新型含受阻胺结构苯并三唑光稳定剂的合成及表征

以2-(2',4'-二羟基苯基)-2H-苯并三唑和5-氯-2-(2',4'-二羟基苯基)-2H-苯并三唑为原料,分别与溴乙酸乙酯进行醚化反应得到中间体2-[2'-羟基-4'-(乙氧酰基甲氧基)苯基]-2H-苯并三唑(Ⅰa)和5-氯-2-[2'-羟基-4'-(乙氧酰基甲氧基)苯基]-2H-苯并三唑(Ⅰb),Ⅰa和Ⅰb再分别与2,2,6,6-四甲基哌啶醇或1,2,2,6,6-五甲基哌啶醇进行酯交换反应得到光稳定剂2-{2'-羟基-4'-[4-(2,2,6,6-四甲基)哌啶氧酰基甲氧基]苯基}-2H-苯并三唑(Ⅱa),2-{2'-羟基-4'-[4-(1,2,2,6,6-五甲基)哌啶氧酰基甲氧基]苯基}-2H-苯并三唑(Ⅱb)、5-氯-2-{2'-羟基-4'-[4-(2,2,6,6-四甲基)哌啶氧酰基甲氧基]苯基}-2H-苯并三唑(Ⅱc),5-氯-2-{2'-羟基-4'-[4-(1,2,2,6,6-五甲基)哌啶氧酰基甲氧基]苯基}-2H-苯并三唑(Ⅱd),两步反应总收率分别为57.5%、59.1%、56.0%和54.4%。通过1HNMR、MS验证了目标化合物的结构,并测定了它们的紫外吸收光谱,4个化合物在270⁴00 nm均有较强的吸收峰,其最大紫外吸收波长(λmax)分别为338.5、338.5、347.0和346.5 nm,摩尔消光系数(εmax×104)分别为2.361 0、2.569 7、2.423 8和2.534 2 L/(mol·cm)。     

一种紫外线吸收剂的合成新方法

采用新方法合成了紫外线吸收剂苯基-(3,5-二叔丁基-4-羟基苄基)丙二酸二(1,2,2,6,6-五甲基-4-哌啶)酯。苯基丙二酸二乙酯和N-甲基-2,2,6,6-四甲基-4-哌啶醇在甲苯中微纳米碳酸钾催化下反应,得到苯基丙二酸二(1,2,2,6,6-五甲基哌啶醇)酯,然后在乙醇中与 4-羟基-3,5-二叔丁基苄基氯反应,得到目标产物,总收率为80%。化合物的结构通过1H NMR和13C NMR进行了表征。     

苯基-(3,5-二叔丁基-4-羟基苄基)丙二酸二(1,2,2,6,6-五甲基-4-哌啶)酯的合成

以苯基丙二酸二乙酯、N-甲基-2,2,6,6-四甲基-4-哌啶醇和2,6-二叔丁基-4-甲基苯酚为主要原料,合成了紫外线吸收剂苯基-(3,5-二叔丁基-4-羟基苄基)丙二酸二(1,2,2,6,6-五甲基-4-哌啶)酯。重点考察了苯基丙二酸二乙酯和N-甲基-2,2,6,6-四甲基-4-哌啶醇的酯交换反应、苯基丙二酸双(1,2,2,6,6-五甲基-4-哌啶)酯与4-羟基-3,5-二叔丁基苄基氯的烃基化反应。结果表明,微纳米碳酸钾具有较好的催化作用,产品总收率达到80%。化合物的结构通过1HNMR和13CNMR进行了表征。     

