200932730 九、發明說明： 【發明所屬之技術領域】 本發明係一種卜曱代烯丙基-2-(2’-羥基-5’-甲基苯 基）苯並三唑化合物及其衍生物之製備方法，尤指一種不 需分離中間產物即可得1-曱代烯丙基- 2- (2’ -羥基- 5’ -曱 基苯基）苯並三唑化合物及其衍生物的製備方法。 【先前技術】 〇 苯並三。坐化合物（Benzotriazole compound)在化妝品中是一 種被廣泛使用的的化學材料，因該化合物具有吸收紫外線的功 能，所以大部分被利用做為化妝品中紫外線吸收劑的有效成份。 該化合物係藉由此類化合物的結構所具有的共振效應來吸 收紫外線，且該化合物尤其對紫外線-B的280nm和320nm波 長與紫外線-A的320nm和400nm波長特別具有吸收的效果， 用於化妝品中隔離霜或是防曬油中皆可避免皮膚受到紫外線的 曬傷或傷害，進一步避免產生皮膚黃斑或其他病變而引起皮膚 癌的產生。 因此近年來各方對於笨並三唑化合物的衍生物都積極的研 究，而使該苯並三唑化合物的衍生物能被廣泛的用來當作紫外 線吸收劑，根據美國專利 US3715334，US3947436，US4051161， US4122233，US4188451，US4233430，US4316033，US4342742， US4373060，US445791卜 US4489057，US4490356，US4696969， US4814162，US4851587，US4859759，US486825卜 US5089250， 歐州專利EP0138321，EP0354145，EP2077280A等所揭示之專 5 200932730 利技術皆可製造苯並三唑化合物及其衍生物的合成方法，但是 而這些方法皆是利用將2-(2-羥基-5-曱基苯基）苯並三唑或其街 生物加入氯烧基丙稀在驗性及有機溶劑存在下，並於高溫下經 克萊森重排反應（Claisen arrangement)而得中間產物，再使該中 間產物於高溫長時間反應下並經由多次分離副產物來合成笨並 三唑化合物及其衍生物’而上述專利文獻所述之方法有具有下 列缺點： (1) 大多使用極性的有機溶劑，由於極性的有機溶劑較易含 水份’而該水分易阻礙反應之進行，而使反應過程中易產生側 反應物’且該反應時間長（24〜3 6小時）。 (2) 該反應不完全，使該產物回收率較低（一般4〇〜65%)。 (3) 該反應所需溫度高大約在180°C〜25(TC之間 (4) 該反應皆須單離中間產物’然後再經下一步驟操作使該 中間產物進行克萊森重排反應（Claisen arrangement)重排才可得 產物，另外，該產物所需的純化處理程序繁複，容易造成產物 0 損失和污染’而使該產物純度和產率降低，而增加生產成本。 (5) 該反應需使用大量溶劑處理與純化，易造成環境影污 染。 (6) 該反應係藉由金屬催化劑催化反應進行，而該金屬 催化劑中的金屬離子易殘留於產物中造成純化的困難。 有鑑於此，目前對該苯並三唑化合物及其衍生物的製 備方法仍有更殷切的需求，故有待進一步的開發。 【發明内容】 本發明者有鑑於現今合成丨_曱代烯丙基_2_(2，·羥基_5，曱基 6 200932730 笨基）笨並二唑化合物及其衍生物的製備方法複雜、費時與成效 不影，因此特別改變其製備的步驟以減少反應時間和提高該化 合物的回收率，進一步達到節省生成本的目的。200932730 IX. Description of the invention: [Technical field to which the invention pertains] The present invention is a diphenylallyl-2-(2'-hydroxy-5'-methylphenyl)benzotriazole compound and a derivative thereof Preparation method, especially a method for preparing 1-deallyl-2-(2'-hydroxy-5'-nonylphenyl)benzotriazole compound and derivative thereof without separating intermediate product . [Prior Art] 苯 Benzotrid. The Benzotriazole compound is a widely used chemical material in cosmetics. Since the compound has a function of absorbing ultraviolet rays, it is mostly used as an active ingredient of a UV absorber in cosmetics. The compound absorbs ultraviolet rays by the resonance effect of the structure of such a compound, and the compound particularly has an absorption effect on the wavelengths of 280 nm and 320 nm of ultraviolet-B and the wavelengths of 320 nm and 400 nm of ultraviolet-A, and is used for cosmetics. In the middle of the cream or sunscreen, the skin can be protected from UV rays or sunburn, further avoiding skin macula or other pathological causes of skin cancer. Therefore, in recent years, all parties have actively studied the derivatives of stupid triazole compounds, and the derivatives of the benzotriazole compounds can be widely used as ultraviolet absorbers, according to US Pat. No. 3,715,334, US Pat. No. 3,947,436, US Pat. , U.S. Patent No. 4,122, 233, U.S. Patent No. 4,184, 851, U.S. Patent No. 4,234, 430, U.S. Patent No. 4,316, 033, U.S. Patent No. 4,342, 742, U.S. Patent No. 4, 430, 036, U.S. Patent No. 4, 489, s, U.S. Patent No. 4, 489, s, U.S. Patent No. 4, 490, 356, U.S. Patent No. 4, 696, s, U.S. Pat. a method for synthesizing benzotriazole compounds and derivatives thereof, but these methods are all based on the addition of 2-(2-hydroxy-5-mercaptophenyl)benzotriazole