EP4613833A1

EP4613833A1 - Fragrance composition and consumer product

Info

Publication number: EP4613833A1
Application number: EP23885791.6A
Authority: EP
Inventors: Kenji TANUMA; Kent H. Lombard; Yuna YORITATE
Original assignee: Takasago International Corp; Takasago Perfumery Industry Co
Current assignee: Takasago International Corp
Priority date: 2022-11-02
Filing date: 2023-10-31
Publication date: 2025-09-10
Also published as: WO2024096037A1; JPWO2024096037A1

Abstract

A fragrance composition contains at least one of the following mixture (A) and mixture (B). The mixture (A) contains 15 mass% or more of the following compound (1a) and 85 mass% or less of the following compound (1b). The mixture (B) containing 55 mass% or more of the following compound (2a) and 45 mass% or less of the following compound (2b) (A total amount of the compound (1a) and the compound (1b) is 100 mass%. A total amount of the compound (2a) and the compound (2b) is 100 mass%.)

Description

TECHNICAL FIELD

The present invention relates to a fragrance composition and a consumer product.

BACKGROUND ART

In people's life currently, a variety of products with preferred scents are being sold on the market. However, in response to the increasingly diverse needs for fragranced products, there is a demand for scents having high-preference scents, and many compounds have been developed.

SUMMARY OF INVENTION

TECHNICAL PROBLEM

On the other hand, since each developed compound has various characteristics in terms of scent or the like, compounds with different aroma notes are required depending on the purpose of use.

SOLUTION TO PROBLEM

The inventors of the present invention have found that a compound having a pulegone oxime structure or a compound having a piperitone oxime structure, or a mixture containing these compounds in a specific ratio, has a unique scent, and have thus completed the present invention.
The present invention relates to the following fragrance composition and the like.

[1] A fragrance composition containing at least one of the following mixture (A) and mixture (B):
1. (A) a mixture containing 15 mass% or more of a compound (1a) represented by the following formula (1a) and 85 mass% or less of a compound (1b) represented by the following formula (1b) (where a total amount of the compound (1a) and the compound (1b) is 100 mass%); and
2. (B) a mixture containing 55 mass% or more of a compound (2a) represented by the following formula (2a) and 45 mass% or less of a compound (2b) represented by the following formula (2b) (where a total amount of the compound (2a) and the compound (2b) is 100 mass%).
[2] A fragrance composition containing at least one of a compound (1a) represented by the following formula (1a) and a compound (2a) represented by the following formula (2a).

ADVANTAGEOUS EFFECTS OF INVENTION

By adding the compound or the mixture according to the present invention, a fragrance composition having a unique scent can be obtained. This composition is used in a wide range of consumer products as a fragranced composition such as a fragrance, fragrances or cosmetics, or health and hygiene products.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the present invention will be described in detail.
In the present description, a fragrance composition according to an embodiment of the present invention is also referred to as "the fragrance composition according to the present embodiment".
In the present description, a compound represented by the formula (1a) is referred to as a "compound (1a)". The same applies to other compounds.
The fragrance composition according to the present embodiment is a fragrance composition containing the following compounds (1a), (1b), (2a), and (2b) or a mixture containing these compounds in a specific ratio. The compounds (1a) and (1b) are compounds having a pulegone oxime structure. The compounds (2a) and (2b) are compounds having a piperitone oxime structure.
In the case of containing the compounds in a specific ratio, the fragrance composition according to the present embodiment is a fragrance composition containing at least one of the following mixture (A) and mixture (B).

