellent sustainability, and has discovered that the above formula (1)-1 compound can be easily synthesized, and has succeeded in its synthesis. Also, using the above formula (1)-1 compound as an active ingredient,
In a wide range of fields such as food and beverages (including luxury goods), cosmetics, health, hygiene, and pharmaceuticals, it provides a novel persistent aroma and flavor imparting agent or improved reinforcing agent that cannot be obtained with the conventionally known formula (A) above. I discovered that it is possible.

Also, the above formulas (1)-2 and (1)-3 are replaced by the above formulas (1,
)-1 compound, it has a flower-like aroma and flavor characteristics that are slightly different from the above formula (1)-1, and has excellent persistence, making it a novel product in various fields of application. It has been discovered that it is possible to provide a long-lasting aroma and flavor imparting or improved reinforcing agent.

The following formula (1) of the present invention Butene derivatives can be obtained, for example, by reacting γ-cyclobandural represented by the following formula (2) with allyl magnesium halide in an organic solvent, and by reacting with the following formula (1) -2H included in the above formula (1). 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-ol represented by the formula (1)-2 is formed to form a compound having the linear formula (1)-2. 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl) represented by the following formula (1)-3 included in the above formula (1) by oxidation reaction in a solvent in the presence of an oxidizing agent -3-Buten-1-one is formed, and the compound of linear formula (1)-3 is subjected to an isomerization reaction in an organic solvent in the presence of an acid catalyst. 1) γ-isodamascone represented by compound-1 can be easily synthesized.

The manufacturing process diagram of the compound of formula (1) of the present invention can be expressed as follows, for example.

(2) (+)-2 The production mode of the compound of formula (1) of the present invention will be explained in detail below according to the process diagram above.

In the above process diagram, the raw material compound γ-cyclolabandural of formula (2) is a compound synthesized for the first time by the present inventors and has not been described in any prior literature, and for example, 5 It can be easily synthesized from 5-dimethyl-1-cyclohexene-1-carbaldehyde in 4 steps. The linear formula (2) compound itself is a compound that is useful in a wide range of fields as an aroma and flavor imparting or flavor modulating agent.
Patent application filed in 1986 by the same applicant dated the same date as the present application
− is the subject of the issue.

From the compound of formula (2) above, the formula (
1) To synthesize 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-ol of -2, for example, γ-cyclolabandural of the above formula (2) It can be easily synthesized by contacting with allyl magnesium halide prepared in advance in an organic solvent.

Preferred examples of the allyl magnesium halide used in the above reaction include allyl magnesium chloride, allyl magnesium iodide, and allyl magnesium bromide. The amount of these allyl magnesium halides to be used is preferably in the range of, for example, about 1 to about 5 moles based on the compound of formula (2). Also, the above! Examples of the solvent include tetrahydrofuran, diethyl ether, dimethyl ether, benzene, toluene, and dioxane. There are 8 of these! There are no particular restrictions on the amount of the solvent used, and it can be selected as appropriate; for example, it can be in the range of about 5 to about 20 times the weight of the compound of formula (2). .

The above reaction varies depending on the organic solvent used, but can be easily carried out by reacting for about 0.5 to about 30 hours, for example, under conditions of a temperature range of about -20 to about 50°C. It can be carried out.

After completion of the reaction, the product is injected into a saturated aqueous ammonium chloride solution, the organic layer is separated, the organic solvent is distilled off, and the compound is purified by means such as distillation to obtain the above formula (1)-2 compound. Obtainable.

To synthesize 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-one of the above formula (1)-3, for example, it can be synthesized as described above. By reacting a compound of formula (1)-2 capable of , can be easily done.

Examples of the oxidizing agent used in the above reaction include jone
's reagent (chromic acid + sulfuric acid) can be exemplified. The amount of these oxidizing agents to be used may range, for example, from about 273 to about 2 mol, based on the compound of formula (1)-2.

Preferable examples of the organic solvent to be used include acetone, methyl ethyl ketone, diethyl ketone, and the like. The amount of these organic solvents to be used may be appropriately selected, but preferably ranges from about 5 to about 20 times the weight of the compound of formula (1)-2.

After the reaction is completed, the excess oxidizing agent is reduced, the product is neutralized with an alkali, the organic solvent is distilled off, and the compound is purified by means such as distillation to obtain the compound of formula (1)-3. I can do it.

For example, formula (1) can be synthesized as described above.
The above formula (1)-1 can be easily synthesized from -3 by, for example, reacting a compound of formula (1)-3 in an organic solvent in the presence of an acid catalyst.