or its street organism to chlorinated propylene In the presence of an organic solvent and an organic solvent, a Claisen arrangement is obtained at a high temperature to obtain an intermediate product, and the intermediate product is subjected to a long-term reaction at a high temperature and synthesized by a plurality of separation of by-products. Triazole compounds and derivatives thereof' and the methods described in the above patent documents have the following disadvantages: (1) Most Polar organic solvents, since the polar organic solvent containing water easier 'and the water is easy to hinder the reaction, the side reaction is easy to produce during the reaction was' and the long reaction time (6 hours 24~3). (2) The reaction is incomplete, resulting in a low recovery of the product (generally 4 〇 to 65%). (3) The temperature required for the reaction is about 180 ° C to 25 (between TC and (4) the reaction must be separated from the intermediate product' and then the next step is carried out to carry out the Claisen rearrangement reaction of the intermediate product. The product can be obtained by rearrangement (Claisen arrangement). In addition, the purification process required for the product is complicated, and it is easy to cause product 0 loss and contamination, which reduces the purity and yield of the product, and increases the production cost. (5) The reaction needs to be treated and purified with a large amount of solvent, which is liable to cause environmental pollution. (6) The reaction is carried out by catalytic reaction of a metal catalyst, and the metal ions in the metal catalyst are easily left in the product, which makes purification difficult. At present, there is still a strong demand for the preparation method of the benzotriazole compound and its derivative, and further development is required. [Invention] The present inventors have in view of the current synthesis of 丨_曱allyallyl_2_( 2,·hydroxyl_5, fluorenyl 6 200932730 stupid base) The preparation method of the stupid oxadiazole compound and its derivative is complicated, time-consuming and effective, so the steps of preparation thereof are particularly changed to reduce the reaction time. In addition, and to improve the recovery rate of the compound, the purpose of saving the cost is further achieved.
本發明之主要目的係在於提供一種有效合成丨·罗代烯丙基_ 2_(2 -羥基-5’甲基苯基）苯並三唑化合物及其衍生物的製造方 法’其係於同一反應器内操作，且無須分離中間產物，以達到 簡化1-甲代烯丙基-2-(2，-經基_5,甲基苯基）苯並三唾化合物及其 何生物的製作過程，並促使該反應能完全反應以縮短製造所需 =時間’並減輕回收有機溶劑之處理工作，而使該製備過程能 節省製造成本以期符合環保的訴求。The main object of the present invention is to provide a method for producing an effective synthesis of ruthenium rotallyl _ 2_(2-hydroxy-5'methylphenyl)benzotriazole compound and a derivative thereof, which is in the same reaction. Operates in-line without the need to separate intermediates to achieve a simplified process for the production of 1-methallyl-2-(2,-trans-based-5,methylphenyl)benzotrisin compounds and their organisms. And the reaction can be fully reacted to shorten the manufacturing time = time 'and reduce the processing of the recovery of organic solvents, so that the preparation process can save manufacturing costs in order to meet environmental protection requirements.
