JP2789271B2 - Fragrance composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to N-substituted anthranilic acid esters which are useful as a compounded perfume material and which have not been described in the prior art. More specifically, the present invention provides the following formula (A)

[0002]

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However, in the formula, R ¹ and R ² have the same meaning as described above, and the present invention relates to a fragrance composition containing an N-substituted anthranilic acid ester represented by the following formula as an active ingredient.

The compound of formula (A) has a soft and sweet floral to fruity-like, herbal-like odor, has particularly excellent persistence, and is useful as a material for various compounded fragrance compositions. It is useful in a wide range of applications such as foods and drinks (including favorite foods), cosmetics, health, hygiene, and pharmaceuticals as a scent or flavor imparting or improving reinforcing material. Furthermore, the present invention relates to a method for producing the above compound.

[0005]

2. Description of the Related Art Conventionally, a compound known as an anthranilic acid derivative and as a fragrance substance is, for example, N- (1-
Methyl benzylidene) methyl anthranilate, N- (4
-Methoxybenzylidene) methyl anthranilate, N-
Methyl (anisilidene) anthranilate, N- (3,7
Methyl-dimethyl-2,6-octadienylidene) anthranilate and methyl N- (pt-butyl-α-methyl-hydroxycinnamylidene) anthranilate are known (Perfum and Flavor Ch).
chemicals, Stephen Arktende
r, 1969).

[0006] It is described that these compounds have different floral nuances, but all have sweet floral, fruity and citrus-like odors. The present inventors have found that condensates of these methyl anthranilate derivatives and various aldehydes have a nuance different from that of the methyl anthranilate derivative and are very sweet, soft floral to fruity-like, herbal-like aroma characteristics and excellent And has already filed a patent application (Japanese Unexamined Patent Publication No.
2-153212).

[0007]

However, the Schiff bases (hereinafter sometimes referred to as enamines) obtained by the invention of Japanese Patent Application Laid-Open No. 62-153212 have excellent persistence, Since it has an unsaturated bond, its stability is somewhat uneasy.

The present inventors have made intensive studies to improve such instability. As a result, it was found that catalytic reduction of the unsaturated bond of these enamines did not bring about a large modulation of aroma, but added a lighter and more gorgeous nuance. In addition, the present invention has been found to be advantageous in formulation because it is remarkably lightened in terms of color tone, and it is harder to be hydrolyzed than enamines, and can impart excellent stability, and thus completed the present invention.

[0009] Accordingly, an object of the present invention is to provide a food or drink, a cosmetic or a health care product comprising the compound of the formula (A) as an active ingredient.
It is an object of the present invention to provide a fragrance composition having useful durability and stability which cannot be obtained with the above-mentioned N-substituted anthranilic acid ester derivatives in a wide range of fields such as hygiene and pharmaceuticals.

The odor characteristics of the N-substituted anthranilates provided by the present invention are shown in Tables 1 and 2 below.

[0011]

[Table 1]

[0012]

[Table 2]

In order to synthesize the N-substituted anthranilic acid esters as described above which can be used as the fragrance composition of the present invention, for example, a lower alkyl ester of anthranilic acid and an aldehyde are subjected to a dehydration condensation reaction to obtain an imine compound.
Then, the imine can be easily synthesized by catalytic reduction of the imine. This reaction can be represented, for example, by the following reaction scheme.

[0014]

Embedded image However, in the formula, R ¹ and R ² are as defined above,

The above condensation reaction is described in
Although it is disclosed in detail in JP-A-153212, the reaction temperature of the above-mentioned dehydration condensation reaction is, for example, described as follows.
Depending on the type of aldehyde, generally, for example, about 15
A temperature range of about to about 100 ° C. can be preferably exemplified. The reaction time is, for example, about 10 to about 50.
A range of about time can be preferably mentioned. As a preferable reaction mode, the reaction is preferably performed while removing water generated in the reaction to the outside of the system.

