JP5027937B2 - Fragrance composition - Google Patents

Fragrance composition Download PDF

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JP5027937B2
JP5027937B2 JP2011017800A JP2011017800A JP5027937B2 JP 5027937 B2 JP5027937 B2 JP 5027937B2 JP 2011017800 A JP2011017800 A JP 2011017800A JP 2011017800 A JP2011017800 A JP 2011017800A JP 5027937 B2 JP5027937 B2 JP 5027937B2
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dimethyl
nonadien
fragrance
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JP2012158647A (en
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公輔 畑野
京助 岡部
善行 和田
修一 村西
弘俊 山口
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Ogawa and Co Ltd
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Priority to KR1020137022891A priority patent/KR101711246B1/en
Priority to MYPI2013701304A priority patent/MY162942A/en
Priority to CN201280005064.XA priority patent/CN103314092B/en
Priority to PCT/JP2012/051759 priority patent/WO2012105430A1/en
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, 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
    • C11B9/00Essential oils; Perfumes
    • C11B9/0007Aliphatic compounds
    • C11B9/0015Aliphatic compounds containing oxygen as the only heteroatom
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52Adding ingredients
    • A23L2/56Flavouring or bittering agents
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20Synthetic spices, flavouring agents or condiments
    • A23L27/202Aliphatic compounds
    • A23L27/2024Aliphatic compounds having oxygen as the only hetero atom
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L27/00Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20Synthetic spices, flavouring agents or condiments
    • A23L27/202Aliphatic compounds
    • A23L27/2024Aliphatic compounds having oxygen as the only hetero atom
    • A23L27/2026Hydroxy compounds

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Description

本発明は、食品香料、香粧品香料等として使用可能な香料組成物に関し、詳しくは4,8−ジメチル−3,7−ノナジエン−2−オール、4,8−ジメチル−3,7−ノナジエン−2−イル アセテート、4,8−ジメチル−3,7−ノナジエン−2−オンの3種の化合物を特定の割合で混合することを特徴とする香料組成物に関する。   The present invention relates to a fragrance composition that can be used as a food fragrance, a cosmetic fragrance, etc., and more specifically, 4,8-dimethyl-3,7-nonadien-2-ol, 4,8-dimethyl-3,7-nonadiene- It is related with the fragrance | flavor composition characterized by mixing three types of compounds of 2-yl acetate and 4,8-dimethyl-3,7-nonadien-2-one in a specific ratio.

シトラールは、レモンやライム、グレープフルーツ等に含有されるレモン様の強いフレッシュ感を有する香気成分であり、飲食品や香粧品等の重要な香料原料の一つとして幅広く使用されている。   Citral is a lemon-like fragrance component with a strong lemon-like sensation contained in lemons, limes, grapefruits, and the like, and is widely used as one of important fragrance raw materials for foods and beverages and cosmetics.

一方、シトラールは加熱もしくは経時的に減少し、オフフレーバー(好ましくない異味・異臭)が生成することが知られている(非特許文献1)。特に酸性条件下ではシトラール含有製品中のシトラールは、製造、流通、保存期間中の各段階で減少し、酸化、環化、水和、異性化等の反応によりその構造が変化することで、フレッシュ感の低下や非常に強い劣化臭の発生が起こり、製品の著しい品質低下を招く。   On the other hand, it is known that citral decreases with heating or with time, and off-flavor (unfavorable taste and odor) is generated (Non-patent Document 1). In particular, under acidic conditions, citral in citral-containing products decreases at each stage during production, distribution, and storage, and its structure changes due to reactions such as oxidation, cyclization, hydration, and isomerization. A feeling of sensation and a very strong deodorizing odor are generated, leading to a significant quality reduction of the product.

従来、シトラールから生成する種々の劣化臭原因物質に関して、その発生防止の目的でイソアスコルビン酸等の酸化防止剤の添加(非特許文献2)等様々な試みがなされたが、その劣化臭原因物質の生成抑制に関して有効な方法はあるものの、シトラールそのものの分解は抑制できず、結果としてシトラールのフレッシュ感が失われるため、シトラール本来の香気特性を保持するにあたっての根本的な解決には至らなかった。   Conventionally, various attempts have been made to add various antioxidant odor-causing substances produced from citral, such as isoascorbic acid and other antioxidants for the purpose of preventing their occurrence (Non-Patent Document 2). Although there is an effective method for suppressing the generation of citral, the decomposition of citral itself cannot be suppressed, and as a result, the freshness of citral is lost, so the fundamental solution for maintaining the original aroma characteristics of citral has not been reached .

これに対し、シトラール類似の香気特性を有し、且つ安定性の高いシトラール類縁物質をシトラールの代わりに使用することにより、化合物の構造変化を抑制し、劣化臭原因物質の生成を防ぐ方法が知られている。
例えば安定性の高いシトラール類縁体として4,8−ジメチル−3,7−ノナジエン−2−オールあるいは4,8−ジメチル−3,7−ノナジエン−2−イル アセテートあるいは4,8−ジメチル−3,7−ノナジエン−2−オン等が知られている。しかしながら、それぞれの物質の香調はシトラールに近いものの異質な香調が混在した独特な香調を有しており単独では使いにくい香料物質であった。
On the other hand, there is a known method for preventing the generation of a detrimental odor-causing substance by using a citral-related substance having an aroma characteristic similar to citral and having a high stability instead of citral. It has been.
For example, as a highly stable citral analog, 4,8-dimethyl-3,7-nonadien-2-ol or 4,8-dimethyl-3,7-nonadien-2-yl acetate or 4,8-dimethyl-3, 7-nonadien-2-one and the like are known. However, although the fragrance of each substance is close to citral, it has a unique fragrance mixed with different fragrances, and is a fragrance material that is difficult to use alone.

