羟基化反应

In some cases, its epimer 4 was also obtained. 22 compounds were synthesized, among them 18 were new.3. Using the intramolecular Pictet-Spengler reaction to form the pentacyclic skeleton of Et-743, the byproducts 25 were obtained under various conditions. The structures of them were determined to be 1, 2-dihydro-isoquinoline compounds, and the mechanism of the reaction was proposed.B. The synthesis of the analogs of Et-743Because of the failure of removing the protective groups in compounds 14, the synthetic strategy was adjusted.

对于苄基保护的羟基化合物13a，顺利得到化合物30，然后与不同的羧酸反应得到18个酯化合物33-50；对于苄氧羰基保护的氨基化合物13b，由于脱除保护基的化合物31在空气中不稳定，所以我们采取不经分离纯化，直接与羧酸反应得到酰胺化合物53-62，然后再分别对其C-21位的羰基进行还原氰基化，得到10个酰胺目标化合物63-72，另外，我们还对羟基转化为氨基的反应进行了探索。3。

Methods 4-Hydroxybenzonitrile (2) as the starting material was transformed to 4-hydroxy-thiobenzamide (3) via thioformylation. And ethyl 2-(4-hydroxyphenyl)-4-methylthiazole-5-carboxylate (4), which was synthesized via cyclization from 3, was treated with hexamethylenetetramine to generate the intermediate ethyl 2-(3-formyl-4-hydroxyphenyl)-4-methylthiazole-5-carboxylate (5). The target compound febuxostat (1) was obtained from 5 by etherification, cyanidation, hydrolysis.

以羟基苯腈为原料，经硫代甲酰化得到对羟基硫代苯甲酰胺(3)，3经环合得到2-（4-羟基苯基）－4-甲基－噻唑－5-羧酸乙酯(4)，4与乌洛托品反应，得到中间体2-（3-甲酰基－4-羟基苯基）－4-甲基－噻唑－5-羧酸乙酯(5)，之后再经醚化、氰化、水解得到目标产物(1)。

Constituting dicycle; 2. region selectively reducing six-membered ring ketocarbonyl radical; 3. introducing 7alpha-hydroxy group; 4. Aldol reaction to introduce side chain and obtain 8alpha-hydroxy group; 5. oxidizing the position 7 hydroxy group into ketone; 6. turning the configuration of the position 7 hydroxy group; 7. glycosidating the position 7 hydroxy group; and 8. eliminating protecting group to obtain the target compound.

该方法包括如下步骤：(1)双环的构建；(2)区域选择性还原六元环酮羰基；(3)7α-羟基的引入；(4)Aldol反应引入侧链，同时得到8α-羟基；(5)7位羟基氧化为酮；(6)7位羟基构型的翻转；(7)7位羟基的糖苷化；(8)脱除保护基得到目标化合物。

In the presence of alkalinity and tetraethyl ammonium bromide, 2,4-dihydroxy benzophenone reacts with allyl glycidyl ether to form an ethylenic derivative of benzophenone, 2-hydroxy-4-(β-hydroxy-γ-allyloxy) propyloxy benzophenone, which can further undergo hydrosilylation with polyhydromethylsiloxane.

在相转移催化剂四乙基溴化按作用下，利用2，4-二羟基二苯甲酮与烯丙基缩水甘油醚在碱性水溶液中的开环加成反应，合成了中间体4-丙氧基－2-羟基二苯甲酮，将其进一步与聚甲基氢硅氧烷进行硅氢化加成反应。

The relative stabilities and probable proton transfer in isolated and monohydrated 2-hydroxyimidazole molecules have been studied in gas phase using ab initio (MP2/6-31＋G *) method.

