JPH02335B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new compound, trans-γ-dihydroilone, which has not been previously described in any literature, a method for producing the compound, and its use. More specifically, the present invention is based on the following formula (1) It relates to trans-γ-dihydroilone represented by Furthermore, the present invention relates to a method for producing the compound of formula (1) above, and also to a persistent aroma and flavor imparting or modulating agent characterized by containing the compound of formula (1) above as an active ingredient. Conventionally, the following formula (1)′ corresponding to the isomer of the above formula (1) compound Cis-γ-dihydroilone represented by is isolated and identified from natural orris rhizome oil and is known. Furthermore, it is also known that the formula (1)′ cis-γ-dihydroilone is a compound having a violet-like aroma. However, the existence of trans-γ-dihydroilone of the present invention formula (1), which corresponds to its trans form, has been completely unknown, both in natural products and synthetically. The present inventors have calculated the following formula (3) We have been conducting research on the synthesis of derivatives of the known compound trans-2-methylene-5,6,6-trimethycyclohexylacetaldehyde. As a result, trans-γ-dihydroirone represented by the formula (1), the existence of which was previously completely unknown, can be synthesized, and the trans-γ-dihydroirone of formula (1) can be synthesized from the compound of the known formula (3). We discovered that it can be easily synthesized industrially with high yield and purity. Furthermore, the trans-γ-dihydroilone of the formula (1) has a much stronger violet-like aroma than its isomer, the above-mentioned formula (1)′ cis-γ-dihydroilone. It was discovered that it is a long-lasting aroma substance. According to the research of the present inventors, the trans-γ-dihydroilone of the formula (1) can be added to various fragrance compositions, such as green, flower, and daylily fragrance compositions, to achieve a long-lasting effect. It is a useful compound that can be used as an aroma and flavor imparting or modulating agent.
In addition, the compound of formula (1) above can be used as a synthetic intermediate for other fragrances,
It was also found to be useful as an intermediate for pharmaceuticals and other organic synthesis. Furthermore, the compound of formula (1) has excellent persistence,
It has remarkable properties as a long-lasting aroma and flavor imparting or modulating agent, and is used in food and beverages, cosmetics, health and hygiene products, etc.
It has been found to be useful as an excellent long-lasting aroma modulator in a wide range of fields such as pharmaceuticals. Therefore, an object of the present invention is to provide the above-mentioned trans-γ-dihydroilone of formula (1), which has not been described in any literature, and a method for producing the same. Another object of the present invention is to provide a long-lasting aroma and flavor imparting or modulating agent containing the above-mentioned compound of formula (1) as an active ingredient. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The above formula (1) compound of the present invention is, for example, the following formula
(3) trans-2-methylene-5,6,
6-trimethylcyclohexyl acetaldehyde is added to the following formula (3)′ in the presence of a base. However, in the formula, R represents a lower alkyl group, and X represents a halogen atom. However, in the formula, R represents a lower alkyl group, trans-alkyl 4-(2-methylene-5,6,6-trimethylcyclohexyl) represented by
It can be easily synthesized by hydrolyzing -2-methyl-2,3-epoxybutyrate with an alkali and decarboxylating it by heating under neutral to acidic conditions. The production mode of the compound of formula (1) of the present invention can be shown as shown in the reaction process diagram below. In the example of the above process diagram, the formula (2) trans-alkyl 4-(2-methylene ―
5,6,6-trimethylcyclohexyl)-2-
To synthesize methyl-2,3-epoxybutyrates, the above formula (3) compound is converted into the above formula (3)'

[Formula] It can be easily synthesized by carrying out a condensation reaction with an alkyl 2-halopropionate, preferably in an organic solvent in the presence of a base. The temperature and time of the above condensation reaction are, for example, about -10° to about 100°C, more preferably about 5 to about 30°C.