これまで4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−オンの混合物を添加することで、すぐれた嗅覚的特性を有し、且つ高い色安定性を有する香料組成物を与えること(特許文献1)や、自然でフレッシュな強いレモン様香気を有する香料組成物を与えること(特許文献2)、4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートの2種とテルペン化合物より誘導されたアルコール等を組合せることによりフレッシュで強いレモン様の呈味および風味を付与することができ、且つ酸性飲料中において高い経時安定性を有する香料組成物を与えること(特許文献3)が開示されている。   By adding a mixture of 4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-one so far, it has excellent olfactory properties, And providing a fragrance composition having high color stability (Patent Document 1), and providing a fragrance composition having a natural and fresh strong lemon-like fragrance (Patent Document 2), 4,8-dimethyl-3, A combination of two kinds of 7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and an alcohol derived from a terpene compound, a fresh and strong lemon-like taste and It is disclosed to provide a fragrance composition that can impart flavor and has high temporal stability in an acidic beverage (Patent Document 3).

上記の文献には4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−オンの混合物の添加あるいは4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートの2種とテルペン化合物より誘導されたアルコール等を組合せることでシトラール類似の香気特性を有し、且つ高い経時安定性を有する香料組成物を製造できることが開示さ
れている。
The above references include the addition of a mixture of 4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-one or 4,8-dimethyl-3,7 -It has citral-like aroma characteristics by combining two kinds of nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate with alcohols derived from terpene compounds, and the like. It is disclosed that a perfume composition having high stability over time can be produced.

しかしながら、4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−オンの2種の組合せでは、単独で用いた場合よりもシトラールの香調に近くはなるものの、同時に感じるフローラル、コスメティックな香調が異質に感じられ、まとまりのある天然感という点では充分ではなかった。   However, the two combinations of 4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-one have a citral scent rather than when used alone. Although it is close to the tone, the floral and cosmetic fragrances felt at the same time are felt in a heterogeneous manner, and it is not sufficient in terms of cohesive natural feeling.

また、4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートの2種とテルペン化合物より誘導されたアルコール等を組合せることによってもシトラールに近い香調になるものの、劣化するに従いライム様の香調が感じられ始めて、もともとの香調から変化が生じる点、あるいは、シトラールの重要香調の一つでありかつ代表的な表現であるレモン感を想起させる点で充分ではなく、さらなる改善の要望が強かった。   Also, combining two kinds of 4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and alcohols derived from terpene compounds However, the lime-like incense tone begins to be felt as it deteriorates and changes from the original incense tone, or one of the important incense tones of citral and typical The point of recalling the feeling of lemon was not enough, and there was a strong demand for further improvement.

特表2003−517052号公報Special table 2003-517052 gazette 特開2001−181670号公報JP 2001-181670 A 欧州特許出願公開第1417896号明細書European Patent Application No. 1417896

Peter Schieberle and Werner Grosch; J. Agric. Food Chem., 36, 797-800 (1988)Peter Schieberle and Werner Grosch; J. Agric. Food Chem., 36, 797-800 (1988) Val E. Peacock and David W. Kuneman; J. Agric. Food Chem., 33, 330-335 (1985)Val E. Peacock and David W. Kuneman; J. Agric. Food Chem., 33, 330-335 (1985)

近年、消費者の嗜好性が多様化してきていることに伴い、各種各様の商品の開発が望まれている。特に、飲食品・香粧品業界はこの傾向が強く、消費者の嗜好に合うバラエティーに富んだ飲食品、香粧品の開発が強く要求されている。これらの要求に対して、飲食品、香粧品のひとつの原料素材である香料においても、従来にない新しい要望が高まっている。
香料物質に対しては特に、より自然な天然感のある香気香味の表現に優れた効果を有すること、嗜好性の高い香気香味を有すること、また、良好な香気香味を付与するだけでなく、経時的に異臭の発生しない、より高い安定性を有することもまた要求されている。
本発明の課題は、消費者の天然志向にマッチした自然な天然感および嗜好性の高い香気香味、特にレモン感を想起させる香調を付与でき、且つ安定性が高く経時的な異臭の発生が軽減された香料組成物、および当該香料化合物を配合した飲食品、香粧品を提供することにある。
In recent years, with the diversification of consumer preferences, development of various products has been desired. In particular, this trend is strong in the food / beverage products / cosmetics industry, and there is a strong demand for the development of food / beverage products and cosmetics that are rich in variety to suit consumer preferences. In response to these demands, unprecedented new demands are increasing in perfume, which is one raw material for foods and beverages and cosmetics.
Especially for perfume substances, it has an excellent effect in expressing a more natural and natural aroma flavor, has a highly flavorful aroma flavor, and not only gives a good aroma flavor, There is also a need for higher stability that does not produce off-flavors over time.
An object of the present invention is to provide a natural taste and a highly flavorful fragrance that matches the consumer's natural orientation, in particular, a fragrance reminiscent of a lemon sensation, and has a high stability and generation of a strange odor over time. The object is to provide a reduced fragrance composition, and a food / beverage product and a cosmetic product containing the fragrance compound.

上記課題を解決するために、本発明者らは鋭意検討を行った結果、驚くべきことに官能基の異なる3種の類縁物質、すなわちアルコール(4,8−ジメチル−3,7−ノナジエン−2−オール)、エステル(4,8−ジメチル−3,7−ノナジエン−2−イル アセテート)及びケトン(4,8−ジメチル−3,7−ノナジエン−3−オン)の3種を混合させることによりレモン感を著しく向上させることを見出した。さらに驚くべきことに、その3種の割合には特定の比率が重要であり、その比率に関しても鋭意検討を行った結果、4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの混
合割合は好ましくは1:0.02:0.04〜1:0.4:0.8であり、特に好ましくは1:0.04:0.08〜1:0.2:0.4であることを見出した。この3種の化合物を上記特定の割合で調合香料中に含有させることで、シトラールを含有した香料組成物や特許文献1〜3の香料組成物と比較し、酸性条件下で保管後も強いレモン感、フレッシュ感を保持し、異臭を殆ど発生すること無く、自然な天然感のあるシトラール様の香味を付与することができる香料組成物および当該香料化合物を配合した飲食品、香粧品の提供を可能にするという驚くべき事実を見出し、本発明を完成するに至った。
In order to solve the above-mentioned problems, the present inventors have conducted extensive studies, and as a result, surprisingly, three related substances having different functional groups, namely alcohol (4,8-dimethyl-3,7-nonadiene-2) -Ol), ester (4,8-dimethyl-3,7-nonadien-2-yl acetate) and ketone (4,8-dimethyl-3,7-nonadien-3-one) It has been found that the feeling of lemon is remarkably improved. Surprisingly, a specific ratio is important for the three ratios, and as a result of intensive studies on the ratio, 4,8-dimethyl-3,7-nonadien-2-ol and 4,4 The mixing ratio of 8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7-nonadien-2-one is preferably 1: 0.02: 0.04 to 1: 0. It was found to be 4: 0.8, particularly preferably 1: 0.04: 0.08 to 1: 0.2: 0.4. Lemons that are strong even after storage under acidic conditions compared to the fragrance compositions containing citral and the fragrance compositions of Patent Documents 1 to 3 by containing these three types of compounds in the blended fragrance at the specific ratio described above. Providing a fragrance composition capable of imparting a natural, natural citral-like flavor, and a food / beverage product and a cosmetic product containing the fragrance compound, while maintaining a feeling of feeling and freshness and generating almost no off-flavor The surprising fact of making it possible was found and the present invention was completed.

