JPS62292739A - Humulene derivative - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (formula II represents single bond or double bond, provided that all the formulas II represent single bond or formula II between the positions 2 and 2' and all the other formula II represent double bond or formula II between the positions 2 and 3 represents single bond and all the other formulas II represent double bond). EXAMPLE:2,6,6,9-Tetramethyl-1-methoxy-cycloundecane. USE:A perfume substance or synthetic intermediate therefor which is a compound having strong woody, amberlike or balsamlike fragrance with improved lasting quality and useful in the filed of perfume industry and used also as an active ingredient for flavoring and improving agent for foods and drinks (including tasty materials), cosmetics, health, hygiene, medicines, etc. PREPARATION:A compound expressed by formula III is reacted with an alcoholate forming agent, e.g. NaH, etc., in an organic solvent and the resultant product is further reacted with a methylating agent, e.g. dimethyl sulfate, etc., to afford the aimed compound expressed by formula I (all the formulas II are single bond).

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a novel compound which has not been previously described in the literature, and which is useful as a fragrance itself and as an intermediate for the synthesis of aroma substances. The invention also relates to methods for producing and using the compounds.

More specifically, the present invention is based on the following formula (A), where = represents a single bond or a diN bond, and where all = represents a single bond or = of 2-2' is a single bond. Humulene represented by: a bond and all other =s represent a double bond, or = between 2-3 represents a single bond and all other =s represent a double bond Regarding derivatives.

Furthermore, the present invention provides that the compound of the formula (A) has a long-lasting and strong wheezy, amber-like, and balsam-like aroma,
The present invention also relates to an aroma and flavor imparting or improving agent characterized by containing the compound of formula (A) as an active ingredient, and furthermore, the present invention relates to a method for producing the compound of formula (A).

(b) Prior art Compounds having a structure similar to the above formula (A) compound of the present invention include, for example, the following formula (B), where 22 represents a single bond or a double bond, where two 2,6,6,9-tetramethyl- of (B)-1 included in the above formula (B), where a single bond and the other represents a double bond. 2,
4,8-cycloundecatrien-1-ol, (B)
-2-2-methylene-6,6,9-)limethyl-4,8
-Cycloundecadien-1-ol is known (
Journal of the Japanese Society of Agricultural Chemistry, 55. (9) 793-797.19
81), and 2, 6, 6. represented by the following formula (B)'.
9-Tetramethyl-cycloundecan-1-ol is known. Tetrahedron, Vol. 24.
4133-4142 (1968).

However, there is no mention at all of the novel compound of formula (A) of the present invention and its production method, and furthermore, there is no mention of the novel compound of formula (A) of the present invention and its production method.
) and chain formula (B)', there are no similar descriptions of their specific aroma characteristics.What is described is that humulene is oxidized with lead acetate in the presence of acetic anhydride. It is only stated that the presence of the chain formula (B) compound was confirmed as one of the oxidation products. or,
Regarding the compound of chain formula (B)', it is only stated that it can be used as an intermediate for the synthesis of hexahydrotumrenone, but there is no description of any other usefulness.

(C) Problems to be solved by the invention In recent years, with the diversification of various food and drink products and cosmetics, there has been a need for flavors for various food and drink products and fragrances for cosmetics, especially new types of fragrances that have not existed before. In particular, there is a demand for the development of fragrance substances that are mild, rich, fresh, and long-lasting.

For this reason, ζ is generally used, for example, to synthesize new compounds discovered through analysis of natural essential oils or their derivatives and provide them as mixed fragrance materials, or to synthesize compounds with structural similarities to conventionally known fragrance compounds or their derivatives. synthesize derivatives,
Among these, we discovered compounds useful as fragrance substances,
It has been provided as a mixed fragrance material. These blended fragrance materials and various known fragrance materials are appropriately combined and blended in amounts to create a composition that is as natural-looking as possible. However, in the past, it cannot be said that such mild, rich, fresh and natural-looking materials, and materials that can provide sustainability, have been available in sufficient quantities and at low prices.

