JPS63101372A - Novel hydantoin derivative - Google Patents
Novel hydantoin derivativeInfo
- Publication number
- JPS63101372A JPS63101372A JP61246309A JP24630986A JPS63101372A JP S63101372 A JPS63101372 A JP S63101372A JP 61246309 A JP61246309 A JP 61246309A JP 24630986 A JP24630986 A JP 24630986A JP S63101372 A JPS63101372 A JP S63101372A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- benzylidene
- dioxo
- acid
- 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.)
- Granted
Links
- 150000001469 hydantoins Chemical class 0.000 title claims abstract description 5
- -1 trimethylcyclohexyl Chemical group 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- UDTSPKADQGPZFS-UHFFFAOYSA-N 5-benzylideneimidazolidine-2,4-dione Chemical compound N1C(=O)NC(=O)C1=CC1=CC=CC=C1 UDTSPKADQGPZFS-UHFFFAOYSA-N 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract description 3
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006845 Michael addition reaction Methods 0.000 abstract description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 abstract description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 abstract description 2
- 229940091173 hydantoin Drugs 0.000 abstract description 2
- 241000212749 Zesius chrysomallus Species 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229940124543 ultraviolet light absorber Drugs 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 description 10
- 230000002745 absorbent Effects 0.000 description 10
- 239000006096 absorbing agent Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 10
- 239000002537 cosmetic Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- FZXRXKLUIMKDEL-UHFFFAOYSA-N 2-Methylpropyl propanoate Chemical compound CCC(=O)OCC(C)C FZXRXKLUIMKDEL-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
- 229960004889 salicylic acid Drugs 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 3
- 239000004808 2-ethylhexylester Substances 0.000 description 3
- 206010015150 Erythema Diseases 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 150000003852 triazoles Chemical class 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000003862 amino acid derivatives Chemical class 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- GUHQWKGQAYBNEW-UHFFFAOYSA-N 2-ethylhexyl propanoate Chemical compound CCCCC(CC)COC(=O)CC GUHQWKGQAYBNEW-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- GLLNVILYFPEBTN-UHFFFAOYSA-N butyl 3-(4-benzylidene-2,5-dioxoimidazolidin-1-yl)propanoate Chemical compound O=C1N(CCC(=O)OCCCC)C(=O)NC1=CC1=CC=CC=C1 GLLNVILYFPEBTN-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
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、日焼は止め、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、化粧品といフた広い分野に対
し適応できる。DETAILED DESCRIPTION OF THE INVENTION Industrial Fields of Application The compound of the present invention can be used as an ultraviolet absorber, preventing sunburn, preventing yellowing of fibers, resins, etc., containers and packaging materials, and their contents. It is effective in protecting from ultraviolet rays, etc.
It can be applied to a wide range of fields including 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。BACKGROUND OF THE INVENTION Conventionally, in the field of cosmetics, ultraviolet absorbers have long attracted attention and have been developed in large numbers in order to prevent the harmful effects of ultraviolet rays on the skin.
紫外線吸収剤としては、ヘンシフエノン系吸収剤、サリ
チル酸系吸収剤、ケイ皮酸系吸収剤、バシアミノ安息香
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, hensifenone-based absorbent, salicylic acid-based absorbent, cinnamic acid-based absorbent, bacyaminobenzoic acid-based absorbent, etc. are used. However, among the above-mentioned ultraviolet absorbers, there are very few that combine effectiveness, safety, solubility, stability, etc.
例えば、ベンゾフェノン系吸収剤は、３２０〜４００ｎ
ｍ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（２９０〜３２０
ｎｍ）に対しては、吸収能が相対的に低い。For example, benzophenone absorbent is 320 to 400n
It has an absorption effect on long-wavelength ultraviolet rays (290-320 m), but medium-wavelength ultraviolet rays (290-320 m), which are thought to cause blisters,
nm), the absorption capacity is relatively low.
バ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。Barraminobenzoic acid-based and cinnamic acid-based absorbents have high absorption effects, but are said to have stability problems. Also,
Salicylic acid-based absorbents have a weak absorption effect and cannot be expected to be effective unless added in large quantities.
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 absorbers, inorganic powders such as titanium dioxide, zinc oxide, and iron oxide, which have the function of physically reflecting and scattering ultraviolet rays, are 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, inorganic powders are limited in the types of cosmetics that can be blended with them, and they also have the problem of coloring when blended in large amounts.
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；ｎ加削としては、サリチ
ル酸系、ヘンシフエノン系吸収剤の他、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〜
３２Ｏｎｍ付近の吸収が弱く、トリアソール系吸収剤は
安全衛生上問題があるといわれている。On the other hand, ultraviolet absorbers are used as additives to prevent resin deterioration. In addition to salicylic acid-based and hesiphenone-based absorbents, triazole-based and cyanoacrylate-based ultraviolet absorbers are used for processing the resin. However, salicylic acid-based and benzophenone-based absorbents have a 300~
Absorption near 32 Onm is weak, and triazole-based absorbents are said to pose health and 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とて種々の紫
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 mentioned above, various UV absorbers have been developed in the cosmetics and resin fields, but they lack UV absorbing ability, safety, solubility in solvents and resins, and The reality is that no one has yet been found that satisfies all of the stability requirements, and a UV absorber that has both of these properties is desired.
問題点を解決する為の手段
本発明者らは、かかる実情を鑑み、鋭意研究を行なった
結果、下記一般式（１）で表わされる新規α−デヒドロ
アミノ酸誘導体が表１に示すように中波長紫外線領域（
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 the Problems In view of the above circumstances, the present inventors have conducted intensive research and have found that a novel α-dehydroamino acid derivative represented by the following general formula (1) has a medium wavelength property as shown in Table 1. UV range (
240 to 360 nm), and furthermore,
Since these novel α-dehydro amino acid derivatives are easily soluble in various animal and vegetable oils, fats and oils, and organic solvents, we have discovered that these novel α-dehydro amino acid derivatives are effective UV absorbers for preventing erythema on the skin and preventing deterioration of resins, etc., and have developed the present invention. completed.
ＸＮ ＮＣＨ２ＣＨ２Ｃ０２Ｒ
Ｉ＋ （１）
（但し、式１中、Ｘは水素原子又は−ＣＨ２−ＣＨ２Ｃ
０２Ｒである。Ｒは炭素数８〜１８のアルキル基、シク
ロヘキシル基又はトリメチルシクロへキシル基である。XN NCH2CH2C02R I+ (1) (However, in formula 1, X is a hydrogen atom or -CH2-CH2C
It is 02R. R is an alkyl group having 8 to 18 carbon atoms, a cyclohexyl group, or a trimethylcyclohexyl group.
〉
本発明に係る一般式（１）表示のα−デヒドロアミノ酸
誘導体は、以下の方法により製造することができる。す
なわち、■芳香属アルデヒドと、ヒダントインの塩基触
媒による縮合、■生成したベンザールヒダントインに、
アクリル酸エステルをマイケル付加して、得られる。
（式１）％式％
ＨＮ ＮＨ
Ｉ
ＨＮ ＮＨ
＋
ＣＨ２＝ＣＨＣ０２Ｒ
ｊ
−−−−−−→ Ｘ Ｎ Ｎ ＣＨ２ＣＨ２Ｃ
０２ＲＣ（１）
（但し、式１中、Ｘは水素原子又は−ＣＨ２−ＣＨ２Ｃ
Ｏ２Ｒである。Ｒは炭素数３〜１８のアルキル基、シク
ロヘキシル基又はトリメチルシクロヘキシル基である。> The α-dehydroamino acid derivative represented by general formula (1) according to the present invention can be produced by the following method. That is, ■ base-catalyzed condensation of aromatic aldehyde and hydantoin, ■ the generated benzalhydantoin,
Obtained by Michael addition of acrylic acid ester.
(Formula 1) % formula % HN NH I HN NH + CH2=CHC02R j ---------→ X N N CH2CH2C
02RC(1) (However, in formula 1, X is a hydrogen atom or -CH2-CH2C
It is O2R. R is an alkyl group having 3 to 18 carbon atoms, a cyclohexyl group, or a trimethylcyclohexyl group.
）
本発明の一般式（１）表示の化合物を例示するならば、
４−ベンジリデン−２，５−ジオキソ−１，３−イミダ
ソリジンジプロピオン酸ジイソプルピルエステル、４−
ベンジリデン−２，５−ジオキソ−１，３−イミダソリ
ジンジプロピオン酸ジｎ−ブチルエステル、４−ベンジ
リデン−２，５−ジオキソ−１，３−イミダゾリジンジ
プロピオン酸ジイソブチルエステル、４−ベンジリデン
−２，５−ジオキソ−１，３−イミダゾリジンジプロピ
オン酸ビス（２−エチルヘキシルエステル）、４−ベン
ジリデン−２，５−ジオキソ−１−イミダゾリジンプロ
ピオン酸イソプロピルエステル、４−ベンジリデン−２
，５−ジオキソ−１−イミダゾリジンプロピオン酸 ｎ
−ブチルエステル、４−ベンジリデン−２，５−ジオキ
ソ−１−イミダゾリジンプロピオン酸 イソブチルエス
テル、４ベンジリデン−２，５−ジオキソ−１−イミダ
ゾリジンプロピオン酸 ２−エチルヘキシルエステル等
が挙げられる。) Examples of compounds represented by general formula (1) of the present invention include:
4-Benzylidene-2,5-dioxo-1,3-imidasolidine dipropionic acid diisopropyl ester, 4-
Benzylidene-2,5-dioxo-1,3-imidazolidine dipropionic acid di-n-butyl ester, 4-benzylidene-2,5-dioxo-1,3-imidazolidine dipropionic acid diisobutyl ester, 4-benzylidene- 2,5-dioxo-1,3-imidazolidine dipropionate bis(2-ethylhexyl ester), 4-benzylidene-2,5-dioxo-1-imidazolidine propionate isopropyl ester, 4-benzylidene-2
,5-dioxo-1-imidazolidinepropionic acid n
-butyl ester, 4-benzylidene-2,5-dioxo-1-imidazolidine propionic acid isobutyl ester, 4-benzylidene-2,5-dioxo-1-imidazolidine propionic acid 2-ethylhexyl ester, and the like.
発明の効果
本発明に用いられる前記一般式（１）表示の新規ヒダン
トイン誘導体は、表１に示すように、２７０〜３３０ｎ
ｍ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。又、一般式（１）表示の化
合物は、Ｒの効果により、既存の化合物、例えば５−ベ
ンザールヒダントイン等に、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、クリ
ーム、乳）夜、ファンデーション、ヘアークリーム、日
焼は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、Ａ
ＢＳ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。本発明に用いられ
る前記一般式（１）表示のヒダントイン誘導体を市販の
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。０２〜１０倍の紫外線分子吸光係数を有する。Effects of the Invention As shown in Table 1, the novel hydantoin derivative represented by the general formula (1) used in the present invention has a molecular weight of 270 to 330n.
Ultraviolet rays of 290 to 320 nm, which have a high molecular extinction coefficient of 104 or more and are thought to cause skin erythema, and 300 to 320 nm, which are thought to cause deterioration of resins such as polyethylene, polypropylene, and polyvinyl chloride. However, it has a high absorption capacity. Furthermore, due to the effect of R, the compound represented by the general formula (1) is more effective than existing compounds, such as 5-benzalhydantoin, in various animal and vegetable oils, fats and oils,
The solubility in organic solvents is significantly improved, and stable formulations can be obtained when added to cosmetics such as creams, creams, night creams, foundations, hair creams, and sunscreen oils. In addition, these compounds can be used as polyethylene, polypropylene, polystyrene, polyvinyl chloride, A
When added to resins such as BS resin and polycarbonate, good compatibility with the resin can be expected. When the hydantoin derivative represented by the general formula (1) used in the present invention is compared with commercially available ultraviolet absorbers (for example, benzophenone-based, triazole-based, and salicylic acid-based absorbers), it is found that: It has an excellent suppressive effect on the effects of ■High thermal stability and photostability, and long-lasting effects. It has an ultraviolet molecular extinction coefficient of 0.2 to 10 times.
■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。■Since it has good compatibility with various polymer materials, it can be used as a plasticizer for fibers, resins, etc., and can also be used as an anti-yellowing agent.
上述したことく、本発明の用途範囲は、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 mentioned above, the scope of use of the present invention is the cosmetics industry, the plastics industry, the organic medicine industry, the photography industry, the food industry,
The textile industry is extremely wide.
殊に、紫外線吸収波長が、２４０〜３６０ｎｍ（最大吸
収波長 ３００〜３４０ｎｍ）にあり、香粧品に用いた
場合は、他に比類のない選択的吸収性をもった日焼け、
紅斑防止化粧品となり、また、ポリエチレン、ポリプロ
ピレン、ポリ塩化ビニルなど、重合体中に、混入した場
合、紫外線による劣化を、著しく軽減する。In particular, the ultraviolet absorption wavelength is 240 to 360 nm (maximum absorption wavelength 300 to 340 nm), and when used in cosmetics, it is a tanning agent with unparalleled selective absorption.
It can be used as an anti-erythema cosmetic product, and when mixed into polymers such as polyethylene, polypropylene, and polyvinyl chloride, it significantly reduces deterioration caused by ultraviolet rays.
次に、本発明に係る代表的な化合物について、最大吸収
波長ならびに、その他の物性値を実施例１としてまとめ
て表１に示す。また実施例２に代表的な製法を示すが、
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。Next, the maximum absorption wavelength and other physical property values of typical compounds according to the present invention are summarized in Table 1 as Example 1. In addition, a typical manufacturing method is shown in Example 2,
The present invention is not limited to these examples.
実施例 ２
合成例１
４−ベンジリデン−２，５−ジオキソ−１−イミダゾリ
ジンプロピオン酸 イソブチルエステルの合成
りＭＦ１５０ｍｌにベンザールヒダントイン２０ ｇ
（０，１０６ｍｏ １）、アクリル酸 イソブチルエス
テル １４．９ｇ（０，１１７ｍｏｌ）及び、水酸化カ
リウム １．２ｇ（０，０２ｍ。Example 2 Synthesis Example 1 Synthesis of 4-benzylidene-2,5-dioxo-1-imidazolidine propionic acid isobutyl ester 20 g of benzalhydantoin to 150 ml of MF
(0,106 mo 1), 14.9 g (0,117 mol) of acrylic acid isobutyl ester, and 1.2 g (0,02 m) of potassium hydroxide.
１）を、加える。１１０℃で２時間攪拌した後、冷却し
、反応液にトルエン３００ｍ ｌを加えて結晶化させた
。結晶を濾取後、乾燥し、４−ベンジリデン−２，５−
ジオキソ−１−イミダゾリジンプロピオン酸 イソブチ
ルエステル ２７・ ２ｇ（８１％）を得た。Add 1). After stirring at 110°C for 2 hours, the mixture was cooled, and 300 ml of toluene was added to the reaction mixture for crystallization. After collecting the crystals by filtration, they are dried to give 4-benzylidene-2,5-
27.2 g (81%) of dioxo-1-imidazolidine propionic acid isobutyl ester was obtained.
合成例２
４−ベンジリデン−２，５−ジオキソ−１，３−イミダ
ゾリジンジプロビオン酸 ビス（２−エチルヘキシルエ
ステル）の合成
りＭＦｌｏｏｍｌにベンザールヒダントイン１０ｇ’（
５３，１ｍｍｏｌ）、アクリル酸 ２−エチルヘキシル
２３．６ｇ （１２７，６ｍｍ。Synthesis Example 2 Synthesis of 4-benzylidene-2,5-dioxo-1,3-imidazolidine diprobionic acid bis(2-ethylhexyl ester) 10 g of benzalhydantoin (
53.1 mmol), 2-ethylhexyl acrylate 23.6 g (127.6 mm).
ｌ）及び、水酸化カリウム ０． ６ｇ （１０，６ｍ
ｍｏｌ）を、加える。１１０℃で２時間撹拌した後、冷
却した。酢酸エチルで抽出し、有機層を、水洗復硫酸ナ
トリウムで乾燥、減圧濃縮した。残さをトルエンに溶解
し、ヘキサンを加えて結晶化させた。結晶を濾取後、乾
燥し、４−ベンジリデン−２，５−ジオキソ−１，３−
イミダゾリジンジプロピオン酸 ビス（２−エチルヘキ
シルエステル）１９．８ｇ （４２，３％）を得た。l) and potassium hydroxide 0. 6g (10,6m
mol). After stirring at 110°C for 2 hours, it was cooled. The organic layer was extracted with ethyl acetate, washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in toluene, and hexane was added for crystallization. After collecting the crystals by filtration, they were dried to give 4-benzylidene-2,5-dioxo-1,3-
19.8 g (42.3%) of imidazolidine dipropionic acid bis(2-ethylhexyl ester) was obtained.
Claims (1)
。 ▲数式、化学式、表等があります▼（１） （但し、式１中、Ｘは水素原子又は−ＣＨ＿２−ＣＨ＿
２ＣＯ＿２Ｒである。Ｒは炭素数３〜１８のアルキル基
、シクロヘキシル基又はトリメチルシクロヘキシル基で
ある。）[Claims] A novel hydantoin derivative represented by the following general formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (However, in formula 1, X is a hydrogen atom or -CH_2-CH_
It is 2CO_2R. R is an alkyl group having 3 to 18 carbon atoms, a cyclohexyl group, or a trimethylcyclohexyl group. )
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61246309A JPH0798809B2 (en) | 1986-10-16 | 1986-10-16 | New hydantoin 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. |
| KR1019870006755A KR900002058B1 (en) | 1986-10-16 | 1987-07-01 | Bernzylidene compounds cosmetic compositions containing the same and ultraviolet absorber comprising the same |
| 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 |
|---|---|---|---|
| JP61246309A JPH0798809B2 (en) | 1986-10-16 | 1986-10-16 | New hydantoin derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63101372A true JPS63101372A (en) | 1988-05-06 |
| JPH0798809B2 JPH0798809B2 (en) | 1995-10-25 |
Family
ID=17146633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61246309A Expired - Lifetime JPH0798809B2 (en) | 1986-04-22 | 1986-10-16 | New hydantoin derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0798809B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01230559A (en) * | 1988-03-11 | 1989-09-14 | Sagami Chem Res Center | 5-substituted methylidenehydantoin derivative |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4954369A (en) * | 1972-06-16 | 1974-05-27 | ||
| JPS5731669A (en) * | 1980-06-21 | 1982-02-20 | Degussa | Manufacture of 5-arylidene hydantoin |
| JPS6245553A (en) * | 1985-08-23 | 1987-02-27 | Nippon Redarii Kk | Production of phenylacetic acid derivative |
-
1986
- 1986-10-16 JP JP61246309A patent/JPH0798809B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4954369A (en) * | 1972-06-16 | 1974-05-27 | ||
| JPS5731669A (en) * | 1980-06-21 | 1982-02-20 | Degussa | Manufacture of 5-arylidene hydantoin |
| JPS6245553A (en) * | 1985-08-23 | 1987-02-27 | Nippon Redarii Kk | Production of phenylacetic acid derivative |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01230559A (en) * | 1988-03-11 | 1989-09-14 | Sagami Chem Res Center | 5-substituted methylidenehydantoin derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798809B2 (en) | 1995-10-25 |
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