JPH04193869A - Production of new benzotriazole compound - Google Patents
Production of new benzotriazole compoundInfo
- Publication number
- JPH04193869A JPH04193869A JP2322205A JP32220590A JPH04193869A JP H04193869 A JPH04193869 A JP H04193869A JP 2322205 A JP2322205 A JP 2322205A JP 32220590 A JP32220590 A JP 32220590A JP H04193869 A JPH04193869 A JP H04193869A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- methyl
- benzotriazole compound
- benzotriazole
- production
- 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
- 239000012964 benzotriazole Substances 0.000 title claims description 18
- -1 benzotriazole compound Chemical class 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title description 9
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract description 4
- DLURHXYXQYMPLT-UHFFFAOYSA-N 2-nitro-p-toluidine Chemical compound CC1=CC=C(N)C([N+]([O-])=O)=C1 DLURHXYXQYMPLT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 235000010288 sodium nitrite Nutrition 0.000 abstract description 2
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 1
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical compound CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 description 1
- PWORFEDVDWBHSJ-UHFFFAOYSA-N 2-methylbenzotriazole Chemical compound C1=CC=CC2=NN(C)N=C21 PWORFEDVDWBHSJ-UHFFFAOYSA-N 0.000 description 1
- UHMONBNAXZUHPY-UHFFFAOYSA-N 2-tert-butyl-4-(2-hydroxyethoxy)phenol Chemical compound CC(C)(C)C1=CC(OCCO)=CC=C1O UHMONBNAXZUHPY-UHFFFAOYSA-N 0.000 description 1
- NBOGODDTOPKOHH-UHFFFAOYSA-N 2-tert-butyl-4-(3-hydroxypropoxy)phenol Chemical compound CC(C)(C)C1=CC(OCCCO)=CC=C1O NBOGODDTOPKOHH-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229940088516 cipro Drugs 0.000 description 1
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、重合性を有する新規ベンゾトリアゾール化合
物を提供するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a novel benzotriazole compound having polymerizability.
有機材料が光により劣化することは広く知られており、
光劣化を防止するために、従来から種々の紫外線吸収剤
が用いられてきた。このうち２− （２’−ヒドロキシ
フェニル）ベンゾトリアゾール化合物がすくれている。It is widely known that organic materials are degraded by light.
Various ultraviolet absorbers have been used to prevent photodeterioration. Among these, 2-(2'-hydroxyphenyl)benzotriazole compound is the least abundant.
しかし、高温で樹脂の加工中に揮発したり、あるいはｍ
脂の表面に浸出して水、溶媒に溶出し、長期にわたって
安定化することができないという問題点があった。However, the resin may volatilize during processing at high temperatures, or m
There was a problem in that it leached onto the surface of the fat and was eluted into water and solvents, making it impossible to stabilize it for a long period of time.
このため、特開昭５５−７２９２号公報において樹脂に
溶解性をもたせるために大きな置換基を導入したり、特
開昭６１−１１８３７３号公報、特開昭６１−１１８３
７３号公報において２分子のペンゾトリアソゝ−ル化合
物をメチレン基で三量化して、分子量を大きいものとし
、樹脂との相溶性を良くすることが提案されている。For this reason, in JP-A No. 55-7292, a large substituent was introduced to give the resin solubility, and in JP-A No. 61-118373,
No. 73 proposes trimerizing two molecules of a penzotriazole compound with methylene groups to increase the molecular weight and improve compatibility with resins.
しかし、これらの工夫された化合物によっても上記の欠
点を満足し得るまでには改善できていない。However, even with these devised compounds, the above drawbacks have not been improved to a satisfactory level.
これらの欠点を解決するために、重合性二重結合を有す
る種々のトリアゾール系紫外線吸収剤が提案されている
。In order to solve these drawbacks, various triazole ultraviolet absorbers having polymerizable double bonds have been proposed.
例えば、特開昭６０−３８４１１号公報、特開昭６３−
１８５９６９号公報、特開平１−２９９５６０号分能
特開平２−６３／１６３冷公報において、 （メタ）ア
クリロイルオキシ基を有するベンゾトリアゾール化合物
およびその共重合体が記載されている。For example, JP-A-60-38411, JP-A-63-
No. 185969, JP-A-1-299560
In JP-A-2-63/163 Cold Gazette, a benzotriazole compound having a (meth)acryloyloxy group and a copolymer thereof are described.