The aldehydes used in the above reaction include 3,4-methylenedioxy-benzaldehyde,
-(3,4-methylenedioxy-phenyl) -2-methylpropanal, 3- (4-ethylphenyl) -2,2
-Dimethylpropanal, 3- (4-methoxyphenyl) -2-methylpropanal, 2,3,5-trimethyl-3-cyclohexenylcarbaldehyde, 2,3,6
-Trimethyl-3-cyclohexenylcarbaldehyde,
2,4-dimethyl-3-cyclohexenylcarbaldehyde, 3,5-dimethyl-3-cyclohexenylcarbaldehyde, 3- (2-methyl-2-pentenyl) -3-cyclohexenylcarbaldehyde, 4- (2- Methyl-2
-Pentenyl) -3-cyclohexenylcarbaldehyde, 3- (2-hydroxy-2-methylpentyl) -3
-Cyclohexenylcarbaldehyde, 4- (2-hydroxy-2-methylpentyl) -3-cyclohexenylcarbaldehyde, 7-hydroxy-3,7-dimethyloctane-1-al (hydroxycitronellal) and the like. Can be. These aldehydes are compounds readily available on the market.

The use amount of these aldehydes is preferably, for example, in the range of about 1 to about 1.2 mol with respect to the lower alkyl ester of anthranilic acid. After completion of the reaction, the reaction product can be purified as it is or, if desired, by means such as distillation.

The N-substituted anthranilates represented by the formula (A) of the present invention can be easily synthesized by subjecting the thus obtained imines or enamines to catalytic reduction by a conventionally known method. it can.

There are no particular restrictions on the conditions for the catalytic reduction reaction, but generally about 0.5 parts by weight per 1 part by weight of the imine compound.
And dissolved in an organic solvent in an amount of about 1 to about 3 parts by weight, charged into an autoclave, added with a catalyst for catalytic reduction of about 1 to about 10% by weight based on the imine compound, and hydrogenated in the autoclave. After replacing with gas, hydrogen gas pressure about 1
About 10 kg / cm ² , temperature about 5 to about 100 ° C.
The N-substituted anthranilates represented by the formula (A) can be easily obtained by catalytic reduction for about 10 hours.

Examples of the organic solvent to be used for the catalytic reduction, such as methanol, ethanol, n- profile Pano <br/> Le, iso- alcohols such as propanol Le; ethers such as diethyl ether and tetrahydrofuran, hexane, Hydrocarbons such as benzene and toluene can be exemplified, and particularly preferred is ethanol.

Examples of the catalytic reduction catalyst include palladium-carbon (Pd-C), palladium-alumina (Pd-Al ₂ O ₃ ), Raney nickel (Ra-Ni), copper-chromium (Cu-Cr) and the like. be able to.

Hereinafter, embodiments of the present invention will be described in more detail with reference to Reference Examples and Examples.

[0023]

[Reference Example 1]N- (7-hydroxy-3,7-dimethyloctyl) a
Synthesis of methyl translanylate (compound of A-1).  N- (7-hydroxy-3,7-dimethyloctylide
3) 30.5 g (0.1 mol) of methyl anthranilate,
50 ml of 99% ethanol and 1.5 g of 5% Pd-C
After charging into a 300 ml autoclave and purging with hydrogen,
_TwoPressure 1-3kg / cm^TwoAt room temperature for 3 hours. catalyst
After filtration, the solvent was removed and extracted with ether.
After washing with saturated saline and sodium bicarbonate solution, light boiling point
(102-200 ° C / 2mmHg) Except 1.5g, kettle
The rest was used as the product. Yield 27.5 g (90% yield). gas
Purity 72% by chromatography (GC). Boiling point 2
00 ° C / 2 mmHg; refractive index (20 ° C) 1.5337.
The structural formula of the compound of A-1 and¹H-NMR data
It is shown below.

[0024]

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[0025]

[Reference Example 2] N-[3- (3,4-methylenedioxyphenyl) -2-Mechirupuropi Le] (compound of A-2) anthranilic acid methyl synthesis. N- [3- (3,4-methylenedioxyphenyl) -2
-Methylpropylidene] 65 g of methyl anthranilate
(0.2 mol), 150 ml of 99% ethanol and 5%
Charge 3 g of Pd-C into a 1 liter autoclave,
The reaction was carried out at room temperature under an H ₂ pressure of 1 to 3 kg / cm ² for 6 hours. After the reaction, treatment was performed in the same manner as in Reference Example 1, and the bp was 190 ° C /
58 g (89% yield) of the title compound having a refractive index (20 ° C.) of 1.5891 was obtained at 2 mmHg. GC purity 91%. Said A
The structural formula and ¹ H-NMR data of the compound ^No. -2 are shown below.

