JP2001163719A - Tyrosinase activity inhibitor - Google Patents
Tyrosinase activity inhibitorInfo
- Publication number
- JP2001163719A JP2001163719A JP34722599A JP34722599A JP2001163719A JP 2001163719 A JP2001163719 A JP 2001163719A JP 34722599 A JP34722599 A JP 34722599A JP 34722599 A JP34722599 A JP 34722599A JP 2001163719 A JP2001163719 A JP 2001163719A
- Authority
- JP
- Japan
- Prior art keywords
- tyrosinase activity
- group
- activity inhibitor
- formula
- methoxy group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Cosmetics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
Description
【発明の属する技術分野】本発明は、チロシナーゼ活性
阻害剤およびそのチロシナーゼ活性阻害剤を含有する皮
膚外用剤と食品褐変防止剤に関するものである。TECHNICAL FIELD The present invention relates to a tyrosinase activity inhibitor, an external preparation for skin containing the tyrosinase activity inhibitor, and a food browning inhibitor.
【従来の技術】チロシナーゼは、種々のカテコール誘導
体を基質とする酸化酵素である。そのほとんどがモノフ
ェノールモノオキシゲナーゼ活性を有し、モノフェノー
ルを基質として、オルト-ジフェノールを生じ、さらに
オルト-キノン類に酸化する。この酸化酵素は広く自然
界に分布し、キノコやジャガイモ、リンゴなどの植物、
動物の色素細胞に存在する。動物中の酸化酵素は、特に
チロシン、ドーパに対して高い活性を示し、メラニンの
生合成に深く関与する。メラニンは、チロシン→Ｌ−ド
ーパ→ドーパキノン→ドーパクロム→５,６ジヒドロキ
シインドール→インドール−５,６−キノン→メラニン
の過程を経て生成され、チロシナーゼは、チロシン→Ｌ
−ドーパ→ドーパキノンの酸化過程に関与している。メ
ラニンは毛髪や肌の色を決定している色素である。この
色素は、皮膚では表皮基底層に存在するメラノサイトに
おいて、光や紫外線に反応して生成される。皮膚におけ
るメラニン生成は、紫外線等による悪影響から人間を防
御する役目を担っている。しかしながら、大量に光や紫
外線を浴びるなどの刺激があると、メラニン生成機能が
局部的に持続し、その部分の皮膚が黒化してしまう。そ
の結果、色素が沈着するなど、しみ・そばかすを形成し
て、やがては皮膚の老化を促進してしまう。また、リン
ゴやヤマイモ、レタスなどの野菜・果物を切断すると、
切断面が褐色変化する現象もメラニン色素が関与してい
る。切断面が褐変した青果物は、商品価値が低下して長
期間保存することは困難である。美白を促進したり、食
品の褐変化を防止する目的で、従来、チロシナーゼの活
性阻害剤が使用されてきている。チロシナーゼの活性阻
害剤としては、例えば、ビタミンＣ（特開平２-４５４
０８号公報等）、アルブチン、植物などから抽出された
エキス（特開平６-４０８９６号公報等）、および亜硫
酸塩類などが知られている。しかしながら、ビタミンＣ
は自身の還元作用から酸化されやすく不安定で、保存上
の問題がある。また、アルブチンは、耐熱安定性などに
問題があり、これも取扱い上の問題がある。植物抽出物
は、化学組成の同定が難しく、ロット間での品質のばら
つきが懸念されている。亜硫酸塩類は、人体への皮膚刺
激性が認められ、安全上の問題がある。一方、食品香料
として用いられている芳香族アルデヒド類に、チロシナ
ーゼ阻害活性を持つものが知られているが（油化学、４
３（７）、５７４〜５７８、１９９４年等）、それ自体
のもつ色調によって食品等を着色してしまうなどの問題
がある。2. Description of the Related Art Tyrosinase is an oxidase using various catechol derivatives as substrates. Most of them have monophenol monooxygenase activity, and use monophenol as a substrate to generate ortho-diphenol and further oxidize to ortho-quinones. This oxidase is widely distributed in nature, such as mushrooms, potatoes, apples and other plants,
Present in animal pigment cells. Oxidases in animals have high activity especially on tyrosine and dopa, and are deeply involved in melanin biosynthesis. Melanin is produced through the process of tyrosine → L-dopa → dopaquinone → dopachrome → 5.6 dihydroxyindole → indole-5,6-quinone → melanin, and tyrosinase is tyrosine → L
-Dopa → involved in the oxidation process of dopaquinone. Melanin is a pigment that determines the color of hair and skin. This pigment is generated in the skin in the melanocytes present in the basal layer of the epidermis in response to light and ultraviolet rays. Melanin production in the skin plays a role in protecting humans from the adverse effects of ultraviolet rays and the like. However, when there is a stimulus such as exposure to a large amount of light or ultraviolet light, the melanin-producing function is locally maintained, and the skin in that part darkens. As a result, spots and freckles are formed, such as the deposition of pigments, and the aging of the skin is eventually promoted. Also, when cutting vegetables and fruits such as apples, yams and lettuce,
The phenomenon in which the cut surface turns brown is also related to the melanin pigment. Vegetables with a brown cut surface have low commercial value and are difficult to store for a long time. Conventionally, tyrosinase activity inhibitors have been used for the purpose of promoting whitening and preventing browning of foods. Examples of the tyrosinase activity inhibitor include vitamin C (Japanese Patent Laid-Open No. 2-454).
