JPS62153212A - Perfumery composition - Google Patents

Abstract

PURPOSE:To provide a perfumey composition containing a methyl anthranylate derivative as an active component, emitting soft, sweet and lasting perfume of floral, fruity or herbal note and useful in the fields of food, drink, cosmetic, medicine, etc. CONSTITUTION:The objective perfumery composition contains 0.001-30 wt% compound of formula I (R is group of formula II, etc.) as an active component. The addition of the composition to a synthetic essential oil such as bergamot oil, lemon oil, etc., is effective in imparting mild, thick and lasting improving effect to the original perfume and flavor of natural essential oil. The composition harmonizes with citrus essential oil, natural essential oil (e.g. lavender oil), etc., and gives a perfumery composition having mild, thick and natural-like lasting perfume. A composition having mild, thick and highly lasting flavor can be produced when compounded to a flavor composition of e.g. strawberry, banana, etc.

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 previously described in the literature and are useful as raw materials for blended fragrances.

More specifically, the present invention relates to an incense [I parabolite] characterized by containing as an active ingredient a methyl anthranilate derivative represented by the following formula (A), where R has the same meaning as above.

The compound of formula (A) has a soft, sweet floral, fruity, or herbal aroma, and has particularly excellent persistence, and is useful as a material for various blended fragrance compositions, and has a long-lasting aroma. It is useful as a flavor imparting or improving reinforcing agent in a wide range of fields such as food and beverages (including luxury goods), cosmetics, health care, hygiene, and pharmaceuticals. Furthermore, the present invention also relates to a method for producing the above-mentioned compounds.

(b) Prior Art Conventionally, as the methyl anthranilate derivative of the above general formula (A) of the present invention, compounds that are anthranilic acid derivatives and are known as fragrance substances include, for example, N-(1-methylbenzylidene) anthranilic acid. Methyl, N-(4-
Methoxybenzylidene) anthranilate, N-(
Anisylidene) methyl anthranilate, N-(3,7-
Methyl dimethyl-2,6-octadienylidene) anthranilate, and Methyl N-(p-t-butyl-α-methyl-hydroxycinnamylidene) anthranilate (Pe
rfum and Flavr Chemica
ls, 5teffen Archtender, 196
9) etc. are known. Also, each of these has different nuances, but they all have sweet floral, fruity,
It is described as having a citrus-like aroma.

(c) Problems to be solved by the invention In recent years, with the diversification of various foods, beverages, and cosmetics, there has been an increasing need for new fragrances that have never existed before. The development of blended fragrance materials with excellent properties is desired.

For this reason, generally, for example, a method of synthesizing a new compound or a derivative thereof found through analysis of natural essential oils and providing it as a mixed fragrance material, or a method of synthesizing a new compound found by analyzing natural essential oils or a derivative thereof, or a method of synthesizing a compound with a structure similar to a conventionally known fragrance compound or a derivative thereof. Among them, compounds useful as fragrance substances have been discovered and provided as mixed fragrance materials.

However, there are few materials that are mild, full-bodied, have a fresh natural feel, and can also be long-lasting.
In particular, it cannot be said that materials with the above-mentioned performance that can be easily and inexpensively produced are always satisfactorily provided.

(d) Means for Solving the Problems In view of the above circumstances, the present inventors have discovered anthranilic acid, which is a condensation product of methyl anthranilate and various aldehydes other than the above-mentioned methyl anthranilate derivative, which is known as the above-mentioned fragrance substance. Regarding methyl derivatives, we have been conducting intensive research on compounds that are useful as flavor substances.

As a result, the methyl anthranilate derivative represented by the above formula (A) has very sweet, soft floral to fruity, herbal-like aroma characteristics that are different in nuance from the above-mentioned known compounds, and has excellent persistence. The above formula (
A) We discovered that compounds can be easily synthesized and succeeded in synthesizing them.

Therefore, the object of the present invention is to use the above-mentioned formula (A) compound as an active ingredient in a wide range of fields such as food and beverages, cosmetics, health, sanitary, and medicinal products. The object of the present invention is to provide a fragrance composition that has a useful persistence that cannot be obtained previously.

The aroma characteristics of each of the methyl anthranilate derivatives of the present invention are shown below.

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

A Flow Sill-like fragrance that aspires to be a sweet, long-lasting rose.

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

A persistent floral fragrance reminiscent of jasmine and lily of the valley with a slight green and fruity feel, as well as a hint of neroli.

(3) Methyl N-[3-(4-ethylphenyl)-2°2-dimethylbropylidenecoanthranilate.

A sweet, persistent floral scent reminiscent of lily of the valley with a hint of green.

(4) Methyl N-[3-(4-methoxyphenyl)-2-methylbropylidenecoanthranilate.

A lily-like floral fragrance with a sweet and heavy border feel.

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

(6) Methyl N-(2,4,6-)dimethyl-3-cyclohexenylmethylidene) anthranilate, sweet and persistent floral with a slight herbal and fruity feel, resembling an orange flower. aroma.

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

A sweet, persistent floral fragrance with a hint of citrus.

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

A sweet, persistent floral fragrance with a pulsamic feel, reminiscent of lily of the valley.

(9) N-[3-(2-methyl-2-pentenyl)-3
-cyclohexenylmethylidene] methyl anthranilate.

A floral-like fragrance with a hint of lily of the valley, with a heavy, sweet, and persistent green and herbal feel.

(10) Methyl N-[:4-(2-methyl-2-pentenyl)-3-cyclohexenylmethylidene coanthranilate.

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

(11) Methyl N-[3-(2-hydroxy-2-methylpentyl)-3-cyclohexenylmethylidene coanthranilate.

A sweet and persistent watermelon scent with a slight green feel.

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

A sweet and persistent tuberose-like aroma with a slight herbal feel.

The above-mentioned methyl anthranilate which can be used as the fragrance composition of the present invention can be easily synthesized by, for example, subjecting methyl anthranilate and an aldehyde to a dehydration condensation reaction. When the reaction is shown in a reaction process diagram, it can be expressed as follows, for example.

However, in the formula, R has the same meaning as above, and the reaction temperature of the dehydration condensation reaction is generally preferably in the range of about 15° to about 100"C, although it depends on the type of aldehyde. In addition, the reaction time is preferably in the range of about 10 to about 50 hours, for example. Preferred reaction embodiments include:
It is preferable to carry out the reaction while removing water produced in the reaction from the reaction system.

Examples of aldehydes used in the above reaction include 3
, 4-methylenedioxy-benzaldehyde, 3-(
3,4-methylenedioxy-phenyl)-2-methylpropanal, 3-(4-ethylphenyl)-2,2-
Dimethylpropanal, 3-(4-methoxyphenyl)
-2-methylpropanal, 2,3.5-trimethyl-
3-cyclohexenyl rubaldehyde, 2,3.6-)
Dimethyl-3-cyclohexenyl rubberdehyde, 2.
4-dimethyl-3-cyclohexenyl rubaldehyde,
3,5-dimethyl-3-cyclohexenyl-rubaldehyde, 3-(2-methyl-2-pentenyl)-3-cyclohexenyl-rubaldehyde, 4-(2-methyl-2-
(pentenyl)-3-cyclohexenyl rubaldehyde,
Examples include 3-(2-hydroxy-2-methylpentyl)-3-cyclohexenyl rubaldehyde and 4-(2-hydroxy-2-methylpentyl)-3-cyclohexenyl rubaldehyde. These aldehydes are compounds that are easily available on the market.

The amount of these aldehydes to be used is preferably in the range of, for example, about 1 to about 1.2 moles based on the late methyl anthranyl. It can also be purified by other means.

The above-mentioned methyl anthranilate derivative of formula (A), which has not been described in any prior literature and which can be used in the fragrance composition of the present invention, has a soft floral to fruity or herbal aroma, is sweet, and has particularly excellent persistence. ing.

The compound of formula (A) of the present invention blends well with various synthetic fragrances, natural essential oils, synthetic essential oils, citrus oils, etc., and novel fragrance compositions can be prepared using the compound of formula (A). More specifically, when the compound of formula (A) is blended into synthetic essential oils such as bergamot oil, lemon oil, geranium oil, lavender oil, and mandarin oil, the aroma and flavor inherent to natural essential oils is mild and rich. Moreover, a sustainable improvement effect can be imparted to the synthetic essential oil. It also blends well with natural essential oils such as citrus essential oils such as orange, lime, lemon, grapefruit, and greige; lavender oil, vetiver oil, cedarwood oil, citronella oil, geranium oil, lavandin oil, sandal oil, etc. In addition, it is possible to prepare a novel fragrance composition that emphasizes the characteristics of the essential oil, is mellow, rich, natural-looking, and has an excellent long-lasting effect. Furthermore, for example,
When blended into flavor compositions prepared from various synthetic fragrances, natural fragrances, natural essential oils, citrus oils, etc., such as strawberry, lemon, orange grapefruit, apple, pineapple, banana, melon, etc., it creates a mild, rich, and natural flavor. Perfume compositions with enhanced and long-lasting properties can be prepared. The amount of the above formula (A) compound varies depending on its purpose and the aroma and flavor composition to be blended, but for example, it is generally in the range of about 0.001 to about 30% by weight of the total. can.

Thus, according to the present invention, it is possible to provide a persistent aroma and flavor imparting or improved reinforcing agent containing the compound of formula (A) as an active ingredient, and the agent can be used to contain the compound of formula (A) as an aroma and flavor component. Foods and beverages characterized by the following, cosmetics characterized by containing the compound of formula (A) as an aroma component, and health/hygiene/medicinal products characterized by containing the compound of formula (A) as an aroma component. etc. can be provided.

For example, fruit juice drinks, fruit alcoholic drinks, milk drinks, carbonated drinks,
Nodoki drinks; ice creams, sherbet,
Frozen desserts such as popsicles; Japanese and Western sweets;
Jams, chewing gums, breads, coffee, cocoa, black tea, luxury goods such as tea; soups such as Japanese soups and Western soups; flavor seasonings, various instant beverages and foods, various snack foods, etc. It is possible to provide food and drink containing an appropriate amount of the unique aroma and flavor. For example, shampoos, hair creams, pomades, and other hair cosmetic bases; cosmetic bases, lipsticks, and other cosmetic bases and cosmetic detergent bases, etc. We can provide blended cosmetics. Furthermore, laundry detergents, disinfectant detergents, deodorizing detergents, room air fresheners, and other various health and hygiene detergents; various health and hygiene materials such as toothpaste, tissues, and toilet vapor; and medicines. For health, hygiene, and pharmaceuticals, such as flavoring and flavoring agents to facilitate
It is possible to provide health and hygiene/pharmaceuticals that are blended or applied in an appropriate amount to impart the unique flavor.

Hereinafter, the present invention will be explained in detail by further referring to reference examples and examples.

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

152 g (1 mol) of methyl anthranilate, 3
．． 4-methylenedioxybenzaldehyde 150g (1
Prepare mole). At this time, heat is generated to 25°C to 40°C. After that, the pressure of the reaction system is reduced to about 3 to BmmHg/Hg, and the reaction temperature is maintained at 50°C to 60°C, and the reaction is carried out for 25 hours while the water produced is discharged from the reaction system. To check for zero reaction, check the refractive index. The end point was when the refractive index became constant. Yield: 93%, refractive index (20°C
) 1.6105° (2) Synthesis of methyl N-[3-(3,4-methylenedioxyphenyl)-2-methylpropylidene] anthranilate.

Methyl anthranilate 105.8g (0.7 mol)
, 3-(3,4-methylenedioxyphenyl)-2-
Methylpropanal 146.9g (0°77mol),
Degree of vacuum: 3-5 mm Hg, reaction temperature: 80°-90°
The same procedure as in Reference Example (1) was carried out except that C was used to obtain 235 g (yield: 98%) of the title compound. Refractive index (20°
C); Synthesis of 1.6250°(3)N-[:3-(4-ethylphenyl)-2°2-dimethylpropylidene]methyl anthranilate.

30.4 g (0.2 mol) of methyl anthranilate,
3-(4-ethylphenyl)-2,2-dimethylpropanal 38.0 g (0.2 mol), 60-80@C
The same procedure as in Reference Example 1 was carried out except that the pressure was adjusted to 15 to 7 mmHg, and 61.2 g (yield: 95%) of the title compound was obtained. Refractive index (20@C); 1.5692° (4) Synthesis of methyl N-[3-(4-methoxyphenyl)-2-methylpropylidene] anthranilate.

Methyl anthranilate 30.4 g (0.2 mol), 3
-(4-methoxyphenyl)-2-methylpropanal 35.6 g (0.2 mol), 50-66@C15-7
The same procedure as in Reference Example 1 was carried out except that the temperature was adjusted to mmHg to obtain 57.6 g (yield: 93%) of the title compound. Refractive index (20°
C);1.616? .

(5) Synthesis of methyl N-(3,5,6-drimethyl-3-cyclohexenylmethylidene) anthranilate.

30.4 g (0.2 mol) of methyl anthranilate,
3,5.6-)methyl-3-cyclohexenyl rubberdehyde 30.4 g (0.2 mol), 50°-55°
The same procedure as in Reference Example 1 was carried out except that the C15-7 mmHg was used to obtain 41.5 g (yield: 73%) of the title compound. Refractive index (20'''C): 1.5888° (6) Synthesis of methyl N-(2,4,6-)trimethyl-3-cyclohexenylmethylidene) anthranilate.

30.4 g (0.2 mol) of methyl anthranilate,
2,4.6-)methyl-3-cyclohexenylrubaldehyde 30.4 g (0.2 mol), 51°~5B"
The same procedure as in Reference Example 1 was performed except that C/4 to 7 mmHH was used to obtain 41.5 g (yield: 73%) of the title compound. Refractive index (20'C); 1.5789° (7) Synthesis of methyl N-(2,4-dimethyl-3-cyclohexenylmethylidene) anthranilate 61.9 g (0.41 mol) of methyl anthranilate , 54.9 g of 2,4-dimethyl-3-cyclohexenyl rubberdehyde
(0.41 mol), 45°~50'''C/4~6mm
The same procedure as in Reference Example 1 was carried out except that HH was used, and 86.6 g (yield: 91%) of the title compound was obtained. Refractive index (20°C
); 1゜5891゜(8) Synthesis of methyl N-(3,5-dimethyl-3-cyclohexenylmethylidene) anthranilate Methyl anthranilate 61.9 g (0.41 mol), 3.5-dimethyl -3-cyclohexenyl rubaldehyde 54.9g
(0.41 mol), 47@~52°C15~8mmH
The title compound 8 was obtained in the same manner as in Reference Example 1, except that g was changed to
6.6 g (yield 91%) was obtained. Refractive index (20”C
); 1°5978°(9)N-[:3-(2-methyl-2-pentenyl)-
Synthesis of methyl 3-cyclohexenylmethylidene] anthranilate.

Methyl anthranilate 28.9 mol (0,191 mol)
, 35.9 g (0,191 mol) of 3-(2-methyl-2-pentenyl)-3-cyclohexenyl rubber, and 100' C/6 mmHg, except for Reference Example 1.
In the same manner as above, 55.7 g of the title compound (yield 79%) was obtained.
) was obtained. Refractive index (20°C); 1.5842°(10)N-[4-(2-methyl-2-pentenyl)-
Synthesis of methyl 3-cyclohexenylmethylidene] anthranilate.

Methyl anthranilate 28.9g (0,191 mol)
, 4-(2-methyl-2-pentenyl)-3-cyclohexenyl 35.9 g (0,191 mol) of rubaldehyde, 100'''C/6 mmHg, and Reference Example 1
Proceed in the same manner as above to obtain 55.7 g of the title compound (yield 79%)
I got it. Refractive index (20" C): 1.5923° (11) Synthesis of methyl N-[3-(2-hydroxy-2-methylpentyl)-3-cyclohexenylmethylidene] anthranilate.

46.8 g (0.31 mol) of methyl anthranilate,
3-(2-hydroxy-2-methylpentyl)-3-cyclohexenyl Rubaldehyde 65.1g (0,31
Mol), 80° to 906C/3 mmg was carried out in the same manner as in Reference Example 1 to obtain 91.4 g of the title compound (yield: 8
6%). Refractive index (20°C); 1.5820
(12) Synthesis of methyl N-[4-(2-hydroxy-2-methylpentyl)-3-cyclohexenylmethylidene] anthranilate.

46.8 g (0.31 mol) of methyl anthranilate,
4-(2-hydroxy-2-methyl-pentyl)-3-
65.1 g of cyclohexenyl rubaldehyde (0,3
1 mole), 87''' to 92°C/4mmHg, the same procedure as Reference Example 1 was carried out to obtain 91.4g (yield: 86%) of the title compound.Refractive index (20°C): 1 .5916
(f) Example (1) Perfume Composition Example The following components (parts by weight) were mixed as a rose type mixed perfume composition.

Phenylethyl alcohol 200 Geraniol 50 Heliotropin 20 Citronellol
10 nerol
100 hydroxycitronellal
30 Methyl phenyl carbinyl acetate
25 Geranium oil 1
0 Linalool 30 Benzyl Acetate 35 Benzyl Alcohol 20 Rose Phenone 10 Rhodinol
280 rose oil
10β-ionone
50 Benzyl salicylate 40 Cyclobentadecalide 30 Guaiyaud oil 50 Total 1
000 A novel rose blend fragrance composition was prepared by mixing 40 g of (2) methyl N-[3-(3°4-methylenedioxyphenyl)-2-methylpropylidene] anthranilate with 960 g of the above composition. This new blended fragrance composition and the above-mentioned rose blended fragrance composition to which the compound was not added were compared by 10 expert panelists. As a result, all 10 expert panelists agreed that the new perfume composition containing the compound was significantly superior in terms of natural rose characteristics and sustainability.

