JPH0686599B2 - Fragrance composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to the use of methyl anthranilate derivatives, which have not been described in the prior art, and which are useful as blended perfume materials.

More specifically, the present invention provides the following formula (A) A perfume composition comprising a methyl anthranilate derivative represented by the formula (1), which represents a group selected from the group consisting of:

The compound of the formula (A) has a soft and sweet floral or fruity-like or herbal-like odor, and has extremely excellent persistence, and is useful as a material for various prepared fragrance compositions, and has a persistent odor. It is useful as a flavor imparting or improving / reinforcing agent in a wide range of fields of use such as foods and drinks (including favorite products), cosmetics, health care, hygiene, and pharmaceuticals. The present invention also relates to methods of making the above compounds.

(B) Conventional Technology Conventionally, examples of the compound which is an anthranilic acid derivative similar to the methyl anthranilate derivative of the general formula (A) of the present invention and which is known as a fragrance substance include, for example, N- (1-methylbenzylidene) anthranilic acid. Methyl, N- (4-
Methoxybenzylidene) anthranilate methyl, N-
(Anisiliden) methyl anthranilate, N- (3,7-
Dimethyl-2,6-octadienylidene) anthranilate and N- (pt-butyl-α-methyl-hydroxycinnamylidene) anthranilate (Perfum
and Flavr Chemicals, Steffen Arctender, 1969)
Are known. Further, it is described that they have different nuances but all have sweet floral, fruity and citrus-like aromas.

(C) Problems to be Solved by the Invention In recent years, with the diversification of various foods and drinks and cosmetics, there has been an increasing need for new aromas that have never existed before. It is desired to develop a blended perfume material having excellent properties.

For this reason, generally, for example, a method of synthesizing a novel compound or a derivative thereof found by analysis of natural essential oils and providing it as a prepared perfume material, or a compound having a structure similar to that of a conventionally known perfume compound or a derivative thereof. , A compound useful as a fragrance substance was discovered from these, and it has been provided as a blended fragrance material.

However, there are few materials that are mild and rich, and have a fresh, natural feel, and can also impart sustainability,
In particular, it cannot be said that the materials having the above-mentioned properties that can be easily and inexpensively obtained are necessarily provided satisfactorily.

(D) Means for Solving the Problems In view of the above circumstances, the present inventors have found that anthranilic acid, which is a condensate of various aldehydes other than the above-mentioned methyl anthranilate derivative known as the perfume substance, and methyl anthranilate. With respect to methyl derivatives, we have conducted intensive research into compounds useful as fragrance substances.

As a result, the methyl anthranilate derivative represented by the above formula (A) has a very sweet and soft floral or fruity-like, herbal-like aroma characteristic different from the above-mentioned known compounds, and excellent persistence, and The inventors have discovered that the compounds of the formula (A) can be easily synthesized and succeeded in their synthesis.

Therefore, the object of the present invention is to use the above-mentioned compound of formula (A) as an active ingredient in a wide range of fields such as foods and beverages, cosmetics, health care, hygiene and medical drugs, etc. In order to provide a perfume composition having a useful longevity, which cannot be obtained by the conventional method.

Aroma characteristics of the methyl anthranilate derivative of the present invention are shown below.

(1) N- (3,4-methylenedioxy-benzylidene)
Methyl anthranilate.

A floral scent that reminds us of a sweet, persistent rose.

(2) Methyl N- [3- (3,4-methylenedioxy-phenyl) -2-methyl-propylidene] anthranilate.

A floral fragrance with a hint of nerolly, reminiscent of jasmine and lily of the valley, which has a slight greenness and sustainability with a fruity feel.

(3) Methyl N- (3,5,6-trimethyl-3-cyclohexenylmethylidene) anthranilate. A floral scent reminiscent of a sweet, persistent orange peel with a green and herbal feel.

(4) Methyl N- (2,4,6-trimethyl-3-cyclohexenylmethylidene) anthranilate. A floral fragrance resembling an orange flower that is sweet and persistent with a slight herbal and fruity feel.