08, etc.), arbutin, extracts extracted from plants and the like (JP-A-6-40896, etc.), sulfites, and the like. However, vitamin C
Is liable to be oxidized by its own reducing action, is unstable, and has a storage problem. Arbutin also has a problem in heat stability and the like, which also has a problem in handling. For the plant extract, it is difficult to identify the chemical composition, and there is a concern about variation in quality among lots. Sulfites are irritating to the human body and cause safety problems. On the other hand, among aromatic aldehydes used as food flavors, those having tyrosinase inhibitory activity are known (Oil Chemistry,
3 (7), 574 to 578, 1994), there is a problem that food and the like are colored by the color tone of the food itself.
【発明が解決しようとする課題】本発明の目的は、人体
への安全性が高く、耐熱性などの安定性に優れ、着色な
どの問題がない、純度の高いチロシナーゼ活性阻害剤を
提供することにある。本発明者らは上記課題を解決する
ために鋭意検討を行なった結果、フラノン化合物、フェ
ネチルメチルエーテル化合物、デセン酸類、芳香族アル
デヒド類に高いチロシナーゼ活性阻害効果を持つことを
見い出し本発明に至った。SUMMARY OF THE INVENTION An object of the present invention is to provide a high-purity tyrosinase activity inhibitor which is highly safe for the human body, has excellent stability such as heat resistance, and has no problems such as coloring. It is in. The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that furanone compounds, phenethyl methyl ether compounds, decenoic acids, and aromatic aldehydes have a high tyrosinase activity inhibitory effect, and have led to the present invention. .
【課題を解決するための手段】本発明のチロシナーゼ活
性阻害剤は、下記一般式（１）〜（６）：Means for Solving the Problems The tyrosinase activity inhibitor of the present invention has the following general formulas (1) to (6):
【化７】 （式中、R1 、R2 は炭素数１〜２のアルキル基を表
す。）、Embedded image (Wherein, R 1 and R 2 represent an alkyl group having 1 to 2 carbon atoms),
【化８】 （式中、R3 はメトキシ基、R4 はアルデヒド基またはメ
トキシ基を表す。）、Embedded image (In the formula, R 3 represents a methoxy group, and R 4 represents an aldehyde group or a methoxy group.)
【化９】 （式中、R5 、R6 は水素または水酸基を表し、少なくと
も一つの水酸基を有することを表す。）、Embedded image (Wherein, R 5 and R 6 represent hydrogen or a hydroxyl group, and have at least one hydroxyl group.)
【化１０】 （式中、R7 〜R10は水素またはメチル基を表し、少なく
とも一つのメチル基を表す。）、Embedded image (Wherein, R 7 to R 10 represent hydrogen or a methyl group, and represent at least one methyl group.)
【化１１】 （式中、R11、R12はどちらか一方がメトキシ基で、他方
が水素であることを表す。)、Embedded image (In the formula, one of R 11 and R 12 represents a methoxy group and the other represents hydrogen.)
【化１２】 （式中、破線部は二重結合の位置を示し、少なくとも１
つの二重結合を有することを表す。）で示される化合物
の少なくとも一つを有効成分とするチロシナーゼ活性阻
害剤である。また、本発明の皮膚外用剤は、下記一般式
（１）〜（６）：Embedded image (Wherein the dashed line indicates the position of the double bond and at least one
It has two double bonds. A tyrosinase activity inhibitor comprising at least one of the compounds represented by the formula (1) as an active ingredient. Further, the external preparation for skin of the present invention has the following general formulas (1) to (6):
【化１３】 （式中、R1 、R2 は炭素数１〜２のアルキル基を表
す。）、Embedded image (Wherein, R 1 and R 2 represent an alkyl group having 1 to 2 carbon atoms),
【化１４】 （式中、R3 はメトキシ基、R4 はアルデヒド基またはメ
トキシ基を表す。）、Embedded image (In the formula, R 3 represents a methoxy group, and R 4 represents an aldehyde group or a methoxy group.)
【化１５】 （式中、R5 、R6 は水素または水酸基を表し、少なくと
も一つの水酸基を有することを表す。）、Embedded image (Wherein, R 5 and R 6 represent hydrogen or a hydroxyl group, and have at least one hydroxyl group.)
