JPH032172A - New benzotriazole compound - Google Patents
New benzotriazole compoundInfo
- Publication number
- JPH032172A JPH032172A JP2664790A JP2664790A JPH032172A JP H032172 A JPH032172 A JP H032172A JP 2664790 A JP2664790 A JP 2664790A JP 2664790 A JP2664790 A JP 2664790A JP H032172 A JPH032172 A JP H032172A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- benzotriazole
- compound expressed
- expressed
- 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.)
- Pending
Links
Landscapes
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は工業上、特に各種樹脂、ラテックスおよび化粧
品などの紫外線吸収剤として、または、写真用薬品をは
じめ工業用化学品の合成中間体とる。[Detailed Description of the Invention] [Industrial Application Field] The present invention is useful in industry, particularly as an ultraviolet absorber for various resins, latex and cosmetics, or as a synthetic intermediate for industrial chemicals such as photographic chemicals. .
［Ｅ、２−（アルキル置換ヒドロキシフェニル）−５−
クロロベンゾトリアゾールおよび２−（ジヒドロキシま
たはトリヒドロキシフェニル）−５−クロロベンゾトリ
アゾールなどのベンゾトリアゾール誘導体が各種樹脂の
紫外線吸収剤として使用されている。[E, 2-(alkyl-substituted hydroxyphenyl)-5-
Benzotriazole derivatives such as chlorobenzotriazole and 2-(dihydroxy or trihydroxyphenyl)-5-chlorobenzotriazole are used as UV absorbers for various resins.
また、ある種のベンゾトリアゾール誘導体が、写真用薬
品などとしても使用されることが知られている。It is also known that certain benzotriazole derivatives are used as photographic chemicals.
本発明は、工業上有用な、特に各種樹脂、ラテックスお
よび化粧品などの紫外線吸収剤として、または、写真用
薬品をはじめ工業用化学品の合成中間体として有用な新
規ベンゾトリアゾール化合物を提供することを目的とす
る。The present invention aims to provide novel benzotriazole compounds that are industrially useful, particularly as ultraviolet absorbers for various resins, latex, and cosmetics, or as synthetic intermediates for industrial chemicals such as photographic chemicals. purpose.
本発明は、−触式
本発明の一般式Ｎ）の化合物は、以下に示す従来公知の
方法によって合成することができる。The compound of the general formula N) of the present invention can be synthesized by the conventionally known method shown below.
本発明の一般式（１）の化合物は、−１ｙ式〜
（式中、Ｒは低級アルキルを、Ｘはハロゲンを示す、）
により表わされるベンゾトリアゾール化合物に関する。The compound of general formula (1) of the present invention has the formula -1y (wherein R represents lower alkyl and X represents halogen)
It relates to a benzotriazole compound represented by
一般式（１）の各記号を定義により説明すると、ハロゲ
ンとは塩素、臭素、フッ素、ヨウ素を、低級アルキルと
は炭素数１〜６個の直鎖状もしくは分枝鎖状のアルキル
であって、メチル、エチル、プロピル、イソプロピル、
ブチル、イソブチル、第２級ブチル、第３級ブチル、ペ
ンチル、イソペンチル、ネオペンチル、ヘキシルなどを
示す。To explain each symbol in general formula (1) by definition, halogen refers to chlorine, bromine, fluorine, and iodine, and lower alkyl refers to linear or branched alkyl having 1 to 6 carbon atoms. , methyl, ethyl, propyl, isopropyl,
Indicates butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, neopentyl, hexyl, etc.
本発明において特に好ましい化合物とは、５クロロ−２
−（３−メチル−２，４−ジヒドロキシフェニル）ベン
ゾトリアゾールである。Particularly preferred compounds in the present invention are 5chloro-2
-(3-methyl-2,4-dihydroxyphenyl)benzotriazole.
（式中、Ｘは前記と同義である。）
により表わされる化合物を酸性媒体（塩酸、硫酸など）
中、亜硝酸（亜硝酸ナトリウム、亜硝酸カリウムなど）
と共にジアゾ化反応に付して一般式（式中、Ｘは前記と
同義である。）
により表わされるジアゾニウム塩とし、これに−般式
（式中、各記号は前記と同義である。）により表わされ
る化合物を滴下してジアゾ・カップリング反応に付して
一般式
（式中、各記号は前記と同義である。）により表わされ
るアゾ化合物とし、次いで水酸化ナトリウムなどのアル
カリの存在下、亜鉛末で還元することによって得ること
ができる。(wherein, X has the same meaning as above) in an acidic medium (hydrochloric acid, sulfuric acid, etc.)
Medium, nitrous acid (sodium nitrite, potassium nitrite, etc.)
A diazonium salt represented by the general formula (wherein, X has the same meaning as above) is obtained by subjecting it to a diazotization reaction. The represented compound is added dropwise and subjected to a diazo coupling reaction to form an azo compound represented by the general formula (in the formula, each symbol has the same meaning as above), and then in the presence of an alkali such as sodium hydroxide, It can be obtained by reduction with zinc dust.
本発明の一般式（１）の化合物は、新規化合物であり、
各種樹脂、ラテックスおよび化粧品の紫外線吸収剤とし
て有用である。また、本化合物は、従来のベンゾトリア
ゾール系紫外線吸収剤に比べて水）容性が高められた化
合物であり、その使用操作上も有用である。The compound of general formula (1) of the present invention is a new compound,
Useful as a UV absorber in various resins, latex and cosmetics. In addition, the present compound has improved water solubility compared to conventional benzotriazole-based ultraviolet absorbers, and is useful in its use.
また、本化合物は写真用薬品をはじめ工業用化学品の合
成中間体としても使用可能である。Furthermore, this compound can be used as a synthetic intermediate for industrial chemicals including photographic chemicals.
本発明の化合物を紫外線吸収剤として用いる場合、樹脂
、ラテックスおよび化粧品に対しｏ、ｏｏｔ〜１０重量
％、好ましくは０．０１〜５重量％の割合で配合するの
がよい。また、本発明の化合物をこれら用途に用いる場
合、公知の紫外線吸収剤、酸化防止剤と併用することも
可能である。When the compound of the present invention is used as an ultraviolet absorber, it is preferably blended into resins, latex and cosmetics in an amount of o,oot to 10% by weight, preferably 0.01 to 5% by weight. Furthermore, when the compound of the present invention is used for these purposes, it can also be used in combination with known ultraviolet absorbers and antioxidants.
以下、実施例により本発明を具体的に説明するが、本発
明はそれらにより何ら限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
実施例
（１１３００ｍ１容の４０フラスコに４−クロロ−２ニ
トロアニリン２４．５ｇ（０，１９８モル）と３５％塩
酸８６ｇを仕込み、懸濁上氷水により冷却する。亜硝酸
ナトリウム１５．２ ｇ （０，２２０モル）を水２７
ｍ１に溶解し、先の懸濁液に１０℃以下で約１時間かけ
て滴下する。滴下終了後、３０分間攪拌し、過剰の亜硝
酸ナトリウムを中和するため、ヨウ化カリウムデンプン
紙で確認しつつスルファミン酸水溶液を滴下する。次い
で、２−メチルツルシノール３４．５ ｇ （０，１９
８モル）をメタノールｌ１ｇに溶解し、これを１０℃以
下でフラスコ中へ約１時間かけて滴下する。滴下中、攪
拌状態を改善するため、メタノール３００ｍ１を少しづ
つ加える。滴下終了後、さらに、１．５時間攪拌して反
応を完結させる。室温にもどした後、水１５００ｍｌに
注ぎ、析出した結晶を濾取する。得られた結晶を水５０
０ｍ１で洗浄した後、乾燥すると２−〔（４−クロロ−
２−ニトロフェニル）ア／’）−６−メチル−１，３−
ジオキシベンゼン７５ｇが得られる。Example (24.5 g (0,198 mol) of 4-chloro-2 nitroaniline and 86 g of 35% hydrochloric acid were placed in a 40 flask with a volume of 11,300 ml, and the suspension was cooled with ice water. Sodium nitrite 15.2 g (0 , 220 mol) in water 27
ml and added dropwise to the above suspension at 10° C. or lower over about 1 hour. After the dropwise addition is completed, the mixture is stirred for 30 minutes, and in order to neutralize excess sodium nitrite, an aqueous sulfamic acid solution is added dropwise while checking with potassium iodide starch paper. Then 34.5 g of 2-methylturcinol (0,19
8 mol) in 1 g of methanol, and this was added dropwise into the flask at 10° C. or below over about 1 hour. During the dropwise addition, 300 ml of methanol was added little by little to improve the stirring condition. After the dropwise addition was completed, the mixture was further stirred for 1.5 hours to complete the reaction. After returning to room temperature, pour into 1500 ml of water, and filter the precipitated crystals. The obtained crystals are mixed with 50% water.
After washing with 0ml and drying, 2-[(4-chloro-
2-nitrophenyl)a/')-6-methyl-1,3-
75 g of dioxybenzene are obtained.
＋２１ （１）で得られた２−（（４−クロロ−２−
ニトロフェニル）アゾ）−６−メチル−１，３−ジオキ
シベンゼン７０ｇ（０，１９８モル）をメタノール２５
０ｇに溶解し、水酸化ナトリウム８５ｇを水１７０ｇに
溶解した液を加える。この反応液に亜鉛末８８ｇを少量
づつ６０℃前後で添加する。+21 2-((4-chloro-2-
70 g (0,198 mol) of methanol (nitrophenyl)azo)-6-methyl-1,3-dioxybenzene
0 g, and add a solution of 85 g of sodium hydroxide dissolved in 170 g of water. 88 g of zinc powder is added little by little to this reaction solution at around 60°C.
添加終了後、３０分間攪拌し、反応を完結させる。After the addition is complete, stir for 30 minutes to complete the reaction.
熱時濾過し、濾液に塩酸を加えｐＨ４にした後、酢酸エ
チル１０００ｍｌで抽出する。抽出液を水５００ｍ１で
洗浄後、減圧上濃縮し、粗結晶４８ｇを得る。得られた
粗結晶を酢酸エチル−ヘキサンの混合溶媒で再結晶する
と融点１８９．５〜１９０．５℃の結晶として、５−ク
ロロ〜２−（３−メチル２．４−ジヒドロキシフェニル
）ベンゾトリアゾール３６ｇが得られる。Filter while hot, add hydrochloric acid to the filtrate to adjust the pH to 4, and then extract with 1000 ml of ethyl acetate. The extract was washed with 500 ml of water and concentrated under reduced pressure to obtain 48 g of crude crystals. When the obtained crude crystals were recrystallized from a mixed solvent of ethyl acetate and hexane, 36 g of 5-chloro-2-(3-methyl-2.4-dihydroxyphenyl)benzotriazole was obtained as crystals with a melting point of 189.5-190.5°C. is obtained.
Claims (2)
ロキシフェニル）ベンゾトリアゾール。(2) 5-chloro-2-(3-methyl-2,4-dihydroxyphenyl)benzotriazole.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-30388 | 1989-02-09 | ||
| JP3038889 | 1989-02-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH032172A true JPH032172A (en) | 1991-01-08 |
Family
ID=12302525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2664790A Pending JPH032172A (en) | 1989-02-09 | 1990-02-06 | New benzotriazole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH032172A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002012202A3 (en) * | 2000-08-03 | 2002-04-11 | Ciba Sc Holding Ag | Processes for the preparation of benzotriazole uv absorbers |
| WO2003013455A3 (en) * | 2001-08-04 | 2003-09-25 | Beiersdorf Ag | Cosmetic and dermatological light protective formulations containing benzotriazole derivatives and latex particles |
| JP2005289916A (en) * | 2004-04-01 | 2005-10-20 | Shiseido Co Ltd | Ultraviolet absorber and skin external preparation containing the same |
-
1990
- 1990-02-06 JP JP2664790A patent/JPH032172A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002012202A3 (en) * | 2000-08-03 | 2002-04-11 | Ciba Sc Holding Ag | Processes for the preparation of benzotriazole uv absorbers |
| WO2003013455A3 (en) * | 2001-08-04 | 2003-09-25 | Beiersdorf Ag | Cosmetic and dermatological light protective formulations containing benzotriazole derivatives and latex particles |
| JP2005289916A (en) * | 2004-04-01 | 2005-10-20 | Shiseido Co Ltd | Ultraviolet absorber and skin external preparation containing the same |
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