JPH0776200B2 - Novel α-dehydroamino acid derivative - Google Patents
Novel α-dehydroamino acid derivativeInfo
- Publication number
- JPH0776200B2 JPH0776200B2 JP61092481A JP9248186A JPH0776200B2 JP H0776200 B2 JPH0776200 B2 JP H0776200B2 JP 61092481 A JP61092481 A JP 61092481A JP 9248186 A JP9248186 A JP 9248186A JP H0776200 B2 JPH0776200 B2 JP H0776200B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- methyl
- dehydrotyrosine
- benzoyl
- ester
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
- A61K8/445—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof aromatic, i.e. the carboxylic acid directly linked to the aromatic ring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/12—Face or body powders for grooming, adorning or absorbing
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dermatology (AREA)
- Emergency Medicine (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、新規α−デヒドロアミノ酸誘導体に関する。
本発明の化合物は、紫外線吸収剤として用いることがで
き、日焼け止め、繊維や樹脂等の黄変防止、容器及び包
材や、その内容物の紫外線からの保護等に有効であり、
塗料、樹脂、医薬、食品、化粧品といった広い分野に対
し適応できる。TECHNICAL FIELD The present invention relates to a novel α-dehydroamino acid derivative.
The compound of the present invention can be used as an ultraviolet absorber, sunscreen, prevention of yellowing of fibers and resins, containers and packaging materials, and is effective in protecting the contents from ultraviolet rays,
It can be applied to a wide range of fields such as paints, resins, medicines, foods, and cosmetics.
［従来の技術］ 従来、化粧品の分野では紫外線の皮膚に対する有害作用
を防ぐ為、紫外線吸収剤が早くから注目され、数多く開
発されてきた。[Prior Art] Conventionally, in the field of cosmetics, in order to prevent harmful effects of ultraviolet rays on the skin, ultraviolet absorbers have been attracting attention from early on and have been developed in large numbers.
紫外線吸収剤としては、ベンゾフェノン系吸収剤、サリ
チル酸系吸収剤、ケイ皮酸系吸収剤、パラアミノ安息香
酸系吸収剤などが、用いられている。しかしながら、上
述した紫外線吸収剤のうち、効果、安全性、溶解性、安
定性等を兼備するものは非常に少ない。As the ultraviolet absorber, benzophenone-based absorbers, salicylic acid-based absorbers, cinnamic acid-based absorbers, para-aminobenzoic acid-based absorbers, etc. are used. However, among the above-mentioned ultraviolet absorbers, very few have the effects, safety, solubility, stability and the like.
例えば、ベンゾフェノン系吸収剤は、320〜400nmの長波
長紫外線には吸収効果をもつが、火ぶくれなどの原因と
考えられている中波長紫外線（290〜320nm）に対して
は、吸収能が相対的に低い。For example, a benzophenone-based absorber has an absorption effect for long-wavelength ultraviolet rays of 320 to 400 nm, but has an absorption ability for medium-wavelength ultraviolet rays (290 to 320 nm), which is considered to cause blistering. Relatively low.
パラアミノ安息香酸系、ケイ皮酸系吸収剤は、吸収効果
は高いが、安定性に問題があるといわれている。また、
サリチル酸系吸収剤は吸収効果が弱く、大量に配合しな
ければ効果が期待できない。Para-aminobenzoic acid-based and cinnamic acid-based absorbents have high absorption effects, but are said to have stability problems. Also,
The salicylic acid-based absorbent has a weak absorption effect and cannot be expected to be effective unless it is mixed in a large amount.
上述の紫外線吸収剤の他に紫外線を物理的に反射、散乱
させる機能を有する二酸化チタン、酸化亜鉛、酸化鉄な
どの無機粉体も用いられる。In addition to the above-mentioned ultraviolet absorber, inorganic powder such as titanium dioxide, zinc oxide, and iron oxide, which has a function of physically reflecting and scattering ultraviolet rays, is also used.
しかし、無機粉体は配合できる化粧品のタイプが限定さ
れ、また多量に配合する際に着色するという問題点があ
る。However, the types of cosmetics that can be blended with inorganic powders are limited, and there is a problem that coloring occurs when a large amount is blended.
一方、樹脂の劣化を防ぐ為、紫外線吸収剤が添加剤とし
てもちいられている。樹脂の添加剤としては、サリチル
酸系、ベンゾフェノン系吸収剤の他、トリアゾール系、
シアノアクリレート系紫外線吸収剤が使用されている。
しかしながら、サリチル酸系、およびベンゾフェノン系
吸収剤では、ポリエチレンやポリプロピレン、塩化ビニ
ル樹脂に影響をおよぼすといわれている300〜320nm付近
の吸収が弱く、トリアゾール系吸収剤は安全上問題があ
るといわれている。On the other hand, an ultraviolet absorber is also used as an additive to prevent the deterioration of the resin. Resin additives include salicylic acid-based, benzophenone-based absorbers, triazole-based absorbers,
A cyanoacrylate-based UV absorber is used.
However, salicylic acid-based and benzophenone-based absorbents have weak absorption around 300 to 320 nm, which is said to affect polyethylene, polypropylene, and vinyl chloride resins, and triazole-based absorbents are said to have safety problems. .
［本発明が解決しようとする問題点］ 上述したごとく、化粧品及び樹脂の分野などで種々の紫
外線吸収剤が開発されてはいるが、紫外線吸収能、安全
性、溶剤や樹脂への溶解性、および安定性をすべて満足
するものは未だ見いだされていないというのが実情であ
り、これらを兼備した紫外線吸収剤が望まれている。[Problems to be Solved by the Present Invention] As described above, although various ultraviolet absorbers have been developed in the fields of cosmetics and resins, their ultraviolet absorbing ability, safety, solubility in solvents and resins, In reality, it has not been found that all of them satisfy the above requirements and stability, and an ultraviolet absorber that combines these is desired.
［問題点を解決する為の手段］ 本発明者らは、かかつ実情を鑑み、鋭意研究を行なった
結果、下記一般式（Ｉ）で表わされる新規α−デヒドロ
アミノ酸誘導体が中波長紫外線領域（240〜360nm）に大
きな吸収効果を有し、更に、各種動植物油、油脂、およ
び、有機溶剤に易溶であることから、これら新規α−デ
ヒドロアミノ酸誘導体が皮膚の紅斑防止、樹脂の劣化防
止等に有効な紫外線吸収剤であることを見いだし、本発
明を完成した。[Means for Solving Problems] As a result of earnest research in view of the present situation, the present inventors have found that the novel α-dehydroamino acid derivative represented by the following general formula (I) has a medium wavelength ultraviolet region ( (240-360 nm), and because it is easily soluble in various animal and vegetable oils, fats and organic solvents, these new α-dehydroamino acid derivatives prevent skin erythema and resin deterioration. The present invention has been completed by discovering that it is an effective ultraviolet absorber.
（但し、Ｂは水素原子またはアセチル基であり、X1、
X2、X3はそれぞれ同一または異なって水素原子、水酸基
またはメトキシ基であり、Ｙは酸素原子またはアミノ基
（−NH−）であり、Ｚはメチル基またはフェニル基であ
る。Ｒは炭素原子数３〜18のアルキル基、シクロヘキシ
ル基またはトリメチルシクロヘキシル基である。） 本発明のα−デヒドロアミノ酸誘導体は、以下の公知の
方法を用いることにより製造することができる。 (However, B is a hydrogen atom or an acetyl group, X 1 ,
X 2, X 3 are each the same or different and each is a hydrogen atom, a hydroxyl group or a methoxy group, Y is an oxygen atom or an amino group (-NH-), Z is a methyl group or a phenyl group. R is an alkyl group having 3 to 18 carbon atoms, a cyclohexyl group or a trimethylcyclohexyl group. ) The α-dehydroamino acid derivative of the present invention can be produced by using the following known method.
すなわち、芳香族アルデヒドと、アセチルグリシン、
ベンゾイルグリシンまたはそれらのアズラクトンとの塩
基触媒による縮合、生成したアズラクトンの加水分
解、次いでエステル化、またはアミド化、もしくはアズ
ラクトンの直接アルコリシス、アミノリシス、必要に
応じ、アミドの窒素原子をアセチル化することにより得
ることができる（式１）。アズラクトンのアルコリシス
はナトリウムアルコラート、カリウムアルコラートなど
の金属アルコラート、水酸化ナトリウム、水酸化カリウ
ムなどの塩基触媒をもちいて行なうことができる。ま
た、アミドの窒素原子のアセチル化は、ジメチルアミノ
ピリジン、ピロリジノピリジンなどを触媒として行なう
ことができる。That is, aromatic aldehyde, acetylglycine,
By base-catalyzed condensation with benzoylglycine or their azlactone, hydrolysis of the resulting azlactone, followed by esterification or amidation, or direct alcoholysis, aminolysis of the azlactone, and optionally acetylation of the amide nitrogen atom. Can be obtained (Equation 1). The alcoholysis of azlactone can be carried out using a metal alcoholate such as sodium alcoholate and potassium alcoholate, and a base catalyst such as sodium hydroxide and potassium hydroxide. In addition, acetylation of the nitrogen atom of the amide can be performed using dimethylaminopyridine, pyrrolidinopyridine or the like as a catalyst.
また、α−ケト酸あるいはそのエステルを原料とし、ホ
スフィンイミン（式２）、またはアミド（式３）との縮
合によっても一般式（Ｉ）の化合物を得ることができ
る。 The compound of the general formula (I) can also be obtained by condensation of an α-keto acid or its ester as a raw material with a phosphinimine (formula 2) or an amide (formula 3).
さらにＮ−ヒドロキシルアミノ酸エステル誘導体の脱水
によっても得ることができる（式４）。 It can also be obtained by dehydration of an N-hydroxyl amino acid ester derivative (formula 4).
（但し、上記式中、X1、X2、X3はそれぞれ同一または異
なって水素原子、水酸基またはメトキシ基であり、Ｙは
酸素原子またはアミノ基（−NH−）であり、Ｚはメチル
基またはフェニル基である。Ｒは炭素原子数３〜18のア
ルキル基、シクロヘキシル基またはトリメチルシクロヘ
キシル基である。） 本発明の化合物を例示するならば、Ｎ−ベンゾイル−Ｏ
−メチル−α−デヒドロチロシン ラウリルアミド、Ｎ
−ベンゾイル−Ｏ−メチル−α−デヒドロチロシン イ
ソプロピルエステル、Ｎ−ベンゾイル−Ｏ−メチル−α
−デヒドロチロシン ラウリルエステル、Ｎ−ベンゾイ
ル−Ｏ−メチル−α−デヒドロチロシン ステアリルエ
ステル、Ｎ−ベンゾイル−Ｏ−メチル−α−デヒドロチ
ロシン ２−エチルヘキシルエステル、Ｎ−ベンゾイル
−Ｏ−メチル−α−デヒドロチロシン シクロヘキシル
エステル、Ｎ−ベンゾイル−Ｏ−メチル−α−デヒドロ
チロシン 3,3,5−トリメチルシクロヘキシルエステ
ル、Ｎ−アセチル−Ｏ−メチル−α−デヒドロチロシン
イソプロピルエステル、Ｎ−アセチル−Ｏ−メチル−
α−デヒドロチロシン ２−エチルヘキシルエステル、
Ｎ−アセチル−Ｏ−メチル−α−デヒドロチロシン ラ
ウリルエステル、Ｎ−アセチル−Ｏ−メチル−α−デヒ
ドロチロシン ステアリルエステル、Ｎ−アセチル−Ｎ
−ベンゾイル−Ｏ−メチル−α−デヒドロチロシン エ
チルエステル、Ｎ−アセチル−Ｎ−ベンゾイル−Ｏ−メ
チル−α−デヒドロチロシン イソプロピルエステル、
Ｎ−アセチル−Ｎ−ベンゾイル−Ｏ−メチル−α−デヒ
ドロチロシン ２−エチルヘキシルエステル、Ｎ−アセ
チル−Ｎ−ベンゾイル−Ｏ−メチル−α−デヒドロチロ
シン ラウリルエステル、Ｎ−アセチル−Ｎ−ベンゾイ
ル−Ｏ−メチル−α−デヒドロチロシン ステアリルエ
ステル、N,N−ジアセチル−Ｏ−メチル−α−デヒドロ
チロシン エチルエステル N,N−ジアセチル−Ｏ−メ
チル−α−デヒドロチロシン イソプロピルエステル、
N,N−ジアセチル−Ｏ−メチル−α−デヒドロチロシン
２−エチルヘキシルエステル、N,N−ジアセチル−Ｏ
−メチル−α−デヒドロチロシン ラウリルエステル、
N,N−ジアセチル−Ｏ−メチル−α−デヒドロチロシン
