WO2024096037A1 - Fragrance composition and consumer product - Google Patents

Fragrance composition and consumer product Download PDF

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Publication number
WO2024096037A1
WO2024096037A1 PCT/JP2023/039359 JP2023039359W WO2024096037A1 WO 2024096037 A1 WO2024096037 A1 WO 2024096037A1 JP 2023039359 W JP2023039359 W JP 2023039359W WO 2024096037 A1 WO2024096037 A1 WO 2024096037A1
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compound
mass
mixture
fragrance composition
fragrance
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PCT/JP2023/039359
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French (fr)
Japanese (ja)
Inventor
健司 田沼
ケント エイチ． ロンバード
結菜 寄立
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高砂香料工業株式会社
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Publication of WO2024096037A1 publication Critical patent/WO2024096037A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes

Definitions

  • the present invention relates to fragrance compositions and consumer products.
  • the compounds developed each have different characteristics in terms of fragrance, etc., so compounds with different fragrance tones are required depending on the purpose of use.
  • the present inventors have discovered that a compound having a pulegone oxime structure or a compound having a piperitone oxime structure, or a mixture containing said compounds in a specific ratio, has a unique odor, and have completed the present invention.
  • the present invention relates to the following fragrance composition, etc.
  • a fragrance composition having a unique fragrance By adding the compound or mixture of the present invention, a fragrance composition having a unique fragrance can be obtained.
  • This composition can be used in a wide range of consumer products as a fragrance or fragrance composition for cosmetics, health and hygiene products, etc.
  • the fragrance composition according to an embodiment of the present invention is also described as "the fragrance composition according to the present embodiment.”
  • the compound represented by formula (1a) will be referred to as “compound (1a)”. The same applies to other compounds.
  • the fragrance composition according to this embodiment is characterized by containing the following compounds (1a), (1b), (2a), and (2b), or a mixture containing said compounds in a specific ratio.
  • Compounds (1a) and (1b) are compounds having a pulegone oxime structure
  • compounds (2a) and (2b) are compounds having a piperitone oxime structure.
  • the fragrance composition according to the present embodiment is a fragrance composition containing at least one of the following mixture (A) and mixture (B).
  • the mixture (A) preferably contains 30% by mass or more of the compound (1a) and 70% by mass or less of the compound (1b).
  • Mixture (B) preferably contains 90% by mass or more of compound (2a) and 10% by mass or less of compound (2b).
  • the fragrance composition according to this embodiment contains at least one of compound (1a) and compound (2a).
  • the ratio of compound (1a) to compound (2a) is preferably such that, when the total of compound (1a) and compound (2a) is 100% by mass, compound (1a) is 100% by mass and compound (2a) is 0 to 100% by mass.
  • a fragrance composition containing substantially at least one of compound (1a) and compound (2a) is particularly preferred.
  • the content of compounds (1a), (1b), (2a), and (2b) in the fragrance composition according to this embodiment is determined depending on the composition, but is preferably 0.00001 to 30% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.01 to 10% by mass, respectively, of the total fragrance composition.
  • Compounds (1a), (1b), (2a), and (2b) in the fragrance composition of the present invention can be synthesized by the method described in the Examples below.
  • the fragrance composition according to this embodiment may also contain one or more of other commonly used fragrance retainers.
  • other fragrance retainers include ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hercolin, and medium-chain fatty acid triglycerides.
  • the fragrance composition according to the present embodiment may contain a commonly used blended fragrance.
  • the fragrance composition thus obtained can impart a fresh and highly palatable fragrance.
  • the fragrance composition according to the present embodiment can be used as a fragrance component in an amount commonly used in the industry to impart a unique fragrance to consumer products, thereby increasing their commercial value.
  • consumer products include fragrance products, cosmetics, toiletry products, air care products, daily necessities, miscellaneous goods, oral care products, detergents, fabric softeners, and quasi-drugs.
  • Fragrance products can include, for example, perfumes, eau de perfumes, eau de toilettes, eau de colognes, and the like.
  • cosmetics include basic cosmetics such as face wash cream, vanishing cream, cleansing cream, cold cream, massage cream, milky lotion, lotion, serum, pack, makeup remover, etc.; makeup cosmetics such as foundation, lipstick, etc.; hair cosmetics such as hair tonic, hair liquid, hair spray, etc.; sunscreen cosmetics such as tanning products and sunscreen products; and medicated cosmetics such as antiperspirants, body deodorants, aftershave lotions and gels, permanent wave agents, medicated soaps, medicated shampoos, and medicated skin cosmetics.
  • Toiletry products include hair care products such as shampoo, rinse, rinse-in-shampoo, conditioner, treatment, hair pack, etc.; skin care products such as lip balm, hand cream, etc., soaps such as cosmetic soap, bath soap, etc.; body care products such as body soap, body shampoo, hand soap, etc.; bath additives such as bath salts (bath salts, bath tablets, bath liquid, etc.), foam baths (bubble baths, etc.), bath oils (bath perfumes, bath capsules, etc.), milk baths, bath jellies, bath cubes, etc.
  • hair care products such as shampoo, rinse, rinse-in-shampoo, conditioner, treatment, hair pack, etc.
  • skin care products such as lip balm, hand cream, etc.
  • soaps such as cosmetic soap, bath soap, etc.
  • body care products such as body soap, body shampoo, hand soap, etc.
  • bath additives such as bath salts (bath salts, bath tablets, bath liquid, etc.), foam baths (bubble baths, etc.
  • Air care products include, for example, aerosols, sprays, powder sprays, etc.
  • Examples of everyday items include deodorants and air fresheners.
  • miscellaneous goods examples include tissue paper, toilet paper, etc.
  • oral care products examples include toothpaste, mouthwash, mouth spray, and gargle.