采用从头算方法在MP2/6-31＋G*水平上研究了2-羟基咪唑分子在孤立分子和一水合物的异构体的相对稳定性和可能的质子迁移反应，分析了一个水分子的参与对2-羟基咪唑分子异构体的相对稳定性和质子迁移速率的影响，采用Monte Carlo模拟方法研究了反应体系在水溶液中反应的溶剂化效应。

As our studies showed, silylation of mesoporous molecular sieves with alkoxysilane was an usual method of linking desired organical groups. However, as a result, the a lot of silanol groups still existed on the surface of mosoporous molecular sieves after silylation, which maybe affect the interface property and its catalystic activity. Based on this consideration, a novel method was proposed that a mixture of trichlorosilanes was used to silylate mesoporous molecular sieves, introducing both the further reactive group and hyhrophobic methyl group in one pot.

正如研究表明，通过硅氧烷与介孔分子筛表面的硅羟基反应是常见的键连有机基团的方法，但表面仍会剩余较多的硅羟基，硅羟基的存在会严重影响到介孔分子筛表面性质及催化活性，为此笔者提出采用混合的三氯化硅烷一步硅烷化介孔分子筛，在孔道内同时引入可进一步功能化的氯丙基或氯苄基和疏水性的甲基。

The pyridinium salts was transformed by the base to 1-hydroxy or 3-hydroxy-quinolizinylides, which undergo 1,3-dipolar cycloadditionreaction with alkenes,and then aromatizated to cycl[3,3,2]azinone in thepresence of oxidant.

实验证明，这是一个连续进行的多步反应：2-羰基吡啶鎓盐在反应中先生成1-羟基或3-羟基喹嗪叶立德，然后与烯烃起1，3—偶极加成反应，最后在氧化剂作用下脱氢芳构化而生成Cycl[3，3，2]azinone。

Starting from the hydroxylamine (dimethyl amino ethanol, triethanolamine) and 1, 3-propane sultone, a series of hydroxyl and sulfonyl dual-functionalized zwitterionic salts were synthesized. Then dual-functionalized ionic liquids containing both hydroxyl and sulfonyl functional groups were produced successfully by zwitterionic salts and three kinds of strong acids (p-toluene sulfonic acid, trifluoromethanesulfonic acid, methanesulfonic acid) respectively. The structure of zwitterionic salts and dual-functional ionic liquids were confirmed by the 1H NMR and IR.

以羟基有机胺(N，N-二甲基乙醇胺，三乙醇胺)为原料与1，3-磺酸内酯反应合成了一系列含有羟基和磺酸基双官能团的内盐，并将所得到的内盐分别与三种强酸(对甲苯磺酸，三氟磺酸，甲磺酸)反应，成功地合成了双功能化室温离子液体，并通过红外光谱、核磁氢谱测定，证实了内盐和双功能化离子液体的结构。

Methods 4-Hydroxy- benzonitrile was treated with sodium hydrogen sulfide and anhydrous magnesium chloride in dimethyl formamide to give thioamide, which was then directly cyclized with ethyl 2-chloroacetoacetate without separation to give ethyl 2-(4-hydroxyphenyl)-4-methylthiazole-5-carboxylate(2) in one-pot; then 2 was formylated with Duff reaction adopting hexamethylenetetramine in trifluoroacetic acid to give ethyl 2-(3-formyl-4-hydroxyphenyl)-4-methylthiazole-5-carboxylate(3); finally, the target compound was obtained by the treatment of 3 with hydroxylamine hydrochloride and sodium formate in formic acid.

采用&一勺烩&方法，以4-羟基苯甲腈为起始原料，首先与硫氢化钠和无水氯化镁在N，N-二甲基甲酰胺中反应，所得中间体不经分离，直接加入2-氯乙酰乙酸乙酯进行环合反应，得到2-(4-羟基)苯基-4-甲基-5-噻唑甲酸乙酯（2）；然后通过六亚甲基四胺/三氟乙酸进行Duff反应，得到2-(3-甲酰基-4-羟基)苯基-4-甲基-5-噻唑甲酸乙酯（3）；再经盐酸羟胺/甲酸/甲酸钠体系脱水得到目标化合物。