【化１６】 （式中、R7 〜R10は水素またはメチル基を表し、少なく
とも一つのメチル基を表す。）、Embedded image (Wherein, R 7 to R 10 represent hydrogen or a methyl group, and represent at least one methyl group.)
【化１７】 （式中、R11、R12はどちらか一方がメトキシ基で、他方
が水素であることを表す。)、Embedded image (In the formula, one of R 11 and R 12 represents a methoxy group and the other represents hydrogen.)
【化１８】 （式中、破線部は二重結合の位置を示し、少なくとも１
つの二重結合を有することを表す。）で示される化合物
の少なくとも一つを有効成分として含有する皮膚外用剤
である。また、本発明の食品褐変防止剤は、下記一般式
（１）〜（６）：Embedded image (Wherein the dashed line indicates the position of the double bond and at least one
It has two double bonds. A skin external preparation containing at least one of the compounds represented by the formula (1) as an active ingredient. Further, the food browning inhibitor of the present invention has the following general formulas (1) to (6):
【化１９】 （式中、R1 、R2 は炭素数１〜２のアルキル基を表
す。）、Embedded image (Wherein, R 1 and R 2 represent an alkyl group having 1 to 2 carbon atoms),
【化２０】 （式中、R3 はメトキシ基、R4 はアルデヒド基またはメ
トキシ基を表す。）、Embedded image (In the formula, R 3 represents a methoxy group, and R 4 represents an aldehyde group or a methoxy group.)
【化２１】 （式中、R5 、R6 は水素または水酸基を表し、少なくと
も一つの水酸基を有することを表す。）、Embedded image (Wherein, R 5 and R 6 represent hydrogen or a hydroxyl group, and have at least one hydroxyl group.)
【化２２】 （式中、R7 〜R10は水素またはメチル基を表し、少なく
とも一つのメチル基を表す。）、Embedded image (Wherein, R 7 to R 10 represent hydrogen or a methyl group, and represent at least one methyl group.)
【化２３】 （式中、R11、R12はどちらか一方がメトキシ基で、他方
が水素であることを表す。)、Embedded image (In the formula, one of R 11 and R 12 represents a methoxy group and the other represents hydrogen.)
【化２４】 （式中、破線部は二重結合の位置を示し、少なくとも１
つの二重結合を有することを表す。）で示される化合物
の少なくとも一つを有効成分として含有する食品褐変防
止剤である。Embedded image (Wherein the dashed line indicates the position of the double bond and at least one
It has two double bonds. A food browning inhibitor comprising at least one of the compounds represented by the formula (1) as an active ingredient.
【発明の実施の形態】チロシナーゼ活性阻害効果を持つ
これらの化合物のうち、下記式（１）：BEST MODE FOR CARRYING OUT THE INVENTION Among these compounds having a tyrosinase activity inhibiting effect, the following formula (1):
【化２５】 （式中、R1 、R2 は炭素数１〜２のアルキル基を表
す。）で示される化合物としては、3-ヒドロキシ-4,5-
ジエチル-2(5H)-フラノン等が挙げられ、特に好ましい
化合物として、3-ヒドロキシ-4,5-ジメチル-2(5H)-フラ
ノンや3-ヒドロキシ-4-メチル-5-エチル-2(5H)-フラノ
ンが挙げられる。また、下記式（２）：Embedded image (Wherein, R 1 and R 2 represent an alkyl group having 1 to 2 carbon atoms).
Diethyl-2 (5H) -furanone and the like, particularly preferred compounds are 3-hydroxy-4,5-dimethyl-2 (5H) -furanone and 3-hydroxy-4-methyl-5-ethyl-2 (5H ) -Furanone. Also, the following equation (2):
【化２６】 （式中、R3 はメトキシ基、R4 はアルデヒド基、または
メトキシ基を表す。）で示される化合物としては、4-メ
トキシフェネチルメチルエーテル等が挙げられ、特に好
ましい化合物としては、フェニルアセトアルデヒドが挙
げられる。また、下記式（３）：Embedded image (Wherein, R 3 represents a methoxy group, R 4 represents an aldehyde group or a methoxy group.) Examples of the compound represented by the formula include 4-methoxyphenethyl methyl ether and the like, and a particularly preferred compound is phenylacetaldehyde. No. Also, the following equation (3):
【化２７】 （式中、R5 、R6 は水素、または水酸基を表し、少なく
とも一つの水酸基を有することを表す。）で示される化
合物としては、3-ヒドロキシベンズアルデヒド等が挙げ
られる。特に好ましい化合物として、4-ヒドロキシベン
ズアルデヒドが挙げられる。また、下記式（４）：Embedded image (Wherein, R 5 and R 6 each represent hydrogen or a hydroxyl group, and have at least one hydroxyl group). Examples of the compound represented by the formula include 3-hydroxybenzaldehyde. Particularly preferred compounds include 4-hydroxybenzaldehyde. Also, the following equation (4):
【化２８】 （式中、R7 〜R10は水素またはメチル基を表し、少なく
とも一つのメチル基を表す。）で示される化合物として
は、2-メチルベンズアルデヒド等が挙げられる。特に好
ましい化合物として3-メチルベンズアルデヒドが挙げら
れる。また、下記式（５）：Embedded image (In the formula, R 7 to R 10 represent hydrogen or a methyl group, and represent at least one methyl group.) Examples of the compound represented by the formula include 2-methylbenzaldehyde. A particularly preferred compound is 3-methylbenzaldehyde. Also, the following equation (5):
【化２９】 （式中R11、R12はどちらか一方がメトキシ基で、他方が
水素であることを表す。）で示される化合物としては、
2-メトキシシンナムアルデヒド等が挙げられる。特に好
ましい化合物として、4-メトキシシンナムアルデヒドが
挙げられる。さらに、下記式（６）：Embedded image (Wherein R 11 and R 12 represent that one of them is a methoxy group and the other is hydrogen.)