Examples include a range of temperatures and reaction times, such as from about 1 to about 24 hours, more preferably from about 2 to about 6 hours. Specific examples of the alkyl 2-halopropionate of formula (3)' used in the above reaction include methyl 2-chloropropionate, ethyl 2-chloropropionate, propyl 2-chloropropionate, and butyl 2-chloropropionate. 2-Chlorpropionate, pentyl 2-chloropropionate, methyl 2-bromopropionate, ethyl 2-bromopropionate, propyl 2-bromopropionate, butyl 2-bromopropionate, pentyl 2- Preferred examples include bromopropionate. The amount of the above formula (3)' compound to be used may be selected as appropriate, and is, for example, about 1 to about 5 times the mole of the above formula (3) compound, more preferably about
For example, the amount used may be in the range of about 1.2 to about 2 moles. Examples of the base used in the above condensation reaction include sodium methylate, sodium ethylate, and potassium t-butoxide. The amount of such a base is, for example, about 1 to about 5 times the mole of the compound of formula (3), more preferably about
It can be used in a range of about 1.2 to about 2 times the mole. Furthermore, specific examples of the organic solvent used in the above reaction include ether, hexane, benzene, toluene, methanol, and ethanol. The amount of the organic solvent to be used is, for example, about 1 to about 10 times the weight of the compound of formula (3) above. Specific examples of the above formula (2) compound, which is a new compound not previously described in the literature, obtained by the above condensation reaction are:
For example, the following compounds can be mentioned. trans-methyl 4-(2-methylene-5,
6,6-trimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate, trans-ethyl 4-(2-methylene-5,6,6-trimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate rate, trans-propyl 4-(2-
methylene-5,6,6-trimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate, trans-butyl 4-(2-methylene-5,
6,6-trimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate, trans-pentyl 4-(2-methylene-6,6-dimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate. According to the present invention, for example, the above formula (2) trans-alkyl 4-
By hydrolyzing (2-methylene-5,6,6-trimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate and then decarboxylating it, the above formula (1) trans-γ-dihydroylon can be obtained easily and in high yield. The above hydrolysis reaction can be carried out, for example, by treating the compound of formula (2), preferably in an organic solvent, at about 0°C to
This can be carried out by contacting with an alkali at a temperature of about 110°C, more preferably about 15°C to 30°C, for a period of about 0.5 to about 24 hours, more preferably about 1 to about 3 hours. can. In carrying out this hydrolysis reaction, the amount of alkali to be used can be selected as appropriate, and for example, about 1 to about 3 moles can be used per 1 mole of the compound of formula (2). Examples of organic solvents when a solvent is used in the reaction include methanol, ethanol, acetone, ether, and toluene. Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium methylate, and sodium ethylate. Among these alkalis, alkalis such as sodium hydroxide and potassium hydroxide are preferably used in the form of an aqueous solution. The reaction product of formula (2) can be prepared by adjusting the pH of the system with inorganic and organic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, perchloric acid, P-toluenesulfonic acid and benzenesulfonic acid. It can be converted to the target product of formula (1) by making it acidic or heating and performing a deoxidizing reaction. This decarboxylation reaction, for example,
150° to about 300°C, more preferably about 170° to about 240°C
The reaction can be carried out by heating under such temperature conditions, for example, for about 3 to about 24 hours, more preferably for about 2 to about 6 hours. The reaction product of formula (1) is
If desired, it can be purified by means such as vacuum distillation. The compound of formula (1) of the present invention blends well with various synthetic fragrances, natural fragrances, natural essential oils, natural citrus oils, etc., and uses the compound of formula (1) as an active ingredient as a long-lasting aroma and flavor imparting or modulating agent. For example, the above formula (1)
