JP5645389B2 - Persistent aromatizing agent - Google Patents
Persistent aromatizing agent Download PDFInfo
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- JP5645389B2 JP5645389B2 JP2009249920A JP2009249920A JP5645389B2 JP 5645389 B2 JP5645389 B2 JP 5645389B2 JP 2009249920 A JP2009249920 A JP 2009249920A JP 2009249920 A JP2009249920 A JP 2009249920A JP 5645389 B2 JP5645389 B2 JP 5645389B2
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Description
本発明は、飲食物等における香気の持続性を向上するために使用可能な持続性香気賦与剤に関する。詳しくは特定の持続性香気賦与剤を含有することにより、飲食時などに口腔内で発現する良質な香気を適度な時間保持することができる持続性香気賦与剤に関する。 The present invention relates to a persistent fragrance imparting agent that can be used to improve the fragrance persistence of food and drink. Specifically, the present invention relates to a long-lasting fragrance imparting agent that can retain a good-quality fragrance that is expressed in the oral cavity at the time of eating and drinking by containing a specific long-lasting fragrance imparting agent.
飲食物等は、嗜好性の高いユニークな香気香味を有することとともに、口に含んだ瞬間に感じる香気・香味の初発性が良いこと、あるいは余韻と謂われる適度な香気・香味の長期持続性を有すること(以下「持続性」という)を中心として、各種商品の特性に適合するように香味の発現を制御することが要求されている。そのため、それらの要件に適合した香気賦与剤を開発することが飲食品業界において極めて重要な課題となっている。 Foods and drinks have a unique aroma and flavor with high palatability, good initial aroma and flavor to be felt at the moment they are put in the mouth, or moderate long-term sustainability of so-called reverberation. It is required to control the expression of the flavor so as to conform to the characteristics of various products centering on having (hereinafter referred to as “sustainability”). Therefore, it has become an extremely important issue in the food and beverage industry to develop a fragrance imparting agent that meets these requirements.
菓子類、薬品、飲料或いは食料品などの可食性製品、さらには口腔用製品などに添加される香気賦与剤が発する香気・香味(以下両者をまとめて「香気」と表現する)の発現の制御に関しては、従来から種々の方法が提案されている。例えば、香気成分を含有するコア物質の表面を親水性重合体で被膜してマトリックスを形成させたり(特許文献1参照)、香料をサイクロデキストリンに包接したり(特許文献2参照)することにより、チューイングガムなどの菓子類への香味の持続性の賦与または改善する方法が開示されている。 Control of the expression of fragrances and flavors (hereinafter collectively referred to as “fragrance”) emitted by fragrance imparting agents added to edible products such as confectionery, medicines, beverages or foodstuffs, and oral products Various methods have been proposed in the past. For example, by coating the surface of the core substance containing a fragrance component with a hydrophilic polymer to form a matrix (see Patent Document 1), or by including a fragrance in a cyclodextrin (see Patent Document 2), A method for imparting or improving the persistence of flavor to confectionery such as chewing gum is disclosed.
また、初発の香気の発現については、食品類を口腔へ入れた場合に、速やかな香味の発現を目的として香料と乳化剤および糖アルコール類などを混合して得られる速放性の粉末香料(特許文献3参照)が開示されている。さらに、香気の持続性を維持させると同時に、初発の香気の発現を意図した食品用香料(特許文献4参照)が開示されている。しかしながら、上記のような物理的・化学的手段を講じた香料類は、未だ初発の発現性あるいは適度な持続性のいずれも制御できているとは言い難く、商品の特性に合わせて香気の発現を制御することは著しく困難な現状である。とりわけ、香気を適度な時間保持し、余韻と謂われる良質な持続性の香気を飲食品商品に賦与することは実現されていない。 In addition, regarding the development of the first fragrance, an immediate release powder fragrance obtained by mixing a fragrance, an emulsifier, a sugar alcohol, etc. for the purpose of swift expression when food is put into the oral cavity (patent Reference 3) is disclosed. Furthermore, the fragrance | flavor for foods (refer patent document 4) which intends the expression of the first fragrance | flavor at the same time it maintains the fragrance persistence is disclosed. However, it is difficult to say that fragrances with the physical and chemical means as described above can control either the initial development or appropriate sustainability, and the development of fragrance according to the characteristics of the product. It is extremely difficult to control the current situation. In particular, it has not been realized to retain aroma for an appropriate period of time and to impart a high-quality and long-lasting aroma called a reverberation to a food or drink product.