(5) Methyl N- (2,4-dimethyl-3-cyclohexenylmethylidene) anthranilate.

A floral-like scent with a sweet-smelling persistence, with a slight citrus feel.

(6) Methyl N- (3,5-dimethyl-3-cyclohexenylmethylidene) anthranilate.

Sweet and persistent floral scent like lily of the valley with a balsamic feel.

(7) N- [3- (2-methyl-2-pentenyl) -3
-Cyclohexenyl methylidene] methyl anthranilate.

A floral-like scent with a hint of green and herbal, with a sweet and long-lasting effect that reminds you of a little lily of the valley.

(8) N- [4- (2-methyl-2-pentenyl) -3
-Cyclohexenyl methylidene] methyl anthranilate.

It has a herbal, green, and slightly orange feel,
A sweet and persistent lily of the valley aroma.

(9) Methyl N- [3- (2-hydroxy-2-methylpentyl) -3-cyclohexenylmethylidene] anthranilate.

A sweet and long-lasting watermelon-like aroma with a slight green sensation.

(10) Methyl N- [4- (2-hydroxy-2-methylpentyl) -3-cyclohexenylmethylidene] anthranilate.

A tuberose-like aroma with sweetness and longevity, with a slight herbal sensation.

In order to synthesize the above-mentioned methyl anthranilates that can be used as the fragrance composition of the present invention, it can be easily synthesized, for example, by subjecting methyl anthranilate and aldehydes to a dehydration condensation reaction. The reaction can be represented by the following reaction process diagram.

However, in the formula, R has the same meaning as described above. The reaction temperature of the dehydration condensation reaction depends on the kind of the aldehyde, but generally, a preferable range is, for example, about 15 ° to about 100 ° C. . The reaction time is preferably in the range of, for example, about 10 to about 50 hours. As a preferable reaction mode, it is preferable to carry out while removing water generated in the reaction from the reaction system.

Examples of aldehydes used in the above reaction include, for example, 3,
4-methylenedioxy-benzaldehyde, 3- (3,4-
Methylenedioxy-phenyl) -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-
Examples thereof include (2-hydroxy-2-methylpentyl) -3-cyclohexenylcarbaldehyde. These aldehydes are compounds that are easily available on the market.

The amount of these aldehydes used is preferably in the range of, for example, about 1 to about 1.2 mol relative to methyl anthranilate. After completion of the reaction, the reaction product can be optionally purified by a means such as distillation.

The above-mentioned unrecorded methyl anthranilate derivative of the formula (A) which can be used in the fragrance composition of the present invention has a soft floral or fruity-like or herbal-like odor, has a sweet and particularly excellent sustainability. ing.

The compound of formula (A) of the present invention is in good harmony with various synthetic fragrances, natural essential oils, synthetic essential oils, citrus oils and the like, and a novel fragrance composition can be prepared using the compound of formula (A). More specifically, when the compound of the formula (A) is blended with a synthetic essential oil such as bergamot oil, lemon oil, geranium oil, lavender oil, mandarin oil, etc., the natural essential oil has a mild aroma and richness. In addition, it is possible to impart a persistent improving effect to the synthetic essential oil. In addition, citrus essential oils such as oranges, limes, lemons, grapefruits and grapes; harmonious with natural essential oils such as lavender oil, vetiver oil, cedarwood oil, citronella oil, geranium oil, lavandin oil and sandal oil. However, the characteristics of the essential oil can be emphasized, and a novel fragrance composition having a mellow, rich and natural taste, and an excellent and long-lasting property can be prepared. Furthermore, for example, various synthetic flavors, natural flavors, natural essential oils, prepared from citrus oils, for example, strawberry, lemon, orange grapefruit, apple, pineapple, banana,
When added to a flavor composition such as melon, a perfume composition with a mild and rich naturalness and an enhanced sustainability can be prepared. The compounding amount of the compound of the formula (A) varies depending on its purpose and the aroma and flavor composition to be compounded, but for example, it is generally about 0.001 to about 3 of the total amount.
A range of about 0% by weight can be exemplified.