  • detergents heavy-duty laundry detergents, light-duty laundry detergents, liquid detergents, laundry soaps, compact detergents, powdered soaps, etc.; as fabric softeners, liquid softeners, dryer sheets, etc.; as cleaning agents, cleansers, furniture care, house cleaners, toilet cleaners, bathroom cleaners, glass cleaners, mold removers, drain cleaners, etc.; as kitchen detergents, kitchen soaps, synthetic kitchen soaps, dishwashing detergents, dishwasher detergents, etc.; as bleaches, oxidation bleaches (chlorine bleaches, oxygen bleaches, etc.), reduction bleaches (sulfur bleaches, etc.), optical bleaches, etc.; air care products include aerosols (spray type, powder spray), candles, wax melts, car fresheners, free-standing, spray type or plug-in type deodorants and fragrances (solid type, gel type, liquid type, etc.); pet care products include pet deodorants, pet toilet deodorants, pet shampoos, pet conditioners; miscellane
  • Quasi-drugs include, for example, patches and ointments.
  • the fragrance composition according to this embodiment when used in the above-mentioned products, it may be used in any form selected according to the purpose, such as in its original state, or in a liquid state dissolved in, for example, alcohols, polyhydric alcohols such as propylene glycol, or glycerin; in a solubilized or dispersed state solubilized or dispersed using a surfactant such as a nonionic surfactant, anionic surfactant, cationic surfactant, or amphoteric surfactant; or in a microcapsule state obtained by treating with an encapsulating agent.
  • a surfactant such as a nonionic surfactant, anionic surfactant, cationic surfactant, or amphoteric surfactant
  • the fragrance composition according to this embodiment may be encapsulated in an encapsulating agent such as cyclodextrin to stabilize and sustain the release of the fragrance composition.
  • an encapsulating agent such as cyclodextrin to stabilize and sustain the release of the fragrance composition.
  • a consumer product comprising the fragrance composition according to any one of [1] to [3].
  • the consumer product is selected from fragrance products, cosmetics, toiletry products, air care products, daily necessities, miscellaneous goods, oral care products, detergents, and quasi-drugs.
  • Example 3 Reference Example 1
  • Example 3 Compared to the mixture of Example 1, the mixture of Example 2, in which the ratio of Z isomer (compound (1a)) was increased, had a clearly stronger odor, and it was found that the pure Z isomer (Example 3, compound (1a)) had an even stronger odor. On the other hand, the E isomer (Reference Example 1, compound (1b)) had a significantly weaker odor, and the quality of the odor was also different from that of the Z isomer, possessing a herbal aroma.
  • Example 5 Increase in the ratio of compound (2a) 100 mL of hexane and 100 mL of ethyl acetate were added to 110 g of the mixture obtained in Example 4, and the mixture was heated to 50° C. and dissolved. The mixture was cooled to room temperature, and the flesh-colored solid that precipitated was collected, thereby obtaining 50 g of a mixture in which the ratio of compound (2a):compound (2b) was 90:10 and the amount of compound (2a) was increased.
  • Example 6 Reference Example 2
  • Example 6 Isolation of Compound (2a) and Compound (2b)
  • Example 5 The mixture of Example 5, in which the ratio of Z isomer (compound (2a)) was increased, was found to have a clearly stronger odor than the mixture of Example 4, and the pure Z isomer (Example 6, compound (2a)) had an even stronger odor.
  • the E isomer Reference Example 2, compound (2b)
  • the quality of the odor was also found to be different from that of the Z isomer, having a green, cassis odor.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)

Abstract

Provided is a fragrance composition containing at least one among a mixture (A) and a mixture (B). The mixture (A) comprises at least 15 mass% of a compound (1a) and 85 mass% of a compound (1b), and the mixture (B) comprises 55 mass% of a compound (2a) and 45 mass% of a compound (2b). (The sum of the compound (1a) and the compound (1b) is 100 mass%, and the sum of the compound (2a) and the compound (2b) is 100 mass%.)

Description

香料組成物および消費者製品Fragrance compositions and consumer products
　本発明は、香料組成物および消費者製品に関する。 The present invention relates to fragrance compositions and consumer products.
　現在の人々の生活の中で好ましい香りを有する様々な製品が販売されているが、さらに多様化した付香製品の要望を踏まえ、嗜好性が高い香りの提供が求められており、多数の化合物が開発されている。 In today's world, there are many products on the market that have pleasant scents, but in response to the ever-increasing demand for more diverse scented products, there is a demand for scents that are highly palatable, and many compounds are being developed.
　一方、開発された化合物は、それぞれが香気等に様々な特徴を持っているため、使用目的によっては香調の異なる化合物が求められている。 On the other hand, the compounds developed each have different characteristics in terms of fragrance, etc., so compounds with different fragrance tones are required depending on the purpose of use.
　本発明者らは、プレゴンオキシム構造を有する化合物もしくはピペリトンオキシム構造を有する化合物、または該化合物を特定の比率で含有する混合物が、特有な香気を有することを見出し、本発明を完成させた。
　本発明は下記の香料組成物等に関する。
〔１〕下記の混合物（Ａ）および混合物（Ｂ）の少なくとも一方を含有する香料組成物。
（Ａ）下記式（１ａ）で表される化合物（１ａ）を１５質量％以上、および下記式（１ｂ）で表される化合物（１ｂ）を８５質量％以下含む混合物
　　（ただし、前記化合物（１ａ）と前記化合物（１ｂ）の総計は１００質量％である）
（Ｂ）下記式（２ａ）で表される化合物（２ａ）を５５質量％以上、および下記式（２ｂ）で表される化合物（２ｂ）を４５質量％以下含む混合物
　　（ただし、前記化合物（２ａ）と前記化合物（２ｂ）の総計は１００質量％である） The present inventors have discovered that a compound having a pulegone oxime structure or a compound having a piperitone oxime structure, or a mixture containing said compounds in a specific ratio, has a unique odor, and have completed the present invention.
The present invention relates to the following fragrance composition, etc.