一方、香気前駆体組成物としては、システインやグルタチオン等のSH基に、分子内にフラン基やチオフェン基を有する置換基を結合させ、還元的に香気を発現させることがコーヒー等の香気発現に有効であることが提案されている(特許文献5)。しかしながら、当該化合物もその香気の発現方法としては未だ改善の余地があった。 On the other hand, as a fragrance precursor composition, a substituent having a furan group or a thiophene group in a molecule is bonded to an SH group such as cysteine or glutathione, and the fragrance is expressed reductively in order to express aroma such as coffee. It has been proposed to be effective (Patent Document 5). However, the compound still has room for improvement as a method for expressing its aroma.
本発明の課題は、従来の問題点を解消し、口腔における良質な香気の持続性を向上することが可能な、飲食物等の口腔内における持続性香気賦与剤、さらには当該香気賦与剤を配合した香料組成物、飲食物、口腔用製品、中でも特に茶飲料を提供することにある。 An object of the present invention is to solve the conventional problems and improve the persistence of a good-quality fragrance in the oral cavity, a persistent fragrance imparting agent in the oral cavity of food and drink, and further the fragrance-imparting agent. The object is to provide a blended fragrance composition, food and drink, oral product, especially a tea beverage.
本発明者らは、上記の目的を達成すべく鋭意研究の結果、下記一般式(1)で表される有機化合物であって、R1−SHがグルタチオンまたはシステインであり、かつR2が4−メチル−2−ペンタノン−4−イル基、1−ヘキサノール−3−イル基または1−ヘキサナール−3−イル基である化合物が、口腔内で主として酵素反応により香気を徐々に発生し、さらにこれらの組合せることによって、自然で良質な香気の持続性を向上するため、飲食物等の口腔内における持続性香気賦与剤の提供が可能になるという新たな事実を見出し、本発明を完成するに至った。
R1−S−R2 (1)
As a result of diligent research to achieve the above object, the inventors of the present invention are organic compounds represented by the following general formula (1), wherein R 1 —SH is glutathione or cysteine, and R 2 is 4 -A compound which is a methyl-2-pentanone-4-yl group, 1-hexanol-3-yl group or 1-hexanal-3-yl group gradually generates a fragrance mainly by an enzymatic reaction in the oral cavity. In order to improve the sustainability of natural and high-quality fragrances by combining the above, a new fact that it is possible to provide a persistent fragrance imparting agent in the oral cavity of food and drinks, etc. is found, and the present invention is completed. It came.
R 1 —S—R 2 (1)
すなわち、本発明は、一般式(1)で表される有機化合物であって、R1−SHがグルタチオンまたはシステインであり、かつR2が4−メチル−2−ペンタノン−4−イル基、1−ヘキサノール−3−イル基または1−ヘキサナール−3−イル基であることを特徴とする持続性香気賦与剤である。さらに本発明は上記持続性香気賦与剤を含有した香料組成物、飲食物、口腔用製品、茶飲料および茶飲料の製造方法である。 That is, the present invention is an organic compound represented by the general formula (1), wherein R 1 —SH is glutathione or cysteine, and R 2 is a 4-methyl-2-pentanone-4-yl group, -A persistent fragrance imparting agent characterized by being a hexanol-3-yl group or a 1-hexanal-3-yl group. Furthermore, this invention is a manufacturing method of the fragrance | flavor composition containing the said persistent fragrance | flavor imparting agent, food / beverage products, oral products, tea drinks, and tea drinks.
本発明の持続性香気賦与剤を飲食物などに使用した場合、良質な香気の持続性を向上することができ、所謂余韻を感じられる上記製品を消費者に提供することができる。 When the persistent fragrance imparting agent of the present invention is used for food and drink, etc., it is possible to improve the sustainability of a good quality fragrance and provide the consumer with the above-mentioned product that feels so-called lingering.
以下に、本発明を実施の形態に即して詳細に説明する。本発明の持続性香気賦与剤は、一般式(1)で表される有機化合物であって、R1−SHがグルタチオンまたはシステインであり、かつR2が4−メチル−2−ペンタノン−4−イル基、1−ヘキサノール−3−イル基または1−ヘキサナール−3−イル基であり、具体的化合物としては好ましくはS−(4−メチル−2−ペンタノン−4−イル)グルタチオンまたはS−(4−メチル−2−ペンタノン−4−イル)システインであり、特に好ましくはS−(4−メチル−2−ペンタノン−4−イル)グルタチオンである。 Hereinafter, the present invention will be described in detail according to embodiments. The persistent fragrance imparting agent of the present invention is an organic compound represented by the general formula (1), wherein R 1 —SH is glutathione or cysteine, and R 2 is 4-methyl-2-pentanone-4- Yl group, 1-hexanol-3-yl group or 1-hexanal-3-yl group, and the specific compound is preferably S- (4-methyl-2-pentanone-4-yl) glutathione or S- ( 4-methyl-2-pentanone-4-yl) cysteine, and particularly preferably S- (4-methyl-2-pentanone-4-yl) glutathione.