しかし、」二記公報記載の化合物は製造が難しく、高純
度の物が得難い。However, the compounds described in Publication No. 2 are difficult to manufacture and are difficult to obtain with high purity.
Ｃ発明か解決しようとする課題〕
本発明者らは、かかる事情を背景としてなされたもので
、その課題とするところは、その製造が容易で、重合性
基を有する紫外線吸収能の高いベンゾトリアゾール化合
物を提供することにある。C Invention or problem to be solved] It was against this background that the present inventors aimed to create a benzotriazole that is easy to manufacture and has a polymerizable group and has high ultraviolet absorption ability. The objective is to provide compounds.
〔！ｌｌ１題を解決するための手段〕
本発明はその！１題を解決するため鋭意検討を重ねた結
果１次式のベンゾトリアゾール化合物を見いだし、本発
明を完成するにいたった。[! Means for Solving Problems] This invention is the solution to the problem! As a result of intensive studies to solve this problem, a benzotriazole compound having a linear formula was discovered, and the present invention was completed.
式中Ｒ２はＣ２〜Ｃ３アルキレンを示し、Ｒ２はＨまた
はＣＨ３を示す。In the formula, R2 represents C2-C3 alkylene, and R2 represents H or CH3.
具体的には、Ｃ２の２− ［２’ −ヒドロキシ−５′
−（β−メタクリロイルオキシエトキシ）−３’−ｔ−
ブチルフェニル］−５−メチル−２Ｈ−ベンゾトリアゾ
ール及びＣ３の２− ［２’−ヒドロキシ−５′ −（
γ−メタクリロイルオキシプロポキシ）−３’−ｔ−ブ
チルフェニル］−５−メチル−２Ｈ−ベンゾトリアゾー
ルである。Specifically, 2-[2'-hydroxy-5' of C2
-(β-methacryloyloxyethoxy)-3'-t-
butylphenyl]-5-methyl-2H-benzotriazole and 2-[2'-hydroxy-5'-(
γ-methacryloyloxypropoxy)-3'-t-butylphenyl]-5-methyl-2H-benzotriazole.
この本発明化合物は、製造が容易で高品位の化合物が得
られる特徴があり、使用に際し重合性二重結合は高い反
応性を有する。しかも紫外線吸収能の高い新規ベンゾト
リアゾール化合物である。The compound of the present invention is characterized in that it is easy to produce and a high-quality compound can be obtained, and the polymerizable double bond has high reactivity when used. Moreover, it is a new benzotriazole compound with high ultraviolet absorption ability.
この化合物は、４−メチル−２−ニトロアニリンを出発
原料とし、亜鞘酸ナトリウムでジアゾ化し、 （２−ｔ
−ブチル−４−（β−ヒドロキシエトキシ）フェノール
叉は２−ｔ−ブチル−４−（γ−ヒドロキシプロポキシ
）フェノール）とカップリングし、０−ニトロアゾベン
ゼン化合物とする。This compound is produced by using 4-methyl-2-nitroaniline as a starting material and diazotizing it with sodium sublacenate (2-t
-butyl-4-(β-hydroxyethoxy)phenol or 2-t-butyl-4-(γ-hydroxypropoxy)phenol) to form an 0-nitroazobenzene compound.
次に、この０−ニトロアゾベンゼン化合物を還元し、ベ
ンゾトリアゾール化合物を生成させる。Next, this 0-nitroazobenzene compound is reduced to produce a benzotriazole compound.
′Ｉ＆後に、県北メタクリロイルでエステル化する事に
より、目的のベンゾトリアゾール化合物を製造すること
ができる。By esterifying with Kenkoku methacryloyl after 'I&, the desired benzotriazole compound can be produced.
以下、実施例により１本発明化合物の製造方法を詳細に
説明する。Hereinafter, a method for producing one of the compounds of the present invention will be explained in detail with reference to Examples.
実施例 １
２− ［２’ −ヒドロキシ−５′−（β−メタクリロ
イルオキシエトキシ）−３’ −ｔ−プチルフェニル
コー５−メチル−２Ｈ−ベンゾトリアゾールの製造
（Ａ） 中間体 ２−ｔ−ブチル−４−（β−ヒドロ
キシエトキシ）フェノールの製造００８２０８２０日
３３２ｇ （２モル）のし−ブチルヒドロキノン、１ｇ
のよう化カリウムを窒素雰囲気下に２１の水に溶解し、
８０ ’Ｃに昇温した。この溶液に２３２ｇ（２，８モ
ル）の４８％水酸化ナトリウム水溶液及び２００ｇ（２
，５モル）のエチレンクロロヒドリンを、常にアルカリ
性を保つようにして、３時間かけて同時に滴下した。Example 1 Production of 2-[2'-hydroxy-5'-(β-methacryloyloxyethoxy)-3'-t-butylphenyl-5-methyl-2H-benzotriazole (A) Intermediate 2-t-butyl -Manufacture of 4-(β-hydroxyethoxy)phenol00820820 days 332 g (2 mol) butylhydroquinone, 1 g
Potassium iodide was dissolved in 21 water under nitrogen atmosphere,
The temperature was raised to 80'C. To this solution are added 232 g (2.8 mol) of 48% aqueous sodium hydroxide solution and 200 g (2.8 mol) of 48% aqueous sodium hydroxide solution.
, 5 mol) of ethylene chlorohydrin was simultaneously added dropwise over a period of 3 hours while maintaining alkalinity at all times.
滴下終了後、還流温度で８時間加熱した。反応液を冷却
し、硫酸で中和後、 トルエンで抽出しく６）
た。そして脱溶媒後、減圧蒸留し、留出物をトルエンか
ら再結晶し、２００ｇの白色の結晶を得た。 融点９
５．９〜９６．７℃
（Ｂ） 中間体 ２−ｔ−ブチル−４−（β−ヒドロ
キシエトキシ）−６−（４’ −メチル−２２−ニトロ
フェニルアゾ）フェノールのＦＪｉｄＱＣ）Ｉ、、Ｃ）
］、、○Ｈ
８０ｇ（０，５２モル）の４−メチル−２−ニトロアニ
リンと４００ｍ１の水と２００ｇの濃塩酸を仕込み、室
温で終夜攪拌後、０℃に冷却した。この混合物に０〜５
℃において、３６゜４ｇ（０，５３モル）の亜硝酸ナト
リウムを８０ｍ１の水に溶かした溶液を滴下した。滴下
終了後○〜５℃において１時間攪拌し、ろ過してからス
ルファミン酸で残存する亜硝酸を分解した。After the dropwise addition was completed, the mixture was heated at reflux temperature for 8 hours. The reaction solution was cooled, neutralized with sulfuric acid, and extracted with toluene6). After removing the solvent, it was distilled under reduced pressure, and the distillate was recrystallized from toluene to obtain 200 g of white crystals. Melting point 9
5.9-96.7°C (B) Intermediate FJidQC of 2-t-butyl-4-(β-hydroxyethoxy)-6-(4'-methyl-22-nitrophenylazo)phenol) I,,C )
],,○H 80 g (0.52 mol) of 4-methyl-2-nitroaniline, 400 ml of water, and 200 g of concentrated hydrochloric acid were charged, stirred overnight at room temperature, and then cooled to 0°C. 0-5 to this mixture
℃, a solution of 36.4 g (0.53 mol) of sodium nitrite in 80 ml of water was added dropwise. After the dropwise addition was completed, the mixture was stirred at ○ to 5°C for 1 hour, filtered, and the remaining nitrous acid was decomposed with sulfamic acid.
一方、 １００ｇ （０，４７モル）の上言己（Ａ）の
生成物と４０ｇ （１モル）の水酸化ナトリウムと４０
ｇ（０，６８モル）の水酸化マグネシウムを４００ｍ１
の水に加え、０℃に冷却した。On the other hand, 100 g (0.47 mol) of the above product (A), 40 g (1 mol) of sodium hydroxide and 40
g (0.68 mol) of magnesium hydroxide in 400 ml
of water and cooled to 0°C.
この混合物にＯ−５℃において、先に得られたジアゾニ
ウム溶液を滴下した。反応終了後、塩酸で酸性化し、
トルエンで抽出した。そのトルエン溶液をろ過液脱溶媒
しメタノールで晶析し、７０ｇの暗赤色の結晶を得た。The previously obtained diazonium solution was added dropwise to this mixture at O-5°C. After the reaction is completed, acidify with hydrochloric acid,
Extracted with toluene. The filtrate was removed from the toluene solution and crystallized with methanol to obtain 70 g of dark red crystals.
（Ｃ） 中間体２− ［２’ −ヒドロキシ−５２−
（β−ヒドロキシエトキシ）−３’−ｔ−ブチルフェニ
ルヨー５−メチル−２Ｈ−ベンゾトリアゾール−Ｎ−オ
キサイドの製造
７０ｇ（０，１８モル）の前述（Ｂ）の生成物と２００
ｍ１の水と１００ｍ１のイソプロピルアルコールと２０
ｇの水酸化ナトリウムと０゜２ｇのハイドロキノンを仕
込み、７０℃において８０％ヒドラジンヒトラード２０
ｍ１を滴下した。滴下後、還流下に２時間攪拌した。反
応終了後硫酸で中和し、ろ過液冷却し、析出した結晶を
ろ別し、水で洗浄した。そして更に精製することなく次
の反応に使用した。(C) Intermediate 2-[2'-hydroxy-52-
Preparation of (β-hydroxyethoxy)-3'-t-butylphenyl-5-methyl-2H-benzotriazole-N-oxide 70 g (0.18 mol) of the product of (B) above and 200
ml of water, 100 ml of isopropyl alcohol and 20
Prepare 20g of sodium hydroxide and 0.2g of hydroquinone, and prepare 80% hydrazine hydroxide at 70°C.
ml was added dropwise. After the dropwise addition, the mixture was stirred under reflux for 2 hours. After the reaction was completed, it was neutralized with sulfuric acid, the filtrate was cooled, and the precipitated crystals were filtered out and washed with water. It was then used in the next reaction without further purification.
（Ｄ） 中間体２− ［２’ −ヒドロキシ−５′−
（β−ヒドロキシエトキシ）−３１−ｔ−プチルフェニ
ルコー５−メチル−２Ｈ−ベンゾトリアゾールの製造
ＯＣ８２ＣＨ２０Ｈ
６０ｇの前述（Ｃ）の生成物と１５０ｍ１のトルエンと
９０ｍ１の水と１００ｍ１のイソプロピルアルコールと
４０ｇの濃硫酸を仕込み、７０℃において、亜鉛末２０
ｇを添加した。反応終了後、分液水洗し、脱溶媒した。(D) Intermediate 2-[2'-hydroxy-5'-
Preparation of (β-hydroxyethoxy)-31-t-butylphenyl-5-methyl-2H-benzotriazole OC82CH20H 60 g of the product of (C) above, 150 ml of toluene, 90 ml of water, 100 ml of isopropyl alcohol and 40 g of Prepare concentrated sulfuric acid, and at 70°C, add 20% zinc powder.
g was added. After the reaction was completed, the mixture was separated and washed with water, and the solvent was removed.
次いで、トルエンに溶かし、活性白土で脱色後、晶析し
た。５２ｇの黄色結晶を得た。 融点１４７゜２〜１
４８．１°Ｃ
（Ｅ） ２−［２″−ヒドロキシ−５′−（β−メタ
クリロイルオキシエトキシ）−３’−ｔ−プチルフェニ
ルコー５−メチル−２Ｈ−ベンゾトリアゾールの製造
５０ｇ（ｏ、１５モル）の前述（Ｄ）のベンゾトリアゾ
ールと２５ｇのピリジンを１０１００Ｏのトルエンに溶
かし、２０〜２５℃において、新しく蒸留した塩化メタ
クリロイル１７゜５ｇ（０，１７モル）を滴下した。滴
下後、２０〜２５℃において１０時間攪拌し、ろ過水洗
液、脱溶媒した。そして、２００ｍ］のトルエンと５０
０ｍ１のイソプロピルアルコールがら晶析し、４８ ｇ
の淡黄色結晶を得た。Next, it was dissolved in toluene, decolorized with activated clay, and then crystallized. 52 g of yellow crystals were obtained. Melting point 147°2~1
48.1°C (E) Preparation of 2-[2″-hydroxy-5′-(β-methacryloyloxyethoxy)-3′-t-butylphenyl-5-methyl-2H-benzotriazole 50 g (o, 15 25 g of pyridine and the benzotriazole of (D) were dissolved in 10100 O toluene, and 17.5 g (0.17 mol) of freshly distilled methacryloyl chloride was added dropwise at 20-25°C. The mixture was stirred at 25°C for 10 hours, filtered and washed with water, and the solvent was removed.
Crystallized from 0ml of isopropyl alcohol, 48g
A pale yellow crystal of was obtained.
融点 １３２．０〜１３２．８℃
赤外分光分析 １．６３０ｃｍ−’ Ｃ＝Ｃ結合最大
吸収波長 ３５５ｎｍ
モル吸光係数 １３８００
実施例 ２
２−［２″−ヒドロキシ−５′−（γ−メタクリロイル
オキシプロポキシ）−３’−ｔ−ブチルフェニル］−５
−メチル−２Ｈ−ベンゾトリアゾールの製造
上記実施例１の（Ａ）において、エチレンクロロヒドリ
ンにかえて、プロピレンクロロヒドリンを用い、そｈ以
外は同様にて実施した。Melting point 132.0-132.8℃ Infrared spectroscopy 1.630cm-' C=C bond maximum absorption wavelength 355nm Molar extinction coefficient 13800 Example 2 2-[2''-hydroxy-5'-(γ-methacryloyloxypropoxy )-3'-t-butylphenyl]-5
-Production of methyl-2H-benzotriazole The procedure of Example 1 (A) above was repeated except that propylene chlorohydrin was used instead of ethylene chlorohydrin.
融点 １．１０．８〜１１２．２℃
赤外分光分析 １６３０ｃｍ−’ Ｃ＝Ｃ結合最大吸
収波長 ３５７ｎｍ
モル吸光係数 １４２００
実施例 ３
共重合体の製造
メチルメタクリレート９６重基部、エチレングリコール
ジメタクリレート３重量部、アゾビスイソブチロニトリ
ル０． １重量部及び実施例１で製造したベンゾトリア
ゾール化合物１重量部を１９ｍｍのガラス製試＠管に入
れ３５℃で４０時間、５０ ’Ｃで８時間１次いで２時
間かけて温度を１３０℃まで上昇させ、さらに１１０°
Ｃで１時間保持し、重合物を得た。Melting point 1.10.8~112.2℃ Infrared spectroscopy 1630cm-' C=C bond maximum absorption wavelength 357nm Molar extinction coefficient 14200 Example 3 Production of copolymer Methyl methacrylate 96 double bases, ethylene glycol dimethacrylate 3 weight parts, azobisisobutyronitrile 0. 1 part by weight and 1 part by weight of the benzotriazole compound prepared in Example 1 were placed in a 19 mm glass test tube at 35°C for 40 hours, then at 50'C for 8 hours, then the temperature was raised to 130°C over 2 hours. and further 110°
The mixture was held at C for 1 hour to obtain a polymer.
この重合物を粉砕し、そしてその１ｇを５０ｍ１のエタ
ノールで３時間還流抽出した。抽出液の吸光度を測定し
、実施例１で製造したベンゾトリアゾール化合物のエタ
ノール溶液の極大吸収波長から作成した検量線を用いて
溶出率を算出した。その結果、実施例１で製造したベン
ゾトリアゾール化合物の溶出率は０．２０％であった。The polymer was ground and 1 g thereof was extracted with 50 ml of ethanol under reflux for 3 hours. The absorbance of the extract was measured, and the elution rate was calculated using a calibration curve created from the maximum absorption wavelength of the ethanol solution of the benzotriazole compound produced in Example 1. As a result, the elution rate of the benzotriazole compound produced in Example 1 was 0.20%.
実施例 ４
共重合体の製造
実施例３において、実施例１で製造したベンゾトリアゾ
ール化合物にかえて、実施例２で製造したベンゾトリア
ゾール化合物を用い、それ以外は同様にて実施した。そ
の結果、実施例２で製造したベンゾトリアゾール化合物
の溶出率は０．１５％であった。Example 4 Production of copolymer In Example 3, the benzotriazole compound produced in Example 2 was used in place of the benzotriazole compound produced in Example 1, and the same procedure was repeated except for the benzotriazole compound produced in Example 2. As a result, the elution rate of the benzotriazole compound produced in Example 2 was 0.15%.
本発明のベンゾトリアゾール化合物は、製造が容易であ
り、重合性モノマーと共重合させたとき定量的に共重合
する反応性の紫外線吸収剤として有用なものである。The benzotriazole compound of the present invention is easy to produce and is useful as a reactive ultraviolet absorber that quantitatively copolymerizes when copolymerized with a polymerizable monomer.
特許出願人 シプロ化成株式会社Patent applicant: Cipro Kasei Co., Ltd.
Claims (1)
はＨまたはＣＨ＿３を示す。[Claims] 1. A benzotriazole compound represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents C_2 to C_3 alkylene, and R_2
indicates H or CH_3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322205A JP2858940B2 (en) | 1990-11-26 | 1990-11-26 | Method for producing novel benzotriazole compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322205A JP2858940B2 (en) | 1990-11-26 | 1990-11-26 | Method for producing novel benzotriazole compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04193869A true JPH04193869A (en) | 1992-07-13 |
| JP2858940B2 JP2858940B2 (en) | 1999-02-17 |
Family
ID=18141131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2322205A Expired - Lifetime JP2858940B2 (en) | 1990-11-26 | 1990-11-26 | Method for producing novel benzotriazole compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2858940B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0673367A (en) * | 1992-08-25 | 1994-03-15 | Ipposha Oil Ind Co Ltd | Cationic high-molecular ultraviolet absorber |
| JPH0688065A (en) * | 1992-09-09 | 1994-03-29 | Toray Ind Inc | Ultraviolet absorber and ultraviolet-absorbing composition containing the same |
| JP2000119262A (en) * | 1998-10-14 | 2000-04-25 | Otsuka Chem Co Ltd | Bisbenzotriazolylphenol compound, ultraviolet absorber, ultraviolet absorbing polymer, resin composition and coating material containing these |
| WO2012015076A1 (en) | 2010-07-29 | 2012-02-02 | Fujifilm Corporation | Polymerizable composition |
| US8153703B2 (en) | 2008-11-04 | 2012-04-10 | Novartis Ag | UV/visible light absorbers for ophthalmic lens materials |
| JP2012236797A (en) * | 2011-05-12 | 2012-12-06 | Adeka Corp | Complex and method for producing the same |
| CN112694446A (en) * | 2020-12-22 | 2021-04-23 | 利安隆（中卫）新材料有限公司 | Preparation method of benzotriazole ultraviolet absorbent |
| JPWO2022050278A1 (en) * | 2020-09-01 | 2022-03-10 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2685980B2 (en) | 1990-11-26 | 1997-12-08 | 株式会社メニコン | UV absorbing intraocular lens |
-
1990
- 1990-11-26 JP JP2322205A patent/JP2858940B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0673367A (en) * | 1992-08-25 | 1994-03-15 | Ipposha Oil Ind Co Ltd | Cationic high-molecular ultraviolet absorber |
| JPH0688065A (en) * | 1992-09-09 | 1994-03-29 | Toray Ind Inc | Ultraviolet absorber and ultraviolet-absorbing composition containing the same |
| JP2000119262A (en) * | 1998-10-14 | 2000-04-25 | Otsuka Chem Co Ltd | Bisbenzotriazolylphenol compound, ultraviolet absorber, ultraviolet absorbing polymer, resin composition and coating material containing these |
| US8153703B2 (en) | 2008-11-04 | 2012-04-10 | Novartis Ag | UV/visible light absorbers for ophthalmic lens materials |
| US8232326B2 (en) | 2008-11-04 | 2012-07-31 | Novartis Ag | UV/visible light absorbers for ophthalmic lens materials |
| WO2012015076A1 (en) | 2010-07-29 | 2012-02-02 | Fujifilm Corporation | Polymerizable composition |
| JP2012236797A (en) * | 2011-05-12 | 2012-12-06 | Adeka Corp | Complex and method for producing the same |
| JPWO2022050278A1 (en) * | 2020-09-01 | 2022-03-10 | ||
| WO2022050278A1 (en) * | 2020-09-01 | 2022-03-10 | 富士フイルム株式会社 | Curable resin composition, cured object, layered product, method for producing cured object, semiconductor device, and photobase generator |
| KR20230045608A (en) * | 2020-09-01 | 2023-04-04 | 후지필름 가부시키가이샤 | Curable resin composition, cured product, laminate, method for producing cured product, semiconductor device, and photobase generator |
| CN112694446A (en) * | 2020-12-22 | 2021-04-23 | 利安隆（中卫）新材料有限公司 | Preparation method of benzotriazole ultraviolet absorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2858940B2 (en) | 1999-02-17 |
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