4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの3種を混合することで高い経時安定性を有し、且つ従来技術よりも強いシトラール様のレモン感、フレッシュ感を有する香料組成物を製造できることはこれまで何ら開示されておらず、ましてやそれら3種の化合物を特定の割合で混合することで、酸性条件下で保管後も強いレモン感、フレッシュ感を保持し、異臭を殆ど発生すること無く、自然な天然感を有するシトラール様の香味を付与することができる香料組成物を製造できることは記載も示唆もされていない。   4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7-nonadien-2-one It has not been disclosed so far that it is possible to produce a fragrance composition having high aging stability by mixing seeds and having a citral-like lemon feeling and fresh feeling stronger than those of the prior art. By mixing these compounds at a specific ratio, they retain a strong lemon and fresh feeling even after storage under acidic conditions, and give a citral-like flavor with a natural natural feeling with almost no off-flavors. There is no description or suggestion that a perfume composition can be produced.

(1)本発明は、4,8−ジメチル−3,7−ノナジエン−2−オール、4,8−ジメチル−3,7−ノナジエン−2−イル アセテート、4,8−ジメチル−3,7−ノナジエン−2−オンの3種の化合物を含有することを特徴とする香料組成物である。
(2)また、本発明は、上記(1)において、4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの混合割合が1:0.02:0.04〜1:0.4:0.8であることを特徴とする香料組成物である。
(3)さらに、本発明は、上記(1)または(2)の香料組成物を配合したことを特徴とする飲食品または香粧品である。
(1) The present invention relates to 4,8-dimethyl-3,7-nonadien-2-ol, 4,8-dimethyl-3,7-nonadien-2-yl acetate, 4,8-dimethyl-3,7- A fragrance composition containing three compounds of nonadien-2-one.
(2) The present invention also relates to the above (1), wherein 4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and The fragrance composition is characterized in that the mixing ratio of 8-dimethyl-3,7-nonadien-2-one is 1: 0.02: 0.04 to 1: 0.4: 0.8.
(3) Furthermore, the present invention is a food or drink or cosmetic characterized by blending the fragrance composition of (1) or (2) above.

本発明の香料組成物は飲食品、香粧品に配合することで、従来技術より自然で天然感のあるシトラール様のレモン感、フレッシュ感を付与することができ、且つ類似の香気特性を有するシトラールを含有した香料組成物に比べ、経時的な異臭の発生が軽減された飲食品、香粧品を製造することができる。   The fragrance composition of the present invention can be added to foods and beverages and cosmetics to give a natural and natural citral-like lemon feeling and fresh feeling, and citral having similar aroma characteristics. Compared with the fragrance | flavor composition containing this, the food / beverage products and cosmetics by which generation | occurrence | production of the off-flavor over time was reduced can be manufactured.

以下、本発明について詳細に説明する。
(1)香料組成物
本発明は、式(1)

Figure 0005027937
(式中、波線の結合はシス型もしくはトランス型またはシス型とトランス型の任意の割合の混合物を示す)
で表される4,8−ジメチル−3,7−ノナジエン−2−オールおよび
式(2)
Figure 0005027937
(式中、波線の結合はシス型もしくはトランス型またはシス型とトランス型の任意の割合の混合物を示し、Acはアセチル基を示す)
で表される4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび
式(3)
Figure 0005027937
(式中、波線の結合はシス型もしくはトランス型またはシス型とトランス型の任意の割合の混合物を示す)
で表される4,8−ジメチル−3,7−ノナジエン−2−オン
の3種の化合物を含有することを特徴とする香料組成物である。 Hereinafter, the present invention will be described in detail.
(1) Fragrance composition The present invention has the formula (1)
Figure 0005027937
(In the formula, the wavy bond indicates cis type or trans type or a mixture of cis type and trans type in any ratio)
4,8-dimethyl-3,7-nonadien-2-ol represented by the formula (2)
Figure 0005027937
(In the formula, the wavy bond represents cis-type or trans-type or a mixture of cis-type and trans-type in any proportion, and Ac represents an acetyl group)
4,8-dimethyl-3,7-nonadien-2-yl acetate represented by the formula (3)
Figure 0005027937
(In the formula, the wavy bond indicates cis type or trans type or a mixture of cis type and trans type in any ratio)
A fragrance composition comprising three compounds of 4,8-dimethyl-3,7-nonadien-2-one represented by:

本発明で使用される4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンは、いずれも公知文献による方法で合成することができる。   4,8-Dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7-nonadiene used in the present invention Any of the 2-ones can be synthesized by a method according to known literature.

