JPH0339059B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is useful in the field of fragrances as an aroma and flavor imparting or modulating agent, and is further useful for other fragrances,
The following formula (1) is useful as a synthetic raw material or intermediate for pharmaceuticals, etc., and is not described in conventional literature. In the formula, the three broken lines between adjacent carbon atoms indicate that only one of those locations is a carbon-carbon double bond, and R represents a C ₁ to C ₅ alkyl group. This invention relates to monocyclophalnesyl acetates represented by: The compound of formula (1) has the following formula (1-1) In the formula, R has the same meaning as above, γ-monocyclophalnesyl acetate represented by the following formula (1-2) In the formula, R has the same meaning as above, and β-monocyclophalnesyl acetate represented by the following formula (1-3) In the formula, R has the same meaning as described above, and includes α-monocyclophalnesyl acetate represented by the following. The present inventors have conducted research on phalnesyl acetic acid derivatives. As a result, we succeeded in synthesizing the compound of formula (1), which has not been described in conventional literature,
It has also been found that the compound of formula (1) is useful as an agent for imparting or modulating a floral-based aroma, and is also useful as a synthetic raw material or intermediate for other fragrances, medicines, and the like. Furthermore, it has been found that the compound of formula (1) is an aroma substance that exhibits excellent persistence and is useful in a wide range of fields of application as a persistent aroma and flavor imparting or modulating agent. Therefore, the object of the present invention is to solve the formula
The object of the present invention is to provide (1) monocyclophalanesyl acetate 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 characterized by containing the compound of formula (1) above 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 compound of the formula (1) of the present invention is, for example, the following formula:
(Five) In the formula, the three broken lines between adjacent carbon atoms indicate that only one of these points is a carbon-carbon double bond. Alternatively, γ-dihydroionone can be expressed by the following formula (4) In the formula, X represents a halogen atom, which is brought into contact with vinylmagnesium halide represented by the following in the presence of an organic solvent, and then hydrolyzed to form the following formula (3). In the formula, the three broken lines between adjacent carbon atoms indicate that only one of these points is a carbon-carbon double bond. Contacting the compound of formula (3) with an orthoacetic acid ester represented by the following formula (2) CH ₃ C (OR) ₃ (2) where R has the same meaning as above in the presence of an acid. By reacting with
It can be manufactured industrially easily and at low cost. In the above, the "C ₁ -C ₅ alkyl group" may be either a straight chain or a branched chain alkyl group. An example of the production of the compound of formula (1) of the present invention is shown in the following reaction formula. In the formula, R, X and the broken line... have the same meanings as described above. The compound of formula (5) above is a known compound per se, and for example,
Specification No. 84842 (Special Publication No. 2-16305), Agr.
Biol.Chem., 30, 759 (1966), Ann.Chem., 652,
115 (1962) and other documents known per se. The compound of formula (3) can be easily synthesized by reacting the compound of formula (5) with the compound of formula (4) in the presence or absence of an organic solvent, and then hydrolyzing the compound. I can do it. This reaction can be carried out at a temperature of, for example, about -20°C to about 150°C, more preferably about 0°C to about 70°C. The incubation time can be selected as appropriate; for example, the reaction time can be about 2 to about 10 hours. Specific examples of the solvent used in the above reaction include ether, tetrahydrofuran, benzene, and toluene. These can be used alone or in combination. There is no particular restriction on the amount used, and for example, the amount used is about 1 to about 50 times, more preferably about 2 to about 10 times the weight of the Grignard reagent of formula (4). I can do it. In addition, the reaction molar ratio of the dihydroionone of formula (5) to the compound of formula (4) used in the above reaction can be appropriately selected, and the compound of formula (4) is added to 1 mole of the compound of formula (5). For example, about 1 to about 10 moles, more preferably about
An example of the amount is about 1.05 to about 1.5 mol. After completion of the above reaction, for example, the reaction product is hydrolyzed by injecting it into water, extracted with a suitable solvent such as ether, hexane, benzene, toluene, etc., washed with water, dried, and concentrated. Monocyclonerolidols represented by formula (3) can be obtained in high yield and with high purity. During the above hydrolysis, a weakly acidic substance such as ammonium chloride may be present to promote the hydrolysis. If desired, it can be further purified by means such as vacuum distillation or column chromatography. The compound of formula (1), which is the object compound of the present invention, can be obtained by adding the compound of formula (3), which can be obtained as described above, to the orthoacetic ester of formula (2) in the presence of an acid catalyst. It can be easily synthesized by bringing these into contact with each other. Examples of vinegar catalysts used in the above reaction include lower fatty acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, malonic acid, succinic acid, and adipic acid; sulfonic acids such as p-toluenesulfonic acid; Examples include mineral acids such as hydrochloric acid and sulfuric acid; and acid catalysts such as Lewis acids such as zinc chloride, iron chloride, boron trifluoride, and aluminum chloride. The amount of these acid catalysts used can be selected as appropriate, for example,
An example of the amount used is about 0.5 to about 10% by weight based on the compound of formula (3). The reaction temperature and reaction time of the above reaction can be selected as appropriate, for example, about
Reaction temperature of about 50° to about 200°C and e.g.
An example of a reaction time is about 24 hours. Further, the amount of the compound of formula (2) used in the reaction can be selected as appropriate, for example, about 1 to about 20 moles per mole of the compound of formula (3). be able to. After the reaction is complete, for example, if an organic acid catalyst is used, the reaction product can be directly distilled, or if an inorganic acid catalyst is used, the reaction product can be injected into water to neutralize it. By extracting with a suitable solvent such as ether, hexane, benzene, toluene, etc., and washing the solvent layer with water, drying, and concentrating, a novel compound of formula (1) can be obtained in high yield and purity. can. The obtained compound of formula (1) can be further purified, if desired, by means such as vacuum distillation or column chromatography. For example, the compound of formula (1) of the present invention, which can be produced as described above, is a novel compound that exhibits a floral-based fragrance, and has a floral-based fragrance with a nuance ranging from a light green feeling to a heavy dullness. It is useful as an aromatic substance. Furthermore, the compound has excellent durability. These representative compounds of the present invention and their aromas are shown below.

