WO2024252982A1 - Fragrance composition - Google Patents

Abstract

The present invention relates to: a compound capable of enhancing a characteristic aroma; and a fragrance composition. The present invention provides: a compound represented by general formula (1); and a fragrance composition containing the compound. (In formula (1), R₁ through R₅ are as defined in the Description.)

Description

Fragrance composition

The present invention relates to compounds and fragrance compositions that are useful as ingredients for blended fragrances.

In recent years, as consumer preferences have become more diverse, there has been a strong demand for flavors that have a strong fruity or natural flavor or a flavor that is differentiated from others, for flavors used in foods, beverages, consumer goods, etc. However, it is sometimes difficult to meet such demands with combinations of conventional flavor raw materials, and there is a strong demand for new flavor materials.
In addition, there are various aromas that are originally contained in foods and beverages or that develop over time; for example, more than 850 types of aroma components have been identified in roasted coffee (Non-Patent Document 1).
On the other hand, some aroma components may become unpleasant or undesirable when combined, and are called off-flavor components. Examples of off-flavors include dusty and earthy odors. When dusty and earthy odors are present in food, the food is perceived as dusty, earthy, grassy, powdery, medicinal, or moldy. For example, Patent Document 1 describes that confectionery such as chewing gum in which the high-sensitivity sweetener aspartame is combined with a certain type of fruit flavoring or the like has a problem of developing a grassy odor, i.e., a dusty odor, over time, which becomes dusty, earthy, powdery, medicinal, or moldy.
In order to study measures against such off-flavor components, it is necessary to provide samples for developing and examining fragrances, such as indicators for determining off-flavors.

JP 2009-131228 A

Takasago International Journal No. 170 (2012)

The present invention provides novel compounds with odors that are useful as blended fragrance ingredients and samples for fragrance development and research, fragrance compositions containing said compounds, and consumer products containing them.

The present inventors synthesized various compounds and investigated their odors, and found that alkyl-substituted pyridine compounds have an excellent and characteristic odor.
That is, the present invention relates to the following [1] to [6].

 
（式（１）中、Ｒ_１～Ｒ_５は、以下の（ａ）または（ｂ）： 
（ａ）Ｒ_１がペンチル基、Ｒ_２がエチル基、Ｒ_３～Ｒ_５が水素原子
（ｂ）Ｒ_１がエチル基、Ｒ_２～Ｒ_５のいずれか一つの基がペンチル基であり残りの基が水素原子
を表す。）
［２］　前記［１］に記載の化合物を含有する香料組成物。
［３］　消費者製品または飲食品用である、前記［２］に記載の香料組成物。
［４］　前記［１］に記載の化合物または前記［２］もしくは［３］に記載の香料組成物を含有する飲食品、口腔用組成物、たばこ製品、または消費者製品。
［５］　前記［１］に記載の化合物または前記［２］もしくは［３］に記載の香料組成物を添加することを含む、飲食品、口腔用組成物、たばこ製品、または消費者製品の製造方法。
［６］　前記［１］に記載の化合物を含有する異臭判定用指標物。 [1] A compound represented by general formula (1):

In formula (1), R ₁ to R ₅ each represent the following (a) or (b):
(a) _R1 is a pentyl group, _R2 is an ethyl group, and _R3 to _R5 are hydrogen atoms; (b) _R1 is an ethyl group, any one of _R2 to _R5 is a pentyl group, and the remaining groups are hydrogen atoms.
[2] A fragrance composition comprising the compound according to [1] above.
[3] The flavor composition according to [2] above, which is for use in consumer products or food and beverage products.
[4] A food or drink, an oral composition, a tobacco product, or a consumer product containing the compound according to [1] above or the flavor composition according to [2] or [3] above.
[5] A method for producing a food or beverage, an oral composition, a tobacco product, or a consumer product, comprising adding the compound according to [1] above or the flavor composition according to [2] or [3] above.
[6] An indicator for determining off-odor containing the compound according to [1] above.

The present invention provides novel compounds with odors that are useful as ingredients for blended fragrances, fragrance compositions containing said compounds, and consumer products containing them.

The present invention will be described in detail below.
In the compound represented by formula (1), R ₁ to R ₅ represent the following (a) or (b).
(a) R ₁ is a pentyl group, R ₂ is an ethyl group, and R ₃ to R ₅ are hydrogen atoms (b) R ₁ is an ethyl group, any one of R ₂ to R ₅ is a pentyl group, and the remaining groups are hydrogen atoms When R ₁ to R ₅ are (a), the compound is 3-ethyl-2-pentylpyridine. On the other hand, when R ₁ to R ₅ are (b), the compound is 2-ethyl-3-pentylpyridine, 2-ethyl-4-pentylpyridine, 2-ethyl-5-pentylpyridine, or 2-ethyl-6-pentylpyridine.