Also, in place of the above compound (2), (1) methyl N-(3,4-methylenedioxybenzylidene) anthranilate,
(6) Methyl N-(3,5,6-)tumethyl-3-cyclohexenylmethylidene) anthranilate, (6) N-
Similar results were obtained when methyl (2,3,6-)trimethyl-3-cyclohexenylmethylidene)anthranyl was used. In this case, some differences were observed in the nuances of each aroma.

(4) Perfume Composition The following components (parts by weight) were mixed as a blended fragrance composition of the Ran type.

Cyclopentadecanolide 50 Coumarin 10 Heliotropin 30 Ylang Ylang Oil
80 methyl ionone
100 anisaldehyde
20 neroli oil
30 hydroxycitronellal
50 linalol 70 isobutyl salicylate) 110 amyl salicylate 1405-cyclohexadecene 20 oakmoss absolute 3 vanillin
7 Phenylacetaldehyde 220 Benzyl acetate 60 Total 1000 By adding 90 g of (3) methyl N-[3-(4-ethylphenyl)-2,2-dimethylpropylidene] anthranilate to 910 g of the above composition, fresh and more A new long-lasting formulated perfume composition with an emphasis on natural orchid type was obtained.

Also, instead of the above compound (3), (4) N-[:3-(
Methyl 4-methoxyphenyl)-2-methylpropylidene] anthranilate, (11) N-[3-(2-hydroxy-2-methylpentyl)-3-cyclohexenylmethylidene] methyl anthranilate, (12) N-[4-
By using methyl (2-hydroxy-2-methylpentyl)-3-cyclohexenylmethylidene] anthranilate, a new formulation with a long-lasting effect that emphasizes a fresher and more natural orchid type, although each has a different aroma nuance. The fragrance composition has been changed.

(3) Fragrance Composition A bouquet type blended fragrance composition includes the following ingredients (heavy and
(Okibe) was mixed.

Phenylethyl alcohol 180 Linalyl acetate 30 Bergamot oil 40 Rhodinol
50 benzyl acetate
40 heliotropin
80 geraniol
110 rose absolute
10β-ionone io.

lavender 20 diasmine absolute) 10 amyl salicylate 45 linalyl acetate 135 vetiver acetate 100 citronellol 50 total 1000 Add (7) N-(2,4-dimethyl-
By adding 20 g of methyl 3-cyclohexenylmethylidene) anthranilate, a novel bouquet-formulated perfume composition with natural and floral persistence was obtained.

(8) N-(3,5-dimethyl-3
-cyclohexenylmethylidene)anthranyl late methyl, (10)N-[4-(2-methyl-2-pentenyl)
By using methyl-3-cyclohexenylmethylidene] anthranilate, the same results as above were obtained, although the nuances were slightly different.

(4) Flavor Composition Example Each ingredient (weight) below as a grape aroma flavor composition.
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 cabroate ゛ 3 ethyl enanthate 8 hydroxycitronellal 1 methyl anthranilate 132 methyl salicylate
12 pettigrain
l turbinyl acetate)
10 ethanol
732 total 1000 N-[3-(4-ethylphenyl)
By adding 5 g of methyl-2,2-dimethylpropylidene] anthranilate, a novel grape-containing fragrance composition with a sweet grape flavor and long-lasting properties was obtained.

The same result, although the nuance is slightly different, is (6)N-(2
, 3,6-drimethyl-3-cyclohexenylmethylidene) methyl anthranilate, (2) N-[3-(3,4
-methylenedioxyphenyl)-2-methyl-propylidene]anthranilic acid, respectively.

A comparative study was conducted by 10 expert panelists with a blended fragrance composition containing the product of the present invention. As a result, all 10 expert panelists agreed that the perfume composition containing the product of the present invention was significantly superior in terms of both aroma and persistence.

(g) Effect The methyl anthranilate derivative of the above formula (A) of the present invention is a novel compound previously described at the end of the literature, and has a soft, sweet floral, fruity, and herbal aroma with an extremely excellent and long-lasting aroma. It is possible to provide a novel blended fragrance composition which cannot be obtained with the conventionally known late methyl anthranyl derivatives containing the compound as an active ingredient, and which can be used in foods and drinks (including luxury goods), fragrances, etc. It is useful in a wide range of fields such as cosmetics, health, hygiene, and pharmaceuticals.

Patent applicant: Hasegawa Perfume Co., Ltd. - 1 other person

Claims (1)

[Claims] 1. The following formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) However, in the formula, -R is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
A fragrance composition comprising, as an active ingredient, a methyl anthranilate derivative represented by the following, which represents a group selected from the group consisting of .