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

For example, fruit juice drinks, fruit wine, milk drinks carbonated drinks,
Beverages such as: ice creams, sherbets,
Frozen desserts such as popsicles; Japanese and Western confectionery,
Jiamus Chewing gums, breads, coffee, cocoa, black tea, tea and other luxury items; Japanese-style soups, western-style soups; flavor seasonings, instant beverages and foods, various snack foods, etc. It is possible to provide foods and drinks containing an appropriate amount capable of imparting the unique aroma and flavor. Also, for example, shampoos, hair creams, pomades, and other hair cosmetic bases; oscilloscopes, lipsticks, other cosmetic bases and cosmetic detergent bases, etc. should be added in appropriate amounts to impart their unique aromas. It is possible to provide blended cosmetics. Furthermore, laundry detergents, disinfecting detergents, deodorant detergents, indoor air fresheners and various other health and hygiene detergents; various health and hygiene materials such as toothpaste, tattoos, toilet paper, etc .; medications It is possible to provide a hygiene / medicine in which an appropriate amount capable of imparting a unique flavor is mixed with or applied to a health / hygiene / pharmaceutical such as a corrigent or a flavoring agent for facilitating the treatment.

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

(E) Reference example (1) Synthesis of methyl N- (3,4-methylenedioxybenzylidene) anthranilate.

152 g (1 mol) of methyl anthranilate was added to a reaction vessel equipped with a device capable of reducing the pressure of the reaction system with a vacuum pump.
Charge 150 g (1 mol) of methylenedioxybenzaldehyde. At this time, heat is generated at 25 ° C to 40 ° C. Then, the reaction system is depressurized to about 3 to 6 mmHg / Hg, the reaction temperature is kept at 50 ° C. to 60 ° C., and the produced water is discharged from the reaction system to carry out the reaction for 25 hours. The reaction check was performed while measuring the refractive index, and the end point was when the refractive index became constant. Yield; 93%. Refractive index (20 ℃) 1.6105.

(2) N- [3- (3,4-methylenedioxyphenyl)
Synthesis of methyl-2-methylpropylidene] anthranilate.

Methyl anthranilate 105.8g (0.7mol), 3- (3,4-
Methylenedioxyphenyl) -2-methylpropanal
235 g (yield 98%) of the title compound was obtained in the same manner as in Reference Example (1) except that the pressure was 146.9 g (0.77 mol), the degree of vacuum was 3 to 5 mmHg, and the reaction temperature was 80 to 90 ° C. Refractive index (20 ℃); 1.6
250.

(3) Synthesis of methyl N- (3,5,6-trimethyl-3-cyclohexenylmethylidene) asuranylate.

Methyl anthranilate 30.4 g (0.2 mol), 3,5,6-trimethyl-3-cyclohexenyl carbaldehyde 30.4 g
(0.2 mol), 50 ° to 55 ° C./5 to 7 mmHg, and the same procedure as in Reference Example 1 gave 41.5 g (yield 73%) of the title compound. Refractive index (20 ℃); 1.5888.

(4) Synthesis of methyl N- (2,4,6-trimethyl-3-cyclohexenylmethylidene) anthranilate.

Methyl anthranilate 30.4 g (0.2 mol), 2,4,6-trimethyl-3-cyclohexenyl carbaldehyde 30.4 g
(0.2 mol) and 51 ° to 56 ° C./4 to 7 mmHg were carried out in the same manner as in Reference Example 1 to obtain 41.5 g of the title compound (yield 73%). Refractive index (20 ℃); 1.5789.

(5) Synthesis of methyl N- (2,4-dimethyl-3-cyclohexenylmethylidene) anthranilate.