4,8−ジメチル−3,7−ノナジエン−2−オールは例えば下記反応式に示すように、シトラールを塩化メチルマグネシウム(MeMgCl)によりグリニャール反応に付すことで得られる(Agarwal et al.; Indian Perfum., 27, 112-118 (1983))。

Figure 0005027937
4,8-Dimethyl-3,7-nonadien-2-ol can be obtained by subjecting citral to Grignard reaction with methylmagnesium chloride (MeMgCl) as shown in the following reaction formula (Agarwal et al .; Indian Perfum ., 27, 112-118 (1983)).
Figure 0005027937

4,8−ジメチル−3,7−ノナジエン−2−イル アセテートは、例えば下記反応式に示すように、4,8−ジメチル−3,7−ノナジエン−2−オールを無水酢酸(Ac2O)とピリジン(Pyr.)によりアセチル化することで得られる(Agarwal et al.; Indian
Perfum., 27, 112-118 (1983))。

Figure 0005027937
For example, 4,8-dimethyl-3,7-nonadien-2-yl acetate is obtained by converting 4,8-dimethyl-3,7-nonadien-2-ol to acetic anhydride (Ac 2 O) as shown in the following reaction formula. And acetylated with pyridine (Pyr.) (Agarwal et al .; Indian
Perfum., 27, 112-118 (1983)).
Figure 0005027937

4,8−ジメチル−3,7−ノナジエン−2−オンは例えば下記反応式に示すように、4,8−ジメチル−3,7−ノナジエン−2−オールをピリジン−三酸化クロム錯体(Pyr.−CrO3)によりサレット酸化に付すことで得られる(Agarwal et al.; Indian Perfum., 27, 112-118 (1983))。

Figure 0005027937
For example, 4,8-dimethyl-3,7-nonadien-2-one is obtained by converting 4,8-dimethyl-3,7-nonadien-2-ol to a pyridine-chromium trioxide complex (Pyr. It can be obtained by subjecting it to salet oxidation with (CrO 3 ) (Agarwal et al .; Indian Perfum., 27, 112-118 (1983)).
Figure 0005027937

但し、4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの合成法はこれらの方法に限定されるものではない。   However, 4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7-nonadien-2-one However, the synthesis method is not limited to these methods.

本発明の有効成分である4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンを香料組成物に用いる場合、これら3種化合物の混合割合は好ましくは1:0.02:0.04〜1:0.4:0.8であり、特に好ましくは1:0.04:0.08〜1:0.2:0.4である。
3種の化合物の合計添加量はその目的あるいは香料組成物の種類によって異なるものの、一般的には、香料組成物全体量の0.000000001質量%(10ppt)〜10質量%、好ましくは0.000001質量%(10ppb)〜5質量%の範囲内を例示することができる。
The active ingredients of the present invention are 4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7- When nonadien-2-one is used in the fragrance composition, the mixing ratio of these three compounds is preferably 1: 0.02: 0.04 to 1: 0.4: 0.8, particularly preferably 1: 0.04: 0.08 to 1: 0.2: 0.4.
Although the total amount of the three kinds of compounds varies depending on the purpose or the type of the fragrance composition, it is generally 0.000000001 mass (10 ppt) to 10 mass%, preferably 0.000001, based on the total amount of the fragrance composition. The range of mass% (10 ppb) -5 mass% can be illustrated.

本発明の香料組成物に配合される他の成分としては、特に制限は無く、用途や目的に応じて従来から使用されていた種々の香料素材を使用することができ、具体的にはアルデヒド類、アルコール類、エステル類等の従来公知の香料素材があげられる。
また、香料組成物の配合方法としても特に制限は無く、例えば香料素材を1種ずつ配合する方法、また例えばいくつかの香料素材を事前に混合したものを配合する方法など従来公知の配合方法があげられる。
The other components blended in the fragrance composition of the present invention are not particularly limited, and various fragrance materials that have been used conventionally can be used depending on the application and purpose. Specifically, aldehydes And conventionally known fragrance materials such as alcohols and esters.
Moreover, there is no restriction | limiting in particular also as the compounding method of a fragrance | flavor composition, For example, conventionally well-known compounding methods, such as the method of mix | blending one fragrance | flavor raw material one by one, for example, the method of mix | blending what mixed several fragrance | flavor raw materials beforehand. can give.

(2)香料組成物の適用
本発明の香料組成物は、(a)緑茶、紅茶、ウーロン茶などの茶飲料、果実飲料、酒類、乳飲料類、炭酸飲料類のごとき飲料類;(b)アイスクリーム類、シャーベット類、アイスキャンディー類のごとき冷菓類;(c)ヨーグルト類、チーズ類のごとき発酵乳製品;(d)和洋菓子類、焼菓子類、ジャム類、チューインガム類、パン類、ココア、コーヒー、茶、タバコのごとき嗜好品類;(e)プリン類、ゼリー類、ババロア類、ムース類のごときデザート類;(f)和風スープ類、洋風スープ類のごときスープ類;(g)風味調味料;(h)各種インスタント飲料乃至食品類、各種スナック食品類、などに添加することにより、自然で天然感のあるシトラール様の香気香味が付与された飲食品を提供することができる。
(2) Application of perfume composition The perfume composition of the present invention comprises (a) tea beverages such as green tea, black tea, oolong tea, beverages such as fruit beverages, alcoholic beverages, milk beverages, carbonated beverages; (b) ice Frozen desserts such as creams, sherbets, ice candy; (c) fermented dairy products such as yoghurts, cheeses; Luxury products such as coffee, tea and tobacco; (e) Desserts such as puddings, jellies, bavarois and mousses; (f) Soups such as Japanese-style soups and Western-style soups; (g) Flavor seasonings ; (H) By adding to various instant beverages or foods, various snack foods, etc., foods and drinks having a natural and natural citral-like aroma flavor can be provided.

また、本発明の香料組成物は、シャンプー類、ヘアクリーム類、ポマード類、その他の毛髪用化粧品、白粉、口紅、その他の化粧品、洗濯用洗剤、消毒用洗剤類、室内芳香剤その他各種の保健・衛生材料類、医薬品などの香粧品全般に広く使用することができる。   In addition, the fragrance composition of the present invention includes shampoos, hair creams, pomades, other hair cosmetics, white powder, lipstick, other cosmetics, laundry detergents, disinfectants, indoor air fresheners, and various other health care products. -It can be widely used for hygiene materials, pharmaceuticals and other general cosmetics.