これらは、口腔においてチオールを有する香気成分を放出する特性を有しており、その放出特性がR1SHとR2Hの種類、すなわちシステインまたはグルタチオンと揮発性香気成分の組み合わせにより異なる。それゆえに、R1SHとR2Hの種類の組合せを調整することにより、口腔における香気の持続性を制御することができる。本発明で用いられるR2Hの揮発性成分は、口腔内の条件により一部R2SHの形態で香気成分として発現するが、これらR2SHはごく微量で各種飲食物の香気を増強する効果を有し、特に茶飲料やコーヒーなどの嗜好性飲料の香気増強に極めて有用な効果を示すものである(例えば特許第3026437号公報など参照)。 These have a characteristic of releasing an aromatic component having a thiol in the oral cavity, and the release characteristic varies depending on the type of R 1 SH and R 2 H, that is, a combination of cysteine or glutathione and a volatile aromatic component. Therefore, by adjusting the combination of the types of R 1 SH and R 2 H, it is possible to control the persistence of the fragrance in the oral cavity. Although the volatile component of R 2 H used in the present invention is partially expressed as an aroma component in the form of R 2 SH depending on the condition in the oral cavity, these R 2 SH enhances the aroma of various foods and drinks in a very small amount. It has an effect, and particularly shows an extremely useful effect for enhancing the aroma of a palatable beverage such as tea beverage or coffee (see, for example, Japanese Patent No. 3026437).
本発明の持続性香気賦与剤の一部は、ある種の植物や動物が含有する成分として、従来の文献に記載されており、動物における代謝やワイン製造における発酵により、チオール化合物を生じることが記されている(非特許文献1参照)。さらに、人の口腔内において、システインと揮発性化合物が結合した化合物(基質)から、チオール化合物を生じる可能性も記されている。しかしながら、一方では、上記従来の文献には、チオール化合物を生成する基質と酵素の関係には特異性があることも記載されており、システインと揮発性化合物が結合した基質以外の化合物が、人の口腔内において香気を放出することはもちろん、その放出特性が揮発性化合物とシステインまたはグルタチオンの組み合わせにより異なることを示唆するものではなかった。 Some of the persistent fragrance imparting agents of the present invention are described in conventional literature as components contained in certain plants and animals, and may produce thiol compounds by metabolism in animals or fermentation in wine production. (See Non-Patent Document 1). Furthermore, the possibility that a thiol compound is generated from a compound (substrate) in which cysteine and a volatile compound are bonded is described. However, on the other hand, the above-mentioned conventional literature also describes that the relationship between the substrate that generates the thiol compound and the enzyme has specificity, and compounds other than the substrate to which cysteine and the volatile compound are bound are Of course, it did not suggest that the release characteristics differ depending on the combination of volatile compounds and cysteine or glutathione.
本発明の持続性香気賦与剤の中で、持続性の向上には、特にR1SHがグルタチオンである場合が効果的であるが、香気の持続性を制御するために、本発明では2種以上を同時に使用することも有用である。 Among the long-lasting fragrance imparting agents of the present invention, the improvement of the long-lasting is particularly effective when R 1 SH is glutathione. However, in order to control the long-lasting fragrance, the present invention has two types. It is also useful to use the above simultaneously.
本発明の持続性香気賦与剤は、天然物から抽出、カラムクロマトグラフィー、液体クロマトグラフィー等の手段で得るか、或いは文献(非特許文献2参照、非特許文献3参照)等記載の合成手段によって得ることができる。 The long-lasting fragrance imparting agent of the present invention can be obtained from natural products by means such as extraction, column chromatography, liquid chromatography, or by synthetic means described in the literature (see Non-Patent Document 2 and Non-Patent Document 3). Can be obtained.
本発明の持続性香気賦与剤は、飲食物等の加工段階で適宜添加することができ、添加量は持続性香気賦与剤の組成や飲食物等の種類により異なるが、一般的には飲食物等に対して0.0001ppb〜10000ppm、好ましくは0.001ppb〜1000ppm、より好ましくは0.01ppb〜100ppm、特に好ましくは0.1ppb〜10ppm、最も好ましくは1ppb〜5ppmの添加量で用いられる。 The persistent fragrance imparting agent of the present invention can be appropriately added at the processing stage of food and drink, etc., and the amount added varies depending on the composition of the persistent fragrance imparting agent and the type of food and drink, but generally food and drink. 0.0001 ppb to 10000 ppm, preferably 0.001 ppb to 1000 ppm, more preferably 0.01 ppb to 100 ppm, particularly preferably 0.1 ppb to 10 ppm, and most preferably 1 ppb to 5 ppm.