ステアリルエステル等が挙げられる。 (However, in the above formula, X 1 , X 2 , and X 3 are the same or different and each is a hydrogen atom, a hydroxyl group, or a methoxy group, Y is an oxygen atom or an amino group (-NH-), and Z is a methyl group. Or a phenyl group, and R is an alkyl group having 3 to 18 carbon atoms, a cyclohexyl group, or a trimethylcyclohexyl group.) To exemplify the compound of the present invention, N-benzoyl-O
-Methyl-α-dehydrotyrosine laurylamide, N
-Benzoyl-O-methyl-α-dehydrotyrosine isopropyl ester, N-benzoyl-O-methyl-α
-Dehydrotyrosine lauryl ester, N-benzoyl-O-methyl-α-dehydrotyrosine stearyl ester, N-benzoyl-O-methyl-α-dehydrotyrosine 2-ethylhexyl ester, N-benzoyl-O-methyl-α-dehydrotyrosine Cyclohexyl ester, N-benzoyl-O-methyl-α-dehydrotyrosine 3,3,5-trimethylcyclohexyl ester, N-acetyl-O-methyl-α-dehydrotyrosine isopropyl ester, N-acetyl-O-methyl-
α-dehydrotyrosine 2-ethylhexyl ester,
N-acetyl-O-methyl-α-dehydrotyrosine lauryl ester, N-acetyl-O-methyl-α-dehydrotyrosine stearyl ester, N-acetyl-N
-Benzoyl-O-methyl-α-dehydrotyrosine ethyl ester, N-acetyl-N-benzoyl-O-methyl-α-dehydrotyrosine isopropyl ester,
N-acetyl-N-benzoyl-O-methyl-α-dehydrotyrosine 2-ethylhexyl ester, N-acetyl-N-benzoyl-O-methyl-α-dehydrotyrosine lauryl ester, N-acetyl-N-benzoyl-O- Methyl-α-dehydrotyrosine stearyl ester, N, N-diacetyl-O-methyl-α-dehydrotyrosine ethyl ester N, N-diacetyl-O-methyl-α-dehydrotyrosine isopropyl ester,
N, N-diacetyl-O-methyl-α-dehydrotyrosine 2-ethylhexyl ester, N, N-diacetyl-O
-Methyl-α-dehydrotyrosine lauryl ester,
Examples thereof include N, N-diacetyl-O-methyl-α-dehydrotyrosine stearyl ester.
［実施例］ 次に、実施例により本発明を更に詳細に説明するが、本
発明はこれらの実施例によって限定されるものではな
い。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
参考例１ ２−フェニル−４−（４−メトキシベンジリデン）−５
−オキサゾロンの合成 アニスアルデヒド20ml、無水酢酸50ml、馬尿酸33.7gお
よび酢酸ナトリウム6.7gを、よく混合し、水浴で30分加
熱した。析出した結晶を、温水で洗浄後、ろ過した。ベ
ンゼンより再結晶し、乾燥することで、２−フェニル−
４−（４−メトキシベンジリデン）−５−オキサゾロン
40gを得た。収率83％。Reference Example 1 2-Phenyl-4- (4-methoxybenzylidene) -5
-Synthesis of oxazolone 20 ml of anisaldehyde, 50 ml of acetic anhydride, 33.7 g of hippuric acid and 6.7 g of sodium acetate were mixed well and heated in a water bath for 30 minutes. The precipitated crystals were washed with warm water and then filtered. By recrystallizing from benzene and drying, 2-phenyl-
4- (4-methoxybenzylidene) -5-oxazolone
I got 40g. Yield 83%.
合成例１ Ｎ−ベンゾイル−Ｏ−メチル−α−デヒドロチロシン
２−エチルヘキシルエステルの合成 参考例１で得られた２−フェニル−４−（４−メトキシ
ベンジリデン）−５−オキサゾロン1kgを、トルエン101
に懸濁させ、２−エチル−１−ヘキサノール0.933kg、
水酸化ナトリウム0.029kgを添加した。25℃で４時間攪
拌した後、酢酸エチル401、水401を加え攪拌する。有機
層を分離し、芒硝で乾燥、減圧濃縮した後、残渣をトル
エン−ヘキサンで再結晶することで、Ｎ−ベンゾイルＯ
−メチル−α−デヒドロチロシン ２−エチルヘキシル
エステル、1.0kgを得た。収率68.2％。Synthesis Example 1 N-benzoyl-O-methyl-α-dehydrotyrosine
Synthesis of 2-ethylhexyl ester 1 kg of 2-phenyl-4- (4-methoxybenzylidene) -5-oxazolone obtained in Reference Example 1 was added to toluene 101
Suspended in 0.933 kg of 2-ethyl-1-hexanol,
0.029 kg of sodium hydroxide was added. After stirring at 25 ° C. for 4 hours, ethyl acetate 401 and water 401 are added and the mixture is stirred. The organic layer was separated, dried over sodium sulfate and concentrated under reduced pressure, and the residue was recrystallized from toluene-hexane to give N-benzoyl O.
-Methyl-α-dehydrotyrosine 2-ethylhexyl ester, 1.0 kg was obtained. Yield 68.2%.
合成例２ Ｎ−ベンゾイル−Ｏ−メチル−α−デヒドロチロシン
ｎ−ラウリルエステルの合成 ｎ−ウラリルアルコール154mlに金属ナトリウム2gを加
え、加熱溶解する。この溶液に、参考例１で得られた２
−フェニル−４−（４−メトキシベンジリデン）−５−
オキサゾロン118.6gおよび、トルエン300mlを加え、25
℃で８時間、攪拌する。反応液に酢酸エチル21を加えた
後、IN塩酸1.51、５％炭酸水素ナトリウム水溶液1.51、
水1.51で洗浄、芒硝で乾燥する。減圧濃縮後、残渣をｎ
−ヘキサンで再結晶することにより、Ｎ−ベンゾイル−
Ｏ−メチル−α−デヒドロチロシン ｎ−ラウリルエス
テル163.5gを得た。収率82.7％。Synthesis Example 2 N-benzoyl-O-methyl-α-dehydrotyrosine
Synthesis of n-lauryl ester 2 g of metallic sodium was added to 154 ml of n-uralyl alcohol and dissolved by heating. In this solution, 2 obtained in Reference Example 1 was added.
-Phenyl-4- (4-methoxybenzylidene) -5-
Add 118.6 g of oxazolone and 300 ml of toluene, and add 25
Stir at ℃ for 8 hours. After adding ethyl acetate 21 to the reaction solution, IN hydrochloric acid 1.51, 5% sodium hydrogen carbonate aqueous solution 1.51,
Wash with water 1.51 and dry with mirabilite. After concentration under reduced pressure, the residue is
-By recrystallizing from hexane, N-benzoyl-
163.5 g of O-methyl-α-dehydrotyrosine n-lauryl ester was obtained. Yield 82.7%.
合成例３ Ｎ−アセチル−Ｎ−ベンゾイル−Ｏ−メチル−α−デヒ
ドロチロシン ｎ−ラウリルエステルの合成 合成例２で得たＮ−ベンゾイル−Ｏ−メチル−α−デヒ
ドロチロシン ｎ−ラウリルエステル10gをピリジン100
mlに溶解し、無水酢酸20ml、ジメチルアミノピリジン0.
5gを加え、25℃で14時間、攪拌する。反応液を減圧濃縮
し、残渣を酢酸エチル300mlに溶解する。水250mlで４回
洗浄した後、再び減圧濃縮する。残渣をシリカゲルカラ
ムクロマトグラフィーにより、分離しＮ−アセチル−Ｎ
−ベンゾイル−Ｏ−メチル−α−デヒドロチロシン ｎ
−ラウリルエステル8.8gを得た。収率81.1％。Synthesis Example 3 Synthesis of N-acetyl-N-benzoyl-O-methyl-α-dehydrotyrosine n-lauryl ester 10 g of N-benzoyl-O-methyl-α-dehydrotyrosine n-lauryl ester obtained in Synthesis Example 2 was added to pyridine. 100
Dissolve in 20 ml acetic anhydride, 20 ml dimethylaminopyridine.
Add 5 g and stir at 25 ° C. for 14 hours. The reaction solution is concentrated under reduced pressure, and the residue is dissolved in 300 ml of ethyl acetate. After washing 4 times with 250 ml of water, the solution is concentrated again under reduced pressure. The residue was separated by silica gel column chromatography to give N-acetyl-N.
-Benzoyl-O-methyl-α-dehydrotyrosine n
-8.8 g of lauryl ester are obtained. Yield 81.1%.
評価例 合成例１〜３ならびにこれに準拠した方法により合成し
た化合物について最大吸収波長並びに、その他の物性値
を測定し、その結果を表１に示した。また、有機溶剤に
対する溶解性を表２に示す。Evaluation Example The maximum absorption wavelength and other physical properties of the compounds synthesized by Synthesis Examples 1 to 3 and the method based thereon were measured, and the results are shown in Table 1. Table 2 shows the solubility in organic solvents.
［発明の効果］ 本発明のα−デヒドロアミノ酸誘導体は、270〜330nm
で、104以上の高い分子吸光係数を有し、皮膚の紅斑の
原因と考えられる290〜320nm、およびポリエチレン、ポ
リプロピレン、ポリ塩化ビニル等の樹脂の劣化原因と考
えられている300〜320nmの紫外線に対し、高い吸収能を
持つ。さらに、既存の化合物、例えばＮ−ベンゾイル−
α−デヒドロチロシン、Ｏ−メチル−Ｎ−ベンゾイル−
α−デヒドロチロシン等に比べ、各種動植物油、油脂、
および有機溶剤に対する溶解性が、著しく向上したた
め、クリーム、乳液、ファンデーション、ヘアークリー
ム、日焼け止め油等の化粧料に添加した際、安定な配合
物を得ることができる。また、これらの化合物をポリエ
チレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニ
ル、ABS樹脂、ポリカーボネートなどの樹脂に添加した
場合、樹脂との良い相溶性が期待できる。 [Effect of the invention] The α-dehydroamino acid derivative of the present invention has a 270 to 330 nm
In addition, it has a high molecular extinction coefficient of 10 4 or more and is considered to be the cause of erythema on the skin, 290 to 320 nm, and ultraviolet rays of 300 to 320 nm, which is considered to be the cause of deterioration of polyethylene, polypropylene, polyvinyl chloride and other resins. In contrast, it has a high absorption capacity. Furthermore, existing compounds such as N-benzoyl-
α-dehydrotyrosine, O-methyl-N-benzoyl-
Compared to α-dehydrotyrosine etc., various animal and vegetable oils, fats and oils,
Since the solubility in organic solvents is remarkably improved, a stable formulation can be obtained when added to cosmetics such as creams, emulsions, foundations, hair creams and sunscreen oils. Further, when these compounds are added to resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, ABS resin and polycarbonate, good compatibility with the resin can be expected.
本発明のα−デヒドロアミノ酸誘導体を市販の紫外線吸
収剤（例えば、ベンゾフェノン系、トリアゾール系、サ
リチル酸系吸収剤）と比較した場合、殊に酸素存在下
に於ける紫外線の作用に対して優れた抑制効果を有す
る。熱安定性、光安定性が高く、効果の持続性が良
い。２〜10倍の紫外線分子吸光係数を有する。各種
重合体材料との相溶性が良好である為、繊維、樹脂など
の可塑剤として使用される一方、黄変防止剤としても用
いることができる等の効果がある。When the α-dehydroamino acid derivative of the present invention is compared with commercially available ultraviolet absorbers (for example, benzophenone-based, triazole-based, salicylic acid-based absorbers), excellent suppression of the action of ultraviolet light is obtained, especially in the presence of oxygen. Have an effect. It has high thermal stability and light stability, and has a long-lasting effect. It has a UV molecular extinction coefficient of 2 to 10 times. Since it has good compatibility with various polymer materials, it can be used not only as a plasticizer for fibers, resins, etc., but also as an anti-yellowing agent.
上述したごとく、本発明のα−デヒドロアミノ酸誘導体
の用途範囲は、香粧品工業、プラスチック工業、有機薬
品工業、写真工業、食品工業、繊維工業などであり、極
めて広い。As described above, the application range of the α-dehydroamino acid derivative of the present invention is extremely wide, such as the cosmetics industry, the plastics industry, the organic chemicals industry, the photography industry, the food industry, and the textile industry.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 237/20 237/22 Ｃ０９Ｋ 3/00 １０４ // Ａ６１Ｋ 7/42 (56)参考文献 特開 昭48−79782（ＪＰ，Ａ)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication location C07C 237/20 237/22 C09K 3/00 104 // A61K 7/42 (56) References Showa 48-79782 (JP, A)
Claims (1)
ロアミノ酸誘導体。 （但し、Ｂは水素原子またはアセチル基であり、X1、
X2、X3はそれぞれ同一または異なって水素原子、水酸基
またはメトキシ基であり、Ｙは酸素原子またはアミノ基
（−NH−）であり、Ｚはメチル基またはフェニル基であ
る。Ｒは炭素原子数３〜18のアルキル基、シクロヘキシ
ル基またはトリメチルシクロヘキシル基である。）1. An α-dehydroamino acid derivative represented by the following general formula (I). (However, B is a hydrogen atom or an acetyl group, X 1 ,
X 2, X 3 are each the same or different and each is a hydrogen atom, a hydroxyl group or a methoxy group, Y is an oxygen atom or an amino group (-NH-), Z is a methyl group or a phenyl group. R is an alkyl group having 3 to 18 carbon atoms, a cyclohexyl group or a trimethylcyclohexyl group. )
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61092481A JPH0776200B2 (en) | 1986-04-22 | 1986-04-22 | Novel α-dehydroamino acid derivative |
| US07/038,364 US4797493A (en) | 1986-04-22 | 1987-04-14 | Benzylidene compounds |
| DE19873713094 DE3713094A1 (en) | 1986-04-22 | 1987-04-16 | BENZYLIDE COMPOUNDS AND THEIR CONTAINING COSMETIC PREPARATIONS AND ULTRAVIOLET ABSORBERS |
| FR878705711A FR2597476B1 (en) | 1986-04-22 | 1987-04-22 | BENZYLIDENIC COMPOUNDS, COMPOSITIONS CONTAINING THE SAME, AND ULTRAVIOLET RADIATION ABSORBING AGENTS MADE THEREFROM. |
| US07/242,166 US5000945A (en) | 1986-04-22 | 1988-09-08 | Method of stabilizing a UVB absorbing compound, a stabilized UV absorber, and a cosmetic composition containing the same |
| US07/259,257 US4985237A (en) | 1986-04-22 | 1988-10-18 | Benzylidene compounds, cosmetic compositions containing the same and ultraviolet absorber comprising the same |
| US07/509,765 US5087729A (en) | 1986-04-22 | 1990-04-17 | Benzylidene compounds, cosmetic compositions containing the same and ultraviolet absorber comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61092481A JPH0776200B2 (en) | 1986-04-22 | 1986-04-22 | Novel α-dehydroamino acid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62249959A JPS62249959A (en) | 1987-10-30 |
| JPH0776200B2 true JPH0776200B2 (en) | 1995-08-16 |
Family
ID=14055498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61092481A Expired - Lifetime JPH0776200B2 (en) | 1986-04-22 | 1986-04-22 | Novel α-dehydroamino acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0776200B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5067831B2 (en) * | 2006-06-16 | 2012-11-07 | 株式会社 資生堂 | Benzylidenemalonamide and its salt, UV absorber, skin external preparation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4879782A (en) * | 1972-01-29 | 1973-10-25 |
-
1986
- 1986-04-22 JP JP61092481A patent/JPH0776200B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62249959A (en) | 1987-10-30 |
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