[1] A fragrance composition containing at least one of the following mixture (A) and mixture (B):
(A) A mixture containing 15% by mass or more of a compound (1a) represented by the following formula (1a) and 85% by mass or less of a compound (1b) represented by the following formula (1b) (wherein the total of the compound (1a) and the compound (1b) is 100% by mass):
(B) A mixture containing 55% by mass or more of a compound (2a) represented by the following formula (2a) and 45% by mass or less of a compound (2b) represented by the following formula (2b), where the total of the compound (2a) and the compound (2b) is 100% by mass.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
〔２〕下記式（１ａ）で表される化合物（１ａ）および下記式（２ａ）で表される化合物（２ａ）の少なくとも一方を含有する香料組成物。 [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):
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　本発明の化合物または混合物を添加することにより、特有な香気を有する香料組成物が得られる。この組成物は、香料あるいは香粧品類、保険衛生材料等の香気付組成物として、消費者製品等の広い範囲に用いられる。 By adding the compound or mixture of the present invention, a fragrance composition having a unique fragrance can be obtained. This composition can be used in a wide range of consumer products as a fragrance or fragrance composition for cosmetics, health and hygiene products, etc.
　以下、本発明について詳細に説明する。
　本明細書において、本発明の実施形態に係る香料組成物を「本実施形態に係る香料組成物」とも記載する。
　本明細書において、式（１ａ）で表される化合物を「化合物（１ａ）」と記載する。他の化合物についても同様である。 The present invention will be described in detail below.
In this specification, the fragrance composition according to an embodiment of the present invention is also described as "the fragrance composition according to the present embodiment."
In this specification, the compound represented by formula (1a) will be referred to as "compound (1a)". The same applies to other compounds.
　本実施形態に係る香料組成物は、下記の化合物（１ａ）、（１ｂ）、（２ａ）、及び（２ｂ）または該化合物を特定の比率で含有する混合物を含有することを特徴とする香料組成物である。化合物（１ａ）、（１ｂ）はプレゴンオキシム構造を有する化合物であり、化合物（２ａ）、（２ｂ）はピペリトンオキシム構造を有する化合物である。 The fragrance composition according to this embodiment is characterized by containing the following compounds (1a), (1b), (2a), and (2b), or a mixture containing said compounds in a specific ratio. Compounds (1a) and (1b) are compounds having a pulegone oxime structure, and compounds (2a) and (2b) are compounds having a piperitone oxime structure.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　各化合物を特定の比率で含有する場合、本実施形態に係る香料組成物は、下記の混合物（Ａ）および混合物（Ｂ）の少なくとも一方を含有する香料組成物である。
（Ａ）化合物（１ａ）を１５質量％以上、および化合物（１ｂ）を８５質量％以下含む混合物（ただし、化合物（１ａ）と前記化合物（１ｂ）の総計は１００質量％である）
（Ｂ）化合物（２ａ）を５５質量％以上、および化合物（２ｂ）を４５質量％以下含む混合物（ただし、化合物（２ａ）と化合物（２ｂ）の総計は１００質量％である） When each compound is contained 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% by mass or more of compound (1a) and 85% by mass or less of compound (1b) (the total of compound (1a) and compound (1b) is 100% by mass).
(B) A mixture containing 55% by mass or more of compound (2a) and 45% by mass or less of compound (2b) (the total of compound (2a) and compound (2b) is 100% by mass).
　混合物（Ａ）としては、化合物（１ａ）を３０質量％以上、および化合物（１ｂ）を７０質量％以下含むことが好ましい。
　混合物（Ｂ）としては、化合物（２ａ）を９０質量％以上、および化合物（２ｂ）を１０質量％以下含むことが好ましい。 The mixture (A) preferably contains 30% by mass or more of the compound (1a) and 70% by mass or less of the compound (1b).
Mixture (B) preferably contains 90% by mass or more of compound (2a) and 10% by mass or less of compound (2b).
　化合物（１ａ）は化合物（１ｂ）よりも香気強度が高く、化合物（２ａ）は化合物（２ｂ）よりも香気強度が高い。したがって本実施形態に係る香料組成物は、化合物（１ａ）および化合物（２ａ）の少なくとも一方のみを含有することがより好ましい。このとき、化合物（１ａ）と化合物（２ａ）の割合は、化合物（１ａ）と化合物（２ａ）の総計を１００質量％としたときに、化合物（１ａ）が～１００質量％、化合物（２ａ）が０～１００質量％であることが好ましい。
　上記化合物の中でも、実質的に化合物（１ａ）および化合物（２ａ）の少なくとも一方のみを含む香料組成物が特に好ましい。 Compound (1a) has a stronger odor intensity than compound (1b), and compound (2a) has a stronger odor intensity than compound (2b). Therefore, it is more preferable that the fragrance composition according to this embodiment contains at least one of compound (1a) and compound (2a). In this case, the ratio of compound (1a) to compound (2a) is preferably such that, when the total of compound (1a) and compound (2a) is 100% by mass, compound (1a) is 100% by mass and compound (2a) is 0 to 100% by mass.
Among the above compounds, a fragrance composition containing substantially at least one of compound (1a) and compound (2a) is particularly preferred.
　本実施形態に係る香料組成物における、化合物（１ａ）、（１ｂ）、（２ａ）、及び（２ｂ）の含有量は、配合によって決まるが、それぞれ、全香料組成物の好ましくは０．００００１～３０質量％であり、より好ましくは０．０１～２０質量％であり、さらに好ましくは０．０１～１０質量％である。 The content of compounds (1a), (1b), (2a), and (2b) in the fragrance composition according to this embodiment is determined depending on the composition, but is preferably 0.00001 to 30% by mass, more preferably 0.01 to 20% by mass, and even more preferably 0.01 to 10% by mass, respectively, of the total fragrance composition.
　本発明の香料組成物における化合物（１ａ）、化合物（１ｂ）、化合物（２ａ）、化合物（２ｂ）は、後述の実施例に記載される方法で合成することができる。 Compounds (1a), (1b), (2a), and (2b) in the fragrance composition of the present invention can be synthesized by the method described in the Examples below.