(d) Means for Solving the Problems In view of the above circumstances, the present inventors have conducted extensive research in order to develop a new type of fragrance substance useful as a material for a blended fragrance composition. As a result, we succeeded in synthesizing the humulene derivative of the above formula (A), which has not been described in any literature, and the chain formula (
It has been discovered that the compound A) exhibits a very strong woody, amber-like, balsam-like aroma and has an extremely excellent persistence, and furthermore, the above compound of formula (A) can be easily synthesized.

In addition, by using the above formula (A) compound as an active ingredient, a useful persistent aroma and flavor imparting or improving reinforcing agent is provided in a wide range of fields such as food and drink (including luxury goods), cosmetics, health, hygiene, and pharmaceuticals. I discovered that it is possible.

Therefore, an object of the present invention is to obtain the above formula (A
) and a method for producing the same. Furthermore,
The present invention provides a fragrance composition characterized by containing a compound of chain formula (A) as an active ingredient.

The following formula (A) of the present invention, where = has the same meaning as above, and the following formula (A)-
1 To synthesize 2,6,6,9-tetramethyl-1-methoxy-cycloundecane represented by -Cycloundecan-1-ol can be easily synthesized by reacting it with an alcoholate-forming agent in an organic solvent and then reacting with a methylating agent such as, for example, dimethyl sulfate.

Further, the following formula (A)- included in the above formula (A) of the present invention
2 and (A)-3 (A) -2(A) -3 2,6,6.9-tetramethyl-I-methoxy-2,4,8-cycloundecatriene and 2-methylene -6,6,9-trimethyl-1-methoxy-4,
To synthesize 8-cycloundecadiene, for example, 2,6,6,9-tetramethyl-2,4,8-cyclo of formula (B)-1 included in the above formula (B) compound, Undecatrien-1-ol and (B)-2 of 2-methylene-6,6,9-)trimethyl-4,8-cycloundecadien-1-ol in an nH medium with an alcoholate forming agent. It can be easily synthesized by reacting with a methylating agent such as dimethyl sulfate.

The compounds of the formulas (B) and (B)', which are raw materials for the synthesis of the compound of the formula (A) of the present invention, can be easily synthesized, for example, according to the methods described in the above-mentioned literatures.

The mode of synthesis of the compound of formula (A) of the present invention can be expressed as follows when shown in a process diagram.

(B)' (A)-1(B)
-1(A) -2 The method for synthesizing the compound of the formula (A) of the present invention will be explained in more detail below according to the example of the process diagram. -1 2.6, 6.9
To synthesize -tetramethyl-1-methoxy-cycloundecane, for example, a compound of formula (B)' above is reacted with an alcoholate-forming agent in an organic solvent to form an alcoholate, and then, for example, dimethyl IirIM, etc. It can be easily synthesized by reacting with a methylating agent.

Examples of the alcoholate-forming agent used in the alcoholate-forming reaction include sodium hydride, metallic sodium, butyllithium, and the like. The amount of the alcoholate forming agent may be selected appropriately, for example, from about 1 to about 1.2 per mole of the compound of formula (B) above.
'tI on the order of moles! You can raise the boundaries. In addition, examples of the n-containing solvent used in the above reaction include toluene,
Preferred examples include hexane, benzene, and tetrahtomifuran. The amount of the organic solvent to be used is not particularly limited and can be selected as appropriate; for example, the amount may be about 50 to about 1000% by weight based on the compound of formula (B)''. The alcoholate formation reaction can be carried out, for example, at a temperature of about 1
This can be easily carried out under reaction conditions of about 10 hours.

Moreover, from the alcoholate obtained as described above, the above formula (
Compound A)-1 can be easily synthesized by injecting, for example, dimethyl sulfate or methyl iodide into the above reaction system and bringing it into contact. The reaction temperature and reaction time of this contact reaction can be selected appropriately, but for example,
Temperature in the range of about 50° to about 100'C, about 5 to about 1
The time can preferably be set in a range of about 0 hours.

The use of a methylating agent such as dimethyl FrfiM, methyl iodide, etc. can be preferably exemplified in a range of about 1 to about 2 mol per 1 mol of the compound of formula (B)'. .

After the reaction is completed, for example, pour the reaction solution into dilute hydrochloric acid and add
Separate one layer, wash with water, wash with alkali, and rinse!
! and purified by means such as distillation to obtain the above formula (A
)-1 compound can be easily synthesized with good yield.

Moreover, the above formula (A) included in the above formula (A) compound of the present invention
To synthesize compounds A)-2 and (A)-3, for example, the alcohols of the above formulas (B)-1 and (B)-2, respectively, are brought into contact with an alcoholate forming agent, and then dimethyl Tits is added. The reaction conditions that can be easily synthesized by contacting with a methylating agent such as a methylating agent can be carried out in the same manner as exemplified for the method for synthesizing the above-mentioned formula (A)-1.

The above formula (
The aroma characteristics of each of the compounds included in A) are shown below.

(A) -1; Balsamic, persistent, strong Utsy-like aroma.

(A) -2: Balsamic and strong amber to woody aroma with excellent persistence.

(A) -3: A strong Uthu-like aroma with a balsamic and persistent sweetness.

The compound of formula (A) of the present invention blends well with various synthetic fragrances, natural essential oils, synthetic essential oils, citrus oils, etc., and novel fragrance compositions can be prepared using the compound of formula (A). More specifically, when the compound of formula (A) is blended into synthetic essential oils such as bergamot oil, lemon oil, geranium oil, lavender oil, and mandarin oil, the aroma and flavor inherent to natural essential oils is mild and rich. Moreover, a sustainable improvement effect can be imparted to the synthetic essential oil. It is also good for citrus essential oils such as orange, lime, lemon, grapefruit, gray 1, etc.; natural essential oils such as lavender oil, vetiver oil, cedarwood oil, citronella oil, geranium oil, lavandin oil, sandal oil, etc. It is possible to prepare a novel fragrance composition that harmonizes and emphasizes the characteristics of the essential oil, is mellow, rich, natural-looking, and has excellent long-lasting properties. Furthermore, for example,
When blended into flavor compositions prepared from various synthetic fragrances, natural fragrances, natural essential oils, citrus oils, etc., such as strawberry, lemon, orange grapefruit, apple, pineapple, banana, melon, etc., it produces a mild, rich, and natural flavor. Perfume compositions with enhanced and long-lasting properties can be prepared. The amount of the compound of formula (A) above can be selected and changed appropriately depending on the purpose and the aroma and flavor composition to be mixed, but for example, it is generally about 0% of the total amount.
．． For example, the range is from about 0.001% to about 30%.

Thus, according to the present invention, it is possible to provide a persistent aroma and flavor imparting or improved reinforcing agent containing the compound of formula (A) as an active ingredient, and the agent can be used to contain the compound of formula (A) as an aroma and flavor component. Foods and beverages characterized by the above, cosmetics characterized by containing the compound of formula (A) as an aroma component, health/hygiene/pharmaceutical products characterized by containing the compound of formula (A) as an aroma component, etc. For example, fruit juice drinks, fruits; beverages such as Category 6, milk drinks, and carbonated drinks; frozen desserts such as ice creams, sherbet, and 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 the appropriate amount of the present invention to impart the unique aroma and flavor. For example, shampoos, hair creams, pomades, and other hair cosmetic bases; cosmetic bases, lipsticks, and other cosmetic bases and cosmetic detergent bases, etc. Can you provide cosmetics containing this product? Furthermore, laundry detergents, disinfectant detergents, deodorizing detergents, room air fresheners, and various health and hygiene detergents; various health and hygiene products such as toothpaste, tissues, and toilet bathers. Materials: We can 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 flavorings and flavoring agents to make medicines easier to take.

Hereinafter, the present invention will be further explained in detail by giving reference examples and examples.

(e) Example (,1) Synthesis of 2,6,6.9-tetramethyl-1-methoxy-cycloundecane [2.25 g of 60% sodium hydride, 160 g of toluene in the formula (A)-11 flask
ml of toluene at room temperature and the formula (
A mixed solution of 10.8 g (0.05 mol) of compound B)' was added dropwise over 30 minutes.

Heat to 115'C and add 9.5g dimethyl sulfate (0,0
A mixed bath containing 75 mol) and 20 ml of toluene was added dropwise over 45 minutes. The reaction was completed by stirring at the same temperature for 3.5 hours.

The reaction solution is washed with dilute hydrochloric acid, then washed with aqueous sodium hydroxide, dried over magnesium sulfate, and concentrated.

Distilled under reduced pressure to boiling point 105@~107@C/3mmH
6.7 g of a fraction having g. Yield: 58.3%. The structure was confirmed by ■R, MS, and GLC.

rR(f i 1m); 2950.1460.1360
．． 101095(').

(2) 2,6,6.9-tetramethyl-1-methoxy-
Synthesis of 2,4,8-cycloundecatriene [formula (A)
-21.

In Example <1), formula (B) − is substituted for formula (B)′.
The title compound was obtained in the same manner as in Example (1), except that 2,6,6,9-tetramethyl-2,4,8-cycloundecatrien-1-ol of Example 1 was used. Yield: 64
．． 2%. Boiling point: 116'~118°C/3 mm
The Hg structure was confirmed by rRlNMR, MS, and GLC.

NMR (CDCI3): 1.04 (6H,S)
.

1.23-2.88 (m), 3. 18 (3H
,S), 4.53-5.58 (5H)TR(f
i 1m); 2920.1710.1640, 1
446, 1382, l 362, 1105.975 (
cm-2).

(3) Synthesis of 2-methylene-6,6,9-)methyl-1-methoxy-4,8-cycloundecadiene [formula (A
)-31° In Example (1), instead of formula (B)'', formula (B)-
2-2-methylene-6,6,9-)lysothyl-4,8-
The title compound was obtained in the same manner as in Example (1) except that cycloundecadien-1-ol was used. Yield: 6
3.5%. Boiling point: 117" ~ 119@C/3mmHg
-Structure was confirmed by IRlNMR, MS, and GLC.

NMR (CDCI3): 1.04 (6H,S).

1.23-2.88 (m), 3.18 (3H,S)
, 4.53-5.58 (6H) IR (f i 1m)
;2920.1710.164O11446, 1382
, 1362, 1105,975,902 (cm-2).

(f) Reference Example (1) Fragrance Composition The following components (weight e parts) were mixed as a rose type mixed fragrance composition.

Phenylethyl alcohol 200 Geraniol 50 Heliotropin 20 Citronellol
100 nerol
10 hydroxycitronellal
30 Methyl phenyl carbinyl acetate 2
5 Geranium oil 10 Linalool 30 Benzyl acetate 35 Benzyl alcohol 20 Rose phenone
10 rhodinol
280 rose oil
10β-ionone
50 Benzyl salicylate 40 Cyclobentadecalide 30 Guaiyaud oil 50 Total 10
00 2,6°6.9- of formula (A)-1 to 960 g of the above composition
Tetramethyl-1-methoxy-cycloundecane 40g
A new rose blended fragrance composition was prepared by mixing the following. This new blended fragrance composition and the above-mentioned rose blended fragrance composition to which the compound was not added were compared by 10 expert panelists.

As a result, all 10 expert panelists agreed that the new perfume composition containing the compound was significantly superior in terms of natural rose characteristics and sustainability. Also, the above (A)
Similar results were obtained when 2,6,6,9-tetramethyl-1-methoxy-2,4,8-cycloundecatriene of formula (A)-2 was used instead of compound -1. Ta. In this case, (2) Fragrance F4 Composition The following components (parts by weight) were mixed as a blended fragrance composition of the Ran type, in which some differences in the nuances of the fragrance were observed.

Cyclopentadecanolide 50 Coumarin 10 Heliotrovin 30 Ylang Ylang Oil
80 methyl ionone
100 anisaldehyde
20 neroli oil
30 hydroxycitronellal
50 linalol 70 isobutyl salicylate 110 amyl salicylate 1405-cyclohexadecene 20 oakmoss absolute 3 vanillin
7 Phenylacetaldehyde
220 benzyl acetate
60 total 1000 2,6°6.9- of formula (A)-2 to 910 g of the above composition
By adding 90 g of tetramethyl-1-methoxy-cycloundecatriene, a new formulated perfume composition with an emphasis on fresher, more natural orchid type and excellent persistence was obtained.

In addition, by using 2-methylene-6,6,9-trimethyl-4°8-cycloundecadiene of formula (A)-3 in place of formula (A)-2 above, the nuance of the aroma is somewhat reduced. A new formulated perfume composition has been created that emphasizes a different but fresher and more natural orchid type and has excellent persistence.

(3) Perfume Composition The following components (parts by weight) were mixed as a bouquet-type mixed perfume composition.

Phenylethyl alcohol 180 Linalyl acetate 30 Bergamot oil 40 Rhodinol 50 Benzyl acetate 40 Heliotropin 80 Geraniol 110 Rose absolute 10 β-ionone
100 lavender
20 diasmine absolute 1
0 amyl salicylate 45 linalyl acetate 135 vetiver acetate 100 citronellol 50 total 1000 2,6°6.9- of formula (A)-1 was added to 980 g of the above composition.
20% of tetramethyl-1-methoxy-cycloundecane
By adding g, a new bouquet-formulated fragrance composition which is natural, floral and has excellent persistence was obtained.

2°6.6 of formula (A)-2 instead of the above formula (A)-1
．． By using 9-tetramethyl-1-methoxy-2.4.8-cycloundecatriene, the same results as above were obtained, although the nuances were somewhat different.

(4) Flavor composition Grape aroma The following ingredients (weight)
were mixed.

Amyl isovalerate 8 Cinnamyl alcohol 5 Cinnamyl isovalerate 3 Cinnamyl propionate 3 Citral
1 Ethyl acetate 62 Ethyl benzoate 3 Ethyl butyrate 16 Ethyl cabroate 3 Ethyl enanthate 8 Hydroxycitronellal l Methyl anthranilate
132 Methyl salicylate 12 Vetigren l-turbinyl acetate 10 Ethanol
732 total 1000 2-methylene-6 of formula (A)-3 was added to 95 g of the above M1 component.
By adding 5 g of ,6,9-trimethyl-4,8-cycloundecadiene, a new grape blended perfume composition with a sweet grape taste and excellent persistence was obtained. The same result, although the nuance is slightly different, is obtained by formula (A) -
It was also obtained by using 2.6,6°9-tetramethyl-1-methoxy-cycloundecane of 1.

Formula (A)-1 or Formula (A) by 10 expert panelists
Comparative studies were conducted between a blended fragrance composition to which the -3 compound was added and the above fragrance composition to which the compound was not added. As a result, all 10 expert panelists agreed that the perfume composition containing the compound was significantly superior in terms of both aroma and persistence.

(g) Effect The humulene derivative of the above formula (A) of the present invention is a new compound that has not been previously described in any literature. It is a useful compound in the field, and it is possible to provide a novel blended fragrance composition containing this compound as an active ingredient, and this composition can be used in foods and beverages (including luxury goods), cosmetics, health care, etc.
It is useful in a wide range of fields such as hygiene and medicine.

Claims (1)

[Claims] 1. The following formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) However, in the formula, ■ represents a single bond or double bond. where all ■ indicate single bonds or ■ between 2 and 2' indicates a single bond, and other All ■ indicate double bonds, or 2 ■ between −3 indicates a single bond, and all other ■ indicates a double bond, A humulene derivative represented by