本発明の持続性香気賦与剤は各種飲食物に特に制限なく使用することができる。例えば、果実類またはその加工品、野菜またはその加工品、魚介類またはその加工品、練製品、調理食品、総菜類、スナック類、珍味類、加工食品、栄養食品、茶飲料およびコーヒー飲料などの嗜好飲料、果汁飲料、炭酸飲料、清涼飲料、機能性飲料、アルコール飲料、アイスクリーム、シャーベット等の冷菓類、ゼリー、プリン、羊かん等のデザート類、クッキー、ケーキ、チョコレート、チューイングガム、饅頭等の菓子類、菓子パン、食パン等のパン類、ジャム類、ラムネ、タブレット、錠菓類などがあげられる。さらに、日本料理のだし、例えば、鰹節、魚介類、昆布、シイタケ、鶏肉、野菜類などのだし汁および和風調味料、または、西洋料理のスープストック、例えば、牛肉、鶏肉、豚肉、魚介類、野菜類などのだし汁および洋風調味料、または、中華料理のタン(湯) 、例えば、牛肉、鶏肉、豚肉、魚介類、野菜類などからとったスープおよび中華調味料などがあげられる。また、持続性香気賦与剤は、適宜、香味成分あるいは色素を調合し香味および色調を増強することもできる。調合に使用される香味成分あるいは色素には特に制限はなく、公知の香味成分あるいは色素が目的に応じて適宜配合して用いられる。また、本発明の持続性香気賦与剤は飲食物用途に限定されるものではなく、口腔内で使用される全ての製品に使用可能であり、例えば練歯磨、潤製歯磨、粉歯磨、液状歯磨などの歯磨類、マウスウオッシュなどの洗口剤、トローチなどの口中清涼剤などの口腔用製品を例示することができる。 The persistent fragrance imparting agent of the present invention can be used for various foods and drinks without any particular limitation. For example, fruits or processed products thereof, vegetables or processed products thereof, seafood or processed products thereof, paste products, cooked foods, prepared vegetables, snacks, delicacies, processed foods, nutritional foods, tea drinks and coffee drinks Taste drinks, fruit juice drinks, carbonated drinks, soft drinks, functional drinks, alcoholic drinks, ice cream, confectionery such as sherbet, desserts such as jelly, pudding, sheep cane, cookies, cakes, chocolate, chewing gum, buns, etc. , Breads such as confectionery bread and bread, jams, ramunes, tablets and tablet confectionery. In addition, soup stock of Japanese cuisine, such as bonito, seafood, kelp, shiitake, chicken, vegetables, etc., or soup stock of Western cuisine, eg, beef, chicken, pork, seafood, vegetables And soup and Chinese seasonings such as beef, chicken, pork, seafood, vegetables and the like. Moreover, a persistent fragrance | flavor imparting agent can also mix | blend a flavor component or a pigment | dye suitably, and can also enhance a flavor and a color tone. There is no restriction | limiting in particular in the flavor component or pigment | dye used for preparation, A well-known flavor component or pigment | dye is suitably mix | blended and used according to the objective. Further, the long-lasting fragrance imparting agent of the present invention is not limited to food and drink applications, and can be used for all products used in the oral cavity. For example, toothpaste, toothpaste, powder toothpaste, liquid toothpaste. Oral products such as toothpastes such as mouthwashes, mouthwashes such as mouthwashes, and mouth fresheners such as troches.
以下に実施例を挙げて本発明を具体的に説明するが、本発明は実施例の記載に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the description of the examples.
(実施例1)
S−(4−メチル−2−ペンタノン−4−イル)グルタチオンの合成
グルタチオン(1.0g;3.3mmol)、4−メチル−3−ペンテン−2−オン(0.33g;3.4mmol)、ピリジン(0.52g;6.6mmol)に8mLの蒸留水を加え、室温にて撹拌した。48時間後、反応液に約20mLの蒸留水を加えた後、塩化メチレン(5mL)にて低極性化合物を除き(2回)水層部を得た。得られた水層を減圧条件下(10mmHg)、50℃にて乾固させた後、残渣に混合溶媒(EtOH:水=80:6)を少量加え、50℃に加温して完溶させた後、室温、次いで冷蔵庫にて再結晶させた。生じた結晶は桐山ロートにてろ別し、少量のエタノールで洗浄後、デシケーター(減圧条件下)中で乾燥させた。
Example 1
Synthesis of S- (4-methyl-2-pentanon-4-yl) glutathione Glutathione (1.0 g; 3.3 mmol), 4-methyl-3-penten-2-one (0.33 g; 3.4 mmol), 8 mL of distilled water was added to pyridine (0.52 g; 6.6 mmol) and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).