The compounds of the present invention can be obtained by reacting an alkyllithium with a pyridine to alkylate the carbon atom (position 2) adjacent to the nitrogen atom of the pyridine ring. For example, 3-ethyl-2-pentylpyridine, described in the examples, can be obtained by the following method.

 

 

Since the compounds of the present invention each have a characteristic odor, they can be suitably used as blended fragrance materials.
The compounds of the present invention are also useful as samples for the development and examination of fragrances, such as indicators for determining off-odors. For example, 3-ethyl-2-pentylpyridine has an odor tone that corresponds to the dusty odor or earthy odor in foods and beverages, and can therefore be used as an indicator for determining off-odors. The compounds of the present invention can be used as indicators for determining off-odors in the development of fragrances for effectively masking off-odors in foods and beverages.
When the compound of the present invention is used as a sample for developing and examining a fragrance, such as a blended fragrance raw material or an indicator for determining off-flavors, the compound of the present invention may be used alone or in combination of two or more kinds. Furthermore, the compound of the present invention may be used in combination with other fragrance ingredients as long as the characteristic odor of the compound of the present invention is not significantly impaired.

The content of the compound of the present invention in the fragrance composition of the present invention is preferably 0.0001 to 100,000 ppm, more preferably 0.001 to 10,000 ppm, and even more preferably 0.01 to 1,000 ppm, based on the mass of the fragrance composition.

The compound of the present invention and the flavor composition of the present invention can be added in extremely small amounts as is to foods and beverages, oral compositions, tobacco products, consumer products, etc., to impart or enhance aroma and flavor to the products.
The content of the compound of the present invention in each product is not particularly limited as long as it is an effective amount, but is preferably 10 ppt to 100 ppm, more preferably 100 ppt to 10 ppm, and even more preferably 1 ppb to 1 ppm, based on the weight of each product. Each product can be obtained by adding the compound of the present invention to a predetermined content.

Specific examples of food and beverages include beverages such as carbonated drinks, soft drinks, fruit juice drinks, dairy drinks, lactic acid bacteria drinks, energy drinks, soy milk, and tea drinks; alcoholic beverages such as chuhai, cocktail drinks, sparkling wine, fruit wine, and condiment wine; desserts such as ice cream, ice milk, lacto ice cream, frozen desserts, yogurt, pudding, jelly, and daily desserts; sweets such as caramel, candy, candy tablets, crackers, biscuits, cookies, pies, chocolate, snacks, and chewing gum; soups such as Japanese-style soup and Western-style soup; jams; flavor seasonings; various instant drinks; and various instant foods.

Examples of oral compositions include toothpaste, mouthwash, mouthwash, lozenges, chewing gums, etc.

Tobacco products include cigarettes and e-cigarettes.

Specific examples of consumer products include fragrance products such as perfume, eau de parfum, eau de toilette, and eau de cologne;
Basic cosmetics such as face wash cream, cleansing cream, milky lotion, toner, and serum;
Finishing cosmetics such as lipstick, lip balm, eyeliner, mascara, eye shadow, eyebrow pencil, eye mask, nail enamel, enamel remover, etc.;
Hair cosmetics such as pomades, Brilantin, setting lotions, hair sticks, hair solids, hair oils, hair treatments, hair creams, hair tonics, hair liquids, hair sprays, Bandolin, hair tonics, hair dyes, etc.;
Suntanning cosmetics such as tanning products and sunscreen products;
Medicinal cosmetics such as antiperspirants, aftershave lotions and gels, permanent wave agents, medicinal soaps, medicinal shampoos, and medicinal skin cosmetics;
Hair care products such as shampoo, rinse, rinse-in shampoo, conditioner, treatment, hair pack, etc.
Soaps such as toilet soap, bath soap, perfumed soap, transparent soap, synthetic soap, etc.;
Personal cleansing products such as body soap, body shampoo, hand soap, and face cream;
Bath additives such as bath salts (bath salts, bath tablets, bath liquids, etc.), foam baths (bubble baths, etc.), bath oils (bath perfumes, bath capsules, etc.), milk baths, bath jellies, bath cubes, etc.;
Detergents such as heavy-duty laundry detergent, light-duty laundry detergent, liquid detergent, laundry soap, compact detergent, powdered soap, etc.;
Fabric softeners, furniture care products, etc.;
Cleaning agents such as cleansers, house cleaners, toilet cleaners, bathroom cleaners, glass cleaners, mould removers, drain cleaners, etc.;
Kitchen detergents such as kitchen soap, synthetic kitchen soap, and dishwashing detergent;
Bleaching agents such as oxidative bleaching agents (chlorine bleaching agents, oxygen bleaching agents, etc.), reductive bleaching agents (sulfur bleaching agents, etc.), and optical bleaching agents;
Aerosol preparations such as spray types and powder sprays;
Deodorizers and fragrances, such as solid types, gel types, and liquid types (water-based and oil-based);
Daily necessities and sundries such as tissue paper and toilet paper;
Examples include non-medicinal products such as liquid bath additives, mouthwash, and repellents (mist spray type, water-based liquid type), medicated cosmetics, and pharmaceuticals such as medicated lotions.