Methyl anthranilate 61.9 g (0.41 mol), 2,4-dimethyl-3-cyclohexenyl carbaldehyde 54.9 g (0.41 mol)
Mol), 45 ° -50 ° C./4-6 mmHg, and in the same manner as in Reference Example 1 to obtain 86.6 g of the title compound (yield 91%).
Refractive index (20 ℃); 1.5891.

(6) Synthesis of methyl N- (3,5-dimethyl-3-cyclohexenylmethylidene) anthranilate 61.9 g (0.41 mol) methyl anthranilate, 54.9 g (0.41 0.43 mol) dimethyl-3-cyclohexenyl carbaldehyde
Mol), 47 ° to 52 ° C./5 to 8 mmHg, and in the same manner as in Reference Example 1 to obtain 86.6 g of the title compound (yield 91%).
Refractive index (20 ℃); 1.5978.

(7) N- [3- (2-methyl-2-pentenyl) -3
-Synthesis of cyclohexenyl methylidene] methyl anthraate.

Methyl anthranilate 28.9 mol (0.191 mol), 3-
(2-Methyl-2-pentenyl) -3-cyclohexenylcarbaldehyde 35.9 g (0.191 mol) and 100 ° C./6 mmHg except that the procedure was the same as in Reference Example 1 to give 55.7 g of the title compound.
(Yield 79%) was obtained. Refractive index (20 ℃); 1.5842.

(8) N- [4- (2-methyl-2-pentenyl) -3
Synthesis of methyl cyclohexenyl methylidene] anthranilate.

Methyl anthranilate 28.9 g (0.191 mol), 4- (2-
Methyl-2-pentenyl) -3-cyclohexenylcarbaldehyde 35.9 g (0.191 mol), 100 ° C./6 mmHg, except that the procedure was the same as in Reference Example 1 and 55.7 g of the title compound (yield 79
%) Was obtained. Refractive index (20 ℃); 1.5923.

(9) Synthesis of methyl N- [3- (2-hydroxy-2-methylpentyl) -3-cyclohexenylmethylidene] anthranilate.

Methyl anthranilate 46.8 g (0.31 mol), 3- (2-
Hydroxy-2-methylpentyl) -3-cyclohexenylcarbaldehyde 65.1 g (0.31 mol), 80 ° -90 ° C / 3m
Except for mg, perform the same procedure as in Reference Example 1 to obtain the title compound 91.4
g (86% yield) was obtained. Refractive index (20 ℃); 1.5820.

(10) Synthesis of methyl N- [4- (2-hydroxy-2-methylpentyl) -3-cyclohexenylmethylidene] anthranilate.

Methyl anthranilate 46.8 g (0.31 mol), 4- (2-
Hydroxy-2-methyl-pentyl) -3-cyclohexenylcarbaldehyde 65.1 g (0.31 mol), 87 ° -92 ° C /
The title compound 9 was obtained in the same manner as in Reference Example 1 except that the pressure was changed to 4 mmHg.
1.4 g (86% yield) was obtained. Refractive index (20 ℃); 1.5916.

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

Phenylethyl alcohol 200 Geraniol 50 Heliotropin 20 Citronellol 10 Nellore 100 Hydroxycitronellal 30 Methylphenylcarbyl acetate 25 Geranium oil 10 Linalool 30 Benzyl acetate 35 Benzyl alcohol 20 Rose phenone 10 Rosinol 280 Rose oil 10 β-Ionone 50 Benzyl salicylate 40 Cyclopentadecanolide 30 Guaya Wood Oil 50 Total 1000 960 g of the above composition was mixed with 40 g of (2) N- [3- (3,4-methylenedioxyphenyl) -2-methylpropylidene] anthranilate. To prepare a new rose blended fragrance composition. This newly prepared fragrance composition and the above-mentioned rose-prepared fragrance composition containing no compound were compared by 10 expert panelists. As a result, 10 professional panelists
All of the people described the newly formulated perfume composition to which the compound was added as being markedly superior in terms of natural rose character and persistence.