(実施例2)
S−(4−メチル−2−ペンタノン−4−イル)システインの合成
システイン(0.44g;3.6mmol)、4−メチル−3−ペンテン−2−オン(0.35g;3.6mmol)、ピリジン(0.54g;6.7mmol)に8mLの蒸留水を加え、室温にて撹拌した。48時間後、脱脂綿にて固形物をろ過した反応液に約20mLの蒸留水を加えた後、塩化メチレン(5mL)にて低極性化合物を除き(2回)水層部を得た。得られた水層を減圧条件下(10mmHg)、50℃にて乾固させた後、残渣に混合溶媒(EtOH:水=80:6)を少量加え、50℃に加温して完溶させた後、室温、次いで冷蔵庫にて再結晶させた。生じた結晶は桐山ロートにてろ別し、少量のエタノールで洗浄後、デシケーター(減圧条件下)中で乾燥させた。
(Example 2)
Synthesis of S- (4-methyl-2-pentanon-4-yl) cysteine Cysteine (0.44 g; 3.6 mmol), 4-methyl-3-penten-2-one (0.35 g; 3.6 mmol), 8 mL of distilled water was added to pyridine (0.54 g; 6.7 mmol) and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution obtained by filtering the solid with absorbent cotton, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).
(実施例3)
S−(1−ヘキサノール−3−イル)グルタチオンの合成
グルタチオン(1.0g;3.3mmol)、(E)−2−ヘキセナール(0.33g;3.4mmol)、ピリジン(0.52g;6.6mmol)に8mLの蒸留水を加え、室温にて撹拌した。48時間後、反応液に約20mLの蒸留水を加えた後、塩化メチレン(5mL)にて低極性化合物を除き(2回)水層部を得た。得られた水層を減圧条件下(10mmHg)、50℃にて乾固させた後、残渣に混合溶媒(EtOH:水=80:6)を少量加え、50℃に加温して完溶させた後、室温、次いで冷蔵庫にて再結晶させた。桐山ロートにてろ別した結晶(100mg;0.33mmol)をエタノールに溶解後、水素化ほう素ナトリウム(30mg;0.7mmol)を加え、室温にて撹拌した。4時間後、反応液に約20mLの希塩酸を加えた後、さらに撹拌した。2時間後、得られた反応液を減圧条件下(10mmHg)、50℃にて乾固させた後、残渣に混合溶媒(EtOH:水=80:6)を少量加え、50℃に加温して完溶させた後、室温、次いで冷蔵庫にて再結晶させた。生じた結晶は桐山ロートにてろ別し、少量のエタノールで洗浄後、デシケーター(減圧条件下)中で乾燥させた。
Example 3
Synthesis of S- (1-hexanol-3-yl) glutathione Glutathione (1.0 g; 3.3 mmol), (E) -2-hexenal (0.33 g; 3.4 mmol), pyridine (0.52 g; 6. 6 mmol) was added with 8 mL of distilled water and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. Crystals (100 mg; 0.33 mmol) separated by filtration with a Kiriyama funnel were dissolved in ethanol, sodium borohydride (30 mg; 0.7 mmol) was added, and the mixture was stirred at room temperature. After 4 hours, about 20 mL of diluted hydrochloric acid was added to the reaction solution, and the mixture was further stirred. After 2 hours, the obtained reaction solution was dried at 50 ° C. under reduced pressure (10 mmHg), a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. After complete dissolution, it was recrystallized at room temperature and then in a refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).
(実施例4)
S−(1−ヘキサノール−3−イル)システインの合成
システイン(0.44g;3.6mmol)、(E)−2−ヘキセナール(0.35g;3.6mmol)、ピリジン(0.54g;6.7mmol)に8mLの蒸留水を加え、室温にて撹拌した。48時間後、脱脂綿にて固形物をろ過した反応液に約20mLの蒸留水を加えた後、塩化メチレン(5mL)にて低極性化合物を除き(2回)水層部を得た。得られた水層を減圧条件下(10mmHg)、50℃にて乾固させた後、残渣に混合溶媒(EtOH:水=80:6)を少量加え、50℃に加温して完溶させた後、室温、次いで冷蔵庫にて再結晶させた。桐山ロートにてろ別した結晶(40mg;0.33mmol)をエタノールに溶解後、水素化ほう素ナトリウム(30mg;0.7mmol)を加え、室温にて撹拌した。4時間後、反応液に約20mLの希塩酸を加えた後、さらに撹拌した。2時間後、得られた反応液を減圧条件下(10mmHg)、50℃にて乾固させた後、残渣に混合溶媒(EtOH:水=80:6)を少量加え、50℃に加温して完溶させた後、室温、次いで冷蔵庫にて再結晶させた。生じた結晶は桐山ロートにてろ別し、少量のエタノールで洗浄後、デシケーター(減圧条件下)中で乾燥させた。
Example 4
Synthesis of S- (1-hexanol-3-yl) cysteine Cysteine (0.44 g; 3.6 mmol), (E) -2-hexenal (0.35 g; 3.6 mmol), pyridine (0.54 g; 6. 7 mmol) was added with 8 mL of distilled water and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution obtained by filtering the solid with absorbent cotton, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. Crystals (40 mg; 0.33 mmol) separated by filtration with a Kiriyama funnel were dissolved in ethanol, sodium borohydride (30 mg; 0.7 mmol) was added, and the mixture was stirred at room temperature. After 4 hours, about 20 mL of diluted hydrochloric acid was added to the reaction solution, and the mixture was further stirred. After 2 hours, the obtained reaction solution was dried at 50 ° C. under reduced pressure (10 mmHg), a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. After complete dissolution, it was recrystallized at room temperature and then in a refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).