[Table] Le style

[Table] As exemplified above, the compound of formula (1) of the present invention is
Although its nuances are diverse, it has a floral-based aroma and flavor, and has excellent persistence, so it is useful as a persistent aroma and flavor imparting or modulating agent. Due to its unique aroma and flavor and excellent persistence, the persistent aroma and flavor imparting or modulating agent is suitable for food and beverages (including luxury goods), soaps, detergents, cosmetics, health, sanitary and pharmaceutical products, It exhibits excellent effects in a wide range of other fields of use. Therefore, according to the present invention, foods and drinks characterized by containing the monocyclophalanesyl acetate of formula (1) as an aromatic flavor component; Soaps, detergents, cosmetics; protection, 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 ice candy;
Unique aromas and flavors can be imparted to various foods and beverages, including favorite foods such as Japanese and Western confectionery; jams; bread; chewing gum; coffee, cocoa, and tea; and various instant beverages and instant foods. Foods and drinks can be provided in appropriate amounts. In addition, for example, cosmetics containing shampoos, hair rinses, hair creams, pomades, other hair cosmetic bases; cosmetic soaps and other makeup/facial cleansing bases are blended in an appropriate amount to impart a unique fragrance. can. Furthermore, its unique fragrance is used in laundry detergents, disinfectant detergents, deodorizing cleaning products, and various other protective and sanitary detergents; various health and hygiene materials such as toothpaste, tissue paper, and toilet paper, as well as pharmaceuticals. Appropriate amounts that can impart flavor can be blended or applied to provide health, hygiene, and medicine. Hereinafter, the present invention will be explained in more detail with reference to Examples and Reference Examples. Reference example 1 α-monocyclonerolidol [compound of formula (3)]
Preparation of tetrahydrofuran in a 1 volume reaction flask.
Charge 200ml and 10.8g (0.45mol) of magnesium. A solution of 48 g (0.45 mol) of vinyl bromide and 200 ml of tetrahydrofuran was added dropwise to this under reflux (66-67°C) over a period of 1 hour. After the dripping is finished,
Stirring was further continued for 30 minutes at the same temperature to prepare a Grignard reagent. A solution of 80 g (0.41 mol) of α-dihydroionone and 200 ml of tetrahydrofuran was added dropwise to the Grignard reagent over a period of 1 hour at a reaction temperature of 5 to 15°C. After the dropwise addition was completed, the reaction was continued by stirring for an additional hour at room temperature. Under reduced pressure, the distillation residue obtained by recovering tetrahydrofuran from the reaction product was poured into an aqueous ammonium chloride solution 1 and extracted with ether. This ether extract was prepared using a conventional method.
After washing with water, washing with alkaline water, dehydration, and recovering ether, the mixture was distilled under reduced pressure to obtain 82 g of α-monocyclonerolidol (yield: 90%) at 102° to 106°C/3 mmHg. The obtained compound exhibited a persistent floral odor.
Similarly, β-monocyclonerolidol with a boiling point of 105° to 108°C/3 mmHg (95% yield) and γ-monocyclonerolidol with a boiling point of 97° to 98°C/1 mmHg (79% yield) were synthesized. . These compounds also exhibited a persistent floral odor. Example 1 Production of ethyl α-monocyclophalnesyl acetate [compound of formula (1)] In a reaction flask with a capacity of 1, 100 g (0.45 mol) of α-monocyclonerolidol and ethyl orthoacetate were added.
Prepare 520g (3.5mol) and 3g of propionic acid,
The reaction is carried out under reflux (115-124°C) with stirring for 15 hours. The ethanol produced in the reaction is distilled off, and a small amount of propionic acid is added.
Perform the heating reaction for a period of time. After the reaction is completed, 106 g of ethyl α-monocyclophalanesyl acetate with a boiling point of 140° to 159°C/3 mmHg is obtained by a conventional process such as distillation.
(yield 81%). This compound exhibited a persistent floral fragrance with a leafy feel. Example 2 According to the method of Example 1, various monocyclophalnesyl acetates were synthesized. The results are shown in Table-2.

[Table]

[Table]

The fragrance tone of the compound of formula (1) above has a nuance ranging from a light green feeling to a heavy dull feeling, such as a floral tone with a green feeling, a leafy feeling, a fruity feeling, a sweet fruity feeling, and a dull feeling, and showed good persistence. Reference Example 2 A fragrant plastic material for shampoo was produced by mixing each component (parts by weight). Linalool 5 Absolute diasmine 2 β-phenylethyl alcohol 15 Rhodinol 15 Absolute rose 1 Hydroxycitronellol 30 Indole 10% benzyl benzoate solution 2 Stilac oil 3 Hexylcinnamic aldehyde 15 Cyclamen alnedehyde 4 Sandalwood oil 5 Phenyl acetaldehyde 10% 3 100 By adding 5 g of ethyl α-monocyclophalanesyl acetate to 95 g of the above composition, a new composition that has a floral-like characteristic with a leafy feeling (lily of the valley) and is long-lasting can be obtained. It was done. Similar results with floral undertones were obtained with α-monocyclonerolidol, methyl α-monocyclophalnesyl acetate, ethyl β-monocyclophalnesyl acetate, i-propyl γ-monocyclophalnesyl acetate, i-amyl β -monocyclophalnesyl acetate, respectively. Reference Example 3 The following components (by weight) were mixed as an aroma and flavor composition for grapes. Amyl isovalerate 8 Cinnamyl alcohol 5 Cinnamyl isovalerate 3 Cinnamyl propionate 3 Citral 1 Ethyl acetate 62 Ethyl benzoate 3 Ethyl butyrate 16 Ethyl caproate 3 Ethyl enanthate 8 Hydroxycitronellal 1 Methyl anthrani Rate 132 Methyl salicylate 12 Pettigrain 1 Terpinyl acetate 10 Ethanol 732 Total 1000 By adding 5 g of i-propyl α-monocyclophalnesyl acetate to 95 g of the above composition, a fruity or sweet fruity floral tone can be produced. A new composition with characteristics and long-lasting properties was obtained. Similar results with floral undertones were obtained by using n-propyl β-monocyclophalnesyl acetate, i-butyl γ-monocyclophalnesyl acetate, and n-butyl α-monocyclophalnesyl acetate, respectively. Obtained.

Claims (1)

[Claims] 1. The following formula (1) In the formula, the three broken lines between adjacent carbon atoms indicate that only one of those locations is a carbon-carbon double bond, and R represents a C ₁ to C ₅ alkyl group. Monocyclophalanesyl acetate esters represented by