Preferred examples of the acid catalyst used in the above reaction include p-)luenesulfonic acid, sulfuric acid, hydrochloric acid, and phosphoric acid. The amount of these acid catalysts to be used is, for example, about 0.01 to about 2
A preferable example is a range of about 0% by weight.

In addition, as the organic solvent, toluene, benzene, xylene, tetrahydrofuran, methylene chloride, etc. can be preferably used, and the amount of these solvents to be used is not particularly limited, but for the compound of formula (1)-3, hand,
For example, a preferred range is about 2 to about 100 times the weight.

After the reaction is completed, the product is neutralized and washed with an alkaline aqueous solution. The compound of formula (1)-1 can be easily obtained by concentrating the organic layer and purifying it by means such as column chromatography or distillation.

The compound names, boiling points, and aroma characteristics included in the compound of formula (1) obtained as described above are as follows.

(1) -1γ-isodamascone Boiling point 73-75°C/2mmHg Sweet flowers and fruits with a rose tone. fruit-like, slightly grass-like persistent Has aroma and flavor.

(1)-21-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-ol Boiling point: 80-812C/2mmHg A fruity, flower-like, persistent aroma. have

(1) -31-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-one Boiling point 70-71°C/2mmHg Slightly sweet flower with a rose-like tone. It has a long-lasting, fruit-like aroma.

The compound of formula (1) has excellent persistence and unique aroma and flavor as an aroma, flavor imparting, or modulating ingredient for various foods and beverages, cosmetics, health care, hygiene products, pharmaceuticals, and the like.

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 in natural essential oils. Flavor imparting or modulating agents can be adjusted. For example, it blends well with citrus essential oils such as orange, lime, lemon, and grapefruit, and can emphasize the characteristics of the essential oil, giving it a fresh, gentle, and more natural-like persistent aroma. It can provide a modulator effect.

Furthermore, when it is incorporated 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 is mild, rich, natural, and long-lasting. can. Furthermore, the compound of formula (1) can be blended well with various synthetic fragrances and natural fragrances to obtain a unique and long-lasting aroma and flavor imparting or modulating agent. Although the amount of the compound of formula (1) varies depending on the purpose, it can generally range from about 0.001 to about 30% 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, modulating, or reinforcing agent comprising the compound of formula (1) as an active ingredient. To provide food and beverages, cosmetics characterized by containing the compound of formula (1) as an aroma component, and health/hygiene/medicinal products characterized by containing the compound of formula (1) as an aroma component, etc. I can do it.

For example, beverages such as fruit juice drinks, fruit 'a', milk drinks, carbonated drinks; ice creams, sherbet,
Frozen desserts such as popsicles; 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 beverages and foods, various snack foods, etc. It is possible to provide food and drink containing an appropriate amount of the unique aroma and flavor. In addition, an appropriate amount that can impart the unique fragrance to, for example, shampoos, hair creams, pomades, and other hair cosmetic bases: oshiroi, lipsticks, other cosmetic bases, and cosmetic detergent bases. We can provide cosmetics containing the following.

Furthermore, laundry detergents, disinfectant detergents, deodorizing detergents, and various health and hygiene detergents; toothpaste, tissues.
, various health and hygiene materials such as toilet paper;
It is possible to provide health, hygiene, and pharmaceutical products that have been blended or applied with an appropriate amount to impart a unique flavor to health, hygiene, and pharmaceutical products, such as flavoring and numbering agents to make medicines easier to take.

Several embodiments of the present invention will be explained in more detail with reference to Reference Examples and Examples below.

(E) Reference Example (1) Synthesis of 6,5-dimethyl-1-cyclohexenylmethanol.

In a flask, add 1 g of sodium borohydride I (0.29 g
), 90 ml of 95% ethanol, and 0.5 g of potassium hydroxide were added, cooled on ice, and 50 g of 5,5-dimethyl-1-cyclohexenecarbaldehyde (0,
36 mol) and 45 ml of 95% ethanol.
It was added dropwise at 0 to 30° for 30 minutes, stirred at room temperature for 2 hours, and the reaction solution was poured into water and extracted with ether.
P! was washed with brine, dried over magnesium sulfate, the ether was distilled off, and distilled under reduced pressure to obtain the target compound at 40.6
I got g. Yield: 80%, boiling point: 7o~71"C/3m
Synthesis of mHg Yu(2)5.5-dimethyl-1-cyclohexenylmethyl mesylate.