(実施例5)
S−(ヘキサナール−3−イル)グルタチオンの合成
グルタチオン(1.0g;3.3mmol)、(E)−2−ヘキセナール(0.33g;3.4mmol)、ピリジン(0.52g;6.6mmol)に8mLの蒸留水を加え、室温にて撹拌した。48時間後、反応液に約20mLの蒸留水を加えた後、塩化メチレン(5mL)にて低極性化合物を除き(2回)水層部を得た。得られた水層を減圧条件下(10mmHg)、50℃にて乾固させた後、残渣に混合溶媒(EtOH:水=80:6)を少量加え、50℃に加温して完溶させた後、室温、次いで冷蔵庫にて再結晶させた。生じた結晶は桐山ロートにてろ別し、少量のエタノールで洗浄後、デシケーター(減圧条件下)中で乾燥させた。
(Example 5)
Synthesis of S- (hexanal-3-yl) glutathione Glutathione (1.0 g; 3.3 mmol), (E) -2-hexenal (0.33 g; 3.4 mmol), pyridine (0.52 g; 6.6 mmol) 8 mL of distilled water was added thereto and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).
(実施例6)
S−(ヘキサナール−3−イル)システインの合成
システイン(0.44g;3.6mmol)、(E)−2−ヘキセナール(0.35g;3.6mmol)、ピリジン(0.54g;6.7mmol)に8mLの蒸留水を加え、室温にて撹拌した。48時間後、脱脂綿にて固形物をろ過した反応液に約20mLの蒸留水を加えた後、塩化メチレン(5mL)にて低極性化合物を除き(2回)水層部を得た。得られた水層を減圧条件下(10mmHg)、50℃にて乾固させた後、残渣に混合溶媒(EtOH:水=80:6)を少量加え、50℃に加温して完溶させた後、室温、次いで冷蔵庫にて再結晶させた。生じた結晶は桐山ロートにてろ別し、少量のエタノールで洗浄後、デシケーター(減圧条件下)中で乾燥させた。
(Example 6)
Synthesis of S- (hexanal-3-yl) cysteine Cysteine (0.44 g; 3.6 mmol), (E) -2-hexenal (0.35 g; 3.6 mmol), pyridine (0.54 g; 6.7 mmol) 8 mL of distilled water was added thereto and stirred at room temperature. After 48 hours, about 20 mL of distilled water was added to the reaction solution obtained by filtering the solid with absorbent cotton, and then the low polarity compound was removed with methylene chloride (5 mL) (twice) to obtain an aqueous layer. The obtained aqueous layer was dried under reduced pressure (10 mmHg) at 50 ° C., a small amount of mixed solvent (EtOH: water = 80: 6) was added to the residue, and the mixture was heated to 50 ° C. for complete dissolution. And then recrystallized at room temperature and then in the refrigerator. The resulting crystals were filtered off with a Kiriyama funnel, washed with a small amount of ethanol, and dried in a desiccator (under reduced pressure).
(実施例7)
緑茶抽出液100質量部に対し、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンの20ppm水溶液を0.1質量部加え、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンを20ppb(5nmol)含有する本発明の緑茶飲料を得た。このものを飲用したところ、口腔において緑茶本来が持つしっかりとしたグリーン香が時間の経過にともなって強まった。
(Example 7)
0.1 parts by mass of 20 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione is added to 100 parts by mass of green tea extract, and S- (4-methyl-2-pentanone-4-yl) is added. ) The green tea beverage of the present invention containing 20 ppb (5 nmol) of glutathione was obtained. When this was drunk, the firm green aroma inherent to green tea in the oral cavity became stronger over time.