Two series of polyurethane acrylate grafted acrylic resins (Acr-g-TPU-PETA and Acr-gPPU-PETA) self-emulsifying systems are obtained by grafting -NCO group modified polyurethane acrylates with acrylic copolymer prepared from n-butyl acrylate, styrene,βhydroxyethyl methacrylate and acrylic acid The self-emulsifying systems showed Newtonian fluidity with viscosity closed to that of water, the solid contents were around 30% The T〓 of 15～4℃ for dried film before photocuring favored film formation at room temperature DSC and DMA results showed that PU-PETA is compatible with acrylic resin in the grafted resin The TG and dTG curves for Acr-g-PU-PETA samples were substantially different from the corresponding blends, and the brodened dTG peaks for photocured grafted resin suggest that there might be multiple interactions among chain segments The photocued film of the grafted resins self-emulsifying system exhibited good overall properties with polyurethane acrylate grafts ranging from 30% to 50%, and Acr-g-TPU-PETA series showed better properties than Acr-gPPU-PETA series The adhesion of the photocured film was 1～2 grade, impact strength was 50kg-cm and flexibility was 1mm The Shore hardness and the adhesion of the film decreased markedly if PETA was replaced by HEMA as photoactive group due to the lower C=C double bond content in the grafted resin The polyhydroxy amine-linked thioxanthones photoinitiators can be evenly dispersed in self-emulsifying system without color spot appearing in the dried film The films photocured with IV〓～IV〓 generally exhibited higher Shore hardness, gloss and solventresistance than that cured with Irgacure 2959 and did not induce the rusting of the iron substrate Pigmenting with titanium oxide had no effect on the photocuring The polyhydroxy amine-linked thioxanthone IV〓 and IV〓 can be new candidates for the formulation of titanium oxide pigmented photocurable water-borne coatings for their pale-yellow appearance and slight interference with the color of the coatings WB 4759 with high water-solubility coalesced and separated from the dried resin film, and even induced the rusting of iron substrate.

以丙烯酸丁酯，甲基丙烯酸-β-羟乙酯，丙烯酸及苯乙烯合成厂丙烯酸共聚树脂，并与含-NCO端基的聚氨酯丙烯酸酯接枝反应，经水性化后，得到两个系列（Acr-g-TPU-PETA和Acr-g-PPU-PETA）各5个不同配比的丙烯酸树脂接枝聚氨酯丙烯酸酯自乳化体系，粘度与水相近，为牛顿流体，固含量30％左右。光固化前干燥涂膜的玻璃化转变温度在-15℃～4℃之间，有利于室温下成膜。DSC及DMA谱表明两种树脂基本相容。Acr-g-PU-PETA的热失重行为明显不同于共混材料，接枝样dTG峰明显宽化，表明接枝样中链段之间的相互作刚有多重性，丙烯酸树脂与聚氨酯之间有一定的相容性。接枝树脂自乳化体系光固化涂层的综合性能以聚氨酯丙烯酸酯成分为50％～30％者相对较好，且以Acr-g-TPU-PETA系列更理想。光固化膜的附着力为1～2级，冲击强度为50kg·cm，柔软性多为1mm。以HEMA代替PETA作为接枝树脂的活性基团，碳—碳双键密度太低，光固化膜交联点太少，硬度和附着力均较差。多羟基胺连硫杂蒽酮光引发剂能均匀分散于树脂自乳化体系和接枝树脂干膜中，不出现色斑，光固化膜肖氏硬度一般高于以Irgacure 2959为光引发剂的光固化膜，光泽度及耐丁酮溶剂性能均有所提高，不会诱导铁基生锈，钛白着色对光固化结果几乎没有影响。本论文所合成的多羟基胺连硫杂蒽酮光引发剂IV〓与IV〓为浅黄色，对光固化涂层的颜色干扰较小，为配制钛白着色光固化水性涂料提供了新的光引发剂。水溶性太强的WB 4759在干膜中易聚结析出，且对所附着的铁基有诱导锈蚀作用。

This one mode pays close attention to network credence foundation of the businessman very much.

这一模式非常关注商人的网络信用基础。

Cell morphology of bacterial ghost of Pasteurella multocida was observed by scanning electron microscopy and inactivation ratio was estimated by CFU analysi.

扫描电镜观察多杀性巴氏杆菌细菌幽灵和菌落形成单位评价遗传灭活率。