The compound or flavor composition of the present invention can also be mixed with other flavor ingredients and added to each of the above-mentioned products and compositions to impart or enhance the desired aroma or flavor, for example, a citrus-like aroma or flavor. Examples of other flavor ingredients include various synthetic flavors, natural flavors, natural essential oils, plant extracts, etc., such as the natural essential oils, natural flavors, and synthetic flavors described in the Japan Patent Office Gazette, Well-Known and Commonly Used Technology Collection (Fragrances), Part II Food Flavors, p. 88-131, published January 14, 2000.

The aromas and flavors that are imparted or enhanced in the present invention include, but are not limited to, galbanum-like, green, floral, spicy, chemical, earthy, dusty, citrus-like, tropical fruit-like, sweet, powdery, clay-like, and rubber-like.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
The analytical instruments used in the examples are as follows:
NMR measurement device: AVANCEIII 500 (manufactured by Bruker Biospin)

(Example 1) Synthesis of 3-ethyl-2-pentylpyridine 5.0 g of pentyl chloride was reacted with 0.65 g of metallic lithium in tetrahydrofuran (THF) at -20 to -10°C to prepare pentyllithium, and then 5.0 g of 3-ethylpyridine was added while cooling with dry ice, and the mixture was stirred and then allowed to warm to room temperature. Water was added, the solvent was distilled off, and the mixture was extracted with toluene, washed with water, and separated by silica gel column chromatography to obtain 296 mg of the target 3-ethyl-2-pentylpyridine as a deep yellow oil.

The spectral data of 3-ethyl-2-pentylpyridine is as follows:
1H NMR (500MHz, CDCl3) δ: 0.91 (t, J = 7.1Hz, 3H), 1.23 (t, J = 7.6Hz, 3H), 1.31-1.44 (m, 4H), 1.66-1.77 (m, 2H), 2.66 (q, J = 7.6Hz, 2 H), 2.79 (t, J=8.0Hz, 2H), 7.05 (dd, J=7.6Hz, J=4.8Hz, 1H), 7. 43 (dd, J=7.7Hz, J=1.5Hz, 1H), 8.37 (dd, J=4.8Hz, J=1.6Hz, 1H)
13C NMR (125MHz, CDCl3) δ: 14.08 (q), 14.77 (q), 22.64 (t), 25.11 (t), 29.36 (t), 32 .10(t), 35.02(t), 121.13(d), 135.79(d), 136.62(s), 146.59(d), 160.30(s).

(Example 2) Synthesis of 3-pentylpyridine 39.6 mL of toluene was added to 39.6 mL of 1.2 M sec-butyllithium hexane solution, and 5.0 g of 3-bromopyridine was added while cooling with dry ice to react, and then 4.54 g of pentyl bromide in THF solution was added and stirred, and the temperature was raised to room temperature. Water was added, the solvent was distilled off, and the product was extracted with toluene, washed with water, and separated by silica gel column chromatography to obtain 829 mg of the target 3-pentylpyridine as a deep yellow oil.
The spectral data of 3-pentylpyridine is as follows:
1H NMR (500MHz, CDCl3) δ: 0.89 (t, J = 6.9Hz, 3H), 1.25-1.39 (m, 4H), 1.56-1.75 (m, 2H), 2.60 (t, J = 7.7Hz, 2H), 7. 19 (dd, J=7.7Hz, J=4.8Hz, 1H), 7.48 (d, J=7.8Hz, 1H), 8.42 (dd, J=4.8Hz, J=1.5Hz, 1H), 8.44 (d, J=1.9Hz, 1H).
13C NMR (125 MHz, CDCl3) δ: 13.98 (q), 22.45 (t), 30.82 (t), 31.33 (t), 33 .00(t), 123.22(d), 135.77(d), 137.98(s), 147.18(d), 150.00(d).