Further, instead of the compound (2), (1) methyl N- (3,4-methylenedioxybenzylidene) anthranilate,
(3) Methyl N- (3,5,6-trimethyl-3-cyclohexenylmethylidene) anthranilate, (4) N- (2,
3,6-Trimethyl-3-cyclohexenylmethylidene)
Similar results were obtained with the use of methyl anthranilate. In this case, a slight difference was found in the nuances of each aroma.

(2) Fragrance composition example The following components (parts by weight) were mixed as an orchid-formulated fragrance composition.

Cyclopentadecanolide 50 Coumarin 10 Heliotropin 30 Ylang ylang oil 80 Methylionone 100 Anisaldehyde 20 Neroli oil 30 Hydroxycitronellal 50 Linalrol 70 Isobutyl salicylate 110 Amyl salicylate 140 5-Cyclohexadecene 20 Oakmoss Absolute 3 Vanillin 7 Phenylacetaldehyde 220 Benzyl Acetate 60 Total 1000 (9) N- [3- (2-hydroxy-
The addition of 90 g of methyl 2-methylpentyl) -3-cyclohexenylmethylidene] anthranilate resulted in a novel formulated perfume composition with a long lasting, fresh and more natural orchid type.

Further, instead of the compound (9), (10) N- [4- (2
-Hydroxy-2-methylpentyl) -3-cyclohexenylmethylidene] anthranilate provides a new blended fragrance composition with different nuances of aroma, but with freshness and more natural orchid type emphasis. I got a thing.

(3) Fragrance Composition Example The following components (parts by weight) were mixed as a bouquet type mixed fragrance composition.

Phenylethyl alcohol 180 Linalyl acetate 30 Bergamotte oil 40 Rosinol 50 Benzyl acetate 40 Heliotropin 80 Geraniol 110 Rose Absolute 10 β-Ionone 100 Lavender 20 Diasmin Absolute 10 Amyl salicylate 45 Linalyl acetate 135 Vetiver acetate 100 Citronellol 50 Total 1000 To 980 g of the above composition, 20% of (5) methyl N- (2,4-dimethyl-3-cyclohexenylmethylidene) anthranilate was added.
The addition of g resulted in a new bouquet-formulated perfume composition with natural and floral sustainability.

Instead of (5) above, (6) N- (3,5-dimethyl-3-
Cyclohexenyl methylidene) methyl anthranilate,
(8) N- [4- (2-methyl-2-pentenyl) -3
By using methyl-cyclohexenylmethylidene] anthranilate, the same result as above was obtained, although the nuance was somewhat different.

(4) Fragrance composition example The following components (weight) as an aroma and flavor composition for grapes
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 Caproate 3 Ethyl Enanthate 8 Hydroxy Citronellal 1 Methyl Anthrani Rate 132 Methyl salicylate 12 Petigren 1 Terpinyl acetate 10 Ethanol 732 Total 1000 95 g of the above composition was (4) N- (2,3,6-trimethyl-3-
Cyclohexenyl methylidene) methyl anthranilate 5g
A new grape-prepared perfume composition having a sweet grape sensation and having a long-lasting effect was obtained. The same result with a slightly different nuance is (2) N- [3- (3,
4-Methylenedioxyphenyl) -2-methyl-propylidene] anthranilic acid, respectively.

A comparison was made with a blended fragrance composition containing the product of the present invention by 10 professional panelists. As a result, all 10 professional panelists all concluded that the blended fragrance composition containing the product of the present invention was remarkably excellent in both aroma and its persistence.