本発明の香料組成物の飲食品又は香粧品への添加量は、飲食品、香粧品の種類によっても異なるが、一般的には飲食品又は香粧品中の4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの3種の化合物の合計濃度が0.000000000001質量%(0.01ppt)〜0.05質量%となるように添加すると、飲食品、香粧品に自然で天然感のあるシトラール様の香気香味を付与することができる。   The amount of the fragrance composition of the present invention added to a food or drink or cosmetic varies depending on the type of the food or drink or cosmetic, but is generally 4,8-dimethyl-3,7 in the food or drink or cosmetic. -The total concentration of the three compounds nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7-nonadien-2-one is 0. When it is added so as to be 000000000001 mass% (0.01 ppt) to 0.05 mass%, a natural and natural citral-like aroma flavor can be imparted to foods and drinks and cosmetics.

次に実施例を示して本発明をさらに具体的に説明するが、本発明は、これらの実施例に限定されるものではない。   EXAMPLES Next, although an Example is shown and this invention is demonstrated further more concretely, this invention is not limited to these Examples.

〔香料の合成例〕
(1)4,8−ジメチル−3,7−ノナジエン−2−オールの合成
窒素気流下、テトラヒドロフラン200mlにメチルマグネシウムクロリド(3Mテトラヒドロフラン溶液)100mlを加え、−5℃まで冷却した後、−10℃〜0℃にてシトラール43.5gを30分掛けて滴下した。−10℃〜0℃にて1時間反応させた後、反応溶液を0〜10℃にて10%塩化アンモニウム水溶液500mlへ加え、ヘプタン90gにて抽出した。ヘプタン層を飽和重曹水、食塩水にて洗浄後、無水硫酸ナトリウムにて乾燥し、ロータリーエバポレーターにてヘプタンを留去し粗油53gを得た。粗油を単蒸留することによりGC純度99.0%の4,8−ジメチル−3,7−ノナジエン−2−オール45gを得た。(沸点:59〜63℃/70Pa)
[Perfume synthesis example]
(1) Synthesis of 4,8-dimethyl-3,7-nonadien-2-ol Under a nitrogen stream, 100 ml of methylmagnesium chloride (3M tetrahydrofuran solution) was added to 200 ml of tetrahydrofuran, cooled to −5 ° C., and then −10 ° C. Citral 43.5 g was added dropwise at ˜0 ° C. over 30 minutes. After reacting at −10 ° C. to 0 ° C. for 1 hour, the reaction solution was added to 500 ml of 10% aqueous ammonium chloride solution at 0 to 10 ° C. and extracted with 90 g of heptane. The heptane layer was washed with saturated aqueous sodium hydrogen carbonate and brine and then dried over anhydrous sodium sulfate, and heptane was distilled off with a rotary evaporator to obtain 53 g of a crude oil. The crude oil was subjected to simple distillation to obtain 45 g of 4,8-dimethyl-3,7-nonadien-2-ol having a GC purity of 99.0%. (Boiling point: 59-63 ° C./70 Pa)

(2)4,8−ジメチル−3,7−ノナジエン−2−イル アセテートの合成
4,8−ジメチル−3,7−ノナジエン−2−オール25gに酢酸ナトリウム5gを加え、65℃に昇温した後、60〜70℃にて無水酢酸59gを10分掛けて滴下した。60〜70℃にて3時間反応させた後、反応溶液を40℃まで冷却し、0〜10℃にて水150gへ加え、ヘプタン50gにて抽出した。ヘプタン層を水、5%ソーダ灰水溶液にて洗浄後、無水硫酸ナトリウムにて乾燥し、ロータリーエバポレーターにてヘプタンを留去し粗油31gを得た。粗油を単蒸留することによりGC純度99.1%の4,8−ジメチル−3,7−ノナジエン−2−イル アセテート30gを得た。(沸点:71℃/80Pa)
(2) Synthesis of 4,8-dimethyl-3,7-nonadien-2-yl acetate 5 g of sodium acetate was added to 25 g of 4,8-dimethyl-3,7-nonadien-2-ol and the temperature was raised to 65 ° C. Thereafter, 59 g of acetic anhydride was added dropwise at 60 to 70 ° C. over 10 minutes. After reacting at 60 to 70 ° C. for 3 hours, the reaction solution was cooled to 40 ° C., added to 150 g of water at 0 to 10 ° C., and extracted with 50 g of heptane. The heptane layer was washed with water and a 5% soda ash aqueous solution and then dried over anhydrous sodium sulfate, and heptane was distilled off with a rotary evaporator to obtain 31 g of crude oil. The crude oil was subjected to simple distillation to obtain 30 g of 4,8-dimethyl-3,7-nonadien-2-yl acetate having a GC purity of 99.1%. (Boiling point: 71 ° C./80 Pa)

(3)4,8−ジメチル−3,7−ノナジエン−2−オンの合成
4,8−ジメチル−3,7−ノナジエン−2−オール2gにアセトニトリル130g、N−メチルモルホリン−N−オキシド2.9g、モレキュラーシーブス4A 4.6g、を加え、−10℃まで冷却した後、過ルテニウム酸テトラプロピルアンモニウム125mgを加え、室温に戻しつつ2時間攪拌した。反応溶液を5%チオ硫酸ナトリウム水溶液へ加え、ヘプタン50gにて抽出した。ヘプタン層を3%塩酸水溶液、食塩水にて洗浄後、無水硫酸ナトリウムにて乾燥し、ロータリーエバポレーターにてヘプタンを留去し粗油2.1gを得た。粗油をシリカゲルカラムクロマトグラフィー(ヘキサン:酢酸エチル=19:1)により精製し、単蒸留することによりGC純度99.7%の4,8−ジメチル−3,7−ノナジエン−2−オン1.3gを得た。(沸点:67℃/70Pa)
(3) Synthesis of 4,8-dimethyl-3,7-nonadien-2-one 130 g of acetonitrile, 2 g of 4,8-dimethyl-3,7-nonadien-2-ol, N-methylmorpholine-N-oxide 9 g and 4.6 g of molecular sieves 4A were added and cooled to −10 ° C., 125 mg of tetrapropylammonium perruthenate was added, and the mixture was stirred for 2 hours while returning to room temperature. The reaction solution was added to a 5% aqueous sodium thiosulfate solution and extracted with 50 g of heptane. The heptane layer was washed with a 3% aqueous hydrochloric acid solution and brine and then dried over anhydrous sodium sulfate, and heptane was distilled off with a rotary evaporator to obtain 2.1 g of a crude oil. The crude oil was purified by silica gel column chromatography (hexane: ethyl acetate = 19: 1) and subjected to simple distillation to obtain 4,8-dimethyl-3,7-nonadien-2-one having a GC purity of 99.7%. 3 g was obtained. (Boiling point: 67 ° C / 70 Pa)

〔実施例1および比較例1〜4〕(レモンフレーバー)
下記処方に従い、常法によって本発明の香料組成物No.1を得た。また、比較例1〜4として4,8−ジメチル−3,7−ノナジエン−2−オール、4,8−ジメチル−3,7−ノナジエン−2−イル アセテート、4,8−ジメチル−3,7−ノナジエン−2−オンの配合割合を変えた香料組成物No.2〜5を得た。
[Example 1 and Comparative Examples 1 to 4] (Lemon flavor)
According to the following prescription, the fragrance composition No. 1 of the present invention was obtained by a conventional method. As Comparative Examples 1 to 4, 4,8-dimethyl-3,7-nonadien-2-ol, 4,8-dimethyl-3,7-nonadien-2-yl acetate, 4,8-dimethyl-3,7 -Perfume composition No.2-5 which changed the mixture ratio of nonadien-2-one was obtained.

Figure 0005027937
Figure 0005027937

得られた香料組成物(No.1〜5)中の4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの配合割合を表2に示した。   4,8-Dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,4 in the obtained fragrance composition (No. 1-5) Table 2 shows the blending ratio of 8-dimethyl-3,7-nonadien-2-one.

Figure 0005027937
Figure 0005027937

即ち、香料組成物No.1は本発明の、4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの混合割合が1:0.02:0.04〜1:0.4:0.8の範囲内である香料組成物である。   That is, the perfume composition No. 1 is 4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8- It is a fragrance composition in which the mixing ratio of dimethyl-3,7-nonadien-2-one is in the range of 1: 0.02: 0.04 to 1: 0.4: 0.8.

一方、香料組成物No.2は本発明の配合割合より4,8−ジメチル−3,7−ノナジエン−2−イル アセテートの配合割合が低い香料組成物であり、香料組成物No.3は本発明の配合割合より4,8−ジメチル−3,7−ノナジエン−2−イル アセテートの配合割合が高い香料組成物であり、香料組成物No.4は本発明の配合割合より4,8−ジメチル−3,7−ノナジエン−2−オンの配合割合が低い香料組成物であり、香料組成物No.5は本発明の配合割合より4,8−ジメチル−3,7−ノナジエン−2−オンの配合割合が高い香料組成物である。   On the other hand, the fragrance composition No. 2 is a fragrance composition in which the blending ratio of 4,8-dimethyl-3,7-nonadien-2-yl acetate is lower than the blending ratio of the present invention. It is a fragrance composition having a higher proportion of 4,8-dimethyl-3,7-nonadien-2-yl acetate than the proportion of the invention, and fragrance composition No. 4 is 4,8-dimethyl from the proportion of the present invention. -3,7-nonadien-2-one is a fragrance composition having a low blending ratio, and fragrance composition No. 5 is 4,8-dimethyl-3,7-nonadien-2-one from the blending ratio of the present invention. It is a fragrance composition with a high blending ratio.

〔比較例5〜8〕
特許文献1および2の発明に従い下記に示した処方により、香料組成物No.6(比較例5)を、特許文献3の発明に従い、実施例1の4,8−ジメチル−3,7−ノナジエン−2−オンの代わりに2,4,8−トリメチル−7−ノネン−2−オールを配合して香料組成物No.7(比較例6)を、実施例1の4,8−ジメチル−3,7−ノナジエン−2−オール、4,8−ジメチル−3,7−ノナジエン−2−イル アセテート、4,8−ジメチル−3,7−ノナジエン−2−オンの代わりにシトラールを配合して香料組成物No.8(比較例7)を、実施例1の4,8−ジメチル−3,7−ノナジエン−2−オール、4,8−ジメチル−3,7−ノナジエン−2−イル アセテート、4,8−ジメチル−3 7−ノナジエン−2−オンの代わりにエチルアルコールを配合して香料組成物No.9(比較例8)をそれぞれ得た。
[Comparative Examples 5 to 8]
Perfume composition No. 6 (Comparative Example 5) was converted into 4,8-dimethyl-3,7-nonadiene of Example 1 according to the invention of Patent Document 3 according to the invention shown in Patent Documents 1 and 2 below. Perfume composition No. 7 (Comparative Example 6) was prepared by blending 2,4,8-trimethyl-7-nonen-2-ol instead of 2-one, and 4,8-dimethyl-3 of Example 1 was used. , 7-nonadien-2-ol, 4,8-dimethyl-3,7-nonadien-2-yl acetate, citral instead of 4,8-dimethyl-3,7-nonadien-2-one Composition No. 8 (Comparative Example 7) was converted to 4,8-dimethyl-3,7-nonadien-2-ol of Example 1, 4,8-dimethyl-3,7-nonadien-2-yl acetate, 4 , 8-dimethyl-3 7-nonadien-2-one instead of ethyl alcohol Narubutsu No.9 (Comparative Example 8) were respectively obtained.

Figure 0005027937
Figure 0005027937

得られた実施例1および比較例1〜8の香料組成物(No.1〜9)の香気香味を10名の専門パネラーにより下記評価基準に基づき行った結果の平均値を表4に、評価の際に得られたコメントを表5に示した。   Table 4 shows the average values of the results obtained by performing the fragrance and flavor of the obtained fragrance compositions (No. 1 to 9) of Example 1 and Comparative Examples 1 to 8 based on the following evaluation criteria by 10 professional panelists. Table 5 shows the comments obtained at the time.

香気香味評価基準; 非常に強く感じる:5
強く感じる:4
感じる:3
やや弱く感じる:2
非常に弱く感じる:1
Aroma and flavor evaluation criteria; feels very strong: 5
Feel strong: 4
Feel: 3
Feel weak: 2
Feels very weak: 1

Figure 0005027937
Figure 0005027937

Figure 0005027937
Figure 0005027937

<結果>
本発明の実施例1の香料組成物No.1および比較例7の香料組成物No.8は強いレモン感、フレッシュ感、自然な天然感のある香りを有していた。
一方、4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの混合割合が1:0.02:0.04〜1:0.4:0.8の範囲外である比較例1〜6および8の香料組成物(No.2〜No.7およびNo.9)では、何れも塩素様の香りやメタリック感、スパイシーさなど、実施例1と比較して異質な香りが感じられたり、レモン感、天然感に欠けるという評価結果となった。
<Result>
The perfume composition No. 1 of Example 1 of the present invention and the perfume composition No. 8 of Comparative Example 7 had a strong lemon feeling, a fresh feeling, and a natural aroma.
On the other hand, 4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7-nonadien-2-one Of the fragrance compositions of Comparative Examples 1 to 6 and 8 (No. 2 to No. 7 and No. 7) in which the mixing ratio is outside the range of 1: 0.02: 0.04 to 1: 0.4: 0.8. In 9), in all cases, a different scent such as chlorine-like scent, metallic sensation, and spiciness was felt, and the evaluation results were lacking in lemon sensation and natural sensation.

〔実施例2〕(レモン飲料(pH=3))
下記処方に従い、常法によって本発明のレモン飲料1(pH=3)を得た。

Figure 0005027937
[Example 2] (Lemon beverage (pH = 3))
According to the following prescription, the lemon drink 1 (pH = 3) of this invention was obtained by the conventional method.
Figure 0005027937

〔比較例9〜11〕
実施例2の香料組成物No.1の代わりに香料組成物No.6〜8をそれぞれ配合してレモン飲料(pH=3)2〜4を得た。
[Comparative Examples 9 to 11]
Instead of the fragrance composition No. 1 of Example 2, the fragrance compositions No. 6 to 8 were blended to obtain lemon beverages (pH = 3) 2 to 4, respectively.

〔試験例1〕
得られたレモン飲料(pH=3)1〜4をそれぞれ350ミリリットルの透明ペットボトル容器に充填し、70℃で10分間殺菌した後、50℃で10日間保管した。保管後のレモン飲料(pH=3)の香気香味の評価を10名の専門パネラーにより下記評価基準に基づき行った結果の平均値を表7に、評価の際に得られたコメントを表8に示した。
[Test Example 1]
The obtained lemon beverages (pH = 3) 1 to 4 were filled in 350 ml transparent PET bottle containers, sterilized at 70 ° C. for 10 minutes, and stored at 50 ° C. for 10 days. Table 7 shows the average value of the results of the evaluation of the aroma and flavor of the lemon beverage (pH = 3) after storage based on the following evaluation criteria by 10 expert panelists, and Table 8 shows the comments obtained during the evaluation. Indicated.

香気香味評価基準; 非常に強く感じる:5
強く感じる:4
感じる:3
やや弱く感じる:2
非常に弱く感じる:1
Aroma and flavor evaluation criteria; feels very strong: 5
Feel strong: 4
Feel: 3
Feel weak: 2
Feels very weak: 1

Figure 0005027937
Figure 0005027937

Figure 0005027937
Figure 0005027937

<結果>
本発明のレモン飲料1は、50℃で10日間保管した後もレモン感、天然感のあるフレッシュな香りを有し、レモン飲料2〜4に比べ、異臭の感じ方が軽減された。
<Result>
The lemon beverage 1 of the present invention has a fresh scent with a sense of lemon and a natural sensation even after being stored at 50 ° C. for 10 days.

〔実施例3〕(グレープフルーツフレーバー)
下記処方に従い、常法によって本発明の香料組成物No.10を得た。

Figure 0005027937
[Example 3] (Grapefruit flavor)
According to the following prescription, perfume composition No. 10 of the present invention was obtained by a conventional method.
Figure 0005027937

〔比較例12〕
実施例3の4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3 7−ノナジエン−2−オンの代わりにエチルアルコールを配合して香料組成物No.11を得た。
[Comparative Example 12]
4,8-Dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3 7-nonadiene-2-ol of Example 3 Perfume composition No. 11 was obtained by blending ethyl alcohol instead of ON.

〔実施例4、比較例13〕
下記処方に従い、常法によって本発明のグレープフルーツ飲料1および比較対象であるグレープフルーツ飲料2を得た。

Figure 0005027937
[Example 4, Comparative Example 13]
According to the following prescription, the grapefruit drink 1 of this invention and the grapefruit drink 2 which is a comparison object were obtained by the conventional method.
Figure 0005027937

〔試験例2〕
本発明のグレープフルーツ飲料1および比較対象である2について10名の専門パネラーにより香気香味を比較評価した。その平均的な香気香味評価結果を表11に示す。

Figure 0005027937
[Test Example 2]
About the grapefruit drink 1 of this invention, and 2 which is a comparison object, the fragrance | flavor flavor was compared and evaluated by 10 expert panelists. The average aroma flavor evaluation result is shown in Table 11.
Figure 0005027937

〔実施例5〕(オレンジフレーバー)
下記処方に従い、常法によって本発明の香料組成物No.12を得た。

Figure 0005027937
[Example 5] (Orange flavor)
According to the following prescription, perfume composition No. 12 of the present invention was obtained by a conventional method.
Figure 0005027937

〔比較例14〕
実施例5の4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3 7−ノナジエン−2−オンの代わりにエチルアルコールを配合して香料組成物No.13を得た。
[Comparative Example 14]
4,8-Dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3 7-nonadien-2-ol of Example 5 Perfume composition No. 13 was obtained by blending ethyl alcohol instead of ON.

〔実施例6、比較例15〕
下記処方に従い、常法によって本発明のオレンジ飲料1および比較対象であるオレンジ飲料2を得た。
[Example 6, Comparative Example 15]
According to the following prescription, the orange drink 1 of this invention and the orange drink 2 which is a comparison object were obtained by the conventional method.