本發明的另一目的係於減少側反應的發生 避兄座物的 損失，進一步提高產物的回收率 為達上述之目的，本發明所採取技術之手段係於；一 2—(2_ 备基+甲基苯基）苯並三唾及其衍生物（化合物1)與—3_氣_2_ 甲基丙烤及其衍生物（化合物2)進行反應，以得其中間產物（化 合物2A) ’之後再藉由加熱以進行克萊森重排反應（ arrangement )藉此獲得丨_甲代烯丙基_2_(2,_經基_5,甲基苯基） 苯並三唾化合物及其衍生物，其反應式如下所示：Another object of the present invention is to reduce the loss of the side reaction and avoid the loss of the sibling, and further improve the recovery rate of the product for the above purpose, and the technical means adopted by the present invention is; 2 - (2_ Methylphenyl)benzotrisin and its derivatives (Compound 1) are reacted with -3_gas_2_methylpropene and its derivatives (Compound 2) to obtain the intermediate product (Compound 2A) Further, by heating to carry out a Claisen rearrangement reaction, thereby obtaining 丨_methallyl_2_(2,_trans-based-5, methylphenyl) benzotrisin compound and its derivative The reaction formula is as follows:
CI^Y^ r2 活化劑 --J (promoter)CI^Y^ r2 Activator --J (promoter)
其中 「 A ' 2A 該R1與R2代表氫原子Wherein "A ' 2A, R1 and R2 represent a hydrogen atom
C1〜的烷基、c4〜C8的烷 7 200932730 氧基、C4〜Cs的矽烷基、C4〜Q的矽烷氧基及苯環，其中v較 佳為氫原子，R2較佳為甲基。 該製備的主要方法係包括以下步驟： 利用—第一試劑溶解2-(2-羥基-5-甲基苯基）笨並三唑及 其衍生物； 利用一第二試劑溶解3—氣_2_甲基丙烯及其衍生物； 置入一鹼性物質於第一試劑中，使該反應環境呈現出一鹼 ❹ 兄並利用氮氣來隔絕空氣以加入活化劑至已溶解2- (2_ 羥基5曱基苯基）苯並三唑及其衍生物的第一試劑中，使該反 應加速進行； 提供一反應溫度使該反應進行，並進行重排反應； 利用一過濾装置過濾1-甲代烯丙基_2_(2，_羥基_5，一甲基苯 基）苯並三唑化合物或其衍生物；以及 利用一再結晶溶劑，溶解使卜甲代烯丙基_2_(2，_羥基_5，_ 甲基苯基）笨並三嗤化合物及其衍生物溶解，以提高其純度。 而該成份比係如下所述： 〇 化合物1與化合物2的莫耳數比為丨：2_4 第一試劑與第二試劑的重量比為2=1〜4 : 1 化合物1與鹼性物質的莫耳數比為丨：O.hi 〇 其中，該鹼性物質係為無機化合物或有機化合物，而該無 機化合物較佳為碳酸鈉、碳酸鉀、碳酸氫鈉或碳酸氫鉀，而該 有機化合物較佳為三乙基胺或三烷基胺。 該活化劑較佳為一多孔性鈉或鈣鋁矽酸塩的分子篩，其中 化合物2與活化劑的重量比為丨：〇.3〜3.〇 ’且該鈣鋁矽酸塩之 8 200932730 孔徑大小較佳為3A〜5A。 、該第-試劑較佳為N，N_二曱基苯胺為溶劑、n，n—二甲 胺或N，N-二烧基苯胺，其中該烧基之碳數為卜3個碳" 碳數劑較佳Μ基乙基㈣燒基酮類，其中該燒基之 碳數為1 ~ 5個碳。 該再結晶溶劑較佳為異丙醇。 ❹ ❹ 本發明係於1〇〇毫升的四頸反應器上架設冷凝管、加料漏 斗’並置人磁石攪拌棒及溫度計，此外並於反應器上包覆加熱 包以供升溫使用。然後將2_(2_經基_5•甲基苯基）苯並三唾(化合 物1)之與三乙基胺一同置人Ν，Ν二甲基苯胺（第—試劑）中，^ 後再加入_料迄授拌混合5分鐘，然後湘加料管並於氮 氣下於10分鐘完成滴加3·氯_2_曱基丙烯（化合物2)，而該3_氣 -2-曱基丙烯溶解於甲基乙基酮（第二試劑）之中，，然後再將該反 應加熱至80C且保持5小時，然後再升溫至18〇〇c且保持3小 時’最後再降溫至80°C，然後趁熱以活性碳過濾活化劑，而該 濾液以異丙醇再結晶，即可得高純度之白色固體，純度^ 99%(HPLC)之1-曱代烯丙基_2_(2，_羥基_5，_甲基苯基）苯並三唑 化合物。 藉由上述鈣鋁矽酸塩除水的特性來加速3_氯_2_曱基丙烯 及其衍生物的氣離子脫除，以利進行親核性取代反應的進行， 而該鈣鋁矽酸塩係可經由烘乾而達到回收再利用及環保的目 的’且該鈣鋁矽酸塩的添加亦能避免側反應的產生，以進一步 提高其生產效率；此外’該反應係於同一反應器中進行，因此 不需分離中間產物（2A)即可合成產物，使該反應時間減少許多； 200932730 且該反應係藉由反應溫度的控制直接進行克萊森重排反應 (Claisen arrangement )’進一步減少其反應的步驟，以達 到節省成本與增加產率的目的。 【實施方式】 本發明係一種1-甲代烯丙基一2-(2,-羥基-5’甲基苯基） 苯並三唑化合物及其衍生物的製備方法，其係主要合成方 法請參考下列之反應方程式··C1~alkyl group, c4~C8 alkyl group 7 200932730 oxy group, C4~Cs decyl group, C4~Q decyloxy group and benzene ring, wherein v is preferably a hydrogen atom, and R2 is preferably a methyl group. The main method of the preparation comprises the steps of: dissolving 2-(2-hydroxy-5-methylphenyl) benzotriazole and a derivative thereof by using a first reagent; and dissolving 3-gas by a second reagent; _Methyl propylene and its derivatives; Put a basic substance in the first reagent, so that the reaction environment presents a base 并 brother and use nitrogen to isolate the air to add the activator to the dissolved 2- (2 _ hydroxy 5 In the first reagent of nonylphenyl)benzotriazole and its derivatives, the reaction is accelerated; a reaction temperature is provided to carry out the reaction, and a rearrangement reaction is carried out; and the 1-methene is filtered by a filtration device. a propyl 2-(2,-hydroxyl-5, monomethylphenyl)benzotriazole