　また、本実施形態に係る香料組成物は、通常使用される他の香料保留剤の１種又は２種以上を含んでいても良い。他の香料保留剤としては、例えば、エチレングリコール、プロピレングリコール、ジプロピレングリコール、グリセリン、ヘキシレングリコール、ベンジルベンゾエート、トリエチルシトレート、ジエチルフタレート、ハーコリン、中鎖脂肪酸トリグリセライド等が挙げられる。 The fragrance composition according to this embodiment may also contain one or more of other commonly used fragrance retainers. Examples of other fragrance retainers include ethylene glycol, propylene glycol, dipropylene glycol, glycerin, hexylene glycol, benzyl benzoate, triethyl citrate, diethyl phthalate, hercolin, and medium-chain fatty acid triglycerides.
　本実施形態に係る香料組成物は、通常使用される調合香料を含有してもよい。この様にして得られる香料組成物は、新鮮で嗜好性の高い香気を付与できる。
　また、本実施形態に係る香料組成物を香気成分として、消費者製品に対し、この業界で通常配合されている量を配合して、そのユニークな香気を付与でき、商品価値を高めることができる。消費者製品としては、例えば、フレグランス製品、化粧品、トイレタリー製品、エアケア製品、日用品、雑貨、オーラルケア製品、洗剤、柔軟剤、および医薬部外品等が挙げられる。 The fragrance composition according to the present embodiment may contain a commonly used blended fragrance. The fragrance composition thus obtained can impart a fresh and highly palatable fragrance.
In addition, the fragrance composition according to the present embodiment can be used as a fragrance component in an amount commonly used in the industry to impart a unique fragrance to consumer products, thereby increasing their commercial value. Examples of consumer products include fragrance products, cosmetics, toiletry products, air care products, daily necessities, miscellaneous goods, oral care products, detergents, fabric softeners, and quasi-drugs.
　フレグランス製品としては、例えば、香水、オードパルファム、オードトワレ、オーデコロン、など；を挙げることができる。
　化粧品としては、例えば、洗顔クリーム、バニシングクリーム、クレンジングクリーム、コールドクリーム、マッサージクリーム、乳液、化粧水、美容液、パック、メイク落とし、などの基礎化粧品；ファンデーション、口紅、などのメイクアップ化粧品；ヘアートニック、ヘアーリキッド、ヘアースプレー、などの頭髪化粧品；サンタン製品、サンスクリーン製品、などの日焼け止め化粧品；制汗剤、ボディデオドラント、アフターシェービングローション及びジェル、パーマネントウェーブ剤、薬用石鹸、薬用シャンプー、薬用皮膚化粧料、などの薬用化粧品、を挙げることができる。 Fragrance products can include, for example, perfumes, eau de parfums, eau de toilettes, eau de colognes, and the like.
Examples of cosmetics include basic cosmetics such as face wash cream, vanishing cream, cleansing cream, cold cream, massage cream, milky lotion, lotion, serum, pack, makeup remover, etc.; makeup cosmetics such as foundation, lipstick, etc.; hair cosmetics such as hair tonic, hair liquid, hair spray, etc.; sunscreen cosmetics such as tanning products and sunscreen products; and medicated cosmetics such as antiperspirants, body deodorants, aftershave lotions and gels, permanent wave agents, medicated soaps, medicated shampoos, and medicated skin cosmetics.
　トイレタリー製品としては、シャンプー、リンス、リンスインシャンプー、コンディショナー、トリートメント、ヘアパック、などのヘアケア製品；リップクリーム、ハンドクリーム等のスキンケア製品、化粧石鹸、浴用石鹸、などの石鹸類；ボディソープ、ボディシャンプー、ハンドソープ、などのボディケア製品；入浴剤（バスソルト、バスタブレット、バスリキッド、等）、フォームバス（バブルバス、等）、バスオイル（バスパフューム、バスカプセル、等）、ミルクバス、バスジェリー、バスキューブ、などの浴用剤、を挙げることができる。 Toiletry products include hair care products such as shampoo, rinse, rinse-in-shampoo, conditioner, treatment, hair pack, etc.; skin care products such as lip balm, hand cream, etc., soaps such as cosmetic soap, bath soap, etc.; body care products such as body soap, body shampoo, hand soap, etc.; bath additives such as bath salts (bath salts, bath tablets, bath liquid, etc.), foam baths (bubble baths, etc.), bath oils (bath perfumes, bath capsules, etc.), milk baths, bath jellies, bath cubes, etc.
　エアケア製品としては、例えば、エアゾール剤、スプレー剤、パウダースプレー剤等を挙げることができる。 Air care products include, for example, aerosols, sprays, powder sprays, etc.
　日用品としては、例えば、消臭・芳香剤等を挙げることができる。 Examples of everyday items include deodorants and air fresheners.
　雑貨としては、例えば、ティッシュペーパー、トイレットペーパー等を挙げることができる。 Examples of miscellaneous goods include tissue paper, toilet paper, etc.
　オーラルケア製品としては、例えば、歯みがき剤、マウスウォッシュ、マウススプレー、うがい薬等を挙げることができる。 Examples of oral care products include toothpaste, mouthwash, mouth spray, and gargle.