Example 3 Synthesis of 2-ethyl-3-pentylpyridine and 2-ethyl-5-pentylpyridine A THF solution of 810 mg of 3-pentylpyridine was cooled with dry ice, and 23.9 mL of a benzene solution of 0.5 M ethyllithium was added to react, and the temperature was then raised to room temperature. Water was added, the solvent was distilled off, and the mixture was extracted with toluene, washed with water, and separated by silica gel column chromatography to obtain 121 mg and 100 mg of the desired 2-ethyl-3-pentylpyridine and 2-ethyl-5-pentylpyridine as reddish brown oils, respectively.

The spectral data of 2-ethyl-3-pentylpyridine is as follows:
1H NMR (500MHz, CDCl3) δ: 0.85-0.96 (m, 3H), 1.29 (t, J = 7.6Hz, 3H), 1.32-1.442 (m, 4H), 1.54-1.65 (m, 2H), 2.61 (t, J = 7.9Hz, 2H) ), 2.83 (q, J = 7.5Hz, 2H), 7.04 (dd, J = 7.6Hz, J = 4.8Hz, 2H), 7.4 1 (dd, J=7.6Hz, J=1.5Hz, 2H), 8.38 (dd, J=4.8Hz, J=1.6Hz, 1H).
13C NMR (125MHz, CDCl3) δ: 13.63 (q), 13.99 (q), 22.52 (t), 27.92 (t), 30.31 (t), 31 .75(t), 32.12(t), 121.01(d), 135.28(s), 136.59(d), 146.62(d), 161.16(s).

The spectral data of 2-ethyl-5-pentylpyridine is as follows:
1H NMR (500MHz, CDCl3) δ: 0.89 (t, J = 6.9Hz, 3H), 1.29 (t, J = 7.6Hz, 3H), 1.25-1.40 (m, 4H), 1.55-1.65 (m, 2H), 2.56 (t, J=7.7Hz, 2H), 2.79 (q, J=7.6Hz, 2H), 7.07 (d, J=7.9Hz, 1H), 7.41 (dd, J=7.9Hz, J=2.2Hz, 1H), 8.34 (d, J=1.8Hz, 1H).
13C NMR (125 MHz, CDCl3) δ: 13.97 (q), 22.45 (t), 30.90 (t), 31.33 (t), 32 .58(t), 121.15(d), 134.96(q), 136.29(d), 149.14(d), 160.72(s).

Example 4 Synthesis of 2-ethyl-4-pentylpyridine A THF solution of 1.0 g of 4-pentylpyridine was cooled with dry ice, and 14.7 mL of a 0.5 M ethyllithium benzene solution was added and stirred, and then the mixture was allowed to warm to room temperature. Water was added, the solvent was distilled off, and the mixture was extracted with toluene, washed with water, and separated by silica gel column chromatography to obtain 694 mg of the target 2-ethyl-4-pentylpyridine as a deep yellow oil.

The spectral data of 2-ethyl-4-pentylpyridine is as follows:
1H NMR (500MHz, CDCl3) δ: 0.90 (t, J = 6.9Hz, 3H), 1.30 (t, J = 7.6Hz, 3H), 1.26-1.39 (m, 4H), 1.57-1.65 (m, 2H) , 2.56 (t, J=7.8Hz, 2H), 2.79 (q, J=7.6Hz, 2H), 6.92 (d, J=5.0Hz, 1H), 6.97 (s, 1H), 8.39 (d, J=5.1Hz, 1H).
13C NMR (125 MHz, CDCl3) δ: 13.96 (q), 13.97 (q), 22.46 (t), 30.07 (t), 31.31 (t), 31 .44(t), 35.29(t), 121.18(d), 122.15(d), 148.97(d), 152.12(s), 163.31(s).

(Example 5) Synthesis of 2-ethyl-6-pentylpyridine A THF solution of 2.5 g of pentyl chloride was reacted with 0.33 g of metallic lithium at -20 to -10°C to prepare pentyllithium, and then 2.0 g of 2-ethylpyridine was added while cooling with dry ice, and the mixture was stirred and then allowed to warm to room temperature. Water was added, the solvent was distilled off, and the mixture was extracted with toluene, washed with water, and separated by silica gel column chromatography to obtain 209 mg of the target 2-ethyl-6-pentylpyridine as a deep yellow oil.