Figure 0005027937
Figure 0005027937

〔試験例3〕
本発明のオレンジ飲料1および比較対象である2について10名の専門パネラーにより香気香味を比較評価した。その平均的な香気香味評価結果を表14に示す。

Figure 0005027937
[Test Example 3]
About the orange drink 1 of this invention and 2 which is a comparison object, the fragrance | flavor flavor was compared and evaluated by 10 expert panelists. The average aroma flavor evaluation result is shown in Table 14.
Figure 0005027937

〔実施例7〕
下記処方に従い、常法によって本発明の香料組成物No.14を調製した。

Figure 0005027937
Example 7
According to the following prescription, perfume composition No. 14 of the present invention was prepared by a conventional method.
Figure 0005027937

〔比較例16〕
実施例7の4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの代わりにリモネンを配合した以外は同様の処方および方法にて香料組成物No.15を調製した。
[Comparative Example 16]
4,8-Dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7-nonadien-2 of Example 7 -Fragrance composition No. 15 was prepared by the same formulation and method except that limonene was blended in place of ON.

〔実施例8、比較例17〕
下記処方に従い、常法によって本発明のシャンプー1および比較対象であるシャンプー2を得た。

Figure 0005027937
[Example 8, Comparative Example 17]
According to the following prescription, the shampoo 1 of the present invention and the shampoo 2 to be compared were obtained by a conventional method.
Figure 0005027937

[試験例4]
本発明のシャンプー1および比較対象であるシャンプー2について10名の専門パネラーにより香気を比較評価した。その平均的な香気評価結果を表17に示す。
[Test Example 4]
For the shampoo 1 of the present invention and the shampoo 2 to be compared, the fragrance was comparatively evaluated by 10 expert panelists. The average fragrance evaluation results are shown in Table 17.

Figure 0005027937
Figure 0005027937

本発明における特定の割合で4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの3種の化合物を香料組成物に添加することにより、類似の
香気特性を有するシトラールを含有した香料組成物に比べ、経時的な異臭の発生が軽減された香料組成物、果汁飲料や飲食品およびシャンプー等の香粧品を製造することができる。また、それらの製品に自然な天然感とシトラール様のレモン感、フレッシュ感を付与することができる。
4,8-dimethyl-3,7-nonadien-2-ol and 4,8-dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7- By adding three compounds of nonadien-2-one to the fragrance composition, a fragrance composition in which the generation of off-flavor over time is reduced compared to a fragrance composition containing citral having similar aroma characteristics, Cosmetic products such as fruit juices, foods and drinks, and shampoos can be produced. In addition, these products can have a natural feeling, a citral-like lemon feeling, and a fresh feeling.

Claims (4)

式(1)
Figure 0005027937
(式中、波線の結合はシス型もしくはトランス型またはシス型とトランス型の任意の割合の混合物を示す)
で表される4,8−ジメチル−3,7−ノナジエン−2−オールおよび
式(2)
Figure 0005027937
(式中、波線の結合はシス型もしくはトランス型またはシス型とトランス型の任意の割合の混合物を示し、Acはアセチル基を示す)
で表される4,8−ジメチル−3,7−ノナジエン−2−イル アセテートおよび
式(3)
Figure 0005027937
(式中、波線の結合はシス型もしくはトランス型またはシス型とトランス型の任意の割合の混合物を示す)
で表される4,8−ジメチル−3,7−ノナジエン−2−オン
の3種の化合物を、質量比で4,8−ジメチル−3,7−ノナジエン−2−オールの1に対
し、4,8−ジメチル−3,7−ノナジエン−2−イル アセテートを0.02〜0.4、4,8−ジメチル−3,7−ノナジエン−2−オンを0.04〜0.8となる割合で混合したも
のを含有することを特徴とする香料組成物。
Formula (1)
Figure 0005027937
(In the formula, the wavy bond indicates cis type or trans type or a mixture of cis type and trans type in any ratio)
4,8-dimethyl-3,7-nonadien-2-ol represented by the formula (2)
Figure 0005027937
(In the formula, the wavy bond represents cis-type or trans-type or a mixture of cis-type and trans-type in any proportion, and Ac represents an acetyl group)
4,8-dimethyl-3,7-nonadien-2-yl acetate represented by the formula (3)
Figure 0005027937
(In the formula, the wavy bond indicates cis type or trans type or a mixture of cis type and trans type in any ratio)
3 compounds of 4,8-dimethyl-3,7-nonadien-2-one represented by the formula (4) with respect to 1 of 4,8-dimethyl-3,7-nonadien-2-ol by mass ratio: , 8-dimethyl-3,7-nonadien-2-yl acetate in a ratio of 0.02 to 0.4, 4,8-dimethyl-3,7-nonadien-2-one in a ratio of 0.04 to 0.8 The fragrance | flavor composition characterized by containing the thing mixed by this.
請求項1記載の香料組成物を配合したことを特徴とする飲食品。   A food or drink comprising the fragrance composition according to claim 1. 請求項1記載の香料組成物を配合したことを特徴とする香粧品。   A cosmetic product comprising the fragrance composition according to claim 1. 飲食品又は香粧品中の4,8−ジメチル−3,7−ノナジエン−2−オールおよび4,8
−ジメチル−3,7−ノナジエン−2−イル アセテートおよび4,8−ジメチル−3,7−ノナジエン−2−オンの3種の化合物の合計濃度が0.000000000001質量%
(0.01ppt)〜0.05質量%となるように請求項1記載の香料組成物を添加することを特徴とする、飲食品又は香粧品にシトラール様の香気香味を付与する方法。
4,8-Dimethyl-3,7-nonadien-2-ol and 4,8 in food and drink or cosmetics
-The total concentration of three compounds of dimethyl-3,7-nonadien-2-yl acetate and 4,8-dimethyl-3,7-nonadien-2-one is 0.000000000001 mass%
A method for imparting a citral-like fragrance to a food or drink or cosmetic, wherein the fragrance composition according to claim 1 is added so as to be (0.01 ppt) to 0.05 mass%.
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