　洗剤としては、衣料用重質洗剤、衣料用軽質洗剤、液体洗剤、洗濯石鹸、コンパクト洗剤、粉石鹸、など；柔軟仕上げ剤としては、リキッドソフナー、ドライヤーシート、など；洗浄剤としては、クレンザー、ファーニチアケアー、ハウスクリーナー、トイレ洗浄剤、浴室用洗浄剤、ガラスクリーナー、カビ取り剤、排水管用洗浄剤、など；台所用洗剤としては、台所用石鹸、台所用合成石鹸、食器用洗剤、食洗器用洗剤など；漂白剤としては、酸化型漂白剤（塩素系漂白剤、酸素系漂白剤、等）、還元型漂白剤（硫黄系漂白剤、等）、光学的漂白剤、など；エアケア製品としてはエアゾール剤(スプレータイプ、パウダースプレー)、キャンドル、ワックスメルト、カーフレッシュナー、置き型、スプレータイプまたはプラグインタイプの消臭・芳香剤(固形状タイプ、ゲル状タイプ、リキッドタイプ、など)；ペットケア製品としては、ペット用消臭剤、、ペットトイレ用消臭剤、ペット用シャンプー、ペット用コンディショナー；雑貨としては、ティッシュペーパー、トイレットペーパー、ディスインフェクタントワイプ、ディスインフェクタントスプレーなどの種々の形態を挙げることができる。 As detergents, heavy-duty laundry detergents, light-duty laundry detergents, liquid detergents, laundry soaps, compact detergents, powdered soaps, etc.; as fabric softeners, liquid softeners, dryer sheets, etc.; as cleaning agents, cleansers, furniture care, house cleaners, toilet cleaners, bathroom cleaners, glass cleaners, mold removers, drain cleaners, etc.; as kitchen detergents, kitchen soaps, synthetic kitchen soaps, dishwashing detergents, dishwasher detergents, etc.; as bleaches, oxidation bleaches (chlorine bleaches, oxygen bleaches, etc.), reduction bleaches (sulfur bleaches, etc.), optical bleaches, etc.; air care products include aerosols (spray type, powder spray), candles, wax melts, car fresheners, free-standing, spray type or plug-in type deodorants and fragrances (solid type, gel type, liquid type, etc.); pet care products include pet deodorants, pet toilet deodorants, pet shampoos, pet conditioners; miscellaneous goods include various forms such as tissue paper, toilet paper, disinfectant wipes, and disinfectant sprays.
　医薬部外品としては、例えば、ハップ剤、軟膏剤等を挙げることができる。 Quasi-drugs include, for example, patches and ointments.
　本実施形態に係る香料組成物を、前記製品に使用する場合、このままの状態、或いはこれらを、例えば、アルコール類、プロピレングリコール、グリセリンなどの多価アルコール類に溶解した液体状態；界面活性剤、例えば、非イオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤などを用いて可溶化或いは分散化した可溶化状態或いは分散化状態；又はカプセル化剤で処理して得られるマイクロカプセル状態など；その目的に応じて任意の形状を選択して用いられている。 When the fragrance composition according to this embodiment is used in the above-mentioned products, it may be used in any form selected according to the purpose, such as in its original state, or in a liquid state dissolved in, for example, alcohols, polyhydric alcohols such as propylene glycol, or glycerin; in a solubilized or dispersed state solubilized or dispersed using a surfactant such as a nonionic surfactant, anionic surfactant, cationic surfactant, or amphoteric surfactant; or in a microcapsule state obtained by treating with an encapsulating agent.
　さらに、本実施形態に係る香料組成物を、サイクロデキストリンなどの包接剤に包接して、上記香料組成物を安定化且つ徐放性にして用いることもある。これらは、最終製品の形態、例えば、液体状、固体状、粉末状、ゲル状、ミスト状、エアゾール状などに適したもので適宜に選択して用いられる。 Furthermore, the fragrance composition according to this embodiment may be encapsulated in an encapsulating agent such as cyclodextrin to stabilize and sustain the release of the fragrance composition. These are appropriately selected and used depending on the form of the final product, for example, liquid, solid, powder, gel, mist, aerosol, etc.
　上記のとおり、本明細書は下記の香料組成物および消費者製品を開示する。
〔１〕下記の混合物（Ａ）および混合物（Ｂ）の少なくとも一方を含有する香料組成物。
（Ａ）下記式（１ａ）で表される化合物（１ａ）を１５質量％以上、および下記式（１ｂ）で表される化合物（１ｂ）を８５質量％以下含む混合物
　　（ただし、前記化合物（１ａ）と前記化合物（１ｂ）の総計は１００質量％である）
（Ｂ）下記式（２ａ）で表される化合物（２ａ）を５５質量％以上、および下記式（２ｂ）で表される化合物（２ｂ）を４５質量％以下含む混合物
　　（ただし、前記化合物（２ａ）と前記化合物（２ｂ）の総計は１００質量％である） As mentioned above, the present specification discloses the following fragrance compositions and consumer products:
[1] A fragrance composition containing at least one of the following mixture (A) and mixture (B):
(A) A mixture containing 15% by mass or more of a compound (1a) represented by the following formula (1a) and 85% by mass or less of a compound (1b) represented by the following formula (1b) (wherein the total of the compound (1a) and the compound (1b) is 100% by mass):
(B) A mixture containing 55% by mass or more of a compound (2a) represented by the following formula (2a) and 45% by mass or less of a compound (2b) represented by the following formula (2b), where the total of the compound (2a) and the compound (2b) is 100% by mass.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
〔２〕下記の混合物（Ａ）および混合物（Ｂ）の少なくとも一方を含有する〔１〕に記載の香料組成物。
（Ａ）前記化合物（１ａ）を３０質量％以上、および前記化合物（１ｂ）を７０質量％以下含む混合物
（Ｂ）前記化合物（２ａ）を９０質量％以上、および前記化合物（２ｂ）を１０質量％以下含む混合物
〔３〕下記式（１ａ）で表される化合物（１ａ）および下記式（２ａ）で表される化合物（２ａ）の少なくとも一方を含有する香料組成物。 [2] The fragrance composition according to [1], which contains at least one of the following mixture (A) and mixture (B):
(A) a mixture containing 30% by mass or more of the compound (1a) and 70% by mass or less of the compound (1b); (B) a mixture containing 90% by mass or more of the compound (2a) and 10% by mass or less of the compound (2b); and [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).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
〔４〕〔１〕～〔３〕のいずれか１つに記載の香料組成物を含む消費者製品。
〔５〕前記消費者製品が、フレグランス製品、化粧品、トイレタリー製品、エアケア製品、日用品、雑貨、オーラルケア製品、洗剤、および医薬部外品から選択される〔４〕に記載の消費者製品。 [4] A consumer product comprising the fragrance composition according to any one of [1] to [3].
[5] The consumer product according to [4], wherein the consumer product is selected from fragrance products, cosmetics, toiletry products, air care products, daily necessities, miscellaneous goods, oral care products, detergents, and quasi-drugs.
　以下に実施例等を挙げ、本発明を具体的に説明するが、本発明はこれらにより何ら限定されるものではない。なお、実施例中における物性の測定には、下記の装置を使用した。
　ＮＭＲ：ＤＲＸ５００（Ｂｒｕｋｅｒ社製）
　ＧＣ／ＭＳ：ＨＰ５９７７Ａ（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製）
　　カラム：Ｉｎｅｒｔｃａｐ－１（長さ３０ｍ×内径０．２５ｍｍ、膜厚０．２５μｍ）（ジーエルサイエンス社製） The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The following devices were used to measure physical properties in the examples.
NMR: DRX500 (manufactured by Bruker)
GC/MS: HP5977A (Agilent Technologies)
Column: Inertcap-1 (length 30 m × inner diameter 0.25 mm, film thickness 0.25 μm) (GL Sciences)
（実施例１）化合物（１ａ）および化合物（１ｂ）の合成 (Example 1) Synthesis of compound (1a) and compound (1b)
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　窒素雰囲気下、反応フラスコにｄ－プレゴン２００ｇ（１．３ｍｏｌ）、エタノール１００ｍＬ、およびピリジン２００ｍＬを加えて６０℃に加熱した。そこにヒドロキシルアミン塩酸塩を１０８ｇ（２．０８ｍｍｏｌ）分割投入し、６０℃で２時間反応させた（転化率９８％）。室温まで冷却し、１０％塩酸を５０ｍＬ加え、酢酸エチルを１５０ｍＬ加えて、水層を除去した。有機層を水洗し、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させた。硫酸マグネシウムをフィルターで濾別し、濾液の溶剤を留去することで、（１ａ）：（１ｂ）＝１８：７８（ＧＣエリア比＝質量比、以下同様）の混合物が得られた。
香気：Ｅａｒｔｈｙ，ｇａｌｂａｎｕｍ In 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 heated to 60° C. 108 g (2.08 mmol) of hydroxylamine hydrochloride was added in portions and reacted at 60° C. for 2 hours (conversion rate 98%). The mixture was cooled to room temperature, 50 mL of 10% hydrochloric acid was added, and 150 mL of ethyl acetate was added, and the aqueous layer was removed. The organic layer was washed with water and saturated saline, and dried over magnesium sulfate. The magnesium sulfate was filtered off, and the solvent of the filtrate was distilled off to obtain a mixture of (1a):(1b)=18:78 (GC area ratio=mass ratio, the same applies below).
Aroma: Earthy, galbanum
（実施例２）化合物（１ａ）の比率増加
　窒素雰囲気下、実施例１で得られた（１ａ）：（１ｂ）＝１８：７８の混合物２２１ｇを１２０℃で７時間加熱攪拌した。その後、室温まで冷却させ、ビグロー蒸留にて８２～８６℃／４４Ｐａの留分を取得することで、粘性のある淡いピンク色のオイルとして（１ａ）：（１ｂ）＝３２：６６の比率で、化合物（１ａ）が増加した混合物を１２２ｇ得た。
香気：Ｓｔｒｏｎｇ，ｅａｒｔｈｙ，ｇａｌｂａｎｕｍ (Example 2) Increase in the 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, it was cooled to room temperature, and a fraction of 82 to 86°C/44 Pa was obtained by Vigreaux distillation, thereby obtaining 122 g of a mixture in which the compound (1a) was increased in the ratio of (1a):(1b) = 32:66 as a viscous pale pink oil.
Aroma: Strong, earthy, galbanum
（実施例３、参考例１）化合物（１ａ）および化合物（１ｂ）の単離
　実施例２で得られた（１ａ）：（１ｂ）＝３２：６６の混合物をシリカゲルカラムクロマトグラフィーにより、淡赤色固体として純粋な化合物（１ａ）を得た（実施例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（５００ＭＨｚ，ＣＤＣｌ３）：　δ　（ｐｐｍ）２．７３（ｄ，Ｊ＝１３．３Ｈｚ，１Ｈ），２．４６（ｄ，Ｊ＝７．８Ｈｚ，１Ｈ），１．９１－１．８５（ｍ，１Ｈ），１．８１－１．７４（ｍ，６Ｈ），１．６６（ｄ，Ｊ＝１．８Ｈｚ，３Ｈ），１．１５－１．０５（ｍ，１Ｈ），０．９７（ｄ，Ｊ＝５．０Ｈｚ，３Ｈ）
１３Ｃ　ＮＭＲ（１２５ＭＨｚ，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）
比旋光度［α］２０ Ｄ＝－９．７ｄｅｇ（ｃ＝１，ＣＨＣｌ３）
香気：Ｓｔｒｏｎｇ，ｅａｒｔｈｙ，ｇａｌｂａｎｕｍ (Example 3, 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 obtain 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] 20 D = -9.7 deg (c = 1, CHCl 3 )
Aroma: Strong, earthy, galbanum
　また、無色固体として純粋な化合物（１ｂ）を得た（参考例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（５００ＭＨｚ，ＣＤＣｌ３）：　δ　（ｐｐｍ）３．１１（ｔｄ，Ｊ＝３．７，１２．３Ｈｚ，１Ｈ），２．４６（ｔｄ，Ｊ＝４．１，１４．４Ｈｚ，１Ｈ），２．１１－２．０４（ｍ，１Ｈ），１．８４（ｄ，Ｊ＝１．０Ｈｚ，３Ｈ），１．８０－１．６８（ｍ，６Ｈ），１．２２－１．１３（ｍ，１Ｈ），０．９６（ｄ，Ｊ＝１．５Ｈｚ，３Ｈ）
１３Ｃ　ＮＭＲ（１２５ＭＨｚ，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）
比旋光度［α］２０ Ｄ＝－２０．５ｄｅｇ（ｃ＝１，ＣＨＣｌ３）
香気：Ｗｅａｋ，ｇｒｅｅｎ，ｈｅｒｂａｌ Moreover, 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 rotation [α] 20 D = -20.5 deg (c = 1, CHCl 3 )
Aroma: Weak, green, herbal
〔香気強度比較〕
　実施例１～３、参考例１で得られたオキシム類の香気比較を行った。
　それぞれの混合物および化合物の１％クエン酸トリエチル溶液を作成し、香気強度比較を行った（調香師によるスコア、強度が強い順で１０～１のスコア）。 [Fragrance strength comparison]
The odors of the oximes obtained in Examples 1 to 3 and Reference Example 1 were compared.
