JPH0959263A - Process for producing 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative - Google Patents
Process for producing 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivativeInfo
- Publication number
- JPH0959263A JPH0959263A JP7227075A JP22707595A JPH0959263A JP H0959263 A JPH0959263 A JP H0959263A JP 7227075 A JP7227075 A JP 7227075A JP 22707595 A JP22707595 A JP 22707595A JP H0959263 A JPH0959263 A JP H0959263A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- diaryl
- dihydroxyphenyl
- producing
- triazine derivative
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】
【課題】 少ない工程数で高収率に２−（２’，４’−
ジヒドロキシフェニル）−４，６−ジアリール−ｓ−ト
リアジン誘導体を製造する方法を提供する。
【解決手段】 塩化シアヌルと特定のフェノール化合物
（Ｉ）を反応させて、フェニルオキシジクロロ−ｓ−ト
リアジンとする工程Ｉと、得られた化合物と特定のフェ
ニル化合物をルイス酸触媒で反応させて２−フェニルオ
キシ−４，６−ジアリール−ｓ−トリアジンとする工程
ＩＩと、得られた化合物と特定のフェノール化合物
（Ｖ）をルイス酸触媒で反応させる下記２−（２’，
４’−ジヒドロキシフェニル）−４，６−ジアリール−
ｓ−トリアジン誘導体（ＶＩ）の製造方法。
【化１】
(57) 【Abstract】 PROBLEM TO BE SOLVED: To obtain 2- (2 ′, 4′−) in high yield with a small number of steps.
Provided are methods of making dihydroxyphenyl) -4,6-diaryl-s-triazine derivatives. SOLUTION: Step I in which cyanuric chloride and a specific phenol compound (I) are reacted to obtain phenyloxydichloro-s-triazine, and the obtained compound and a specific phenyl compound are reacted with a Lewis acid catalyst to obtain 2 -Phenyloxy-4,6-diaryl-s-triazine in step II and the following 2- (2 ', which reacts the obtained compound with a specific phenol compound (V) with a Lewis acid catalyst.
4'-dihydroxyphenyl) -4,6-diaryl-
Process for producing s-triazine derivative (VI). Embedded image
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、２−（２’，４’
−ジヒドロキシフェニル）−４，６−ジアリール−ｓ−
トリアジン誘導体の製造方法に関し、詳しくは、モノフ
ェノキシトリアジン誘導体を経由して少ない工程数で高
収率に２−（２’，４’−ジヒドロキシフェニル）−
４，６−ジアリール−ｓ−トリアジン誘導体を製造する
方法に関する。TECHNICAL FIELD The present invention relates to 2- (2 ′, 4 ′).
-Dihydroxyphenyl) -4,6-diaryl-s-
Regarding the method for producing a triazine derivative, specifically, 2- (2 ′, 4′-dihydroxyphenyl) -can be obtained in a high yield with a small number of steps via a monophenoxytriazine derivative.
It relates to a method for producing a 4,6-diaryl-s-triazine derivative.
【０００２】[0002]
【従来の技術及び問題点】２−（２’，４’−ジヒドロ
キシフェニル）−４，６−ジアリール−ｓ−トリアジン
誘導体は紫外線吸収物質または紫外線吸収物質を製造す
る際の出発物質として重要である。2. Description of the Related Art A 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative is important as an ultraviolet absorber or a starting material for producing an ultraviolet absorber. .
【０００３】この２−（２’，４’−ジヒドロキシフェ
ニル）−４，６−ジアリール−ｓ−トリアジン誘導体の
製造方法としては、特公昭４２−１５７００号公報に
は、ジアリールクロロトリアジンとｍ−レゾルシノール
を三塩化アルミニウム触媒で反応することが提案されて
いる。また、ここで用いられるジアリールクロロトリア
ジンは、英国特許８８４８０２号において、塩化シアヌ
ルとアリール化合物から合成することが提案されてい
る。しかし、塩化シアヌルとアリール化合物の反応の選
択性が低いため、前記の反応ではモノ体やトリ体を副生
するために低収率であり、実用的ではなかった。As a method for producing the 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative, Japanese Patent Publication No. 42-15700 discloses a diarylchlorotriazine and m-resorcinol. Has been proposed to react with an aluminum trichloride catalyst. The diaryl chlorotriazine used here is proposed in British Patent No. 884802 to be synthesized from cyanuric chloride and an aryl compound. However, since the selectivity of the reaction between cyanuric chloride and the aryl compound is low, the above reaction is not practical since the mono-form and tri-form are by-produced and the yield is low.
【０００４】また、特開平５−７０４４３号公報にはベ
ンズアミジンハロゲン化水素酸塩から２−ヒドロキシ−
４，６−ジアリールトリアジンを経由して製造する方法
が提案されているが、収率については改善されるものの
工程が煩雑で実用化には満足のいくものではなかった。Further, in JP-A-5-70443, benzamidine hydrohalide is treated with 2-hydroxy-.
A method for producing via 4,6-diaryltriazine has been proposed, but although the yield is improved, the process is complicated and not satisfactory for practical use.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記の現
状に鑑み鋭意検討を重ねた結果、（ａ）塩化シアヌルと
下記一般式（Ｉ）で表されるフェノール化合物を反応さ
せ、下記一般式（ＩＩ）で表されるフェニルオキシジク
ロロ−ｓ−トリアジンとする工程Ｉと、（ｂ）一般式
（ＩＩ）の化合物と下記一般式（ＩＩＩ）で表されるフ
ェニル化合物をルイス酸触媒で反応させ、下記一般式
（ＩＶ）で表される２−フェニルオキシ−４，６−ジア
リール−ｓ−トリアジンとする工程ＩＩと、（ｃ）一般
式（ＩＶ）の化合物と下記一般式（Ｖ）で表されるフェ
ノール化合物をルイス酸触媒で反応させ、下記一般式
（ＶＩ）で表されるトリアジン誘導体とする工程ＩＩＩ
から、２−（２’，４’−ジヒドロキシフェニル）−
４，６−ジアリール−ｓ−トリアジン誘導体が容易に高
収率で得られることを見出し、本発明に到達した。以
下、上記要旨をもってなる本発明について詳述する。Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above situation, and as a result, (a) cyanuric chloride is reacted with a phenol compound represented by the following general formula (I), Step I, which is a phenyloxydichloro-s-triazine represented by the general formula (II), and (b) a compound of the general formula (II) and a phenyl compound represented by the following general formula (III) with a Lewis acid catalyst. Step II of reacting to give 2-phenyloxy-4,6-diaryl-s-triazine represented by the following general formula (IV), (c) compound of general formula (IV) and the following general formula (V) Step III of reacting a phenol compound represented by the formula (1) with a Lewis acid catalyst to form a triazine derivative represented by the following general formula (VI)
From 2- (2 ', 4'-dihydroxyphenyl)-
The inventors have found that a 4,6-diaryl-s-triazine derivative can be easily obtained in a high yield, and arrived at the present invention. Hereinafter, the present invention having the above-mentioned gist will be described in detail.
【０００６】[0006]
【化７】 [Chemical 7]
【０００７】[0007]
【化８】 Embedded image
【０００８】[0008]
【化９】 Embedded image
【０００９】[0009]
【化１０】 Embedded image
【００１０】[0010]
【化１１】 Embedded image
【００１１】[0011]
【化１２】 [Chemical 12]
【００１２】前記各式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、
Ｒ6、Ｒ7およびＲ8で表される炭素数１〜１０のアルキ
ル基としては、メチル、エチル、プロピル、ブチル、ペ
ンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシ
ルがあげられ、アルコキシ基、アルコキシカルボニル基
としては前記アルキル基に対応する基があげられる。In the above formulas, R 1 , R 2 , R 3 , R 4 , R 5 ,
Examples of the alkyl group having 1 to 10 carbon atoms represented by R 6 , R 7 and R 8 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, an alkoxy group and an alkoxy group. Examples of the carbonyl group include groups corresponding to the above alkyl groups.
【００１３】Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5、Ｒ6、Ｒ7およ
びＲ8で表されるハロゲン原子としては、フッ素原子、
塩素原子、臭素原子があげられる。The halogen atom represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a fluorine atom,
Examples thereof include chlorine atom and bromine atom.
【００１４】工程Ｉにおいては、化合物（Ｉ）／塩化シ
アヌルのモル比が０．８〜１．２であることが好まし
く、０．９〜１．１であることがより好ましい。この範
囲を外れると目的物の生成率が低下して収率が低下する
ほか、精製が困難になる。In step I, the compound (I) / cyanuric chloride molar ratio is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1. If the amount is out of this range, the production rate of the target product decreases, the yield decreases, and purification becomes difficult.
【００１５】また、反応の触媒は用いても用いなくても
よく、触媒としては、塩基性触媒でもルイス酸でもよ
い。ルイス酸触媒を用いると反応時間が短縮され、後の
工程と共にワンポットで化合物（ＶＩ）を製造できるの
で、ルイス酸触媒を用いることが好ましい。反応温度は
５０℃以下が好ましい。５０℃より高いと反応の選択性
が低下してジ体が生成し、収率が低下するほか、精製が
困難になる。The reaction catalyst may or may not be used, and the catalyst may be a basic catalyst or a Lewis acid. When the Lewis acid catalyst is used, the reaction time is shortened and the compound (VI) can be produced in one pot together with the subsequent steps. Therefore, it is preferable to use the Lewis acid catalyst. The reaction temperature is preferably 50 ° C or lower. If the temperature is higher than 50 ° C, the selectivity of the reaction is lowered, the di-form is produced, the yield is lowered, and the purification becomes difficult.
【００１６】工程ＩＩにおいては、化合物（ＩＩＩ）／
化合物（ＩＩ）のモル比が１．８〜２０であることが好
ましく、２．２〜１５であることがより好ましい。１．
８以下では収率が低く、２０以上用いると反応時間が長
くなる。In step II, compound (III) /
The molar ratio of the compound (II) is preferably 1.8 to 20, and more preferably 2.2 to 15. 1.
If it is 8 or less, the yield is low, and if it is 20 or more, the reaction time becomes long.
【００１７】反応温度は、８０〜１２０℃が好ましく、
９０〜１２０℃がより好ましい。８０℃以下では反応が
ほとんど進行せず、１２０℃以上では副生物が増大して
収率が低くなる。The reaction temperature is preferably 80 to 120 ° C.,
90-120 degreeC is more preferable. If the temperature is 80 ° C or lower, the reaction hardly progresses, and if it is 120 ° C or higher, the amount of by-products increases and the yield decreases.
【００１８】また、反応触媒としては、ルイス酸が用い
られ、通常は無水三塩化アルミニウムが用いられ、化合
物（ＩＩＩ）の０．２〜１．２倍モル用いることが好ま
しい。これ以下では生成率が低下し、これ以上用いても
反応時間はほとんど短縮されず経済的に不利になる。As the reaction catalyst, a Lewis acid is used, usually anhydrous aluminum trichloride is used, and it is preferable to use 0.2 to 1.2 times mol of the compound (III). If it is less than this, the production rate is lowered, and even if it is used more than this, the reaction time is hardly shortened and it is economically disadvantageous.
【００１９】工程ＩＩＩにおいては、化合物（Ｖ）／化
合物（ＩＶ）のモル比が０．８〜１．２とすることが好
ましく、０．９〜１．１とすることがより好ましい。
０．８以下では収率が低く、１．２以上用いても収率は
改善されず経済的に不利になる。In step III, the compound (V) / compound (IV) molar ratio is preferably 0.8 to 1.2, more preferably 0.9 to 1.1.
If it is 0.8 or less, the yield is low, and if it is 1.2 or more, the yield is not improved, which is economically disadvantageous.
【００２０】反応温度は、８０〜１２０℃が好ましく、
９０〜１２０℃がより好ましい。８０℃以下では反応が
ほとんど進行せず、１２０℃以上では副生物が増大して
収率が低くなる。The reaction temperature is preferably 80 to 120 ° C,
90-120 degreeC is more preferable. If the temperature is 80 ° C or lower, the reaction hardly progresses, and if it is 120 ° C or higher, the amount of by-products increases and the yield decreases.
【００２１】また、反応触媒としては、ルイス酸が用い
られ、通常は無水三塩化アルミニウムが用いられ、化合
物（ＩＶ）の０．５〜１．２倍モル用いることが好まし
い。これ以下では生成率が低下し、これ以上用いても反
応時間はほとんど短縮されず経済的に不利になる。As the reaction catalyst, a Lewis acid is used, usually anhydrous aluminum trichloride is used, and it is preferable to use 0.5 to 1.2 times mol of the compound (IV). If it is less than this, the production rate is lowered, and even if it is used more than this, the reaction time is hardly shortened and it is economically disadvantageous.
【００２２】本発明の製造方法においては、各工程の終
了毎に精製工程を取り入れてもよいが、反応工程を連結
してワンポットで連続して反応させて化合物（ＶＩ）を
製造することが、効率的であるため好ましい。また、原
料の仕込み方法としては、連続して反応を行う場合に
は、塩化シアヌル、化合物（Ｉ）、化合物（ＩＩＩ）お
よびルイス酸触媒を一括して仕込み、低温で工程Ｉを行
ない、そのまま昇温して工程ＩＩを行なってもよく、工
程Ｉの原料と溶媒のみで工程Ｉを行なった後、工程ＩＩ
の原料を仕込んで昇温して工程ＩＩを行ってもよい。こ
のようにして化合物（ＩＶ）を合成した後、化合物
（Ｖ）と必要に応じてルイス酸触媒を追加添加して工程
ＩＩＩを行ない、化合物（ＶＩ）を製造する。In the production method of the present invention, a purification step may be incorporated at the end of each step, but the reaction step may be linked to continuously react in one pot to produce compound (VI), It is preferable because it is efficient. In addition, as a method of charging the raw materials, when the reaction is continuously carried out, cyanuric chloride, compound (I), compound (III) and a Lewis acid catalyst are collectively charged, and step I is carried out at a low temperature, and the mixture is heated as it is. The step II may be carried out by heating, or after performing the step I only with the raw material and the solvent of the step I, the step II
The step II may be carried out by charging the above raw materials and raising the temperature. After synthesizing the compound (IV) in this manner, the compound (V) and, if necessary, a Lewis acid catalyst are additionally added to carry out the step III to produce the compound (VI).
【００２３】本発明によって得られる上記一般式（Ｖ
Ｉ）で表される化合物としては、例えば、下記の化合物
Ｎｏ．１〜Ｎｏ．６等の化合物が挙げられる。The above general formula (V
Examples of the compound represented by I) include the following compound No. 1 to No. 6 and the like.
【００２４】[0024]
【化１３】 Embedded image
【００２５】[0025]
【化１４】 Embedded image
【００２６】[0026]
【化１５】 Embedded image
【００２７】[0027]
【化１６】 Embedded image
【００２８】[0028]
【化１７】 Embedded image
【００２９】[0029]
【化１８】 Embedded image
【００３０】[0030]
【発明の実施の形態】本発明の方法による前記一般式
（ＶＩ）で表される化合物の具体的な合成の実施例を以
下に示す。BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the synthesis of the compound represented by the general formula (VI) by the method of the present invention will be shown below.
【００３１】（実施例１：化合物Ｎｏ．１の合成）塩化
シアヌル５５．３ｇ（０．３モル）、ｐ−クロロフェノ
ール３６．０ｇ（０．２８モル）、ｍ−キシレン３５０
ｇ（３．３モル）に５〜１０℃で三塩化アルミニウム３
７．３ｇ（０．２８モル）を加え、３５℃で３時間攪拌
した。ガスクロマトグラフィー分析により、反応液中の
ｍーキシレンおよび塩化シアヌルを除く成分の面積強度
において９９％の強度を示す２−（４’−クロロフェノ
キシ）−４，６−ジクロロトリアジンの生成を確認し
た。Example 1 Synthesis of Compound No. 1 55.3 g (0.3 mol) of cyanuric chloride, 36.0 g (0.28 mol) of p-chlorophenol, 350 of m-xylene.
Aluminum trichloride 3 to 5 g (3.3 mol) at 5 to 10 ° C
7.3 g (0.28 mol) was added, and the mixture was stirred at 35 ° C. for 3 hours. Gas chromatographic analysis confirmed the formation of 2- (4′-chlorophenoxy) -4,6-dichlorotriazine showing 99% strength in the area strength of components other than m-xylene and cyanuric chloride in the reaction solution.
【００３２】前記反応液に三塩化アルミニウム１８．７
ｇ（０．１４モル）を追加し、１０５℃で４時間反応さ
せた。ガスクロマトグラフィー分析により反応液中のｍ
ーキシレンを除く成分の面積強度において９４％の強度
を示す２−（４’−クロロフェノキシ）−４，６−ビス
（２’’，４’’−ジメチルフェニル）トリアジンの生
成を確認した。Aluminum trichloride 18.7 was added to the reaction solution.
g (0.14 mol) was added, and the mixture was reacted at 105 ° C. for 4 hours. M in the reaction solution by gas chromatography analysis
The formation of 2- (4′-chlorophenoxy) -4,6-bis (2 ″, 4 ″ -dimethylphenyl) triazine showing 94% strength in the area strength of the components excluding xylene was confirmed.
【００３３】この反応液を４０℃まで冷却してレゾルシ
ノール３７．０ｇ（０．３４モル）、三塩化アルミニウ
ム３７．３ｇ（０．２８モル）を加え、９０℃で５時間
反応させた。３Ｎ塩酸水溶液および氷を加えて攪拌後、
水蒸気蒸留によりｐ−クロロフェノールおよび過剰のｍ
ーキシレンを除去した。沈澱をろ取して乾燥し、ヘキサ
ンで洗浄し、さらにキシレンより再結晶して融点２２９
℃の淡黄色粉末８７．３ｇ（収率７８．５％）を得た。The reaction solution was cooled to 40 ° C., 37.0 g (0.34 mol) of resorcinol and 37.3 g (0.28 mol) of aluminum trichloride were added, and the reaction was carried out at 90 ° C. for 5 hours. After adding a 3N hydrochloric acid aqueous solution and ice and stirring,
P-chlorophenol and excess m by steam distillation
-Xylene was removed. The precipitate was collected by filtration, dried, washed with hexane and recrystallized from xylene to give a melting point of 229.
87.3 g (yield 78.5%) of pale yellow powder having a temperature of 0 ° C. was obtained.
【００３４】（比較例１：英国特許８８４８０２号およ
び特開昭４２−１５７００号公報に基づく化合物Ｎｏ．
１の合成）塩化シアヌル５５．３ｇ（０．３モル）、ｍ
−キシレン１２７．２ｇ（１．２モル）、三塩化アルミ
ニウム４８ｇ（０．３６モル）を室温で６０時間反応さ
せた。ガスクロマトグラフィーにより反応液中のｍーキ
シレンを除く成分の面積強度において、モノ−体／ジ−
体／トリ−体の比は２０／５４／２６であった。この反
応液にレゾルシノール３７．４ｇ（０．３４モル）、三
塩化アルミニウム４０ｇ（０．３モル）を加え、１１０
℃で５時間反応した。冷却して３Ｎ水溶液、氷を加えて
処理した。水蒸気蒸留により過剰のレゾルシノールとｍ
ーキシレンを除去して、沈澱をろ取して乾燥し、さらに
キシレンより再結晶して融点２２９℃の淡黄色粉末３
４．７ｇ（収率３１．２％）を得た。(Comparative Example 1: Compound No. 1 based on British Patent No. 884802 and Japanese Patent Laid-Open No. 42-15700).
Synthesis of 1) 55.3 g (0.3 mol) of cyanuric chloride, m
-127.2 g (1.2 mol) of xylene and 48 g (0.36 mol) of aluminum trichloride were reacted at room temperature for 60 hours. The area intensity of the components other than m-xylene in the reaction solution was determined by gas chromatography to indicate the mono-form / di-form.
The body / tri-body ratio was 20/54/26. To this reaction solution, 37.4 g (0.34 mol) of resorcinol and 40 g (0.3 mol) of aluminum trichloride were added, and 110
The reaction was carried out at 5 ° C. for 5 hours. After cooling, 3N aqueous solution and ice were added for treatment. Excess resorcinol and m by steam distillation
-Xylene was removed, the precipitate was collected by filtration, dried, and recrystallized from xylene to give a pale yellow powder with a melting point of 229 ° C.
4.7 g (yield 31.2%) was obtained.
【００３５】[0035]
【発明の効果】上記実施例と比較例の結果から、本発明
の特定の製造方法を用いた場合には、従来知られていた
方法に比較して、著しく高い収率で、しかも、ワンポッ
トで目的物が得られることが明らかである。From the results of the above Examples and Comparative Examples, when the specific production method of the present invention is used, the yield is remarkably higher than that of the conventionally known methods, and moreover, in one pot. It is clear that the desired product is obtained.
Claims (8)
で表されるフェノール化合物を反応させ、下記一般式
（ＩＩ）で表されるフェニルオキシジクロロ−ｓ−トリ
アジンとする工程Ｉと、 （ｂ）一般式（ＩＩ）の化合物と下記一般式（ＩＩＩ）
で表されるフェニル化合物をルイス酸触媒で反応させ、
下記一般式（ＩＶ）で表される２−フェニルオキシ−
４，６−ジアリール−ｓ−トリアジンとする工程ＩＩ
と、 （ｃ）一般式（ＩＶ）の化合物と下記一般式（Ｖ）で表
されるフェノール化合物をルイス酸触媒で反応させ、下
記一般式（ＶＩ）で表されるトリアジン誘導体とする工
程ＩＩＩからなる２−（２’，４’−ジヒドロキシフェ
ニル）−４，６−ジアリール−ｓ−トリアジン誘導体の
製造方法。 【化１】 【化２】 【化３】 【化４】 【化５】 【化６】 1. A cyanuric chloride (a) and the following general formula (I):
A step I of reacting a phenol compound represented by the formula (II) to obtain phenyloxydichloro-s-triazine represented by the following general formula (II), (b) a compound of the general formula (II) and the following general formula (III)
The phenyl compound represented by is reacted with a Lewis acid catalyst,
2-phenyloxy-represented by the following general formula (IV)
Step II to give 4,6-diaryl-s-triazine II
And (c) reacting a compound represented by the general formula (IV) with a phenol compound represented by the following general formula (V) using a Lewis acid catalyst to obtain a triazine derivative represented by the following general formula (VI): From step III And a method for producing a 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative. Embedded image Embedded image Embedded image Embedded image Embedded image [Chemical 6]
アヌルの０．８〜１．２倍モル用いることを特徴とする
請求項１記載の２−（２’，４’−ジヒドロキシフェニ
ル）−４，６−ジアリール−ｓ−トリアジン誘導体の製
造方法。2. The 2- (2 ′, 4′-dihydroxyphenyl)-according to claim 1, wherein the compound (I) is used in Step I in an amount of 0.8 to 1.2 times the molar amount of cyanuric chloride. A method for producing a 4,6-diaryl-s-triazine derivative.
化合物（ＩＩ）の１．８〜２０倍モル用いることを特徴
とする請求項１記載の２−（２’，４’−ジヒドロキシ
フェニル）−４，６−ジアリール−ｓ−トリアジン誘導
体の製造方法。3. The 2- (2 ′, 4′-dihydroxyphenyl)-according to claim 1, wherein in the step II, the compound (III) is used in an amount of 1.8 to 20 times the molar amount of the compound (II). A method for producing a 4,6-diaryl-s-triazine derivative.
合物（ＩＶ）の０．８〜１．２倍モル用いることを特徴
とする請求項１記載の２−（２’，４’−ジヒドロキシ
フェニル）−４，６−ジアリール−ｓ−トリアジン誘導
体の製造方法。4. The 2- (2 ′, 4′-dihydroxyphenyl) according to claim 1, wherein the compound (V) is used in the step III in an amount of 0.8 to 1.2 times the molar amount of the compound (IV). ) A method for producing a 4,6-diaryl-s-triazine derivative.
以下で行うことを特徴とする請求項１記載の２−
（２’，４’−ジヒドロキシフェニル）−４，６−ジア
リール−ｓ−トリアジン誘導体の製造方法。5. Step I using a Lewis acid catalyst at 50 ° C.
2. The method according to claim 1, which is performed as follows.
A method for producing a (2 ′, 4′-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative.
１．２倍モルのルイス酸触媒を用いて、８０〜１２０℃
で行うことを特徴とする請求項１記載の２−（２’，
４’−ジヒドロキシフェニル）−４，６−ジアリール−
ｓ−トリアジン誘導体の製造方法。6. The step II is carried out by adding 0.2 to 0.2 of the compound (II).
80 to 120 ° C. using 1.2 times mole of Lewis acid catalyst
2- (2 ′, 2) according to claim 1, characterized in that
4'-dihydroxyphenyl) -4,6-diaryl-
A method for producing an s-triazine derivative.
１．２倍モルのルイス酸触媒を用いて、８０〜１２０℃
で行うことを特徴とする請求項１記載の２−（２’，
４’−ジヒドロキシフェニル）−４，６−ジアリール−
ｓ−トリアジン誘導体の製造方法。7. Step III is carried out by adding 0.5 to 0.5 of compound (IV).
80 to 120 ° C. using 1.2 times mole of Lewis acid catalyst
2- (2 ′, 2) according to claim 1, characterized in that
4'-dihydroxyphenyl) -4,6-diaryl-
A method for producing an s-triazine derivative.
にワンポットで行うことを特徴とする請求項１記載の２
−（２’，４’−ジヒドロキシフェニル）−４，６−ジ
アリール−ｓ−トリアジン誘導体の製造方法。8. The method according to claim 1, wherein step I, step II and step III are continuously performed in one pot.
A method for producing a-(2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22707595A JP3844307B2 (en) | 1995-08-11 | 1995-08-11 | Method for producing 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22707595A JP3844307B2 (en) | 1995-08-11 | 1995-08-11 | Method for producing 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0959263A true JPH0959263A (en) | 1997-03-04 |
| JP3844307B2 JP3844307B2 (en) | 2006-11-08 |
Family
ID=16855133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22707595A Expired - Lifetime JP3844307B2 (en) | 1995-08-11 | 1995-08-11 | Method for producing 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3844307B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11315072A (en) * | 1998-03-02 | 1999-11-16 | Ciba Specialty Chem Holding Inc | New production of trisaryl-o-hydroxyphenyl-s-triazine |
| WO2000014077A1 (en) * | 1998-09-04 | 2000-03-16 | Cytec Technology Corp. | Process for making 2- (2,4- dihydroxyphenyl) or 2- (2,4- dialkoxyphenyl)- 4,6- bisaryl- 1,3,5- triazines |
| WO2000014074A1 (en) * | 1998-09-04 | 2000-03-16 | Ciba Specialty Chemicals Holding Inc. | Process for making 2-hydroxy-4-alkoxyphenyl or 2,4-dihydroxyphenyl substituted 1,3,5-triazine uv absorbers |
| US6297378B1 (en) | 1998-09-04 | 2001-10-02 | Cytec Technology Corp. | Process for making 2-(2-hydroxy-4-alkoxyphenyl)-4,6-bisaryl-1,3,5-triazines |
| US6297377B1 (en) | 1998-06-22 | 2001-10-02 | Cytec Technology Corporation | Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers |
| US6486316B1 (en) | 1998-11-17 | 2002-11-26 | Cytec Technology Corp. | Process for making triazine UV absorbers using Lewis acids and reaction promoters |
| US6509399B2 (en) | 1998-06-22 | 2003-01-21 | Cytec Technology Corp | Non-yellowing part-tertiary-alkyl phenyl substituted triazine and pyrimidine ultraviolet light absorbers |
| US6632944B2 (en) | 2001-06-22 | 2003-10-14 | Cytec Technology Corp. | Process for isolation of monophenolic-bisaryl triazines |
| US6855269B2 (en) | 2001-11-09 | 2005-02-15 | Cytec Technology Corp. | Phenyl ether-substituted hydroxyphenyl triazine ultraviolet light absorbers |
| US6867250B1 (en) | 2000-10-30 | 2005-03-15 | Cytec Technology Corp. | Non-yellowing ortho-dialkyl aryl substituted triazine ultraviolet light absorbers |
| KR100577935B1 (en) * | 1997-05-16 | 2007-10-17 | 시바 스페셜티 케미칼스 홀딩 인크. | Resorcinyl-triazine, preparation method thereof and perfume composition containing the same |
| WO2010081625A2 (en) | 2009-01-19 | 2010-07-22 | Basf Se | Organic black pigments and their preparation |
-
1995
- 1995-08-11 JP JP22707595A patent/JP3844307B2/en not_active Expired - Lifetime
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100577935B1 (en) * | 1997-05-16 | 2007-10-17 | 시바 스페셜티 케미칼스 홀딩 인크. | Resorcinyl-triazine, preparation method thereof and perfume composition containing the same |
| EP0941989A3 (en) * | 1998-03-02 | 2000-01-12 | Ciba SC Holding AG | Process for the preparation of 2,4-diaryl-6-o-hydroxyphenyl-1,3,5-triazine derivatives in the presence of a protic acid catalyst |
| JPH11315072A (en) * | 1998-03-02 | 1999-11-16 | Ciba Specialty Chem Holding Inc | New production of trisaryl-o-hydroxyphenyl-s-triazine |
| US6242598B1 (en) | 1998-03-02 | 2001-06-05 | Ciba Specialty Chemicals Corporation | Methods for the preparation of tris-aryl-o-hydroxyphenyl-s-triazines |
| US6297377B1 (en) | 1998-06-22 | 2001-10-02 | Cytec Technology Corporation | Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers |
| US6509399B2 (en) | 1998-06-22 | 2003-01-21 | Cytec Technology Corp | Non-yellowing part-tertiary-alkyl phenyl substituted triazine and pyrimidine ultraviolet light absorbers |
| US6384113B1 (en) | 1998-06-22 | 2002-05-07 | Cytec Technology Corp. | Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers |
| US6486317B1 (en) | 1998-09-04 | 2002-11-26 | Ciba Specialty Chemicals Corporation | Process for making 2-hydroxy-4-alkoxyphenyl or 2,4-dihydroxyphenyl substituted 1,3,5-triazine UV absorbers |
| US6297378B1 (en) | 1998-09-04 | 2001-10-02 | Cytec Technology Corp. | Process for making 2-(2-hydroxy-4-alkoxyphenyl)-4,6-bisaryl-1,3,5-triazines |
| WO2000014077A1 (en) * | 1998-09-04 | 2000-03-16 | Cytec Technology Corp. | Process for making 2- (2,4- dihydroxyphenyl) or 2- (2,4- dialkoxyphenyl)- 4,6- bisaryl- 1,3,5- triazines |
| US6225468B1 (en) | 1998-09-04 | 2001-05-01 | Cytec Technology Corp. | Process for making 2-(2,4,-dihydroxyphenyl) or 2-(2,4-dialkoxyphenyl)-4,6-bisaryl-1,3,5-triazines |
| WO2000014074A1 (en) * | 1998-09-04 | 2000-03-16 | Ciba Specialty Chemicals Holding Inc. | Process for making 2-hydroxy-4-alkoxyphenyl or 2,4-dihydroxyphenyl substituted 1,3,5-triazine uv absorbers |
| US6730785B2 (en) | 1998-11-17 | 2004-05-04 | Cytec Technology Corp. | Process for making triazine UV absorbers using lewis acids and reaction promoters |
| US6710177B2 (en) | 1998-11-17 | 2004-03-23 | Cytec Technology Corp. | Process for making triazine UV absorbers using Lewis acids and reaction promoters |
| US6900314B2 (en) | 1998-11-17 | 2005-05-31 | Cytec Technology Corp. | Process for making triazine UV absorbers using lewis acids and reaction promoters |
| US6486316B1 (en) | 1998-11-17 | 2002-11-26 | Cytec Technology Corp. | Process for making triazine UV absorbers using Lewis acids and reaction promoters |
| US6867250B1 (en) | 2000-10-30 | 2005-03-15 | Cytec Technology Corp. | Non-yellowing ortho-dialkyl aryl substituted triazine ultraviolet light absorbers |
| US6632944B2 (en) | 2001-06-22 | 2003-10-14 | Cytec Technology Corp. | Process for isolation of monophenolic-bisaryl triazines |
| EP2280005A1 (en) | 2001-06-22 | 2011-02-02 | Cytec Technology Corp. | Process for isolation of monophenolic bisaryl triazines |
| EP2289884A1 (en) | 2001-06-22 | 2011-03-02 | Cytec Technology Corp. | Process for isolation of monophenolic bisaryl triazines |
| EP2835368A1 (en) | 2001-06-22 | 2015-02-11 | Cytec Technology Corp. | Process for Isolation of Monophenolic-Bisaryl Triazines |
| US6855269B2 (en) | 2001-11-09 | 2005-02-15 | Cytec Technology Corp. | Phenyl ether-substituted hydroxyphenyl triazine ultraviolet light absorbers |
| WO2010081625A2 (en) | 2009-01-19 | 2010-07-22 | Basf Se | Organic black pigments and their preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3844307B2 (en) | 2006-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4629814B2 (en) | Novel process for producing trisaryl-o-hydroxyphenyl-s-triazine | |
| US6156925A (en) | Process for the preparation of halogenated phenylmaloates | |
| EP0274379B1 (en) | Process for preparing pyridine-2,3-dicarboxylic acid compounds | |
| JP2857219B2 (en) | Method for producing 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-S-triazine | |
| JPH0959263A (en) | Process for producing 2- (2 ', 4'-dihydroxyphenyl) -4,6-diaryl-s-triazine derivative | |
| KR20100054809A (en) | Method for producing b-nitrostyrene compound | |
| JP3586288B2 (en) | Preparation of biphenyl derivatives | |
| US4769493A (en) | Process for producing tetrafluorophthalic acid | |
| US5869722A (en) | Process for producing aluminum phosphinates | |
| US5268479A (en) | Process for the preparation of tertiary phosphines | |
| EP3608324B1 (en) | Method for preparing 2-arylmalonamide and applications of this method | |
| JP4345095B2 (en) | Method for highly selective O-alkylation of amide compounds using copper salts | |
| JPH0458468B2 (en) | ||
| EP0259663B1 (en) | Process for producing tetrafluorophihalic acid | |
| EP1002788B1 (en) | Process for preparing halogenated phenylmalonates | |
| JP2000229934A (en) | Production of 13c-containing urea | |
| JP4435447B2 (en) | Method for producing methoxymethyltriarylphosphonium chloride | |
| JP4663105B2 (en) | Method for producing 2-sulfonyl-4-oxypyridine derivative | |
| JP2546067B2 (en) | Method for producing methanediphosphonic acid compound | |
| JPH08325245A (en) | Production of 1,3,5-tris-(2-hydroxyalkyl)-isocyanurate | |
| JP4662649B2 (en) | Novel phosphine compounds | |
| KR20180081276A (en) | Method for producing 5-(3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1(2h)-pyrimidinyl)phenylthiol compounds | |
| JP4171965B2 (en) | Method for producing 4,4-difluoro-3-buten-1-ol derivative | |
| JP2002179612A (en) | Method for producing 2,3-dibromosuccinic acids | |
| KR950002863B1 (en) | Process for preparing phosphate ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20050825 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060811 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060814 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090825 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100825 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110825 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110825 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120825 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130825 Year of fee payment: 7 |
|
| EXPY | Cancellation because of completion of term |