2-methoxycinnamaldehyde and the like. Particularly preferred compounds include 4-methoxycinnamaldehyde. Further, the following formula (6):
【化３０】 （式中、破線部は二重結合の位置を示し、少なくとも１
つの二重結合を有することを表す。）で示される化合物
としては、9-デセン酸等が挙げられ、特に好ましい化合
物としてはtrans-3-デセン酸、trans-4-デセン酸、5-デ
セン酸、6-デセン酸、もしくはこれら化合物の混合物等
が挙げられる。本発明で用いられる上記一般式で示され
る化合物は、チロシナーゼ活性阻害作用を持つことか
ら、メラニン生成抑制を作用機序とする化粧品、医薬
品、医薬部外品、外用薬、食品、食品添加物および、飼
料等に、従来のチロシナーゼ活性阻害剤と同様に利用可
能であり、特に皮膚外用剤および食品褐変防止剤に好適
に用いられる。また、本発明のチロシナーゼ活性阻害剤
は、従来のチロシナーゼ活性阻害剤と併用することが可
能である。本発明のチロシナーゼ活性阻害剤の適用量
は、目的や用途等によるが、通常０.００１〜１０重量
％、好ましくは０.０１〜１重量％程度である。本発明
のチロシナーゼ活性阻害剤は、皮膚外用剤に好適であ
る。本発明のチロシナーゼ活性阻害剤を皮膚外用剤とし
て利用する場合の剤型としては、クリーム、乳液、ファ
ウンデーション、パック、ローション、ゲル状、溶液
状、スティック状等がある。また、これらには適宜の成
分、例えば、油剤、保湿剤、増粘剤、防腐剤、乳化剤、
顔料、pH調製剤、他の薬効成分、紫外線吸収剤、香料等
など一般に用いられる各種成分を配合することもでき
る。また、本発明のチロシナーゼ活性阻害剤は、食品等
に好適である。本発明のチロシナーゼ活性阻害剤を食品
等に適用する場合は、野菜や果物等の青果物の切断面に
適当量を噴霧、塗布、浸漬すればよい。Embedded image (Wherein the dashed line indicates the position of the double bond and at least one
It has two double bonds. 9) -Decenoic acid and the like, and particularly preferred compounds are trans-3-decenoic acid, trans-4-decenoic acid, 5-decenoic acid, 6-decenoic acid, or a compound of these compounds. Mixtures and the like can be mentioned. The compound represented by the above general formula used in the present invention has a tyrosinase activity inhibitory action, so that cosmetics, pharmaceuticals, quasi-drugs, topical drugs, foods, food additives, and the like have melanin production inhibition as a mechanism of action. It can be used in feeds and the like in the same manner as conventional tyrosinase activity inhibitors, and is particularly suitably used as an external preparation for skin and an anti-browning agent for food. Further, the tyrosinase activity inhibitor of the present invention can be used in combination with a conventional tyrosinase activity inhibitor. The application amount of the tyrosinase activity inhibitor of the present invention is usually 0.001 to 10% by weight, preferably about 0.01 to 1% by weight, depending on the purpose and use. The tyrosinase activity inhibitor of the present invention is suitable for a skin external preparation. When the tyrosinase activity inhibitor of the present invention is used as an external preparation for skin, examples of the dosage form include creams, emulsions, foundations, packs, lotions, gels, solutions, and sticks. In addition, these have appropriate components, for example, oils, humectants, thickeners, preservatives, emulsifiers,
Various commonly used components such as pigments, pH adjusters, other medicinal components, ultraviolet absorbers, fragrances and the like can also be blended. The tyrosinase activity inhibitor of the present invention is suitable for foods and the like. When the tyrosinase activity inhibitor of the present invention is applied to foods or the like, an appropriate amount of the tyrosinase activity inhibitor may be sprayed, applied, or dipped on cut surfaces of fruits and vegetables such as vegetables and fruits.