(実施例8)
紅茶抽出液100質量部に対し、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンの1000ppm水溶液を0.1質量部加え、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンを1ppm含有する本発明の紅茶飲料を得た。このものを飲用したところ、口腔において紅茶本来のコクのあるグリーン香が時間の経過にともなって強まった。
(Example 8)
0.1 parts by mass of a 1000 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione was added to 100 parts by mass of black tea extract, and S- (4-methyl-2-pentanone-4-yl) was added. ) A tea beverage of the present invention containing 1 ppm of glutathione was obtained. When this was drunk, the green aroma of the original black tea in the mouth increased with time.
(実施例9)
コーヒー抽出液100質量部に対し、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンの1000ppm水溶液を0.1質量部加え、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンを1ppm含有する本発明のコーヒー飲料を得た。このものを飲用したところ、口腔においてコーヒー特有のロースト香が時間の経過にともなって強まった。
Example 9
0.1 parts by mass of a 1000 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione was added to 100 parts by mass of the coffee extract, and S- (4-methyl-2-pentanone-4-yl) was added. ) A coffee beverage of the present invention containing 1 ppm glutathione was obtained. When this was drunk, the roasted odor unique to coffee in the oral cavity increased with time.
(実施例10)
紅茶抽出液100質量部に対し、S−(1−ヘキサノール−3−イル)グルタチオンの1000ppm水溶液を0.1質量部加え、S−(1−ヘキサノール−3−イル)グルタチオンを1ppm含有する本発明の紅茶飲料を得た。このものを飲用したところ、口腔において紅茶本来の発酵感が時間の経過にともなって強まった。
(Example 10)
0.1 mass part of 1000 ppm aqueous solution of S- (1-hexanol-3-yl) glutathione is added to 100 mass parts of black tea extract, and the present invention contains 1 ppm of S- (1-hexanol-3-yl) glutathione. Got a tea drink. When this was drunk, the original fermented feeling of black tea in the oral cavity increased with time.
(実施例11)
紅茶抽出液100質量部に対し、S−(ヘキサナール−3−イル)グルタチオンの1000ppm水溶液を0.1質量部加え、S−(ヘキサナール−3−イル)グルタチオンを1ppm含有する本発明の紅茶飲料を得た。このものを飲用したところ、口腔において紅茶本来の発酵感やグリーン香が時間の経過にともなって強まった。
(Example 11)
The tea beverage of the present invention containing 1 ppm of S- (hexanal-3-yl) glutathione by adding 0.1 parts by mass of a 1000 ppm aqueous solution of S- (hexanal-3-yl) glutathione to 100 parts by mass of black tea extract. Obtained. When this product was drunk, the original fermented feeling and green scent of black tea in the oral cavity became stronger over time.
(実施例12)
緑茶抽出液100質量部に対し、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンの20ppm水溶液を0.05質量部加え、さらに、S−(4−メチル−2−ペンタノン−4−イル)システインの10ppm水溶液を0.047質量部加え、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンが10ppb(2.5nmol)とS−(4−メチル−2−ペンタノン−4−イル)システインを各々4.7ppb(2.5nmol)含有する本発明の緑茶飲料を得た。このものを飲用したところ、口腔において緑茶本来が持つしっかりとしたコクのあるグリーン香が長時間に亘って持続した。
(Example 12)
0.05 parts by mass of a 20 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione is added to 100 parts by mass of the green tea extract, and further S- (4-methyl-2-pentanone-4 -Il) 0.047 parts by mass of a 10 ppm aqueous solution of cysteine was added, and S- (4-methyl-2-pentanone-4-yl) glutathione was 10 ppb (2.5 nmol) and S- (4-methyl-2-pentanone- The green tea beverage of the present invention containing 4.7 ppb (2.5 nmol) of 4-yl) cysteine was obtained. When this was drunk, the firm and rich green incense inherent in green tea in the oral cavity persisted for a long time.
(実施例13)
無水ケイ酸43質量部、カルボキシメチルセルロースナトリウム1.2質量部、プロピレングリコール2.2質量部、ソルビット液(60%)23質量部、ラウリル硫酸ナトリウム1.4質量部、パラオキシ安息香酸メチル0.1質量部、安息香酸ナトリウム0.3質量部、緑茶抽出物1.0質量部、サッカリンナトリウム0.2質量部、精製水27.6質量部からなる練歯磨を定法に従い得た。この練歯磨100質量部に対し、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンの20ppm水溶液を0.1質量部加え、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンを20ppb(5nmol)含有する本発明の練歯磨を得た。このものを使用したところ、口腔において緑茶本来が持つしっかりとしたグリーン香が時間の経過にともなって強くなった。
(Example 13)
43 parts by weight of anhydrous silicic acid, 1.2 parts by weight of sodium carboxymethylcellulose, 2.2 parts by weight of propylene glycol, 23 parts by weight of sorbite solution (60%), 1.4 parts by weight of sodium lauryl sulfate, 0.1 parts of methyl parahydroxybenzoate A toothpaste consisting of part by mass, 0.3 part by mass of sodium benzoate, 1.0 part by mass of green tea extract, 0.2 part by mass of sodium saccharin, and 27.6 parts by mass of purified water was obtained according to a conventional method. 0.1 parts by mass of a 20 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione was added to 100 parts by mass of this toothpaste, and S- (4-methyl-2-pentanone-4-yl) was added. ) A toothpaste of the present invention containing 20 ppb (5 nmol) of glutathione was obtained. When this product was used, the firm green scent inherent in green tea in the oral cavity became stronger over time.