[0026]

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[0027]

[Reference Example 3]N- (2,4-dimethyl-3-cyclohexenylmethyl
R) Synthesis of methyl anthranilate (compound of A-3).  N- (2,4-dimethyl-3-cyclohexenylmethyl
Den) Refers to 26 g (0.1 mol) of methyl anthranilate
Catalytic reduction under the same conditions as in Example 1 and bp 186 ° C / mm
Hg, title compound 2 having a refractive index (20 ° C.) of 1.5635
2.5 g (88% yield) were obtained. Structure of the compound of A-3
Modeling and¹The H-NMR data is shown below.

[0028]

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[0029]

REFERENCE EXAMPLE 4 Table 3 below summarizes the physical properties of other compounds included in the formula (A) of the present invention obtained in the same manner as in Reference Examples 1 to 3. In the following description, other compounds included in the formula (A) of the present invention are represented by the numbers of the compound No. in Table 3.

[0030]

[Table 3]

[0031]

Example 1 The following components (parts by weight) were mixed as a rose-type compounded fragrance composition.

A novel rose blended flavor was prepared by mixing 960 g of the above composition with 40 g of methyl N- (3,4-methylenedioxyphenylmethyl) -anthranilate (Compound A-4). This new compounded perfume composition was compared by 10 expert panelists. As a result, all the ten expert panelists found that the new compounded fragrance composition containing the compound was significantly superior in characteristics and sustainability of natural rose.

[0033]

Examples 2 to 4 In place of compound A-4, compound A
-2 of N- [3- (3,4-methylenedioxyphenyl) -2-methylpropyl] anthranilate (Example 2), N- (7-hydroxy-3,
7-Dimethyloctyl) -methyl anthranilate (Example 3), N- (2,4-dimethyl-3-) of compound A-3
When methyl (cyclohexenylmethyl) anthranilate (Example 4) was used, similar results were obtained in basic effects, although the nuances of the respective aromas were slightly different.

[0034]

Examples 5 to 8 The following components (parts by weight) were mixed as an orchid-type compounded fragrance composition.

910 g of the above composition was treated with N of compound A-10.
A new compounded perfume with the addition of 90 g of ethyl [-(3- (4-methoxyphenyl) -2-methylpropyl] anthranilate (Example 5), with a fresher and more natural orchid type with enhanced persistence A composition was obtained.

Further, instead of the compound of the above-mentioned A-10, N- [3- (4-ethylphenyl) -2,
Methyl 2-dimethylpropyl] anthranilate (Example 6), N- [3- (4-hydroxy-
4-methylpentyl) -3-cyclohexenylmethyl]
Methyl anthranilate (Example 7), N- [4- (4-hydroxy-4-methylpentyl)-of compound A-25
By using ethyl 3-cyclohexenylmethyl] anthranilate (Example 8), a new compounded fragrance composition having a different persistence with different nuances but with an emphasis on fresh and more natural orchid types is obtained. Was.

[0037]

Examples 9 to 12 The following components (parts by weight) were mixed as a bouquet-type compounded perfume composition.

910 g of the above composition was treated with N of compound A-17.
-(3,5-dimethyl-3-cyclohexenylmethyl)
The addition of 90 g of ethyl anthranilate (Example 9) resulted in a new formulated perfume composition having a fresh and more natural bouquet type with a sustained emphasis.

In place of the compound of A-17, A
-20 N- [4- (4-methyl-3-pentenyl)-
3-Cyclohexenylmethyl] methyl anthranilate (Example 10), N-7-hydroxy-6 of A-26
7-Dimethyloctyl-ethyl anthranilate (Example 11), N- [3- (4-methyl-3) of compound A-18
- pentenyl) -3 by using a cyclohexenyl methyl] anthranilic acid methyl (Example 12), nuances of each is different but has the persistence is naturally bouquet Thai <br/> flop more fresh highlighted A new compounded perfume composition was obtained.

[0040]

Examples 13 to 16 The following components (by weight) were mixed as a flavor composition for grape.

N- of compound A-8 was added to 95 g of the above composition.
5 g of ethyl [3- (4-ethylphenyl) -2,2-dimethylpropyl] anthranilate is added (Example 1).
3) As a result, a novel grape-mixed fragrance composition having a sweet natural grape sensation and having more sustainability was obtained.

In place of the compound of A-8, A-
11 methyl N- (3,5,6-trimethyl-3-cyclohexenylmethyl) anthranilate (Example 14),
Ethyl N- [3- (3,4-methylenedioxyphenyl) -2-methylpropyl] anthranilate of A-6 (Example 15), N- [3- (4-methoxyphenyl)-of A-9 The use of ethyl 2-methylpropyl] anthranilate (Example 16) resulted in a new compounded perfume composition with a slightly different nuance but a fresher, more natural grape tone with a sustained duration. .

[0043] Ten expert panelists compared and studied the compounded fragrance composition to which the product of the present invention was added and the non-added product. As a result, all 10 expert panelists all found that the compounded fragrance composition to which the product of the present invention was added was excellent in both aroma and sustainability.

[0044]

The compounds included in the formula (A) provided by the present invention are provided with a lighter and more gorgeous nuance by catalytically reducing the unsaturated bond of a conventionally known enamine. In addition, the color tone is remarkably lightened, which is advantageous in formulating, and has the advantage of being less likely to be hydrolyzed than enamines. Therefore, the compound of the formula (A) of the present invention is well harmonized with various synthetic fragrances, natural essential oils, synthetic essential oils, citrus oils and the like which can impart excellent stability,
A novel fragrance composition can be prepared using the compound of the formula (A). More specifically, when the compound of the formula (A) is blended in a synthetic essential oil such as bergamot oil, lemon oil, geranium oil, lavender oil, mandarin oil, etc., the natural aroma inherent in the essential oil has a mild flavor. A certain and lasting improvement effect can be imparted to the synthetic essential oil. Also, citrus essential oils such as orange, lime, grapefruit, etc .; lavender oil, vetiver oil, cedarwood oil,
It harmonizes well with natural essential oils such as citronella oil, geranium oil, lavandin oil, sandal oil, etc., and can emphasize the characteristics of the essential oils, and is mellow, full-bodied and natural, and has excellent sustainability. A novel perfume composition having the property can be prepared.

Further, for example, strawberry, lemon, orange, grapefruit, apple, etc. prepared from various synthetic flavors, natural flavors, natural essential oils, citrus essential oils and the like.
When incorporated into a flavor composition such as pineapple, banana, melon or the like, a fragrance composition having a mild, full-bodied naturalness and a long-lasting emphasis can be prepared.

The amount of the compound of formula (A) varies depending on the purpose and the flavor composition to be blended.
Generally, for example, about 0.001 to about 3 of the entire perfume composition
A range of about 0% by weight can be exemplified.

Thus, according to the present invention, it is possible to provide a persistent fragrance imparting or improving reinforcing agent comprising the compound of the formula (A) as an active ingredient, and the compound of the formula (A) can be provided with the fragrance flavor by using the agent. Foods and drinks characterized by containing as a component, and health, hygiene and pharmaceuticals characterized by containing a compound of formula (A) as a flavor component can be provided.

For example, drinks such as fruit drinks, fruit liquors, milk drinks, carbonated drinks; cold desserts such as ice creams, sorbets, popsicles;
Preferred drinks such as Western confectionery, jams, chewing gum, breads, coffee, cocoa, black tea, green tea; Japanese soups, soups such as Western soups, flavor seasonings, various instant drinks and foods, various snacks Foods and beverages can be provided in which foods and the like are blended in an appropriate amount that can impart the unique aroma and flavor. Also, for example, shampoos, hair creams, pomades, and other cosmetic bases for hair; oscilloscopes, lipsticks, other cosmetic bases, cosmetic detergent bases, and the like can impart an appropriate amount of unique fragrance. Can be provided. Furthermore, laundry detergents, disinfectant detergents, deodorant detergents, indoor air fresheners and other health and hygiene detergents; various health and hygiene materials such as toothpaste, tissue, toilet paper, etc .; Health, hygiene and pharmaceutical products, such as flavoring and flavoring agents, can be provided by blending or applying an appropriate amount to impart a unique flavor to the health, hygiene and pharmaceutical products.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 317/58 C07D 317/58

Claims (1)

(57) [Claims] (1) The following formula (A): However, in the formula, -R ¹ is A perfume composition comprising, as an active ingredient, an N-substituted anthranilic acid ester represented by the following formula: wherein R ² represents a methyl group or an ethyl group.