新型杀菌剂氟噻唑吡乙酮的合成

[目的]改进合成工艺,缩短合成路线,提高总收率。[方法]以4-哌啶腈和氯代乙酰氯为起始原料,经酰胺化反应得到1-(2-氯乙酰)-4-氰基哌啶、然后与3-甲基-5-三氟甲基吡唑和硫化氢气体生成关键中间体1-[2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酰基]-4-硫代甲酰胺哌啶;以1,3-二氯丙酮为原料,在氯化氢存在下与亚硝酸叔丁基酯反应生成3-氯-N-羟基-2-氧代-丙胺氯,然后与2,6-二氟苯乙烯环化得到关键中间体2-氯-1-[5-(2,6-二氟苯基)-4,5-二氢异唑-3-基]乙酮。最后2-氯-1-[5-(2,6-二氟苯基)-4,5-二氢异唑-3-基]乙酮与1-[2-[5-甲基-3-(三氟甲基)-1H-吡唑-1-基]乙酰基]-4-硫代甲酰胺哌啶反应得到目标产物氟噻唑吡乙酮。[结果]经1H NMR手段鉴定,产品结构与氟噻唑吡乙酮结构一致,总收率28.4%。[结论]该工艺简单经济,条件温和,适合工业化生产。     

含受阻胺结构的苯并三唑光稳定性和热稳定性研究

测试了4种2-[2’-羟基-3’-叔丁基-5’-（3-丙酸-4-哌啶酯基）苯基]-2H-苯并三唑结构类光稳定剂紫外吸收光谱、光稳定性及热稳定性。4种化合物在270～400nm均有较强的吸收峰,与引入受阻胺结构前苯并三唑光稳定剂相比．紫外吸收波长和摩尔消光系数不变。4种化合物的光稳定性和热稳定性明显高于引入受阻胺结构前的苯并三唑光稳定剂。光老化12h后,4种化合物仅分解3．2％～6．9％,引入受阻胺结构前苯并三唑则分解35．0％～36．3％。热稳定性测试表明。4种化合物失重1％时的温度为264～272℃．而引入受阻胺结构前苯并三唑失重1％时的温度分别为227℃和235℃。该类化合物分子内同时具有紫外吸收剂和自由基捕获剂两种功能,为高效光稳定剂。     

新型吡唑啉酮类化合物的合成及生物活性测定

[目的]制备新型吡唑啉酮类化合物。[方法]以唑菌酯关键中间体3-(4-氯苯基)-1-甲基-1H-吡唑-5-醇为起始原料,经过羟醛缩合反应合成中间体4-(4-羟基-3-甲氧基苯亚甲基)-3-(4-氯苯基)-1-甲基-1H-吡唑-5(4H)-酮,再经亲核取代反应、酯化反应制备了11个新型吡唑啉酮类化合物。[结果]目标化合物的结构经过1H NMR进行了确证。[结论]室内生测结果表明该类化合物具有较好的杀菌和杀虫活性。     

双功能受阻胺与紫外线吸收剂并用的协同效应研究

本文用IR、UV、ESR、TLC等方法研究了新型的双功能受阻胺光稳定剂,Tinuvin-144 [2-(4′-羟基-3′,5′-二叔丁基)苄基-2-正丁基丙二酸五甲基哌啶醇酯]与紫外线吸收剂,UV-531(2-羟基-4-正辛氧基二苯甲酮)和UV-327(2-[2′-羟基-3′,5′-二叔丁基]-5-氯 代苯并三唑)并用体系对聚丙烯光稳定化的并用效应。结果表明,Tinuvin-144与UV-531,UV-327并用时均具有良好的协同效应,144对531,327或531,327对144的光分解均具有相互的保护作用。结果还表明,144与531或327无论在模拟体系或聚丙烯中,在诱导期内均不存在促使他们消耗的化学反应,提出了协同作用的机理。     

1,3,5三嗪类稳定剂

研制了2—(3—特丁基—4—羟基—5—甲基苯胺基)—4—氯—6—(2,2,6,6四甲基—4—哌啶氨基)—1,3,5三嗪、2,4—双(3—特丁基4—羟基5—甲基苯胺基)6—(2,2,6,6—四甲基4—哌啶氨基)—1,3,5三嗪,化合物Ⅰ[R为P(O)(OC_2H_5)_2]、化合物Ⅰ(R为癸硫基)(Ⅱ)、2,4双[2—(3,5二特丁基—4—羟基苯基)—2—甲基丙基氨基]—6—(2—(2,2,6,6四甲基—1—哌啶基)乙氧基]     

光稳定剂GW-540合成工艺研究

研究了受阻胺类光稳定剂GW-540[磷酸三(1,2,2,6,6-五甲基哌啶醇)酯]的合成工艺.合成分两步进行,第一步为2,2,6,6-四甲基哌啶(哌啶醇)与甲醛反应,再经蒸馏得到1,2,2,6,6-五甲基哌啶醇(中间体);第二步中间体与滴加的PCl3在苯中反应生成GW-540.反应的最佳条件如下,第一步:反应原料摩尔比:n哌啶醇:n甲醛为1:2.15,反应温度68～72℃,反应时间7h,中间体收率约96%.第二步:反应原料摩尔比nPCl3:n中间体为1:6.1～6.2,反应温度55～60℃,反应时间5h.GW-540收率98%,熔点118～124℃.     

双功能光稳定剂的合成及性能测试

以2-[2’-羟基-4～（2-氧基乙酸乙酯基）苯基]-2H-苯并三唑和5-氯-2-[2’-羟基-4-（2-氧基乙酸乙酯基）苯基]-2H-苯并三唑为原料分别与2,2,6,6-四甲基哌啶醇和1’2,2,6,6～四甲基哌啶醇进行酯交换反应得到4个含受阻胺结构的苯并三唑类双功能光稳定剂（I、Ⅱ、Ⅲ和IV）。测试了该四个双功能光稳定剂紫外吸收光谱、光稳定性及热稳定性,在270～400rim均有较强的吸收峰,其摩尔消光系数分别为（8。。。×10。）2．3610、2．5697、2．4238和2．5342,与未含受阻胺结构间苯二酚型苯并三唑类紫外线吸收剂UV-366波长和摩尔消光系数相同,是烷基取代酚苯并三唑紫外线吸收剂UV—P的1．7—1．8倍。该双功能光稳定剂的光稳定性和热稳性与UV-366和UV．P相比有明显提高,光老化24h后该四个双功能光稳定剂只分解了14％～18％,添加该四个光稳定剂的石蜡光老化24h后变黄指数为0．73～1．45,而添加UV—P和UV-366则分解了75％和33．81％,光老化24h后黄变指数为3．75和3．33;该双功能光稳定剂失重1％时的温度为263～280℃,而UV．P和UV-366失重1％时温度则分别为153℃和192℃。     

Benzotriazole and benzothiadiazole containing conjugated copolymers for organic solar cell applications

2-Dodecyl benzotriazole (BTz) and benzothiadiazole (BTd) containing copolymers poly(4-(2-dodecyl-2H-benzo[d][1,2,3]triazol-4-yl)benzo[c][1,2,5]thiadiazole (P1), poly(4-(5-(2-dodecyl-7-(thiophen-2yl)-2H-benzo[d][1,2,3]triazol-4-yl)thiophen-2-yl)benzo[c][1,2,5] thiadiazole (P2) and poly(4-(5-(2-dodecyl-7-(4-hexylthiophen-2-yl)-2H-benzo[d] [1,2,3]triazol-4-yl)-3-hexylthiophen-2-yl) benzo[c][1,2,5] thiadiazole (P3) were synthesized via Suzuki polycondensation. We report the application of conjugated copolymers in bulk heterojunction photovoltaic devices. When the copolymers were blended with [6,6]phenyl-C₆₁-butyric acid methyl ester (PCBM), P2 showed the best performance with an open circuit voltage (V_oc), a short-circuit current density (J_sc) and a power conversion efficiency (PCE) of 0.45 V, 3.48 mA cm^?2 and 0.45%, respectively, under AM 1.5G illumination conditions (100 mW cm^?2). The hole mobilities of the devices were calculated from J–V curves using Space Charge Limited Current (SCLC) method and the maximum mobility value was found to be 3.15 × 10^?5 cm² V^?1 s^?1 for the P2:PCBM blend.     

From Oxadiazole to Triazole Analogues: Optimization toward a Dual Orexin Receptor Antagonist with Improved in vivo Efficacy in Dogs

The orexin system is responsible for regulating the sleep-wake cycle. Suvorexant, a dual orexin receptor antagonist (DORA) is approved by the FDA for the treatment of insomnia disorders. Herein, we report the optimization efforts toward a DORA, where our starting point was (5-methoxy-4-methyl-2-[1,2,3]triazol-2-yl-phenyl)-{(S)-2-[5-(2-trifluoromethoxy-phenyl)-[1,2,4]oxadiazol-3-yl]-pyrrolidin-1-yl}methanone ( 6 ), a compound which emerged from our in-house research program. Compound 6 was shown to be a potent, brain-penetrating DORA with in vivo efficacy similar to suvorexant in rats. However, shortcomings from low metabolic stability, high plasma protein binding (PPB), low brain free fraction (f_u brain), and low aqueous solubility, were identified and hence, compound 6 was not an ideal candidate for further development. Our optimization efforts addressing the above-mentioned shortcomings resulted in the identification of (4-chloro-2-[1,2,3]triazol-2-yl-phenyl)-{(S)-2-methyl-2-[5-(2-trifluoromethoxy-phenyl)-4H-[1,2,4]triazol-3-yl]-pyrrolidin-1-yl}l-methanone ( 42 ), a DORA with improved in vivo efficacy compared to 6 .     

Preparation of polyethylene with controlled bimodal molecular weight distribution using zirconium complexes

Four zirconium complexes containing fully deprotonated 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4,6-di-tert-pentylphenol were used as catalysts for the polymerization of ethylene. In the presence of methylalumoxane (MAO) as a cocatalyst, the precursors were highly active for polyethylene with bimodal or multimodal molecular weight distribution.     

Oxadiazole Derivatives as Dual Orexin Receptor Antagonists: Synthesis,Structure–Activity Relationships,and Sleep-Promoting Properties in Rats

The orexin system plays an important role in the regulation of wakefulness. Suvorexant, a dual orexin receptor antagonist (DORA) is approved for the treatment of primary insomnia. Herein, we outline our optimization efforts toward a novel DORA. We started our investigation with rac-[3-(5-chloro-benzooxazol-2-ylamino)piperidin-1-yl]-(5-methyl-2-[1,2,3]triazol-2-ylphenyl)methanone ( 3 ), a structural hybrid of suvorexant and a piperidine-containing DORA. During the optimization, we resolved liabilities such as chemical instability, CYP3A4 inhibition, and low brain penetration potential. Furthermore, structural modification of the piperidine scaffold was essential to improve potency at the orexin 2 receptor. This work led to the identification of (5-methoxy-4-methyl-2-[1,2,3]triazol-2-ylphenyl)-{(S)-2-[5-(2-trifluoromethoxyphenyl)-[1,2,4]oxadiazol-3-yl]pyrrolidin-1-yl}methanone ( 51 ), a potent, brain-penetrating DORA with in vivo efficacy similar to that of suvorexant in rats.     

5-硝基苯并三唑-1-乙酸镝与1,10-邻菲啰啉配合物的合成和性质研究

采用溶液合成法,合成了标题化合物,通过元素分析、摩尔电导率、紫外光谱、红外光谱和热分析法确定配合物的组成为Dy(L)3phen.1.5H2O(HL=5-硝基苯并三唑-1-乙酸;phen=1,10-邻菲啰啉)。荧光光谱表明:镝配合物的荧光强度较强,说明配体5-硝基苯并三唑-1-乙酸和1,10-邻菲啰啉是很好的敏化剂。     

氯虫酰胺的合成与杀虫活性

以2,3-二氯吡啶和2-甲基-4-氯苯胺为起始原料,经过多步反应得到6-氯-2-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-8-甲基-4H-3,1-苯并嗪-4-酮,再与甲胺反应得到目标产物氯虫酰胺,经核磁验证其结构,生物活性测定结果表明该化合物对鳞翅目害虫如小菜蛾、甜菜夜蛾、稻纵卷叶螟等具有优异的杀虫活性。     

Multichromic polymers of benzotriazole derivatives: Effect of benzyl substitution

Two electroactive monomers 1-benzyl-4,7-di(thiophen-2-yl))-2H-benzo[d][1,2,3]triazole (BBTA) and 2-benzyl-4,7-di(thiophen-2-yl))-2H-benzo[d][1,2,3]triazole (BBTS) were synthesized with satisfactory yields. The effect of substitution site on electrochemical and optical properties was investigated with cyclic voltammetry and spectroelectrochemical studies. Results showed that position of pendant group alters the electronic structure of the resulting polymer causing different optical and electrochemical behaviors. Symmetrically positioned benzyl unit on benzotriazole moiety resulted in a neutral state red polymer, PBBTS, having multi-colored property in its different oxidized and reduced states. Its analogue PBBTA exhibited maximum absorption at 390 nm in its neutral state and also revealed multicolored electrochromic property upon stepwise oxidation. Very different optical band gap values were calculated: 1.55 eV and 2.25 eV for PBBTS and PBBTA, respectively.     

选择测定Co~(2+)的荧光探针化合物合成及性质研究(英文)

以邻苯二胺和水杨醛为原料合成了2-(5-((3-(1H-苯并[d]咪唑-2基)-4-羟基苯基)甲叉基)-4-氧-2-硫代噻唑-3-基)乙酸。其结构通过红外光谱、核磁共振氢谱和质谱进行了表征,并进行了紫外和荧光性质测定。通过测定甲醇溶液中15种金属离子对该化合物荧光性质的影响,发现钴离子对该化合物的荧光有优于其他金属离子的淬灭效果。表明该化合物对钴离子有较好的选择性,可作为钴离子的淬灭型荧光传感器做进一步的研究。     

苯并[1,2,3]噻二唑-7-醛的合成

以2-氯-3,5-二硝基苯甲酸为起始原料,经过取代、酯化、还原重氮化等反应,合成了苯并[1,2,3]噻二唑-7-羧酸乙酯。并采用二异丁基氢化铝将其一步还原制备了苯并[1,2,3]噻二唑-7-醛。     

Efficient synthesis of functionalized bis-(4-oxo-1,3-thiazolan-5-ylidene)acetates

Reaction of 1-(2,2-dimethyl-propionyl)-3-{4-[3-(2,2-dimethyl-propionyl)thioureido]phenyl}thiourea or 1-(2,2-dimethyl-propionyl)-3-{5-[3-(2,2-dimethyl-propionyl)thioureido]naphthalen-1-yl}thiourea with dialkyl acetylenedicarboxylates in CH₂Cl₂ leads to alkyl (2-(2,2-dimethyl-propionylimino)-3-{4-[-(,2-dimethyl-propionylimino)-5-alkoxycarbonylmethylene-4-oxo-thiazolidin-3-yl]-phenyl}-4- oxo-thiazolidin-5-ylidene)acetates or alkyl (2-(2,2-dimethyl-propionylimino)-3-{5-[2-(2,2-dimethyl-propionylimino)-5-alkoxycarbonylmethylene-4-oxo-thiazolidin-3-yl]naphthalen-1-yl}-4-oxo-thiazo lidin-5-ylidene)acetates in good yields.