【実施例】以下、試験例および実施例によって本発明に
よるチロシナーゼ活性阻害効果を明らかにするが、本発
明はこれらに限定されるものではない。EXAMPLES The tyrosinase activity inhibitory effect of the present invention will be clarified by Test Examples and Examples, but the present invention is not limited thereto.
【実施例１】（試験例１〜９、比較例１、２）チロシナ
ーゼ活性阻害試験測定原理は、L-ドーパにチロシナーゼ
を作用させて生成するドーパクロムを測定するものであ
る。１％Tween 80を含む10mMリン酸緩衝液（pH6.8）2.7
ml に1200ユニット/ml のチロシナーゼ（SIGMA社製）溶
液0.1ml とジメチルスルフォキシド（以下DMSO）に適宜
希釈した表１の各香料化合物0.2ml をそれぞれ混合し
て、30℃で10分間インキュベートした。次いで、10mM L
-ドーパ溶液1ml を加えて30℃で10分間インキュベート
した後、アジ化ナトリウムを加えて酵素反応を停止し、
475nmにおける吸光度を測定した。チロシナーゼ活性阻
害の効果は、以下の式により算出し、表１に示した。 ｛[（B−Bc）−（S−Sc）]/（B−Bc）｝×１００（％） S：サンプル添加時の吸光度 Sc：サンプル添加時の比較対照として、酵素溶液の代わ
りにリン酸緩衝液を加えて同様の操作をしたときの吸光
度。 B：サンプルの代わりにＤＭＳＯを加えて同様に操作し
た時の吸光度。 Bc：サンプルの代わりにＤＭＳＯを、酵素の代わりにリ
ン酸緩衝液を加えて同様に操作した時の吸光度。 この結果、表１に示すようにフラノン化合物、および4-
メトキシフェネチルメチルエーテル、およびフェニルア
セトアルデヒド、およびデセン酸類は、既知のチロシナ
ーゼ活性阻害剤であるオイゲノールやコウジ酸に比べて
チロシナーゼ活性阻害効果が高いことが示された。Example 1 (Test Examples 1 to 9, Comparative Examples 1 and 2) Tyrosinase activity inhibition test The measurement principle is to measure dopachrome produced by allowing tyrosinase to act on L-dopa. 10 mM phosphate buffer (pH 6.8) containing 1% Tween 80 2.7
To each ml, 0.1 ml of a tyrosinase (manufactured by SIGMA) solution at 1200 units / ml and 0.2 ml of each of the flavor compounds shown in Table 1 appropriately diluted in dimethyl sulfoxide (hereinafter referred to as DMSO) were mixed and incubated at 30 ° C. for 10 minutes. . Then 10mM L
-Add 1 ml of dopa solution, incubate for 10 minutes at 30 ° C, stop the enzymatic reaction by adding sodium azide,
The absorbance at 475 nm was measured. The effect of tyrosinase activity inhibition was calculated by the following equation and is shown in Table 1. {[(B-Bc)-(S-Sc)] / (B-Bc)} × 100 (%) S: Absorbance at sample addition Sc: Phosphoric acid instead of enzyme solution as a control for sample addition Absorbance when the same operation was performed with the addition of a buffer. B: Absorbance when DMSO was added instead of the sample and the same operation was performed. Bc: Absorbance when DMSO was added in place of the sample and phosphate buffer was added in place of the enzyme and the same operation was performed. As a result, as shown in Table 1, the furanone compound and 4-
It was shown that methoxyphenethyl methyl ether, phenylacetaldehyde, and decenoic acids have a higher tyrosinase activity inhibitory effect than known tyrosinase activity inhibitors, eugenol and kojic acid.
【表１】 [Table 1]
【実施例２】下記表２の組成の化粧水は、常法に従い、
下表、をそれぞれ室温で混合溶解した後、をに
徐々に加えて撹拌混合して調製した。Example 2 A lotion having the composition shown in Table 2 below was prepared according to a conventional method.
After mixing and dissolving each of the following tables at room temperature, the mixture was gradually added to and stirred and mixed.
【表２】 得られた化粧水は、美白作用に優れ、さっぱりした使用
感のものであった。また、保存安定性にも優れていた。[Table 2] The obtained lotion was excellent in whitening action and had a refreshing feeling. In addition, the storage stability was excellent.
【実施例３】下記表３の組成の乳液は、常法に従い、下
表、をそれぞれ８０℃に加熱溶解し、撹拌しながら
をに徐々に加えて乳化して調製した。Example 3 Emulsions having the compositions shown in Table 3 below were prepared by dissolving each of the following Tables by heating at 80 ° C. and gradually adding the resulting mixture while stirring to emulsify the emulsions according to a conventional method.