compound or a derivative thereof; and a solution of a recrystallization solvent to dissolve the methallyl-2-(2,_hydroxyl group) The 5,-methylphenyl) benzotriazine compound and its derivatives are dissolved to increase their purity. The composition ratio is as follows: The molar ratio of the compound 1 to the compound 2 is 丨: 2_4 The weight ratio of the first reagent to the second reagent is 2 = 1 to 4: 1 Compound 1 and the alkaline substance The ratio of the ears is 丨: O.hi 〇 wherein the basic substance is an inorganic compound or an organic compound, and the inorganic compound is preferably sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, and the organic compound is more It is preferably triethylamine or trialkylamine. The activator is preferably a molecular sieve of porous sodium or barium aluminosilicate, wherein the weight ratio of the compound 2 to the activator is 丨: 〜.3~3.〇' and the calcium barium strontium strontium 8 200932730 The pore size is preferably from 3A to 5A. Preferably, the first reagent is N,N-dimercaptoaniline as a solvent, n, n-dimethylamine or N,N-dialkylaniline, wherein the carbon number of the alkyl group is 3 carbons " The carbon numbering agent is preferably a mercaptoethyl (tetra)alkyl ketone, wherein the alkyl group has a carbon number of 1 to 5 carbons. The recrystallization solvent is preferably isopropanol. ❹ ❹ The present invention is to erect a condenser tube, a feed funnel, a juxtaposed magnet stirrer rod and a thermometer on a 1 liter four-necked reactor, and a heating pack is coated on the reactor for heating. Then 2_(2_transyl-5-methylphenyl)benzotrisole (Compound 1) is placed in the same place as triethylamine, in the dimethyl aniline (the first reagent), and then Adding _ material to the mixing and mixing for 5 minutes, then adding the tube and adding 3·chloro-2-indolyl propylene (compound 2) under nitrogen for 10 minutes, and dissolving the 3 气-2-mercapto propylene In methyl ethyl ketone (second reagent), the reaction was then heated to 80 C for 5 hours, then warmed to 18 〇〇c for 3 hours and finally cooled to 80 ° C, then The activator is filtered with activated carbon while hot, and the filtrate is recrystallized from isopropanol to obtain a white solid of high purity, purity of 99% (HPLC) of 1-decylallyl_2_(2,_hydroxyl _5, _methylphenyl) benzotriazole compound. Accelerating the gas ion removal of 3_chloro-2-indolyl propylene and its derivatives by the above-mentioned characteristics of water removal by calcium aluminosilicate, in order to facilitate the nucleophilic substitution reaction, and the calcium aluminosilicate The lanthanide can be recycled and reused for environmental protection purposes' and the addition of the calcium barium strontium sulphate can also avoid the side reaction to further increase its production efficiency; in addition, the reaction is in the same reactor. This is carried out, so that the product can be synthesized without separating the intermediate product (2A), and the reaction time is reduced a lot; 200932730 and the reaction is directly reduced by the control of the reaction temperature by the Claisen arrangement. The steps of the reaction are to achieve cost saving and increase in productivity. [Embodiment] The present invention relates to a method for preparing a 1-methallyl-1-(2,-hydroxy-5'methylphenyl)benzotriazole compound and a derivative thereof, which is a main synthesis method. Refer to the following reaction equations··
HOHO
其中RhR2代表氫原子、Cl〜C8的烷基、烷氧基、矽烷基 及苯環，其中Ri較佳為氫原子；R2較佳為甲基。 其製備的主要係包括下列步驟： Q 利用一第一試劑溶解2-(2-羥基-5-甲基苯基）苯並三唑及 其衍生物； 利用一第二試劑溶解3-氯-2-甲基丙烯及其衍生物； 置入一鹼性物質於第一試劑中’使該反應環境呈現出一鹼 性環境’並利用氮氣來隔絕空氣以加入活化劑至已溶解2-(2- 經基-5-曱基苯基）苯並三唑及其衍生物的第一試劑中，使該反 應加速進行； 提供一反應溫度使該反應進行，並進行重排反應； 利用一過濾裝置過濾；以及 200932730 利用一再結晶溶劑進行再結晶步驟，，以提高卜曱代烯丙 基_2-(2’-羥基-5’-曱基苯基）笨並三唑化合物及其衍生物的純 而該成份比係如下所述： 化合物1與化合物2的莫耳數比為丨：2_4 第一試劑與第二試劑的重量比為2=1〜4 : 1 化合物1與鹼性物質的莫耳數比為〗： φ 其中，該鹼性物質係為無機化合物或有機化合物，而該無 機化合物較佳為碳酸鈉、碳酸鉀、碳酸氫鈉或碳酸氫鉀，而該 有機化合物較佳為三乙基胺或三烷基胺。 該活化劑較佳為一多孔性鈉或鈣鋁矽酸塩的分子篩，其中 化合物2與活化劑的重量比& i : 〇 3〜3 〇 ;其中該活化劑最佳 為3A〜5A孔徑的約铭石夕酸盘。 該第一試劑較佳為N，N•二甲基苯胺為溶劑（溶劑U N，N_二 曱基笨胺和N，N-二烷基苯胺，其中該烷基之碳數為卜3個碳 〇 該第二試劑較佳為曱基乙基酮或烷基_類，其中該烷基之 碳數為1〜5個碳。 該再結晶溶劑較佳為異丙醇。 本發明係於100毫升的四頸反應器上架設冷凝管、加料漏 斗，並置入磁石攪拌棒及溫度計，此外並於反應器上包覆加熱 包以供升溫使用。然後將2_(2_經基_5_甲基苯基）苯並三唾(化合 物1)之與二乙基胺以N，N_二曱基苯胺為溶劑（第一試劑）加入 100毫升反應器内’然後加人㈣碎酸盘搜拌混合5分鐘，然 後利用加料管並於氮氣下於1G分鐘完成滴加3_氯_2_甲基丙烤 11 200932730 (化合物2)，而該3-氯-2-甲基丙稀溶解於甲基乙基酮（第二試劑） 之中，而該反應加熱至80C且保持5小時，然後再升溫至180 C且保持3小時’最後再降溫至80。〇 ’然後趁熱以活性碳過遽 活化劑，而該濾液以異丙醇再結晶，即可得高純度之白色固體， 純度2 99%(HPLC)之1-曱代浠丙基_2-(2’-經基-5’-曱基苯基）苯 並三唾化合物。 本發明其他的特徵及優點將可明顯見於下列較佳具體事實 及申請專利範圍。 <實施例一 > 於100毫升四頸反應器上架設冷凝管、加料漏斗，並置入 磁石、攪拌棒及溫度計，此外並於反應器上包覆加熱包以供升 使用，然後將10克2-(2-經基-5-曱基苯基）苯並三嗤（0.044莫 耳）與4.5克二乙基胺（0.044莫耳）及16_1克N，N-二曱基苯胺(〇.13 莫耳）依序加入100毫升反應瓶内，之後攪拌混合5分鐘，然後 利用加料管，並於氮氣下於1〇分鐘完成滴加〇.〇9莫耳3_氣_2_ 曱基丙烯，而該3-氣-2-甲基丙烯係以甲基乙基酮為溶劑，並加 熱至80°C保持5小時，然後升溫至180^保持3小時，隨之降 溫至80°C，趁熱以活性碳過濾濾液，然後將濾液以4〇毫升異 丙醇進行再結晶後，以濾紙過濾其濾液，可得乾重14 8克的橘 黃色固體，再以管柱色層分析法分離可得31克的2_(2_羥基_5_ 曱基苯基）苯並三唑、0.2克的2_[5·甲基_2-(2_甲基·丙烯氧基）· 酚基]-2H-笨並三唑、4.9克（回收率：40%)的丨_甲代烯丙基·2·(2，_ 羥基-5’-曱基苯基）苯並三唑和副產物〇1克的2-苯並三唑 12 200932730 甲基-6-(2-甲基-丙烯基)_苯酚。 <實施例二> 於100毫升四頸反應器上架設冷凝管、加料漏斗，並置入 磁石攪拌棒及溫度計，此外並於反應器上包覆加熱包以供升溫 使用，然後將10克2-(2-羥基-5-曱基苯基）苯並三唑（〇 〇44莫耳） 與4.5克三乙基胺（0.044莫耳）及161克N N二曱基苯胺 莫耳）依序加入100毫升反應瓶内，然後加入16克3入分子篩 ❹（molecular sieve UOP type 3A beads 購自 Fluka 公司），之後攪伴 混合5分鐘，然後用加料管，並於氮氣下於1〇分鐘完成滴加〇 〇9 莫耳3-氣-2-曱基丙稀，而該3-氯-2-甲基丙稀係以曱基乙基酮為 溶劑，並加熱至80。(：保持5小時並以高效率管柱層析（HpLC)檢 測反應，而當反應完全時再升溫至18〇。(：保持3小時，然後以 尚效率管柱層析（HPLC)追蹤至反應結束，隨之降溫至8〇〇c，趁 熱以活性碳過濾濾液，而該濾液再以40毫升異丙醇進行再結 ❾晶’然後再以濾紙過濾其濾液，可得白色固體8.9克（收率： 72%) ’純度99.1% ’熔點：95 C的1-曱代稀丙基-2-(2，_經基_5，_ 甲基苯基）苯並三唑。 <實施例三> 於100毫升四頸反應器上架設冷凝管、加料漏斗，並置入 磁石授摔棒及溫度計’此外並於反應器上包覆加熱包以供升溫 使用’然後將10克2-(2-羥基-5-曱基苯基）苯並三唑（0 044莫耳） 與4.5克三乙基胺（〇_〇44莫耳）及16.1克N，N-二甲基苯胺（0.13 莫耳）依序加入1〇〇毫升反應瓶内，然後加入16克4A分子_ 13 200932730 (molecular sieve UOP type 4A beads 購自 Fluka 公司），之後攪伴 混合5分鐘，然後用加料管，並於氮氣下於10分鐘完成滴加0.09 莫耳3-氣-2-甲基丙烯，而該3-氯-2·甲基丙烯係以甲基乙基酮為 溶劑，並加熱至80°C保持5小時並以高效率管柱層析（HPLC)檢 測反應’而當反應完全時再升溫至180°C保持3小時，然後以 高效率管柱層析（HPLC)追蹤至反應結束，隨之降溫至80。(：，趁 熱以活性碳過濾濾液，而該濾液再以40毫升異丙醇進行再結 ^ 晶，然後再以濾紙過濾其濾液，可得白色固體10.7克（收率： 86%)，純度 99.9%(HPLC)，熔點：95°C 的 1-曱代烯丙基-2-(2，-羥基-5’-甲基苯基）苯並三唑。 <實施例四> 於100毫升四頸反應器上架設冷凝管、加料漏斗，並置入 磁石攪拌棒及溫度計’此外並於反應器上包覆加熱包以供升溫 使用，然後將10克2-(2-羥基-5-曱基苯基）苯並三唑（〇.〇44莫耳） ❹ 與4.5克三乙基胺（0.044莫耳）及16.1克Ν,Ν-二曱基苯胺（0.13 莫耳）依序加入100毫升反應瓶内，然後加入16克5人分子篩 (molecular sieve UOP type 5Α beads 購自 Fluka 公司），之後攪伴 混合5分鐘，然後用加料管，並於氮氣下於1〇分鐘完成滴加〇〇9 莫耳3-氣-2-曱基丙烯，而該3-氣-2-曱基丙烯係以甲基乙基酮為 /谷劑，並加熱至80 C保持5小時並以高效率管柱層析（HpLC)檢 測反應，而當反應完全時再升溫至18〇它保持3小時，然後以 咼效率官柱層析（HPLC)追蹤至反應結束，隨之降溫至。匸，趁 熱以活性碳過濾濾液，而該濾液再以4〇毫升異丙醇進行再結 200932730 可得白色固體10克（收率： :95°(：的1-曱代烯丙基-2-(2，- 晶’然後再以濾紙過濾其濾液，1 81%)，純度 99.6%(HPLC)，熔點： 經基- 5’ -甲基苯基）苯並三吐。 綜合上述之實施例，可得知本發明只需選用適當比例的反 應物和反應條件並添加-定_之活化劑於反應Μ，即可在Wherein RhR2 represents a hydrogen atom, an alkyl group of C1 to C8, an alkoxy group, a decyl group and a benzene ring, wherein Ri is preferably a hydrogen atom; and R2 is preferably a methyl group. The main steps of the preparation include the following steps: Q: Dissolving 2-(2-hydroxy-5-methylphenyl)benzotriazole and a derivative thereof by using a first reagent; dissolving 3-chloro-2 by using a second reagent - methacrylic acid and its derivatives; placing an alkaline substance in the first reagent 'to make the reaction environment exhibit an alkaline environment' and using nitrogen to insulate the air to add the activator to the dissolved 2-(2- In the first reagent of the 5-yl-nonylphenyl)benzotriazole and its derivative, the reaction is accelerated; a reaction temperature is provided to carry out the reaction, and a rearrangement reaction is carried out; And 200932730 using a recrystallization solvent for the recrystallization step to improve the purity of the di-alkalyl allyl-2-(2'-hydroxy-5'-nonylphenyl) benzotriazole compound and its derivatives. The composition ratio is as follows: The molar ratio of the compound 1 to the compound 2 is 丨: 2_4 The weight ratio of the first reagent to the second reagent is 2 = 1 to 4: 1 The molar number of the compound 1 and the basic substance Ratio: φ where the basic substance is an inorganic compound or an organic compound, and the inorganication The compound is preferably sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate, and the organic compound is preferably triethylamine or trialkylamine. Preferably, the activator is a molecular sieve of porous sodium or barium aluminosilicate, wherein the weight ratio of compound 2 to the activator is & i: 〇3~3 〇; wherein the activator is preferably a pore size of 3A~5A The name of the Ming Shi Xi acid tray. The first reagent is preferably N,N•dimethylaniline as a solvent (solvent UN, N-dimercaptoamine and N,N-dialkylaniline, wherein the carbon number of the alkyl group is 3 carbons The second reagent is preferably a mercaptoethyl ketone or an alkyl group, wherein the alkyl group has a carbon number of 1 to 5 carbons. The recrystallization solvent is preferably isopropanol. The present invention is in 100 ml. A four-neck reactor is provided with a condensing tube, an addition funnel, and a magnet stirring rod and a thermometer are placed, and a heating pack is coated on the reactor for heating, and then 2_(2_base_5_methyl Phenyl)benzotrisole (Compound 1) and diethylamine are added to the 100 ml reactor with N,N-didecylphenylamine as the solvent (first reagent), and then added (4) broken acid tray for mixing and mixing After 5 minutes, the addition of 3_chloro-2-methylpropene bake 11 200932730 (compound 2) was then carried out using a feed tube under nitrogen for 1 G minutes, and the 3-chloro-2-methylpropane was dissolved in methyl Ethyl ketone (second reagent), while the reaction was heated to 80 C for 5 hours, then warmed to 180 C and held for 3 hours 'finally cooled again to 80. 〇' then hot The activated carbon is passed through the activator, and the filtrate is recrystallized from isopropanol to obtain a white solid of high purity. The purity is 2 99% (HPLC) of 1-deuteropropyl 2 - 2'- -5'-nonylphenyl)benzotrisole compound. Other features and advantages of the present invention will be apparent from the following preferred specific facts and claims. <Example 1> in a 100 ml four neck reactor A condensing tube, an addition funnel are placed on top, and a magnet, a stirring rod and a thermometer are placed, and a heating pack is coated on the reactor for use, and then 10 g of 2-(2-pyridyl-5-fluorenylbenzene) is placed. Benzotriazine (0.044 mol) and 4.5 g of diethylamine (0.044 mol) and 16_1 g of N,N-dimercaptoaniline (〇.13 mol) were sequentially added to a 100 ml reaction flask. After that, the mixture was stirred and mixed for 5 minutes, and then the addition of 〇.〇9mol 3_gas_2_ mercaptopropene was carried out by using a feeding tube and under nitrogen for 1 minute, and the 3-gas-2-methylpropene was Methyl ethyl ketone was used as a solvent and heated to 80 ° C for 5 hours, then heated to 180 ° for 3 hours, followed by cooling to 80 ° C, and the filtrate was filtered with activated carbon while hot. After the filtrate was recrystallized from 4 liters of isopropanol, the filtrate was filtered through a filter paper to obtain an orange solid having a dry weight of 14 8 g, and then separated by a column chromatography to obtain 31 g of 2_(2). _hydroxy_5_nonylphenyl)benzotriazole, 0.2 g of 2_[5·methyl_2-(2-methyl·propenyloxy)·phenolic]-2H-benzotriazole, 4.9 g (Recovery: 40%) of 丨_methallyl·2·(2,_hydroxy-5'-nonylphenyl)benzotriazole and by-product 〇1 g of 2-benzotriazole 12 200932730 Methyl-6-(2-methyl-propenyl)-phenol. <Example 2> A condenser tube and an addition funnel were placed on a 100 ml four-necked reactor, and a magnet stirring rod and a thermometer were placed, and a heating pack was coated on the reactor for heating, and then 10 g was applied. 2-(2-Hydroxy-5-mercaptophenyl)benzotriazole (〇〇44 mol) with 4.5 g of triethylamine (0.044 mol) and 161 g of NN dimercaptoaniline) Add 100 ml reaction flask, then add 16 g of 3 molecular sieves (molecular sieve UOP type 3A beads from Fluka), then mix for 5 minutes, then use a feeding tube and complete the drop in 1 minute under nitrogen. The oxime 9 is a 3-mer-2-mercaptopropene, and the 3-chloro-2-methylpropane is a solvent of mercaptoethyl ketone and heated to 80. (: Maintain the reaction for 5 hours and high-efficiency column chromatography (HpLC), and then raise the temperature to 18 当 when the reaction is complete. (: Hold for 3 hours, then trace to the reaction by column chromatography (HPLC) At the end, the temperature was lowered to 8 〇〇c, and the filtrate was filtered with activated carbon while hot, and the filtrate was recrystallized by 40 ml of isopropyl alcohol. Then the filtrate was filtered through a filter paper to obtain 8.9 g of a white solid ( Yield: 72%) 'purity 99.1% 'melting point: 95 C of 1-deutero-l-propyl-2-(2,-trans)- 5,-methylphenyl)benzotriazole. Three > erecting a condenser tube, an addition funnel on a 100 ml four-neck reactor, and placing a magnet to give a wrestling rod and a thermometer 'In addition to coating the heating pack on the reactor for warming up' then 10 g 2-( 2-Hydroxy-5-mercaptophenyl)benzotriazole (0 044 mol) with 4.5 g of triethylamine (〇_〇44 mol) and 16.1 g of N,N-dimethylaniline (0.13 Mo) Ear) sequentially added to a 1 ml bottle, then add 16 g of 4A molecule _ 13 200932730 (molecular sieve UOP type 4A beads from Fluka), then mix 5 Then, using a feeding tube, and dropwise adding 0.09 mol of 3-gas-2-methylpropene under nitrogen for 10 minutes, and the 3-chloro-2·methylpropene was methyl ethyl ketone as a solvent. And heated to 80 ° C for 5 hours and high performance column chromatography (HPLC) to detect the reaction 'and when the reaction is complete, then warmed to 180 ° C for 3 hours, then high efficiency column chromatography (HPLC) After the end of the reaction, the temperature was lowered to 80. (: The filtrate was filtered with activated carbon while hot, and the filtrate was recrystallized with 40 ml of isopropyl alcohol, and then the filtrate was filtered through a filter paper to obtain a white solid. 10.7 g (yield: 86%), purity 99.9% (HPLC), melting point: 95 ° C 1-nonylallyl-2-(2,-hydroxy-5'-methylphenyl)benzotriene [Example 4] A condenser tube, an addition funnel, a magnet stirring rod and a thermometer were placed on a 100 ml four-necked reactor, and a heating pack was coated on the reactor for heating, and then 10 g of 2-(2-hydroxy-5-mercaptophenyl)benzotriazole (〇.〇44 mol) ❹ with 4.5 g of triethylamine (0.044 mol) and 16.1 g of hydrazine, hydrazine-dioxin Base benzene Amine (0.13 mol) was added to the 100 ml reaction flask in sequence, then 16 g of 5 human molecular sieves (molecular sieve UOP type 5Α beads from Fluka) was added, followed by mixing for 5 minutes, then using a feeding tube and nitrogen. The addition of hydrazine 9 molar 3-methoxy-2-mercaptopropene was carried out in 1 minute, and the 3-vapor-2-mercaptopropene was methyl ethyl ketone as a /column and heated to 80. C was kept for 5 hours and the reaction was detected by high efficiency column chromatography (HpLC), and when the reaction was completed, the temperature was raised to 18 Torr for 3 hours, and then traced to the end of the reaction by hydrazine efficiency column chromatography (HPLC). Cool down to.匸, the filtrate was filtered with activated carbon while hot, and the filtrate was further re-knotted with 4 liters of isopropanol. 200932730. 10 g of a white solid was obtained (yield: 95 ° (: 1-decylallyl-2) - (2, - crystal 'and then filtered through a filter paper, 1 81%), purity 99.6% (HPLC), melting point: trans- 5'-methylphenyl) benzotrim. Synthesis of the above examples It can be seen that the present invention only needs to select an appropriate ratio of reactants and reaction conditions and add an activator to the reaction,
〇 甲代稀丙基_2-(2’-經基_5，·甲基笨基）苯並三唾的製備方法，並 使该製作方法具有簡易及且不需分離中間產物等優點，並能藉 由活化劑可有效減少侧反應的發生，以提高其產率，進一步降 低反應於有基溶劑中的需求，進一步降低對環境的汙染。 以上所述，僅是本發明的較佳實施例，並非對本發明作任 何形式上的限制，任何所屬技術領域中具有通常知識者，若在 不，離本發明所提技術特徵的範圍内，利用本發明所揭示技術 内容所做出局部更動或修飾等效實施例，並且未脫離本發明的 Q 技術特徵内容，均仍屬於本發明技術特徵範圍》 【圖式簡單說明】 【主要元件符號說明】 無 15a method for preparing benzotriphenyl 2-(2'-trans-based-5, methylphenyl) benzotrisole, and the preparation method has the advantages of being simple and without separating intermediate products, and The activator can effectively reduce the occurrence of side reactions, thereby increasing the yield thereof, further reducing the demand for the reaction in the base solvent, and further reducing the environmental pollution. The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any one of ordinary skill in the art may, if not, be utilized within the scope of the technical features of the present invention. The local embodiment of the present invention is not limited to the technical features of the present invention, and the technical features of the present invention are still within the scope of the technical features of the present invention. No 15