(5) Comparative Test Example Regarding Sustainability A sensory evaluation was conducted on the sustainability characteristics of the compound of the present invention by a panel test method generally used in the perfume industry for evaluating the sustainability characteristics of a perfume compound. That is, the compound of the present invention and 10 of the representative compounds described in the known literature
6% of the same amount of% ethyl alcohol solution,
We attached to the tip of 120 mm long odor paper and compared and examined the residual aroma (persistence) strength of the fragrance that changes with time. The panel test of the change with time was repeated 4 times with 10 panelists 1 day, 2 days and 3 days after applying the present invention and the known compound to the odor paper, and analyzed for a significant difference, The persistence of aroma was determined. The results after 1 day are shown in Table-1,
The results after 2 days are shown in Table-2 and the results after 3 days are shown in Table-3.
The numbers in the table indicate the number of panelists who compared the compound of the present invention with known compounds to determine that the compound of the present invention has longer-lasting properties. From these results, it can be seen that the compound of the present invention has excellent durability over time as compared with known compounds.

The compounds of the present invention and known compounds used in this test are as follows.

Compound of the present invention (1) N- (3,4-methylenedioxy-benzylidene)
Methyl anthranilate (2) N- [3- (3,4-methylenedioxy-phenyl) -2-methyl-propylidene] methyl anthranilate (3) N- (3,5,6-trimethyl-3-cyclohexenyl) Methylidene methyl anthranilate (4) N- (2,4,6-Trimethyl-3-cyclohexenyl methylidene) anthranilate (5) N- (2,4-Dimethyl-3-cyclohexenyl methylidene) anthranil Methyl acid salt (6) Methyl N- (3,5-dimethyl-3-cyclohexenylmethylidene) anthranilate (7) N- [3- (2-Methyl-2-pentenyl) -3
-Methyl cyclohexenyl methylidene) anthranilate (8) N- [4- (2-methyl-2-pentenyl) -3
Methyl cyclohexenyl methylidene) anthranilate (9) Methyl N- [3- (2-hydroxy-2-methylpentyl) -3-cyclohexenyl methylidene) anthranilate (10) N- [4- (2-hydroxy Methyl 2-methylpentyl) -3-cyclohexenylmethylidene) anthranilate Known compounds (a): Schiff's base of hydroxycitronellal and methylanthranilate (b): Cynamic aldehyde and methylanthranilate Schiff's base (c): amylcinnamic aldehyde and methyl anthranilate Schiff's base (d): vanillin and methyl anthranilate's Schiff's base (e): ionone and methyl anthranilate's Schiff's base (f) : Schiff salt of methyl naphthyl ketone and methyl anthranilate (G): Schiff bases cyclamen aldehyde and methyl anthranilate (h): N- (2- methyl-benzylidene) anthranilic acid methyl (i): 2-ethylidene - bicyclo [2.2.1] hept -5
-Ilmethylidene-o-methoxycarbonylaniline Note: Compounds (a) to (f) are the same as The American Perfumer,
Vol.52, pp218-220 (1948); Compound (g) is Food Cosmet. Toxicol., 17 (3),
P269 (1979); compound (h) is the compound described in Example 1 of JP-A-49-118841; and compound (i) is JP-A-60-78951. It is the compound described in Example 1 of the publication.

(G) Effect The methyl anthranilate derivative of the above formula (A) of the present invention is a novel compound that has not been described in the prior art, and has a soft and sweet floral or fruity-like, herbal-like extremely excellent and persistent aroma and flavor. A novel compounded fragrance composition which cannot be obtained by the conventionally known methyl anthranilate derivatives containing the compound as an active ingredient and which can provide foods and drinks (including luxury items) It is useful in a wide range of applications such as cosmetics, health, hygiene, and pharmaceuticals.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C11B 9/00 V 2115-4H // C07C 25/18 9280-4H C07D 317/58 (56) Reference References JP 49-118841 (JP, A) JP 60-78951 (JP, A) JP 60-292000 (JP, A) AM. PERFUMER Vol. 52 P. 218-220 (1948) FOOD COSMET. TOXIC OL. 17 (3), P. 269-272 (1979)

Claims (1)

[Claims] 1. The following formula (A) In the formula, -R is A perfume composition comprising as an active ingredient a methyl anthranilate derivative represented by: which is a group selected from the group consisting of: