JPS591461A - Cyclohexene and its utilization - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R is H, methyl; the dotted lines mean that double bonds are between the 2-3 or 3-4 positions). EXAMPLE:1,3-Dimethyl-4-(1-oxo-3-butenyl)-1-cyclohexene. USE:Durative smell or flavor intensifier or modifier: it has flower-like or fruit- like smell, moreover the smell is durative. It can develop excellent effects over a wide range of fields such as hygiene and medicines. PREPARATION:The reaction of 1,3-dimethyl-4-formyl-1-cyclohexene of formula 3 with an allylmagnesium halide of formula 4 (X is halogen) is carried out in an organic solvent such as benzene at -20- about 60 deg.C for about half to 5hr to give a compound of formula 2. The product is oxidized in a solvent such as acetone with chromic anhydride to give the compound of formula 1-2. The compound of formula 1-2 is isomerized in the presence of a catalyst such as sulfuric acid to give the compound of formula 1-1.

Description

[Detailed description of the invention] The present invention relates to cyclohexanes that have not been described in prior American literature.

Regarding its manufacturing method and its use.

Furthermore, permissibly, the present invention is represented by the following formula (1), where R represents a hydrogen atom or a methyl group, and a broken line represents double payment at the 2nd or 3rd position.

This article relates to cyclohexene represented by , its production method, and its use.

In one of the above uses, the present invention relates to a long-lasting aroma and flavor imparting or modulating agent characterized by containing the compound of the present invention as an active ingredient.

The inventors have discovered that q! is important as a fragrance. We have been conducting intensive research on the knowledge of r-type cyclohexene and its synthesis.

As a result, it was discovered that a cyclohexene of the above formula (1), which had not been previously described in any literature, could be synthesized.

Furthermore, the cyclohexene of formula (1) has a sweet, soft, floral or fruit-like aroma and flavor, has excellent sustainability, and is an extremely useful and unique ingredient as an aroma and flavor component for food and drink products. I discovered that. Furthermore, it has been discovered that the compound 2 (11) is a compound that is noteworthy as a long-lasting aroma and flavor imparting or flavor modulating agent, and is useful in foods and beverages (including luxury goods), cosmetics, and the like.

The present invention provides a compound of formula (1) and a method for producing the same. Another object of the present invention is to provide a persistent aroma and flavor imparting or modulating agent containing the compound of formula (1) as an active ingredient.

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

In the present invention, the above formula (1) is the following formula (1-1).

υ However, in the formula, R represents a hydrogen atom or a methyl group.

A compound represented by the following formula (1-2).

() However, in the formula, R has the same meaning as described above.

This includes compounds represented by

Specific examples of the compound of formula (1-1) include the following compounds.

(α) l,3-trimethyl-4-(1-oxo-2-phthynyl)-1-cyclohexene (b) 1,3,5-trimethyl-4-(1-oxo-2
-butenyl)-1-cyclohexene Also, the formula (1-2
) Specific examples of the compound include the following compounds.

(C) 1,3-trimethyl-4-(1-oxo-3-butenyl)-1-cyclohexene (1,3,5-trimethyl-4-(l-oxo-3
-Gutynyl)-1-cyclohexene superposition @-The following procedure is used.

Fake tile ladder point ('c) (a)
s a ~91 c7srmHg (b)
9 a~95C/3rd hand II Q(6)
82-85C/3. Hg (ψ 87~
90C/3. HQ The above-mentioned formula (1) compound comprising the above-mentioned formula (1-1) compound and the above-mentioned formula (1-2) compound of the present invention is 1, for example, the following formula (3), provided that in the formula, R41 hydrogen atom or 1,3-dimethyl-4-formyl-1-cyclohexene which represents a methyl group and is represented by the following formula (4) % formula % However, in the formula, X represents a halodane atom.

The following formula (2) is obtained by contacting allylmagnesium halide represented by the formula (2), where R represents a hydrogen atom or a methyl group.

The known compound 1,3-dimethyl-4-(1-
It can be easily produced from hydroxy-3-butenyl-1-cyclohexene. For example, the formula (2)
By oxidizing, 1,3-methyl-4-(1-oxo-3-butenyl)-1-cyclohexene represented by the following formula (1-2) can be formed. In addition, by isomerizing the adduct of formula (1-2), 1,3-dimethyl-4-(1-oxo-2
-butenyl) -1-cyclohexene can be produced industrially easily and inexpensively.

The formula (1) included in the formula (1) of the present invention described above
-, 1) and (1-2) Compounds can be shown as follows in a process diagram.

(1-2) (1-1) However, in the formula, R represents a hydrogen atom or a methyl group, and X represents a halodane atom.

The compound of formula (3), which is the starting material of the present invention, is a known adduct and can be prepared by, for example, Diels-Alder reaction of 2-methyl-1,3-pentadiene and acrolein or crotonaldehyde. Can be easily synthesized.

The compound of formula (2) is also a known adduct and can be easily synthesized by bringing the compound of formula (3) into contact with the Grignard reagent of formula (4) in the presence of an organic solvent.

The amount of magnesium chloride expressed by formula (4) used in the above reaction, which can be easily synthesized according to a conventional method, is 1, which is expressed by formula (3).
For example, the amount used can be in the range of about 1.0 to about 3.0 moles relative to 3-methyl-4-formyl-1-cyclohexene.

Examples of organic solvents used in the reaction include:

Examples include organic solvents such as benzene, toluene, diethyl ether, zoinpyl ether, tetrahydrofuran, dioxane, somethoxyethane, and the like. There is no particular restriction on the amount used, but the amount used may be, for example, about 2 to about 20 times the weight of the compound of formula (3). The reaction temperature and reaction time of the above reaction can be selected as appropriate and vary depending on the type of solvent employed. Time can be given as an example. After the reaction is completed, the compound represented by the formula (2) can be easily produced in a good yield by hydrolysis and by employing purification means such as distillation.

The compound of formula (1-2) of the present invention can be easily synthesized by contacting the compound of formula (2), which can be obtained as described above, with an oxidizing agent in the presence of an organic bath medium. can do. Examples of oxidizing agents used in the reaction include chromic anhydride (Soyons reagent), chromic acid tertiary butyl ester, dibirizonium chromate, pyrinonium chlorochromate, kyochromate, permanganate, etc. Examples include oxidizing agents such as. The amount of these oxidizing agents to be used can be selected as appropriate, and for example, the amount used can be about 2 to about 5 times the mole of the compound of formula (2). Examples of organic solvents used in this reaction include acetone, tertiary butanol, tertiary amyl alcohol, sochloromethane, pyridone, and acetic acid. There is no particular restriction on the amount used, but for example, about 2 to about 2
Examples include lids that can be used in a range of about 0 times the weight.

The reaction temperature and reaction time of the above reaction can be appropriately selected depending on the type of oxidizing agent employed and the organic solution process.
An example of the reaction time is about 0.5 to about 5 hours. After the reaction is completed, a purification method such as distillation is employed to obtain the formula (1-
2) Chemical adducts can be obtained easily and in good yields.

The compound of formula (ii) of the present invention can be easily obtained by contacting the compound of formula (1-2), which can be obtained as described above, with an isomerization catalyst in the presence of an organic solvent. Can be synthesized.

Examples of isomerization catalysts used in the reaction include sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, toluenesulfonic acid, naphthalenesulfonic acid, zinc chloride, aluminum chloride, tin tetrachloride, titanium tetrachloride, Examples include boron trifluoride, caustic soda, caustic potash, sodium methoxide, sodium ethoxide, potassium tert-butoxide, and sodium hydride. The amount of the stiff isomerization catalyst to be used can be selected as appropriate, for example, in an amount of about 5 to about 20% by weight based on the compound of formula (1-2). Examples of organic solvents used in the reaction include benzene, toluene, xylene, hexane, siglohexane, and soethyl ether.

Examples include diimpropyl ether, tetrahydrofuran, sooxane, monoglyme, diglyme, methanol, ethanol, n-propanol, impropanol, n-butanol, isobutanol, and tertiary butanol. There is no particular restriction on the amount used, but for example, it can be used in an amount of about 2 to about 50 times the weight of the compound of formula (1-2). The reaction temperature and reaction time of the above reaction can be appropriately selected depending on the type of isomerization catalyst and organic solvent employed, but for example, the reaction temperature is about 0 to about 100C, and the reaction time is about 1 to about 20 hours. 11f] can be shown as 9.11 at the time of reaction. After the reaction is completed, the compound of formula (1-1) can be easily produced in a good yield by employing purification means such as distillation.

The illumination compound of the present invention has a flower-like, fruit-like aroma and flavor, and is very long-lasting, so that it is useful as a long-lasting aroma and flavor imparting or modulating agent. Due to its unique aroma and flavor imparting or modulating agent, it is suitable for use in foods, beverages, soaps, detergents, cosmetics, health and hygiene products, and pharmaceuticals due to its unique aromatic taste and excellent persistence. It can demonstrate excellent effects in a wide range of other fields of use.

Therefore, 5. A collection of foods and beverages characterized by containing the cyclohexene of the formula (1) as an aroma component by utilizing the persistent aroma and flavor imparting or modulating agent of the present invention. Soaps, detergents, cosmetics; health, hygiene, pharmaceuticals, etc. can be provided.

For example, juices, fruit alcoholic drinks, milk drinks; lactic acid bacteria drinks; drinks such as carbonated drinks; frozen desserts such as ice creams and popsicles; Japanese and Western sweets; soyams; breads; chewing gum, coffee. It is possible to provide food and drink products including various types of food and drink products, instant beverages, and instant foods containing favorite foods such as coffee, cocoa, black tea, etc., in appropriate amounts capable of imparting their unique aroma and flavor. Furthermore, it is possible to provide cosmetics containing, for example, shampoos, hair rinses, hair creams, pomades, other hair cosmetic bases; cosmetic soaps and other makeup/facial cleansing bases in an appropriate amount that imparts the unique fragrance. .

Furthermore, laundry detergents, disinfectant detergents, deodorant cleaning products, and other Japanese health and hygiene detergents; toothpaste, tissues,
An appropriate amount that can impart the unique aroma and flavor to various health and hygiene materials and medicines such as toilet penose can be blended or applied to provide health, hygiene, and medicines.

Hereinafter, several examples of implementation of the present invention will be shown in Examples.

Reference Example 1 Preparation of 1.3-dimethyl-4-(1-hydroxy-3-butenyl)-1-cyclohexene (2) @.

Allylmagnesium chloride is prepared by charging 5.81 (0.24 moles) of magnesium metal, 17f (0.22 moles) of allyl chloride, and 1002 of ether into a reaction flask. To this preparation was added an ether of 28 f (0.20%) of l,3-methyl-4-formyl-1-cyclohexene, 5 G? flIK is reacted dropwise at 20-25C for about 20 minutes.

After completion of the dropwise addition, the reaction is further continued for about 1 hour at room temperature.

After completion of the reaction, one reaction solution was poured into a saturated aqueous ammonium chloride solution, the ether layer was washed with water, and the ether layer was dried and distilled to obtain pure 1.3-tmethyl-4-(1-hydroxy-3-butenyl)-. 1-Cyclohexene aa, 1y (yield: 92%) was obtained.

Reference example 2 1.3.5-trimethyl-4-(1-hydroxy-3-
Production of (butenyl)-1-cyclohexene (2).

In the method of Reference Example 1, 1, 3.5-)dimethyl-4-(1-hydroxy-3-butenyl)-1-cyclohexene (yield 90
h) was obtained.

Example 1 1,3-dimethyl-4-(l-oxo-3-butenyl)
-1-cyclohexene (1-2) OR structure.

1,3-dimethyl-4-(1-hydroxy-3-butenyl)-1-cyclohexene 24F (0,
13 mol) and 300 mol of acetone. Add John's reagent [chromium oxide 18f (0,1
8 mol), water 33.3 m/! .

A mixed solution of concentrated sulfuric acid (16)] was added dropwise at a reaction temperature of 20 to 25C. When the solution no longer changes from red to green, stop dropping and add a small amount of isopropyl alcohol to stop the reaction. Decant the reaction solution, neutralize it, and collect the acetone solution.

Ether and water were added to the residual solution, extracted, the ether layer was separated, washed with water, dried, distilled, etc. to obtain pure 1゜3-dimethyl-4-(l-oxo-3-butenyl)-1-cyclohexene 19.7r. (yield: 83 cm). Boiling point 82-85
C/3rIaRhg0 Example 2 1.3-dimethyl-4-(1-oxo-2-butenyl)
-1-Cyclohexene (1-1) (7) Production.

A reaction flask was charged with 9.52% of 1,3-dimethyl-4-(]-]oxo-3-butenyl-1-cyclohexene, 0.!M' of p-toluenesulfonic acid, and 100F of toluene, and heated to a temperature of about 80 to 90C. The reaction is carried out for about 3 hours while stirring at 1° C. for isomerization.