(A) A mixture containing 15 mass% or more of the compound (1a) and 85 mass% or less of the compound (1b) (where a total amount of the compound (1a) and the compound (1b) is 100 mass%)
(B) A mixture containing 55 mass% or more of the compound (2a) and 45 mass% or less of the compound (2b) (where a total amount of the compound (2a) and the compound (2b) is 100 mass%)

The mixture (A) preferably contains 30 mass% or more of the compound (1a) and 70 mass% or less of the compound (1b).
The mixture (B) preferably contains 90 mass% or more of the compound (2a) and 10 mass% or less of the compound (2b).
The compound (1a) has a higher scent intensity than the compound (1b), and the compound (2a) has a higher scent intensity higher than the compound (2b). Therefore, the fragrance composition according to the present embodiment more preferably contains only at least one of the compound (1a) and the compound (2a). In this embodiment, the ratio of the compound (1a) and the compound (2a) is preferably such that the compound (1a) is to 100 mass%, and the compound (2a) is 0 mass% to 100 mass% when the total amount of the compound (1a) and the compound (2a) is 100 mass%.
Among these compounds, a fragrance composition containing substantially only at least one of the compound (1a) and the compound (2a) is particularly preferred.
In the fragrance composition according to the present embodiment, contents of the compounds (1a), (1b), (2a), and (2b) are determined depending on the blending, and are each preferably 0.00001 mass% to 30 mass%, more preferably 0.01 mass% to 20 mass%, and still more preferably 0.01 mass% to 10 mass% in the entire fragrance composition.
The compound (1a), the compound (1b), the compound (2a), and the compound (2b) in the fragrance composition according to the present invention can be synthesized by the methods described in Examples to be described later.
In addition, the fragrance composition according to the present embodiment may contain one or more kinds of other fragrance retaining agents commonly used. Examples of the other fragrance retaining agents include ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hercolin, and medium chain fatty acid triglyceride.
The fragrance composition according to the present embodiment may contain a mixed fragrance commonly used. The fragrance composition thus obtained can impart a fresh and high-preference scent.
In addition, the fragrance composition according to the present embodiment can be blended as a scent component into a consumer product in an amount commonly used in the industry to impart a unique scent and enhance the commercial value. Examples of the consumer product include a fragrance product, a cosmetic, a toiletry product, an air care product, daily necessities, household goods, an oral care product, a detergent, a softener, and a quasi-drug.
Examples of the fragrance product include perfumes, eau de parfum, eau de toilette, and eau de cologne.
Examples of the cosmetic include: basic cosmetics such as facial cleansing cream, vanishing cream, cleansing cream, cold cream, massage cream, emulsion, lotion, serum, pack, and a makeup remover; make-up cosmetics such as foundation and lipstick; hair cosmetics such as a hair tonic, a hair liquid, and a hair spray; sunscreen cosmetics such as a suntan product and a sunscreen product; and medicated cosmetics such as an antiperspirant, a body deodorant, an aftershave lotion and gel, a permanent waving agent, a medicated soap, a medicated shampoo, and a medicated skin cosmetic.
Examples of the toiletry product include: hair care products such as a shampoo, a rinse, a rinse-in-shampoo, a conditioner, a treatment, and a hair pack; skin care products such as lip balm and hand cream; soaps such as a cosmetic soap and a bath soap; body care products such as a body soap, a body shampoo, and a hand soap; and bath agents such as a bath additive (a bath salt, a bath tablet, a bath liquid, etc.), a foam bath (a bubble bath, etc.), bath oils (a bath perfume, a bath capsule, etc.), a milk bath, a bath jelly, and a bath cube.
Examples of the air care product include an aerosol, a spray, and a powder spray.
Examples of the daily necessities include a deodorant/fragrant agent.
Examples of the household goods include tissue paper and toilet paper.
Examples of the oral care product include a toothpaste, a mouthwash, a mouth spray, and gargle.
Examples of the detergent include a heavy laundry detergent, a light laundry detergent, a liquid detergent, a laundry soap, a compact detergent, and a powder soap. Examples of a fabric softener include a liquid softener and a dryer sheet. Examples of a cleaner include a cleanser, a furniture care product, a house cleaner, a toilet cleaner, a bathroom cleaner, a glass cleaner, a mold remover, and a drain cleaner. Examples of a kitchen detergent include a kitchen soap, a synthetic kitchen soap, a dish detergent, and a dishwasher detergent. Examples of a bleach include an oxidizing bleach (a chlorine-based bleach, an oxygen-based bleach, etc.), a reducing bleach (a sulfur-based bleach, etc.), and an optical bleach. Examples of the air care product include an aerosol (a spray type aerosol and a powder spray aerosol), a candle, a wax melt, a car freshener, and a free-standing, spray-type or plug-in deodorant/fragrant agent (in a solid form, gel form, liquid form, etc.). Examples of a pet care product include a pet deodorant, a pet toilet deodorant, a pet shampoo, and a pet conditioner. Examples of the household goods include various forms of tissue paper, toilet paper, a disinfectant wipe, a disinfectant spray, and the like.
Examples of the quasi-drug include a poultice and an ointment.
In the case where the fragrance composition according to the present embodiment is used in the above product, the fragrance composition according to the present embodiment is used as it is, or used in any desired state selected depending on the purpose, such as: a liquid state dissolved in polyhydric alcohols such as alcohols, propylene glycol, or glycerin; a solubilized state or dispersed state obtained by being solubilized or dispersed using surfactants such as a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant; or a microcapsule state obtained by a treatment with an encapsulating agent.
Further, the fragrance composition according to the present embodiment may be stabilized and sustained-released by being included in an inclusion agent such as cyclodextrin. These are appropriately selected and used depending on the form of the final product, for example, a liquid form, a solid form, a powder form, a gel form, a mist form, or an aerosol form.
As described above, the present description discloses the following fragrance composition and consumer product.

[1] A fragrance composition containing at least one of the following mixture (A) and mixture (B):
1. (A) a mixture containing 15 mass% or more of a compound (1a) represented by the following formula (1a) and 85 mass% or less of a compound (1b) represented by the following formula (1b) (where a total amount of the compound (1a) and the compound (1b) is 100 mass%); and
2. (B) a mixture containing 55 mass% or more of a compound (2a) represented by the following formula (2a) and 45 mass% or less of a compound (2b) represented by the following formula (2b) (where a total amount of the compound (2a) and the compound (2b) is 100 mass%).
[2] The fragrance composition according to [1], containing: at least one of the following mixture (A) and mixture (B):
1. (A) a mixture containing 30 mass% or more of the compound (1a) and 70 mass% or less of the compound (1b); and
2. (B) a mixture containing 90 mass% or more of the compound (2a) and 10 mass% or less of the compound (2b).
[3] A fragrance composition containing at least one of a compound (1a) represented by the following formula (1a) and a compound (2a) represented by the following formula (2a).
[4] A consumer product containing the fragrance composition according to any one of [1] to [3].
[5] The consumer product according to [4], in which the consumer product is selected from a fragrance product, a cosmetic, a toiletry product, an air care product, daily necessities, household good, an oral care product, a detergent, and a quasi-drug.

Examples

Hereinafter, the present invention will be specifically described with Examples, but the present invention is not limited to thereto in any way. The following devices were used to measure physical properties in Examples.

NMR: DRX500 (manufactured by Bruker)
GC/MS: UP5977A (manufactured by Agilent Technologies)
Column: Inertcap-1 (length: 30 m × inner diameter: 0.25 mm, film thickness: 0.25 µm) (manufactured by GL Sciences Inc.)

(Example 1) Synthesis of Compound (1a) and Compound (1b)

Under a nitrogen atmosphere, 200 g (1.3 mol) of d-pulegone, 100 mL of ethanol, and 200 mL of pyridine were added to a reaction flask, and the mixture was heated to 60°C. Hydroxylamine hydrochloride was added thereto in portions in an amount of 108 g (2.08 mmol) and the reaction was carried out at 60°C for 2 hours (conversion rate: 98%). After cooling to room temperature, 50 mL of 10% hydrochloric acid and 150 mL of ethyl acetate were added, and the aqueous layer was removed. The organic layer was washed with water and rinsed with saturated saline, and dried with magnesium sulfate. Magnesium sulfate was filtered off, and the solvent was distilled off from the filtrate to give a mixture of (1a):(1b) = 18:78 (GC area ratio = mass ratio, the same applies below).
Scent: earthy and galbanum

(Example 2) Increase in Ratio of Compound (1a)

Under a nitrogen atmosphere, 221 g of the mixture of (1a):(1b) = 18:78 obtained in Example 1 was heated and stirred at 120°C for 7 hours. Thereafter, the mixture was cooled to room temperature, and Vigreux distillation was performed to give a fraction at 82°C to 86°C and 44 Pa, giving 122 g of a mixture of (1a):(1b) = 32:66 as a viscous pale pink oil, in which the amount of the compound (1a) was increased.
Scent: strong, earthy, and galbanum

(Example 3 and Reference Example 1) Isolation of Compound (1a) and Compound (1b)

The mixture of (1a):(1b) = 32:66 obtained in Example 2 was subjected to silica gel column chromatography to give a pure compound (1a) as a pale red solid (Example 3).

GC/MS (EI): m/z (%) 167.1 (M⁺, 2), 152.1 (8), 150.1 (6), 134.1 (1), 124.1 (2), 110.1 (6), 108.1 (4).94.1 (7), 85.1 (10), 67.1 (4), 57.1 (3), 43.0 (4), 41.1 (5)
1H NMR (500 MHz, CDCl₃): δ (ppm) 2.73 (d, J = 13.3 Hz, 1H), 2.46 (d, J = 7.8 Hz, 1H), 1.91-1.85 (m, 1H), 1.81-1.74 (m, 6H), 1.66 (d, J = 1.8 Hz, 3H), 1.15-1.05 (m, 1H), 0.97 (d, J = 5.0 Hz, 3H)
13C NMR (125 MHz, CDCl₃): δ (ppm) 159.7 (C), 130.1 (C), 125.4 (C), 42.2 (CH₂), 35.7 (CH₂), 35.1 (CH), 30.2 (CH₂), 23.4 (CH₃), 22.1 (CH₃), 19.3 (CH₃)
Specific optical rotation [α]²⁰D = -9.7 deg (c = 1, CHCl₃)
Scent: strong, earthy, and galbanum

In addition, a pure compound (1b) was obtained as a colorless solid (Reference Example 1).

GC/MS (EI): m/z (%) 167.1 (M⁺, 3), 152.1 (9), 150.1 (6), 124.1 (1), 110.1 (5), 108.1 (3).94.1 (6), 93.1 (2), 85.1 (4), 67.1 (2), 53.1 (1), 41.1 (3)
1H NMR (500 MHz, CDCl₃): δ (ppm) 3.11 (td, J = 3.7, 12.3 Hz, 1H), 2.46 (td, J = 4.1, 14.4 Hz, 1H), 2.11-2.04 (m, 1H), 1.84 (d, J = 1.0 Hz, 3H), 1.80-1.68 (m, 6H), 1.22-1.13 (m, 1H), 0.96 (d, J = 1.5 Hz, 3H)
13C NMR (125 MHz, CDCl₃): δ (ppm) 159.7 (C), 130.5 (C), 127.4 (C), 34.1 (CH₂), 33.7 (CH₂), 31.6 (CH), 29.4 (CH₂), 22.2 (CH₃), 21.8 (CH₃), 20.6 (CH₃)
Specific optical rotation [α]²⁰D = -20.5 deg (c = 1, CHCl₃)
Scent: weak, green, and herbal

[Scent Intensity Comparison]
The scents of the oximes obtained in Examples 1 to 3 and Reference Example 1 were compared.
A 1% triethyl citrate solution of each mixture and compound was prepared, and the scent intensity was compared (scored by perfumers, rated from 10 to 1 in descending order of intensity). Table 1

Example 1 Compounds (1a):(1b) = 18:78 Example 2 Compounds (1a):(1b) = 32:66 Example 3 Compound (1a) Reference Example 1 Compound (1b)

Scent intensity 7.5 9 10 3
It was revealed that compared to the mixture in Example 1, the mixture in Example 2 in which the ratio of the Z isomer (compound (1a)) was increased had a clearly higher scent intensity, and the pure Z isomer (Example 3, compound (1a)) had an even higher scent intensity. On the other hand, the E isomer (Reference Example 1, compound (1b)) had a considerably low scent intensity, and the scent quality is different from that of the Z isomer and had an herbal scent.

(Example 4) Synthesis of Compound (2a) and Compound (2b)

Under a nitrogen atmosphere, 100 g (657 mmol) of L-piperitone, 50 mL of ethanol, and 100 mL of pyridine were added to a reaction flask, and the mixture was heated to 60°C. Hydroxylamine hydrochloride was added thereto in portions in an amount of 73.0 g (1.05 mol) and the reaction was carried out at 60°C for 2 hours (conversion rate: 98%). After cooling to room temperature, 50 mL of 10% hydrochloric acid and 150 mL of ethyl acetate were added, and the aqueous layer was removed. The organic layer was washed with water and rinsed with saturated saline, and dried with magnesium sulfate. Magnesium sulfate was filtered off, and the solvent was distilled off from the filtrate to give 110 g of a viscous solid mixture of compound (2a):compound (2b) = 55:45.
Scent: green, earthy, and cassis
(Example 5) Increase in Ratio of Compound (2a)
To 110 g of the mixture obtained in Example 4, 100 mL of hexane and 100 mL of ethyl acetate were added, and the mixture was heated to 50°C for dissolution. The mixture was cooled to room temperature, and the flesh-colored solid that precipitated was collected, to give 50 g of a mixture of compound (2a):compound (2b) = 90:10, in which the amount of the compound (2a) was increased.

Specific optical rotation [α]²⁰D = +12.9 deg (c = 1, CHCl₃)
Scent: strong, earthy, and galbanum

(Example 6 and Reference Example 2) Isolation of Compound (2a) and Compound (2b)

The mixture obtained in Example 5 was separated by preparative LC (two Cosmosil 5LS-2, eluent: hexane/ethyl acetate = 80/20) to isolate the compound (2a) as a colorless oil (Example 6).

Compound (2a):

GC/MS (EI): m/z (%) 167.1 (M⁺, 5), 152.1 (1), 150.1 (1), 139.1 (2), 135.1 (1), 126.1 (1), 126.1 (1), 125.1 (11), 124.1 (5), 110.1 (2), 109.1 (2), 108.1 (8), 106.1 (2), 94.1 (1), 93.1 (2), 91.1 (2), 81.1 (2), 79.1 (2), 77.1 (2), 41.1 (2)
1H NMR (500 MHz, CDCl₃): δ (ppm) 6.53 (s, 1H), 2.25-2.19 (m, 1H), 2.01-1.98 (m, 2H), 1.95-1.85 (m, 1H), 1.86 (s, 3H), 1.84-1.77 (m, 1H), 0.95 (d, J = 6.7 Hz, 3H), 0.91 (d, J = 6.7 Hz, 3H)
13C NMR (125 MHz, CDCl₃): δ (ppm) 156.5 (C), 148.8 (C), 112.5 (CH), 44.0 (CH), 28.6 (CH₂), 26.8 (CH), 24.1 (CH₂), 24.1 (CH₃), 21.5 (CH₃), 19.9 (CH₃)
Scent: strong, earthy, and galbanum
Similarly, the compound (2b) was isolated as a colorless oil by preparative LC (Reference Example 2).

Compound (2b):

GC/MS (EI): m/z (%) 167.1 (M⁺, 5), 152.1 (1), 150.1 (1), 139.1 (2), 126.1 (1), 125.1 (11), 124.1 (4), 110.1 (2), 109.1 (2), 108.1 (7), 106.1 (2), 94.1 (1), 93.1 (2), 91.1 (1), 81.1 (2), 79.1 (2), 77.1 (2), 53.1 (1), 41.1 (2), 39.1 (1)
1H NMR (500 MHz, CDCl₃): δ (ppm) 5.82 (s, 1H), 2.98 (dt, J = 3.4, 12.8 Hz, 1H), 2.24-2.17 (m, 1H), 1.98-1.91 (m, 2H), 1.80 (s, 3H), 1.75-1.62 (m, 2H), 1.00 (d, J = 6.6 Hz, 3H), 0.91 (d, J = 6.6 Hz, 3H)
13C NMR (125 MHz, CDCl₃): δ (ppm) 190.4 (C), 144.5 (C), 119.2 (CH), 36.7 (CH), 27.4 (CH), 27.0 (CH₂), 24.0 (CH₂), 23.8 (CH₃), 21.4 (CH₃), 20.7 (CH₃)
Scent: green, cassis, and weak

[Scent Intensity Comparison]

The scents of the oximes obtained in Examples 4 to 6 and Reference Example 2 were compared.
A 5% ethanol solution of each mixture and compound was prepared, and the scent intensity was compared (scored by perfumers, rated from 10 to 1 in descending order of intensity). The results are shown in Table 2 below. Table 2

Example 4 Compounds (2a):(2b) = 55:45 Example 5 Compounds (2a):(2b) = 90:10 Example 6 Compound (2a) Reference Example 2 Compound (2b)

Scent intensity 7 8.5 10 5
It was revealed that compared to the mixture in Example 4, the mixture in Example 5 in which the ratio of the Z isomer (compound (2a)) was increased had a clearly higher scent intensity, and the pure Z isomer (Example 6, compound (2a)) had an even higher scent intensity. On the other hand, it was also revealed that the E isomer (Reference Example 2, compound (2b)) had a low scent intensity and the scent quality is different from that of the Z isomer and had a green and cassis scent.

(Example 7) Fragrance Composition for Shampoo

A fragrance composition for shampoo was prepared according to the formulation shown in the table below.

Table 3

Formulation	part by mass
Undecyl aldehyde	2
Dodecyl aldehyde	1
Isoamyl salicylate	80
Citronellol	350
Tricyclodecenyl propionate	60
Diphenyl oxide	5
α-hexyl cinnamic aldehyde	70
HINDINOL	20
α-Ionone	10
ORBITONE	35
Patchouli oil	30
Phenylethyl alcohol	80
Terpineol	150
p-t-butylcyclohexyl acetate	100
β-naphthyl methyl ether	5
Mixture in Example 5 or Compound (2a) in Example 6	2
Total	1000

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on United State Patent Application No. 63/421,772 filed on November 2, 2022 , the contents of which are incorporated herein by reference.

Claims

A fragrance composition comprising at least one of the following mixture (A) and mixture (B):
(A) a mixture containing 15 mass% or more of a compound (1a) represented by the following formula (1a) and 85 mass% or less of a compound (1b) represented by the following formula (1b) (wherein a total amount of the compound (1a) and the compound (1b) is 100 mass%); and

(B) a mixture containing 55 mass% or more of a compound (2a) represented by the following formula (2a) and 45 mass% or less of a compound (2b) represented by the following formula (2b) (wherein a total amount of the compound (2a) and the compound (2b) is 100 mass%).
The fragrance composition according to claim 1, comprising at least one of the following mixture (A) and mixture (B):
(A) a mixture containing 30 mass% or more of the compound (1a) and 70 mass% or less of the compound (1b), and

(B) a mixture containing 90 mass% or more of the compound (2a) and 10 mass% or less of the compound (2b).
A fragrance composition comprising at least one of a compound (1a) represented by the following formula (1a) and a compound (2a) represented by the following formula (2a).
A consumer product comprising the fragrance composition according to any one of claims 1 to 3.
The consumer product according to claim 4, wherein the consumer product is selected from a fragrance product, a cosmetic, a toiletry product, an air care product, daily necessities, household goods, an oral care product, a detergent, and a quasi-drug.