40 g (0.2 mol) of the alcohol obtained above, 300 g of dry diethyl ether, 42 g of triethylamine.
4 g (0.42 mol) was placed in a flask and cooled with water. In this, 35.3 g (0.31 mol) of mesyl chloride was added to 1
0 to 15° (dropwise for 41 hours. Then, stir at the same temperature for 1 hour. Pour the reaction solution into ice water. * Pi
are separated, and the organic layer is washed twice with diluted hydrochloric acid, further washed with brine, and then washed with an aqueous alkaline solution. Yes 81
After drying N with magnesium sulfate, the solvent was distilled off and ffl
59g of the target compound was obtained. Yield: 97%.

(3) Synthesis of 2-(2-methylene-4,4-dimethylcyclohexyl)-1-N,N-dimethylaminoacetonitrile.

A flask contains 9.35 g (55 mmol) of silver nitrate, 59 g (0.28 mol) of the mesylate obtained above, 58 g (0.42 mol) of potassium carbonate, and 25.8 g (25.8 g) of N,N-dimethylacetonitrile.

Add 260 ml of dimethylformamide (1 mol) and stir at room temperature for 2 days. After the reaction is complete, the solvent is distilled off, water is added to the residue, and the mixture is extracted with hexane.

[F' was washed with water, dried over magnesium sulfate, and the solvent was distilled off to obtain 40 g of the target compound manufactured by M.

Yield: 75.6%.

(4) Synthesis of γ-cyclolabandural.

In a flask, add 9.35 g (55 mmol) of silver nitrate and 1 liter of water.
Add 10ml. Add to this the nitrile 10 obtained above.
．． A mixed solution of 3 g (50 mmol) and 110 ml of ether was added dropwise at room temperature over 1 hour, and the mixture was stirred overnight at the same temperature. The formed crystals are filtered off, the filtrate is separated, and the organic layer is washed with water, followed by washing with brine, aqueous alkali solution, and brine in this order. After drying the ether layer with magnesium sulfate, the ether was distilled off and distilled under reduced pressure to obtain γ.
- 5.1 g of cyclolabandural was obtained.

Yield: 67%. Boiling point: 85-87°C/20mmHg・ (F) Example (1) 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-ol Formula (1)
4.2 g (0,175 mol) of synthetic magnesium metal of -2 was added to 500 ml with 150 ml of dry tetrahydrofuran.
Pour into a flask. In this, 11.5 g of allyl chloride
(0,15 mol) and 50 m dry tetrahydrofuran
1 of the mixed solution is added dropwise to prepare a Grignard reagent. (After the reaction starts, the temperature range is 20 to 25°C.) After the dropwise addition is completed, stirring is continued for an additional 30 minutes at room temperature.

Next, 15 g (0.1 mol) of γ-cyclolabandural
and 50 ml of dry tetrahydrofuran.
Add dropwise at a temperature of 12°C. (Dropping time: 30 minutes) After the completion of the addition, continue to stir at room temperature for another 1 hour to complete the reaction.The reaction solution was poured into saturated ammonium chloride water, the organic layer was separated, the aqueous layer was extracted with ether, and the organic layer Combine with After drying this solvent layer with magnesium sulfate, the solvent was distilled off and then distilled under reduced pressure to obtain 9.5 g of a fraction having a boiling point of 80 to 813 C/mmHg. Yield: 49% (2) 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-one Formula (1)-
Synthesis of 3 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-3-buten-1-ol 7.8 g (4
0 mmol) and 70 g of acetone were placed in a 300 ml flask. Cool in a water bath and maintain internal temperature at 20-25°C. 24.5 g of J ONE'S reagent (5.5 g of chromic anhydride, 10 g of water, 9 g of iJ sulfuric acid) was added dropwise into the solution over 30 minutes. After the dropwise addition was completed, stirring was continued for another 30 minutes at the same temperature, and then isopropyl alcohol was added to reduce excess hexavalent chromium. Next, add a soda ash aqueous solution to neutralize the sulfuric acid. 7! ! Solids are removed by filtration, and acetone is distilled off from the mother liquor using an evaporator. After adding ether to the residual liquid and washing with saline, the ether was dried and distilled under reduced pressure to a boiling point of 70-71.
5.3 g of fraction having 8C/2 mmHg were obtained. yield;
68%.