The spectral data of 2-ethyl-6-pentylpyridine is as follows:
1H NMR (500MHz, CDCl3) δ: 0.85-0.93 (m, 3H), 1.28 (t, J = 7.6Hz, 3H), 1.30-1.39 (m, 4H), 1.65-1.75 (m , 2H), 2.75 (t, J = 7.9Hz, 2H), 2.79 (q, J = 7.6Hz, 2H), 6.95 (t, J = 7.3Hz, 2H), 7.49 (t, J = 7.7Hz, 1H).
13C NMR (125MHz, CDCl3) δ: 14.03 (q), 14.23 (q), 22.56 (t), 29.88 (t), 31.52 (t), 31 .68(t), 38.58(t), 118.83(d), 119.59(d), 136.50(d), 161.90(s), 162.94(s).

Example 6: Aroma evaluation of synthesized 3-ethyl-2-pentylpyridine, 2-ethyl-3-pentylpyridine, 2-ethyl-4-pentylpyridine, 2-ethyl-5-pentylpyridine, and 2-ethyl-6-pentylpyridine An aroma evaluation was carried out on the alkyl-substituted pyridines obtained in Examples 1, 3, 4, 5, and 6. Representative comments from expert panelists are shown in Table 1 below.

Example 7: Fragrance composition with floral, green and powdery notes containing 3-ethyl-2-pentylpyridine Fragrance compositions having floral, green and powdery notes were prepared using the 3-ethyl-2-pentylpyridine obtained in Example 1, and the odor was evaluated. The formulation containing 3-ethyl-2-pentylpyridine (fragrance composition 1) and the formulation not containing 3-ethyl-2-pentylpyridine (fragrance composition 2) are listed in Table 2 below. The amount of each component is expressed in parts by mass.

It was confirmed that fragrance composition 1, which contains 3-ethyl-2-pentylpyridine, imparts a natural galbanum-like green, earthy note.

Example 8: Fragrance composition with citrus, fruity and grapefruit notes containing 3-ethyl-2-pentylpyridine Fragrance compositions with citrus, fruity and grapefruit notes were prepared using the 3-ethyl-2-pentylpyridine obtained in Example 1, and the odor was evaluated. The formulation containing 3-ethyl-2-pentylpyridine (fragrance composition 3) and the formulation not containing 3-ethyl-2-pentylpyridine (fragrance composition 4) are listed in Table 3 below. The amount of each component is expressed in parts by mass.

 

 

It was confirmed that fragrance composition 3, which contains 3-ethyl-2-pentylpyridine, imparts a fresh, green note reminiscent of citrus peel.

(Example 9) Apple fragrance composition containing 3-ethyl-2-pentylpyridine Using the 3-ethyl-2-pentylpyridine obtained in Example 1, apple fragrance composition 5 was prepared according to the recipe in Table 4. For comparison, apple fragrance composition 6 was prepared according to the recipe in Table 4. The amount of each component is expressed in parts by mass.

 

 

(Example 10) Tablet candy using apple flavor Tablet candy was prepared according to the recipe in Table 5 using apple flavor compositions 5 and 6 prepared in Example 9. It was confirmed that tablet candy 7 immediately after preparation had a similar off-odor as the sample in which tablet candy 8 was stored at 40°C for two weeks and an earthy, dusty off-odor was developed. This confirmed that 3-ethyl-2-pentylpyridine can be used as an indicator for determining off-odors. The amount of each component is expressed in parts by mass.

 
 

 
 

Claims (6)

A compound represented by general formula (1):

In formula (1), R ₁ to R ₅ each represent the following (a) or (b):
(a) _R1 is a pentyl group, _R2 is an ethyl group, and _R3 to _R5 are hydrogen atoms; (b) _R1 is an ethyl group, any one of _R2 to _R5 is a pentyl group, and the remaining groups are hydrogen atoms. A fragrance composition containing the compound described in claim 1. The fragrance composition according to claim 2, which is for use in consumer products or food and beverage products. A food or drink, an oral composition, a tobacco product, or a consumer product containing the compound according to claim 1 or the flavor composition according to claim 2 or 3. A method for producing a food or beverage, an oral composition, a tobacco product, or a consumer product, comprising adding a compound according to claim 1 or a flavor composition according to claim 2 or 3. An indicator for determining off-odor, comprising the compound according to claim 1.