(実施例14)
エタノール15質量部、グリセリン10質量部、ポリオキシエチレン硬化ヒマシ油2.0質量部、サッカリンナトリウム0.15質量部、安息香酸ナトリウム0.15質量部、リン酸二水素ナトリウム0.1質量部、緑茶抽出物1.0質量部、精製水71.6質量部からなる洗口剤を定法に従い得た。この洗口剤100質量部に対し、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンの20ppm水溶液を0.1質量部加え、S−(4−メチル−2−ペンタノン−4−イル)グルタチオンを20ppb(5nmol)含有する本発明の洗口剤を得た。このものを使用したところ、口腔において緑茶本来が持つしっかりとしたグリーン香が時間の経過にともなって強くなった。
(Example 14)
Ethanol 15 parts by weight, glycerin 10 parts by weight, polyoxyethylene hydrogenated castor oil 2.0 parts by weight, saccharin sodium 0.15 parts by weight, sodium benzoate 0.15 parts by weight, sodium dihydrogen phosphate 0.1 parts by weight, green tea A mouthwash comprising 1.0 part by mass of extract and 71.6 parts by mass of purified water was obtained according to a conventional method. 0.1 parts by mass of a 20 ppm aqueous solution of S- (4-methyl-2-pentanone-4-yl) glutathione was added to 100 parts by mass of this mouthwash, and S- (4-methyl-2-pentanone-4- I) A mouthwash of the present invention containing 20 ppb (5 nmol) of glutathione was obtained. When this product was used, the firm green scent inherent in green tea in the oral cavity became stronger over time.
(比較例1)
緑茶抽出液100質量部に対し、4−メルカプト−4−メチルペンタン−2−オンの10ppm水溶液を0.1質量部加え、4−メルカプト−4−メチルペンタン−2−オンを6.5ppb(5nmol)含有する本発明の緑茶飲料を得た。
(Comparative Example 1)
0.1 parts by mass of a 10 ppm aqueous solution of 4-mercapto-4-methylpentan-2-one is added to 100 parts by mass of green tea extract, and 6.5 ppb (5 nmol) of 4-mercapto-4-methylpentan-2-one is added. The green tea beverage of the present invention contained was obtained.
〔試験例1〕
実施例1、12および比較例1で得られたそれぞれの緑茶飲料について、5名のパネルによる官能評価を行った結果を表1に示す。それぞれの緑茶飲料を飲用し、30秒あるいは60秒後の口腔に残る香味(緑茶本来が持つしっかりとしたコクのあるグリーン香)の強さについて、「強い:7〜弱い:1」の7段階で評価した。
[Test Example 1]
Table 1 shows the results of sensory evaluation of each of the green tea beverages obtained in Examples 1 and 12 and Comparative Example 1 using a panel of five people. Seven levels of “strong: 7 to weak: 1” regarding the strength of the flavor (green tea with a firm and rich green tea inherent in the green tea) remaining in the oral cavity after 30 or 60 seconds of drinking each green tea beverage It was evaluated with.
本発明の持続性香気賦与剤を飲食物等の口腔内製品に添加することにより、口腔における良質な香気の持続性を向上でき、さらには当該持続性香気賦与剤を配合した香料組成物、飲食物、口腔用製品、中でも特に優れた茶飲料を提供することができる。 By adding the persistent fragrance imparting agent of the present invention to oral products such as foods and drinks, it is possible to improve the persistence of good quality fragrance in the oral cavity, and further, a fragrance composition containing the persistent fragrance imparting agent, food and drink Products, products for oral cavity, and particularly excellent tea beverages can be provided.
Claims (9)
R1−S−R2 (1) An organic compound represented by the following general formula (1), R 1 -SH is glutathione, and R 2 is 4-methyl-2-pentanone-4-yl group, 1-hexanol-3-yl A persistent fragrance imparting agent composition comprising an organic compound which is a group or a 1-hexanal-3-yl group.
R 1 -S-R 2 (1)
RR 11 −S−R-S-R 22 (2) (2)
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