(3) Synthesis of γ-isodamascone formula (1)-1 1-(4
, 2.5 g (13 mmol) of 4-dimethyl-2-methylenecyclohexan-1-yl)-2-buten-1-one, 0.2 g of P-)luenesulfonic acid and 10 g of toluene.
Charge 0ml, heat to 80°, and react for 1 hour and 30 minutes. The reaction solution is cooled and neutralized and washed with hydrogenated sodium chloride water. The solvent layer is dried over magnesium sulfate, concentrated, and the remaining liquid is separated and purified using 5i02 column chromatography. [5i02 Wako Gel-200, 100g, n-hexane/ethyl acetate = n/
1 (V/V) ] Yield of obtaining 1.5 g of target product; 6
0%. Boiling point: 73-75°C/2 mm Ha (4) Example of perfume composition The following components (parts by weight) were mixed as a rose type mixed perfume composition.

Phenylethyl alcohol 200 Geraniol 50 Heliotropin 20 Citronellol
10 nerol
100 hydroxycitronellal
30 Methyl phenyl carbinyl acetate 2
5 Geranium oil 10 Linalool 30 Benzyl acetate 35 Benzyl alcohol 20 Rose phenone
10 Lodizole
280 rose oil
lOβ-ionone
50 benzyl salicylate 4
0 Cyclobentadecatulide 30 Guaiyaud oil 50 Total 10
00 By mixing 40 g of the compound of formula (1)-1 with $960 g of the above composition, a new rose blend fragrance that is natural, fresh, and has excellent persistence was created. Furthermore, by mixing 40 g of the compound of formula (1)-2 with 960 g of the above composition, almost the same results as above were obtained. However, in this case, the sweetness was suppressed.

(5) Perfume Composition The following components (parts by weight) were mixed as a blended fragrance composition.

Cyclopentadecanolide 50 Coumarin 10 Heliotrovin 30 Ylang Ylang Oil
80 methyl ionone
100 anisaldehyde
20 neroli oil
30 hydroxycitronellal 5
0 Linalol 70 Isobutyl salicylate 110 Amyl salicylate 1405-Cyclohexadecene 20 Oakmoss absolute 3 Vanillin
7 Phenylacetaldehyde
220 Benzyl Acetate 60 Total 1000 By adding 90 g of the compound of formula (1)-1 to 910 g of the above composition, a new formulated perfume composition with a fresh and more natural orchid type and a long-lasting effect was obtained.

Further, 90 g of the compound of formula (1)-3 was added to 910 g of the above composition.
was added to prepare a blended fragrance composition. As a result, equation (1)
Almost the same results as in the case of adding -1 were obtained, but in this case, there was a somewhat green feel.

(6) Flavor Composition Example The following components (by weight) were mixed as an aroma composition for apricots.

Allylcyclohexylcaproate 0.2 Benzaldehyde 11.5 Amyl acetate 7.5 Amyl butyrate 7.5 Amyl formula 10.0 Amyl valerate 15.0 Cinnamic aldehyde 0.5 Ethyl acetate 14.5 Ethyl butyrate 4.5 ethylhexanony)
10.0 Ethyl Valley)
50.0 Geranium oil
0.5isoamyl phenyl acetate 0
．． 1 Benzyl acetate 9.5 Lemon oil 5.0 Orange oil 10.5 Propyl cinnamate 0.2 α-Undecalactone 213.0 Vanillin
85.0 ethanol
535.0 total 1000.0 Above composition ¥! Formula (1)-1 compound 20 to 1000 g of IJ
By adding g, an extremely excellent new composition having a long-lasting aroma and flavor component of apricots was obtained.

(g) Effect The novel compound of the present invention has the following formula (1), where -X
and the dotted line represents 1-(4,4-
dimethyl-2-methylenecyclohexan-1-yl)-
A 2-butene derivative has a persistent floral, fruit-like, and grass-like aroma with a rose-like tone, and a novel compounded fragrance that cannot be obtained with conventional fragrance materials uses the compound of the formula as an active ingredient. A composition can be provided. The blended fragrance composition is useful as an aroma and flavor imparting or modulating agent for various food and drink products, cosmetics, and health/hygienic/pharmaceutical products. Also, the formula (
The compounds of formula (1)-2 and formula (1)-3 included in 1) are also useful as intermediates for the synthesis of compounds of formula (1)-1 included in formula (1)-.

Patent applicant: Hasegawa Perfume Co., Ltd. 1j Agent
Patent attorney Chifuru Odajima / 1 other person

Claims (1)

[Claims] (1) The following formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) However, in the formula, -X indicates = 0 or -OH, and the dotted line indicates the presence of a double bond on either side. , 1-(4,4-dimethyl-2-methylenecyclohexan-1-yl)-2- or - when -X is -OH indicates the presence of a double bond at the 3-position. 3-butene derivative.