Food and drink products, including tobacco and other luxury goods, characterized by containing trans-γ-dihydroilone as an aroma component; Soaps, detergents, characterized by containing the compound of formula (1) above as an aroma component; Cosmetics; health/hygiene products, pharmaceuticals, etc., characterized by containing the compound of formula (1) above as an aromatic flavor component, etc. can be provided. For example, luxury goods such as cigarettes; juice drinks, fruit alcoholic drinks, milk drinks; frozen desserts such as ice creams and ice cream cakes; Japanese and Western sweets; jams; breads; chewing gum, coffee, cocoa, black tea, It is possible to provide food and drink products containing a variety of foods, instant beverages, and food products, including favorite foods such as tea, in appropriate amounts that can impart their unique aroma and flavor. Further, for example, cosmetics can be provided in which an appropriate amount of the present invention is blended with shampoos, hair rinses, hair creams, pomades and other hair cosmetic bases; cosmetic soaps and other makeup/facial cleansing bases, etc. in an appropriate amount to impart the unique fragrance. Furthermore, it is blended or applied in an appropriate amount to impart its unique aroma and flavor to laundry detergents, disinfectant detergents, deodorizing detergents; various health and hygiene materials such as toothpaste, tissue paper, toilet paper, and pharmaceuticals. We can provide quality health, hygiene, and medicines. Example 1 Trans-ethyl 4-(2-methylene-5,
Synthesis of 6,6-trimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate 60% sodium hydride 4.8 in 100 ml of toluene
Prepare sodium ethoxide from g and 6 g of ethanol, add trans-2-methylene-5,
A solution of 18 g (0.1 mol) of 6,6-trimethylcyclohexylacetaldehyde and 21.5 g (0.12 mol) of ethyl α-bromopropionate was added at 5°C for 2 hours, and the mixture was stirred at room temperature for 3 hours. The reaction solution was added to an aqueous acetic acid solution, and the organic layer was washed with heavy sodium chloride, dried, the solvent was distilled off, and then distilled to give trans-ethyl 4-(2-methylene-5,6,6-trimethylcyclohexyl)-2- 22 g (yield 79%) of methyl-2,3-epoxybutyrate was obtained. boiling point
115°~118°C/0.2mmHg. Example 2 Synthesis of trans-γ-dihydroilone Trans-ethyl 4-(2-methylene-5,
Add 14 g (0.05 mol) of 6,6-trimethylcyclohexyl)-2-methyl-2,3-epoxybutyrate to a solution of 24 g of ethanol and 4.2 g (0.075 mol) of caustic potassium, and stir at room temperature for 2 hours.
The reaction solution was neutralized with aqueous hydrochloric acid, extracted with ether, washed with water, dried, the solvent was distilled off, and 0.5 g of sodium acetate was added.
Add and heat under reduced pressure (3 mmHg) (180° to 230°C)
and trans-γ-dihydroirone 7.3g (yield
70%) is obtained as a distillate. IR (liquid film) 1720, 1625, 895cm ^-1 . NMR (CDCl ₃ ) δ = 0.77 (3H, s), 0.88 (3H,
d,, J=4Hz), 0.94 (3H, s), 2.09 (3H,
s), 4.50 (1H, broad s), 4.69 (1H,
broads). Example 3 A rose-like fragrance composition was produced by mixing the following components (parts by weight). hydroxycitronellal 20 nerol 30 rose oxide 20 geraniol 100 phenylethyl propionate 30 phenylethyl alcohol 385 citronellol 100 cinnamic alcohol 30 musk ketone 10 rhodinol 85 methylionone 5 phenylethylmethylcarbinol 100 eugenol 5 geranyl acetate 80 1000 By mixing 5 g of trans-γ-dihydroilone with 100 g of the above composition, a novel fragrance composition with enhanced rose-like aroma and excellent persistence was obtained. Example 4 A bouquet-type fragrance composition was produced by mixing the following components (parts by weight). (Part) Fenyl Eleethyl alcohol 180 Linaril Acetate 30 Bergamottoshin Settatek 40 Gelanium 50 Benzyl Acetate 60 Heritropin 80 Gelaniol 110 Lavender 20 P -Ionon 100 Amyl Sali Section rate 45 Tar Pinyil Acetate 135 Cedar Oil 5 Cedar Oil 5 0 1000 above composition A new fragrance composition was prepared by mixing 10 g of trans-γ-dihydroilone with 100 g.
The aroma of this product had a strong characteristic of a soft flower-like aroma and excellent fragrance persistence.

Claims (1)

[Claims] 1 The following formula (1) trans-γ-dihydroilone represented by 2 The following formula (2) However, in the formula, R represents a lower alkyl group, trans-alkyl 4-(2-methylene-5,6,6-trimethylcyclohexyl) represented by
-2-Methyl-2,3-epoxybutyrate is hydrolyzed with an alkali, and the following formula (1) is characterized by heating and decarboxylating it under neutral or acidic conditions. A method for producing trans-γ-dihydroilone represented by 3 The following formula (3) trans-2-methylene-5,6,
6-trimethylcyclohexyl acetaldehyde is added to the following formula (3)′ in the presence of a base. However, in the formula, R represents a lower alkyl group, X represents a halogen atom, and the following formula (2) obtained by condensation reaction with an alkyl 2-halopropionate represented by However, in the formula, R represents a lower alkyl group, trans-alkyl 4-(2-methylene-5,6,6-trimethylcyclohexyl) represented by
3. The method according to claim 2, wherein -2-methyl-2,3-epoxybutyrate is hydrolyzed with an alkali and then heated and decarboxylated under neutral to acidic conditions.