After the reaction is complete, cool and perform operations such as neutralization, water washing, and distillation.
．． 3-Tmethyl-4-(1-oxo-2-butenyl)
-1-cyclohexene s, 6 y (yield $90%)
get. 1 item 88~91 C/ 3 tramBQ
Example 3 1.3. Preparation of 5-)dimethyl-4-(1-oxo-2-butenyl)-1-cyclohexene (1-1).

In the method of implementation fl12, ■, 3-trimethyl-4-
1.3.5-)dimethyl-4-(1-oxo-3 instead of (1-oxo-3-butenyl)-1-cyclohexene
-butenyl)-1-cyclohexene was used in the same manner as 1,3.5-)dimethyl-4-(1-oxo-2
-butenyl)-1-cyclohexene (yield: 85 cm) was obtained. Buddha point 93-9 sc'/3gHg0 Example 4 The following components (one drop) were mixed as an apple aroma composition.

ethyl acetate) 50 ethyl propionate 2゜ethelbutylade 3゜ethyl isoparelate 6゜isoamyl acetate 3゜butyl alcohol 150゛amyl alcohol 5゜butylprobioner) 70 butyl butylade 1゜2-hexenol io.

2-hexenyl acetate 180 isobutyric acid 40 vanillin
20 hexyl butyrad
10 ethyl alcohol
180 Total 1000 By adding 102 1,3-dimethyl-4-(1-oxo-3-butenyl)-1-cyclohexene to 100v of the above composition, the apple aroma and flavor component are sweet, soft, very excellent and long-lasting. A novel fragrance composition with good properties was obtained. Similar results were obtained for 1,3-dimethyl-4-
(1-oxo-3-butenyl) -In place of 1-cyclohexene.

Obtained by using 1.3.5-trimethyl-4-(1-oxo-3-butenyl)-1-cyclohexene. However, in this case, the apple character had a characteristic reminiscent of the aroma of ripe nine apples.

Example 5 0.1 ft of a 0.01% alcohol fi solution of 7'cl, 3-dimethyl-4-(1-oxo-2-butenyl)-1-cyclohexene dissolved in 95 thiol was added to 500 tons of commercially available apple juice. . The added product produced a juice with a stronger fresh green color than commercially available apple juice, as well as a soft and long-lasting aroma and flavor. Similar results were obtained with 1,3,5-trimethyl-4-(1-oxo-2-butenyl)-1 instead of 1,3-dimethyl-4-(1-oxo-2-butenyl)-1-cyclohexene. -Also obtained by using cyclohexene.

Example 6 Composition for Soap A Narcisse-like fragrance composition was produced by mixing the following components (coulometric parts).

Bergamotu oil 1 fillan
Ylang oil 5 linalool
2゜pentyl acetate 5benzyl alcohol
25 Terpineol
12-paracresyl acetate
1 Cinnamic alcohol 5 Eugenol 4 Heliotropin 4 Absolute jasmine 200 A fragrance composition was prepared by mixing 1,3-methyl-4-(l-oxo-2-butenyl)-1-cyclohexene iF with the above composition 99f. . This and a composition without addition of 1,3-dimethyl-4-(1-oxo-2-butenyl)-1-cyclohexene were added to a scented f+, unflavored stone paste at a ratio of 1% by weight. We added incense, molded it, and manufactured soap.

L,S-trimethyl-4-(1-oxo-2-butenyl)
-'1-Cyclohexene-added 7'C soap had a strong natural Narcissus-like aroma and a soft, excellent fragrance persistence compared to soap without addition.

Similar results were obtained for 1,3-dimethyl-4-(1-oxo-
1,3.instead of 2-butenyl)-1-cyclohexene.
5-) Dimethyl-4-(l-oxo-2-butenyl)-
It was also obtained using 1-cyclohexene.

(1 other person)

Claims (1)

[Claims] 1. The following formula flll, where R is a hydrogen atom or a methyl group, 7r, cy,
The broken line indicates that there is a double bond in the 2nd or 3rd place. Expressed as 1. Cyclohexenes. 2 The following formula (1) However, in the formula, Rf-1' represents a hydrogen atom or a methyl group, and a broken line represents a double bond at the 2- or 3-position. A persistent aroma and flavor imparting or modulating agent characterized by containing a cyclohexene represented by the following as an active ingredient.