JPH02158694A - Perfumery composition - Google Patents

Abstract

PURPOSE:To obtain a perfumery composition useful for providing an agent to impart or modify a lasting perfume or taste and useful in the field of foods, drinks, cosmetics, health and sanitation, medicine, etc., by compounding a specific 2 alkyl-pyrane derivative as an active component. CONSTITUTION:The objective composition contains about 0.001-30wt.% of a 2-alkyl-pyrane derivative of formula (R is 4-7C alkyl; dotted line is single or double bond) (e.g. 2-hexyl-3,4-dihydropyrane), The above derivative emits bright, fresh and greenish fragrance having excellent diffusing and lasting property.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a group of 2-alkyl-bilane derivatives represented by the following formula (1), which is a known compound, and where R and the broken line are the same as described above. The present invention relates to use as an aroma and flavor imparting or modulating agent.

The present inventors have discovered that the 2-alkyl-pyran derivative of the above formula (1) has a very characteristic flower-like tone and is accompanied by a gorgeous and fresh green feeling; aroma and flavor characteristics and excellent diffusibility; These compounds have a long-lasting aroma, and can be used as long-lasting aroma imparting or flavor modulating agents in various fragrance compositions, such as food and beverages (including luxury goods), cosmetics, health care, hygiene, pharmaceuticals, etc. It has been discovered that it is useful in a wide range of fields.

Therefore, an object of the present invention is to provide a persistent aroma and flavor imparting or modulating agent which can be used in various fields and which contains the 2-alkyl-bilane of the above formula (1) as an active ingredient.

(Prior Art) Some of the 2-alkyl-bilane derivatives of the above formula (1) are already known. For example, JP-A-59-164
No. 748 describes 2-butyl-2,3-dihydropyran and 2-hexyl-2,3-dihydrobyran. However, in this specification, the above formula (1)
The aroma and flavor characteristics of the compound are not disclosed at all, and are only exemplified as raw materials for synthesizing aliphatic carboxylic acids and the like. The aroma and flavor characteristics and excellent long-lasting characteristics of the compound of formula (1) were first clarified by the present inventors.

Further, regarding the synthesis method of the compound of formula (1), for example, He1veiica Chimica Acta, V
ol, 64.1247-1256 (1981), ma
2 as an intermediate to synthesize ssoia 1actone
-panLyJ-3,4-dihydro-28-py
A method of synthesizing ran is described.

However, this document only describes the synthesis method, but does not mention the aroma and flavor characteristics and persistence of the compound.

(Problems to be Solved by the Invention) In recent years, with the diversification of various food and drink products, cosmetics, etc., there has been an increasing need for new, unprecedented aromas as flavors for various food and drink products or fragrances for cosmetics. In particular, there is a need for the development of fragrance substances that are mild, rich, fresh, natural-looking, and long-lasting.

For this reason, attempts have been made to combine various known fragrance materials appropriately and in varying amounts to create a formulation that has naturalness and sustainability.

However, despite the desire for a material that is mild, full-bodied, has a fresh, natural appearance, and has properties that can provide sustainability, there have been few materials that have such properties, and it is especially easy to find materials that have such properties. At present, there is a shortage of materials with the above performance that can be obtained at low cost.

(Means for Solving the Problem) In view of the above circumstances, the present inventors have discovered that various 2-alkyl-
We have been conducting intensive research on biran derivatives.

As a result, the 2-alkyl biranes represented by the following formula (1), where R and the broken line are the same as above, have a very distinctive flower-like aroma with a gorgeous and fresh green feel. Flavor Characteristics and Superiority I: It was discovered that it has a diffused and long-lasting aroma.

In addition, foods and drinks (
It has also been found that it is possible to provide a persistent aroma and flavor imparting or modulating agent that is useful in a wide range of fields of use, including luxury goods), cosmetics, health, sanitary, and pharmaceutical products.

In order to synthesize the 2-alkyl biranes represented by the following formula (1) of the present invention, R and the broken line are the same as above, for example, the He1veLica Chimica Act
A, Vol. 64.1247-1256 (1981).

(a) (b) (c)
According to this method, acrolein of the above formula (a) and 1-heptene of the above formula (b) are combined with BIT (2,6 di-t-b
util-p-cresol),
2-pentyl-3,4-dihydro-2H of the above formula (c)
- You can get villains.

Further, the compound of formula (C) thus obtained is hydrogenated in an autoclave using, for example, a Raney Ni catalyst in n-hexane solvent to obtain 2-pentyl-tetrahydrobilane (d). be able to.

Similarly, in the above formula, each compound (b) is
For example, by changing to ■-hexene, l-heptene, 1-octene, l-nonene, etc., the following 2
- Obtaining alkylbilane is a monkey.

(Left below) 2-Butyl-3,4-dihydro-2H-bilane 2-butyl-tetrahydrobilane 2-pentyl-3,4-dihydro-2H-bilane 2-pentyl-tetrahydrobilane 2-hexyl-3,4 -dihydro-2H-bilane 2-hexyl-tetrahydrobilane 2-hegtyl-3,4-dihydro-2H-bilane 2-heptyl-tetrahydropyran The 2-alkylbilanes that can be synthesized in this way are very characteristic. Based on a flower-like fragrance, it has aroma characteristics with a gorgeous and fresh green feel, excellent diffusibility, and a long-lasting aroma.It is used in various synthetic fragrances, natural essential oils, synthetic essential oils, citrus oils, etc. It harmonizes well with the expression (
1) Novel fragrance compositions can be prepared using the compound.

More specifically, when the compound of formula (1) is blended into synthetic essential oils such as bergamot oil, lemon oil, geranium oil, lavender oil, and mandarin oil, the aroma and flavor inherent in natural essential oils is mild and rich. It is possible to impart a long-lasting improvement effect to these synthetic essential oils.

It also blends well with natural essential oils, such as citrus essential oils such as orange, lime, lemon, grapefruit, etc.; lavender oil, vetiver oil, cedarwood oil, citronella oil, geranium oil, lavandin oil, sandalwood oil, etc.; It is possible to prepare a novel fragrance composition that is mellow, full-bodied, natural-looking, and has excellent long-lasting properties.

In particular, the floral aroma with a light and gorgeous green feel,
With a fragrance that gives a lively, natural feel to the whole, it is suitable for fragrance compositions for cosmetics, such as rose, hyacinth, magnolia, strawberry, lily, watermelon, etc., as well as leafy scents with a natural feel. - It was found to be the most suitable fragrance substance to match the green tone very well and to enhance the atmosphere of those fragrances.

Furthermore, when blended into flavor compositions such as strawberry lemon, orange, grapefruit, apple, pineapple, banana, melon, etc. prepared from various synthetic fragrances, natural fragrances, citrus oils, etc., it has a mild and rich flavor. A fragrance composition can be prepared that has a natural appearance and is long-lasting.

The amount of the compound of the above formula (1) 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 30% by weight of the entire composition. can do.

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 (1) as an active ingredient, and to use the compound of formula (1) as an aroma and flavor component using a nucleating agent. Food and drink products characterized by containing the formula (1
) compound as an aromatic and flavoring ingredient; cosmetics and cosmetics that contain a compound of formula (1) as an aromatic ingredient; and cosmetics containing a compound of formula (1) as an aromatic and flavoring ingredient. We can provide health, hygiene, pharmaceuticals, etc. characterized by

More specifically, for example, beverages such as fruit juice drinks, fruit alcoholic beverages, milk drinks, and carbonated drinks; ice cream;
Frozen desserts such as sherbet and popsicles,
Japanese and Western sweets, jams, chewing gums, breads,
Its unique aroma and flavor can be used in luxury goods such as coffee, cocoa, black tea, green tea, and tobacco; soups such as Japanese-style soups and Western-style soups; flavor seasonings; various instant beverages and foods; and various snack foods. It is possible to provide food and drink products that contain the appropriate amount of alcohol.

In addition, an appropriate amount can be used to impart the unique aroma to, for example, shampoos, hair creams, pomades, and other hair cosmetic bases; white powder, lipstick, and other cosmetic bases and cosmetic detergent bases. We can provide cosmetics containing the following. Furthermore, laundry detergents, disinfectant detergents, deodorizing detergents, indoor air fresheners and other health and hygiene detergents; toothpaste,
Tissue paper Various health and hygiene materials such as toilet paper; Flavoring and flavoring agents to make it easier to take medicines; Mixed with or added in an appropriate amount to impart a unique flavor to health, hygiene and medicines. We can provide applied health and hygiene medicines.

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

[! i! Example] Reference M1. Production of 2-hexyl-3,4-dihydropyran 314 g of 1-octene (
2.8 mol), acrolein 209 (0.36 mol) and 3 g of BHT, N, after substitution, N, initial pressure IK
Start heating and stirring at 190°C1 pressure 8-10g.
The reaction was carried out at Kg/cR' for 24 hours.

After the reaction is completed, unreacted l-octene is collected at normal pressure, and the reaction product is distilled under reduced pressure to give a BP of 60 to 98'C/2mm.
Hg fraction 219 was obtained. This fraction was subjected to precision distillation, and the following results were obtained.

Fr, 1 bp-60'C/2mmHgi, 5gFr
, 2 bp ~67°C/ // 10.09
(Y=17%) Fr, 3 bp ~85+7
tt 3.2g F", 2 GC-MS%P-N
As a result of MR analysis, it was confirmed that it was 2-hexyl-3,4-dihydropyran.

Reference Example 2 Production of 2-hexyl-tetrahydrobyran 6 g of 2-hexyl-3,4-dihydropyran obtained in Reference Example 1, 30 wQ of n-hexane, R-Ni(R2
00) 0.3g to 0. H! After charging the autoclave and replacing with hydrogen, the initial pressure of H2 was 30 kg/C1l'
Start heating and stirring as H2 pressure 37.5-42k
g/cm''; hydrogenation was carried out by reacting at a temperature of 130 to 160''G for 5 hours.

Cool, filter through Celite (diatomaceous earth) to remove R-Ni, distill off n-hexane, and then perform vacuum distillation.

Fr, l bp65-68'C/2amHg 4
g (Y・67%)Fr, 2n ~80
°C/〃 1gRe5ide
trace above Fr, l is G
It was confirmed by C-MS to be 2-hexyl-tetrahydropyran.

Reference Example 3° and below, Reference Example 1.2 and 01 to C7 synthesized in the same manner
-Alkylpyrans are collectively shown below.

Example 1 (1) Fragrance composition A rose-type blended fragrance composition contains the following components (I
i parts) were mixed.

Phenylethyl alcohol 200 Geraniol 50 Heliotropin 20 Citronellol
lO Nellore
100 human a-xycitronellal
30 Methyl phenyl carbinyl acetate 25 Geranium oil
IO linalool
30 Benzyl Acetate 35 Benzyl Alcohol 20a-
Zufenon lO rhodinol 280 rose oil
lOβ-ionone
50 benzyl salicylate
40 cyclobentadecaturide
30 guaiyaud oil
50 Total 1000 2-hexyl-3,4-dihydropyran 309 was mixed with 970 g of the above composition to prepare a new rose blend fragrance composition. A sensory comparison between this new blended fragrance composition and the above-mentioned rose blended fragrance composition to which the compound was not added was conducted by 10 expert panelists. As a result, all 10 expert panelists added the compound and judged that the new blended fragrance composition was extremely superior in terms of long-lasting properties and giving a fresh image to the characteristics of natural rose. did.

(2) Perfume Composition The following components (parts by weight) were mixed as a floral bouquet type perfume composition.

Phenylethyl alcohol 180 Linalyl acetate 30 Bergamot oil 40 Rhodinol
50 benzyl acetate
40 heliotropin
80 Geraniol 110 Rose absolute lO β-ionone 100 Lavender oil 20 Diasmine absolute 10 Amyl salicylate
45 linalyl acetate
135 vetiver acetate
100 citronellol
50 Total 1000 By adding 5 g of 2-hexyl-tetrahydropyran to 995 g of the above composition, a novel floral bouquet-like perfume composition having a fresh, natural feel and long-lasting properties was obtained.

(3) Preparation of fragrance composition The following components (parts by weight) were prepared as a straw-type fragrance composition.

Cyclopentadecanolide 50 Coumarin 10 Heli No. 1
Robin 30 Ylang Ylang Oil 80 Methyl Ionone
100 anisaldehyde
20 neroli oil
30 hydroxycitronellal
50 linalool 70
Isobutyl salicylate 1.00 Amyl salicylate 1405-cyclohexadecene 20 Oakmoss absolute 3 Vanillin
7 Phenylacetaldehyl'
220 benzyl acetate
60 total 1000 By adding 15 g of 2-butyl-3,4-dihydrobilane to 985 g of the above composition, a new long-lasting formulated perfume composition with emphasis on fresher and more natural orchid type was obtained. .

Example 4. Flavor Composition Each ingredient (weight) below as a grape aroma flavor composition
was prepared.

Amyl isovalerate 8 Cinnamyl alcohol Cinnamic isovalerate 3 Cinnamic propionate 3 Citral
l ethyl acetate
62 ethyl benzoate
3 ethyl butyrate
16 ethyl caproate
3 ethyl enanthate
8 hydroxycitronellal
l Methyl anthranilate 132 Methyl salicylate 12 Petygrain l Turbinyl acetate 10 Ethanol
732 Total 1000 By adding 1 g of 2-heptyl-3,4-dihydrobilane to 999 g of the above composition, a novel grape-containing fragrance composition having a sweeter grape feeling and lasting effect was obtained. 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 more natural and significantly superior in terms of both aroma and flavor and persistence.

Example 5. Flavor Composition The following components (by weight) were prepared as pineapple-like flavor components.

Ethyl acetate Ethyl butyrate Isoamyl acetate Isoamyl valerate Isobutyric acid Invaleric acid Allyl caproate Ethyl acetate Ethyl caprylate Ethyl caprate Isoamyl alcohol Diethyl malonate Citral Linalool Maltol 70' Total 1000 Novel pineapple with long-lasting properties A perfume composition was obtained.

[Effect of the Invention 1] The 2-alkyl-bilane of the above formula (1) of the present invention is a compound known in the literature, but the aroma and flavor characteristics of the compound and its usefulness in the field of fragrances have been completely unknown until now. This was first revealed by the present inventors. This compound is based on a very characteristic flower-like aroma, and has aroma and flavor characteristics with a gorgeous and refreshing green feel, as well as excellent diffusibility and long-lasting aroma. As a result, it is possible to provide a blended fragrance composition with novel sustainability that cannot be obtained conventionally, and the compound can be widely used in food and beverages (including luxury goods), cosmetics, insurance, hygiene, pharmaceuticals, etc. useful in the field.

By adding 10 g of 2-pentyl-tetrahydrobilane to 1000 g of the above composition, natural patent applicant Hasegawa Perfume Co., Ltd.

Claims (1)

[Claims] The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [Here, R represents an alkyl group of C_4 to C_7, and the broken line is a single bond or a double bond. A fragrance composition characterized by containing a 2-alkyl-pyran derivative represented by the following as an active ingredient.