A 1% solution of each mixture and compound in triethyl citrate was prepared and the fragrance intensity was compared (scored by perfumers, with scores from 10 to 1 in descending order of intensity).
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　実施例１の混合物に対し、Ｚ体（化合物（１ａ））の比率を向上させた実施例２の混合物は明らかに香気強度が高く、純粋なＺ体（実施例３、化合物（１ａ））はさらに香気強度が高いことが見出された。一方、Ｅ体（参考例１、化合物（１ｂ））はかなり香気強度が低く、香気の質もＺ体とは異なりＨｅｒｂａｌ香を有していた。 Compared to the mixture of Example 1, the mixture of Example 2, in which the ratio of Z isomer (compound (1a)) was increased, had a clearly stronger odor, and it was found that the pure Z isomer (Example 3, compound (1a)) had an even stronger odor. On the other hand, the E isomer (Reference Example 1, compound (1b)) had a significantly weaker odor, and the quality of the odor was also different from that of the Z isomer, possessing a herbal aroma.
（実施例４）：化合物（２ａ）および化合物（２ｂ）の合成 (Example 4): Synthesis of compound (2a) and compound (2b)
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　窒素雰囲気下、反応フラスコにＬ－ピペリトン１００ｇ（６５７ｍｍｏｌ）、エタノール５０ｍＬ、ピリジンを１００ｍＬ加えて６０℃に加熱した。そこにヒドロキシルアミン塩酸塩を７３．０ｇ（１．０５ｍｏｌ）を分割投入し、６０℃で２時間反応させた（転化率９８％）。室温まで冷却し、１０％塩酸を５０ｍＬ加え、酢酸エチルを１５０ｍＬ加えて、水層を除去した。有機層を水洗し、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させた。硫酸マグネシウムをフィルターで濾別し、濾液の溶剤を留去することで、化合物（２ａ）：化合物（２ｂ）＝５５：４５の粘性固体状の混合物１１０ｇが得られた。
香気：Ｇｒｅｅｎ，ｅａｒｔｈｙ，ｃａｓｓｉｓ 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 heated to 60° C. 73.0 g (1.05 mol) of hydroxylamine hydrochloride was added in portions and reacted at 60° C. for 2 hours (conversion rate 98%). The mixture was cooled to room temperature, 50 mL of 10% hydrochloric acid was added, and 150 mL of ethyl acetate was added, and the aqueous layer was removed. The organic layer was washed with water, washed with saturated saline, and dried over magnesium sulfate. The magnesium sulfate was filtered off with a filter, and the solvent of the filtrate was distilled off to obtain 110 g of a viscous solid mixture of compound (2a):compound (2b)=55:45.
Aroma: Green, earthy, cassis
（実施例５）化合物（２ａ）の比率増加
　実施例４で得られた混合物１１０ｇに対し、ヘキサン１００ｍＬ、酢酸エチル１００ｍＬを加えて５０℃まで加熱し溶解させた。これを室温まで冷却し、析出してきた肌色の固体を回収することで化合物（２ａ）：化合物（２ｂ）＝９０：１０の、化合物（２ａ）が増加した混合物が５０ｇ得られた。
比旋光度［α］２０ Ｄ＝＋１２．９ｄｅｇ（ｃ＝１，ＣＨＣｌ３）
香気：Ｓｔｒｏｎｇ，ｅａｒｔｈｙ，ｇａｌｂａｎｕｍ (Example 5) Increase in the ratio of compound (2a) 100 mL of hexane and 100 mL of ethyl acetate were added to 110 g of the mixture obtained in Example 4, and the mixture was heated to 50° C. and dissolved. The mixture was cooled to room temperature, and the flesh-colored solid that precipitated was collected, thereby obtaining 50 g of a mixture in which the ratio of compound (2a):compound (2b) was 90:10 and the amount of compound (2a) was increased.
Specific optical rotation [α] 20D = +12.9 deg (c = 1, CHCl3 )
Aroma: Strong, earthy, galbanum
（実施例６、参考例２）化合物（２ａ）および化合物（２ｂ）の単離
　実施例５で得られた混合物を分取ＬＣ（Ｃｏｓｍｏｓｉｌ　５ＬＳ－２×２本、溶離液：ヘキサン／酢酸エチル＝８０／２０）にて分離することにより、無色油状物として化合物（２ａ）を単離した（実際例６）。
化合物（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（５００ＭＨｚ，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＝６．７Ｈｚ，３Ｈ），０．９１（ｄ，Ｊ＝６．７Ｈｚ，３Ｈ）
１３Ｃ　ＮＭＲ（１２５ＭＨｚ，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）
香気：Ｓｔｒｏｎｇ，ｅａｒｔｈｙ，ｇａｌｂａｎｕｍ (Example 6, Reference Example 2) Isolation of Compound (2a) and Compound (2b) The mixture obtained in Example 5 was separated by preparative LC (Cosmosil 5LS-2 × 2, eluent: hexane/ethyl acetate = 80/20) to isolate compound (2a) as a colorless oil (Actual 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 ).
Aroma: Strong, earthy, galbanum
　また、同様に分取ＬＣにより無色油状物として化合物（２ｂ）を単離した（参考例２）。
化合物（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（５００ＭＨｚ，ＣＤＣｌ３）：　δ　（ｐｐｍ）５．８２（ｓ，１Ｈ），２．９８（ｄｔ，Ｊ＝３．４，１２．８Ｈｚ，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＝６．６Ｈｚ，３Ｈ），０．９１（ｄ，Ｊ＝６．６Ｈｚ，３Ｈ）
１３Ｃ　ＮＭＲ（１２５ＭＨｚ，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）
香気：Ｇｒｅｅｎ，ｃａｓｓｉｓ，ｗｅａｋ Similarly, 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 ).
Aroma: Green, cassis, weak
〔香気強度比較〕
　実施例４～６、参考例２で得られたオキシム類の香気比較を行った。
　それぞれの混合物および化合物の５％エタノール溶液を作成し、香気強度比較を行った（調香師によるスコア、強度が高い順で１０～１のスコア）。結果を以下の表２に示す。 [Fragrance strength comparison]
The odors 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 fragrance intensity was compared (perfumer's score, 10 to 1 in descending order of intensity). The results are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　Ｚ体（化合物（２ａ））の比率を向上させた実施例５の混合物は、実施例４の混合物に比較して明らかに香気強度が高く、純粋なＺ体（実施例６、化合物（２ａ））はさらに香気強度が高いことが見出された。一方、Ｅ体（参考例２、化合物（２ｂ））は香気強度が低く、香気の質もＺ体とは異なりＧｒｅｅｎ，ｃａｓｓｉｓ香を有することが分かった。 The mixture of Example 5, in which the ratio of Z isomer (compound (2a)) was increased, was found to have a clearly stronger odor than the mixture of Example 4, and the pure Z isomer (Example 6, compound (2a)) had an even stronger odor. On the other hand, the E isomer (Reference Example 2, compound (2b)) had a weaker odor, and the quality of the odor was also found to be different from that of the Z isomer, having a green, cassis odor.
（実施例７）シャンプー用香料組成物
　下記表に示す処方で、シャンプー用香料組成物を調製した。 (Example 7) Fragrance composition for shampoo A fragrance composition for shampoo was prepared according to the formulation shown in the table below.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は２０２２年１１月２日出願の米国特許出願（６３／４２１，７７２）に基づくものであり、その内容はここに参照として取り込まれる。 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 U.S. patent application no. 63/421,772, filed November 2, 2022, the contents of which are incorporated herein by reference.

Claims (5)

  1. 　下記の混合物（Ａ）および混合物（Ｂ）の少なくとも一方を含有する香料組成物。
    （Ａ）下記式（１ａ）で表される化合物（１ａ）を１５質量％以上、および下記式（１ｂ）で表される化合物（１ｂ）を８５質量％以下含む混合物
    　　（ただし、前記化合物（１ａ）と前記化合物（１ｂ）の総計は１００質量％である）
    （Ｂ）下記式（２ａ）で表される化合物（２ａ）を５５質量％以上、および下記式（２ｂ）で表される化合物（２ｂ）を４５質量％以下含む混合物
    　　（ただし、前記化合物（２ａ）と前記化合物（２ｂ）の総計は１００質量％である）
    Figure JPOXMLDOC01-appb-C000001
         A fragrance composition comprising at least one of the following mixture (A) and mixture (B).
    (A) A mixture containing 15% by mass or more of a compound (1a) represented by the following formula (1a) and 85% by mass or less of a compound (1b) represented by the following formula (1b) (wherein the total of the compound (1a) and the compound (1b) is 100% by mass):
    (B) A mixture containing 55% by mass or more of a compound (2a) represented by the following formula (2a) and 45% by mass or less of a compound (2b) represented by the following formula (2b), where the total of the compound (2a) and the compound (2b) is 100% by mass.
    Figure JPOXMLDOC01-appb-C000001
  2. 　下記の混合物（Ａ）および混合物（Ｂ）の少なくとも一方を含有する請求項１に記載の香料組成物。
    （Ａ）前記化合物（１ａ）を３０質量％以上、および前記化合物（１ｂ）を７０質量％以下含む混合物
    （Ｂ）前記化合物（２ａ）を９０質量％以上、および前記化合物（２ｂ）を１０質量％以下含む混合物     The fragrance composition according to claim 1, which contains at least one of the following mixture (A) and mixture (B).
    (A) a mixture containing 30% by mass or more of the compound (1a) and 70% by mass or less of the compound (1b); (B) a mixture containing 90% by mass or more of the compound (2a) and 10% by mass or less of the compound (2b).
  3. 　下記式（１ａ）で表される化合物（１ａ）および下記式（２ａ）で表される化合物（２ａ）の少なくとも一方を含有する香料組成物。
    Figure JPOXMLDOC01-appb-C000002
         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):
    Figure JPOXMLDOC01-appb-C000002
  4. 　請求項１から３のいずれか１項に記載の香料組成物を含む消費者製品。 A consumer product comprising the fragrance composition according to any one of claims 1 to 3.
  5. 　前記消費者製品が、フレグランス製品、化粧品、トイレタリー製品、エアケア製品、日用品、雑貨、オーラルケア製品、洗剤、および医薬部外品から選択される請求項４に記載の消費者製品。 The consumer product according to claim 4, wherein the consumer product is selected from fragrance products, cosmetics, toiletry products, air care products, daily necessities, miscellaneous goods, oral care products, detergents, and quasi-drugs.
PCT/JP2023/039359 2022-11-02 2023-10-31 Fragrance composition and consumer product WO2024096037A1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258684A (en) * 1994-03-18 1995-10-09 Givaudan Roure Internatl Sa Odorant and/or flavor composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258684A (en) * 1994-03-18 1995-10-09 Givaudan Roure Internatl Sa Odorant and/or flavor composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BERRADA, M. ET AL.: " Essais de valorisation de l'essence de menthe Pouliot (mentha plegium), Synthese de diverses aziridines a partir des oximes de la (+)pulegone et de l'un de ses derives, la (-)methyl-2 isopulegone. ", BULLETIN DE LA SOCIÉTÉ CHIMIQUE DE FRANCE / 2, SOCIETY FRANCAISE DE CHIMIE , PARIS, FRANCE, no. 5, 1 January 1985 (1985-01-01), France , pages 937 - 946, XP009554575, ISSN: 0037-8968 *
FERRERO, LOUIS: "Aziridines saturCes et insaturCes. Synth'eses par rCduction de cyclohexCnones oximes et Ctudes spectroscopiques", CANADIAN JOURNAL OF CHEMISTRY., vol. 53, no. 21, 1 January 1975 (1975-01-01), pages 3227 - 3239, XP093169106 *

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