【表３】 得られた乳液は、美白作用に優れ、しっとりした使用感
のものであった。また、保存安定性にも優れていた。[Table 3] The obtained emulsion was excellent in whitening effect and had a moist feeling. In addition, the storage stability was excellent.
【実施例４】下記表４の組成のクリームは、常法に従
い、下表、をそれぞれ８０℃に加熱溶解し、撹拌し
ながらをに徐々に加えて乳化し、３５℃まで冷却し
て調製した。Example 4 A cream having the composition shown in Table 4 below was prepared by heating and dissolving each of the following at 80 ° C., gradually adding to the mixture with stirring to emulsify, and cooling to 35 ° C. in accordance with a conventional method. .
【表４】 得られたクリームは美白作用に優れ、しっとりした使用
感のものであった。また、耐熱性もあり保存安定性にも
優れていた。[Table 4] The resulting cream had an excellent whitening effect and had a moist feeling. In addition, it had heat resistance and excellent storage stability.
【実施例５】リンゴ果実を裁断し、厚さ１cm、長さ３cm
の直方体の断片を作製した。上述の式（１）で、R1 、R
2 がメチル基であるフラノン化合物 [ 3-ヒドロキシ-4,
5-ジメチル-2(5H)-フラノン ] を含有するエタノール溶
液を調製して、この溶液を水に希釈して上記フラノン化
合物を２μg/ml 含有する水溶液を調製した。この溶液
に作製直後のリンゴ断片を入れ、３時間後、リンゴ断片
の褐変度を観察したが、目視で褐変を確認できなかっ
た。Example 5 An apple fruit was cut into a piece having a thickness of 1 cm and a length of 3 cm.
Was prepared. In the above equation (1), R 1 , R
Furanone compound in which 2 is a methyl group [3-hydroxy-4,
5-dimethyl-2 (5H) -furanone] was prepared, and this solution was diluted with water to prepare an aqueous solution containing the above furanone compound at 2 μg / ml. The apple fragment immediately after preparation was added to this solution, and after 3 hours, the degree of browning of the apple fragment was observed, but no browning could be confirmed visually.
【実施例６】3-ヒドロキシ-4-メチル-5-エチル-2(5H)-
フラノンを含有するエタノール溶液と4-メトキシシンナ
ムアルデヒドを含有するエタノール溶液を混合して、そ
れぞれを１μg/ml 含有する水溶液を調製した。この溶
液に作製直後のリンゴ断片を入れて、５時間後、リンゴ
断片の褐変度を観察したが、目視で褐変を確認できなか
った。Example 6 3-hydroxy-4-methyl-5-ethyl-2 (5H)-
An ethanol solution containing furanone and an ethanol solution containing 4-methoxycinnamaldehyde were mixed to prepare an aqueous solution containing 1 μg / ml of each. The apple fragments immediately after preparation were added to this solution, and after 5 hours, the degree of browning of the apple fragments was observed, but no browning could be confirmed visually.
【比較例３】実施例５および実施例６と同様に、水に作
製直後のリンゴ断片を入れて、５時間後リンゴ断片の褐
変度を観察した。この場合は目視で容易に褐変化を確認
することができた。Comparative Example 3 In the same manner as in Examples 5 and 6, the freshly prepared apple pieces were placed in water, and after 5 hours, the degree of browning of the apple pieces was observed. In this case, the browning could be easily confirmed visually.
【発明の効果】以上記載のごとく、本発明のチロシナー
ゼ活性阻害剤は、その構成成分が既に香料として一般的
に使用されていて安全性も高いことから、皮膚外用剤や
食品・食品添加物として用いても人体に対する副作用の
心配がない。しかも、本発明で用いられる化合物は、低
濃度で高いチロシナーゼ活性阻害効果を有するが、これ
らを、紫外線などによるメラニンの過剰生成の結果形成
されるシミ・ソバカスや色素沈着を予防する化粧品等皮
膚外用剤への配合や、食品の褐色変化の防止への利用が
可能なチロシナーゼ活性阻害剤として提供することがで
きる。As described above, the tyrosinase activity inhibitor of the present invention is already used as a fragrance and its safety is high. There is no concern about side effects on the human body when used. Moreover, the compound used in the present invention has a high tyrosinase activity inhibitory effect at a low concentration, but these compounds are used for external application to skin such as cosmetics for preventing spots and freckles formed as a result of excessive production of melanin by ultraviolet rays and the like and pigmentation. The present invention can be provided as a tyrosinase activity inhibitor that can be used in an agent or for preventing browning of food.
フロントページの続き (72)発明者 長谷部 昭雄 千葉県野田市船形1573−４ 曽田香料株式 会社野田支社内 Ｆターム(参考） 4C083 AA082 AC022 AC072 AC102 AC122 AC211 AC212 AC242 AC251 AC432 AC442 AC841 AC842 BB60 CC04 CC05 EE16 4C086 AA01 AA02 BA03 MA04 NA14 ZA89 ZC20 Continuing on the front page (72) Inventor Akio Hasebe 1573-4 Funagata, Noda City, Chiba Prefecture F-term (reference) 4C083 AA082 AC022 AC072 AC102 AC122 AC211 AC212 AC242 AC251 AC432 AC442 AC841 AC842 BB60 CC04 CC05 EE16 4C086 AA01 AA02 BA03 MA04 NA14 ZA89 ZC20
Claims (4)
す。）、 【化２】 （式中、R3 はメトキシ基、R4 はアルデヒド基またはメ
トキシ基を表す。） 【化３】 （式中、R5 、R6 は水素または水酸基を表し、少なくと
も一つの水酸基を有することを表す。）、 【化４】 （式中、R7 〜R10は水素またはメチル基を表し、少なく
とも一つのメチル基を表す。）、 【化５】 （式中、R11、R12はどちらか一方がメトキシ基で、他方
が水素であることを表す。)、 【化６】 （式中、破線部は二重結合の位置を示し、少なくとも１
つの二重結合を有することを表す。）で示される化合物
の少なくとも一つを有効成分として含有するチロシナー
ゼ活性阻害剤。1. The following general formulas (1) to (6): (In the formula, R 1 and R 2 each represent an alkyl group having 1 to 2 carbon atoms.) (In the formula, R 3 represents a methoxy group, and R 4 represents an aldehyde group or a methoxy group.) (Wherein, R 5 and R 6 represent hydrogen or a hydroxyl group, and have at least one hydroxyl group). (Wherein, R 7 to R 10 represent hydrogen or a methyl group, and represent at least one methyl group). (In the formula, one of R 11 and R 12 represents a methoxy group and the other represents hydrogen.) (Wherein the dashed line indicates the position of the double bond and at least one
It has two double bonds. A tyrosinase activity inhibitor comprising at least one of the compounds represented by the formula (1) as an active ingredient.
剤において、3-ヒドロキシ-4,5-ジメチル-2(5H)-フラノ
ン、3-ヒドロキシ-4-メチル-5-エチル-2(5H)-フラノ
ン、4-メトキシフェネチルメチルエーテル、フェニルア
セトアルデヒド、4-ヒドロキシベンズアルデヒド、3-メ
チルベンズアルデヒド、4-メトキシシンナムアルデヒ
ド、9-デセン酸、3-デセン酸、4-デセン酸、5-デセン
酸、6-デセン酸の少なくとも一つを有効成分として含有
することを特徴とするチロシナーゼ活性阻害剤。2. The tyrosinase activity inhibitor according to claim 1, wherein 3-hydroxy-4,5-dimethyl-2 (5H) -furanone and 3-hydroxy-4-methyl-5-ethyl-2 (5H) are used. -Furanone, 4-methoxyphenethyl methyl ether, phenylacetaldehyde, 4-hydroxybenzaldehyde, 3-methylbenzaldehyde, 4-methoxycinnamaldehyde, 9-decenoic acid, 3-decenoic acid, 4-decenoic acid, 5-decenoic acid, 6 -A tyrosinase activity inhibitor comprising at least one of decenoic acid as an active ingredient.
活性阻害剤を含有する皮膚外用剤。3. An external preparation for skin containing the tyrosinase activity inhibitor according to claim 1 or 2.
活性阻害剤を含有する食品褐変防止剤。A food browning inhibitor comprising the tyrosinase activity inhibitor according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34722599A JP4239126B2 (en) | 1999-12-07 | 1999-12-07 | Tyrosinase activity inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34722599A JP4239126B2 (en) | 1999-12-07 | 1999-12-07 | Tyrosinase activity inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001163719A true JP2001163719A (en) | 2001-06-19 |
| JP4239126B2 JP4239126B2 (en) | 2009-03-18 |
Family
ID=18388781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34722599A Expired - Lifetime JP4239126B2 (en) | 1999-12-07 | 1999-12-07 | Tyrosinase activity inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4239126B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006056858A (en) * | 2004-08-24 | 2006-03-02 | Soda Aromatic Co Ltd | Body temperature-raising agent |
| JP2006219471A (en) * | 2004-03-30 | 2006-08-24 | Soda Aromatic Co Ltd | Arachidonic acid metabolism inhibitor |
| JP2013067659A (en) * | 2013-01-10 | 2013-04-18 | Soda Aromatic Co Ltd | Platelet aggregation inhibitor |
| WO2013146437A1 (en) * | 2012-03-26 | 2013-10-03 | シーシーアイ株式会社 | 3-decenoic acid derivative and use for same |
| WO2014077334A1 (en) | 2012-11-15 | 2014-05-22 | 株式会社資生堂 | Melanin production inhibitor |
| JP5783612B2 (en) * | 2010-02-24 | 2015-09-24 | 国立大学法人北海道大学 | Maillard reaction inhibitor, α-dicarbonyl compound decomposing agent, and Maillard reaction suppression method |
| WO2021070851A1 (en) * | 2019-10-07 | 2021-04-15 | 花王株式会社 | Anti-browning agent for leafy vegetables |
-
1999
- 1999-12-07 JP JP34722599A patent/JP4239126B2/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006219471A (en) * | 2004-03-30 | 2006-08-24 | Soda Aromatic Co Ltd | Arachidonic acid metabolism inhibitor |
| JP4657778B2 (en) * | 2004-03-30 | 2011-03-23 | 曽田香料株式会社 | Arachidonic acid metabolism inhibitor |
| JP4657653B2 (en) * | 2004-08-24 | 2011-03-23 | 曽田香料株式会社 | Body temperature raising agent |
| JP2006056858A (en) * | 2004-08-24 | 2006-03-02 | Soda Aromatic Co Ltd | Body temperature-raising agent |
| JP5783612B2 (en) * | 2010-02-24 | 2015-09-24 | 国立大学法人北海道大学 | Maillard reaction inhibitor, α-dicarbonyl compound decomposing agent, and Maillard reaction suppression method |
| JPWO2013146437A1 (en) * | 2012-03-26 | 2015-12-10 | 飯沼 宗和 | 3-Decenoic acid derivatives and uses thereof |
| WO2013146437A1 (en) * | 2012-03-26 | 2013-10-03 | シーシーアイ株式会社 | 3-decenoic acid derivative and use for same |
| WO2014077334A1 (en) | 2012-11-15 | 2014-05-22 | 株式会社資生堂 | Melanin production inhibitor |
| KR20150082191A (en) | 2012-11-15 | 2015-07-15 | 가부시키가이샤 시세이도 | Melanin production inhibitor |
| JP2013067659A (en) * | 2013-01-10 | 2013-04-18 | Soda Aromatic Co Ltd | Platelet aggregation inhibitor |
| WO2021070851A1 (en) * | 2019-10-07 | 2021-04-15 | 花王株式会社 | Anti-browning agent for leafy vegetables |
| JP2021058130A (en) * | 2019-10-07 | 2021-04-15 | 花王株式会社 | Browning inhibitor for leaf vegetable |
| JP7390844B2 (en) | 2019-10-07 | 2023-12-04 | 花王株式会社 | Anti-browning agent for leafy vegetables |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4239126B2 (en) | 2009-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3638832B2 (en) | Cosmetic and / or dermatological composition comprising at least one mulberry extract, at least one seaweed extract and at least one salicylic acid derivative | |
| JP3805798B2 (en) | Cosmetics | |
| US7704285B2 (en) | Composition for coloring a keratin material, comprising at least two components, and coloring processes | |
| US5916576A (en) | Method of scavenging free radicals using orange extract | |
| JP2903412B2 (en) | Cosmetics | |
| JP2903240B2 (en) | External preparation for skin | |
| JP2001163719A (en) | Tyrosinase activity inhibitor | |
| JPH05271046A (en) | Dermal medicine for external use | |
| KR101551243B1 (en) | Cosmetic Composition for Skin Whitening Having Fomes Fomentarius | |
| JP3460100B2 (en) | Whitening agent | |
| KR102277525B1 (en) | Cosmetic or pharmaceutical composition for melanism, elasticity, anti-wrinkle, skin moisturizing or anti-inflammation comprising fargesin | |
| KR101462692B1 (en) | Skin whitening cosmetics | |
| JPH04235112A (en) | Tyrosinase-inhibitor | |
| WO1999034676A1 (en) | Method of synthesis of derivatives of aloesin | |
| JPH03127714A (en) | Skin cosmetic | |
| JP2001316268A (en) | Skin care preparation | |
| KR101525090B1 (en) | Cosmetic Composition for skin Whitening | |
| JP2023535534A (en) | Gray hair control composition and use thereof | |
| KR20100061978A (en) | Skin whitening agent | |
| JP2000191504A (en) | Cosmetic composition for whitening skin | |
| KR101551240B1 (en) | Cosmetic Composition for Skin Whitening Having Kaempferia Parviflora | |
| KR102272476B1 (en) | Cosmetic or pharmaceutical composition for melanism, elasticity, anti-wrinkle, skin moisturizing or anti-inflammation comprising isopimpinellin | |
| KR102600558B1 (en) | Composition for promoting hair growth and preventing hair loss comprising atraric acid | |
| JP4148862B2 (en) | Tyrosinase activity inhibitor | |
| JPS60188306A (en) | Cosmetic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061006 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080529 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080610 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080808 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080930 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081112 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20081209 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20081211 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120109 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4239126 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080808 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130109 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130109 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |