羟基化反应

Then Doripenem came into the market in the July ,2005. We studied the synthesis of Doripemen.Firstly, we synthesized the chemical 2 from the starting material------o-hydroxylphenylacylamine through Reformastky reaction, alkylation, Diekmann reaction, enolization, esterification and etc. Secondly, we synthesized the chemical 3 from L — hydroxylproline through the protection of carboxyl, amidogen and hydroxyl group, reduction by NaBr, SN_2 substitution and Mitsumobu reaction.

我们以水杨酰胺为起始原料，经Reformatsky反应、烷基化、Diekmann环合、烯醇化、酯化等反应合成双环母核2；再从L-羟基脯氨酸出发，经酯化保护羧基、保护氨基、保护羟基、硼氢化还原酯得醇、Sn2取代和Mitsumobu反应等合成巯基侧链3；最后由化合物3经脱保护、水解得硫醇，和化合物2在二异丙基乙基胺的作用下缩合，最后Pd／C催化脱保护，历经16步反应最终得到产物多尼培南。

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。

The pigment in colored cotton fibers was extracted by methanol at room temperature. The results of color reactions HCl-Mg reaction, NaBH4 reaction, NaOH reaction, FeCl3 reaction and Pb(Ac2 reaction of the pigment extractive showed that the pigment extracted by methanol was flavone or flavonol with two adjacent hydroxide groups (Table 2, Fig. 1). The results of UV spectral analysis further proved that the pigment extracted by methanol from brown fiber belonged to flavone with two adjacent hydroxide groups in B ring, and that from the green fiber contained not only flavone but also flavonols with two adjacent hydroxide groups both in A ring and B ring and indican replaced a hydroxide group at 3-site of A ring Fig.

通过盐酸－镁粉反应、四氢硼钠还原反应、碱反应、醋酸铅反应、氯化铁反应和紫外光谱吸收的分析表明，甲醇室温提取的棕色棉纤维色素可能是黄酮类化合物，B环上带有邻二酚羟基；甲醇室温提取的绿色棉纤维色素除黄酮类化合物外，还含有3-位羟基被糖甙化的黄酮醇类化合物，A、B环上都带有邻二酚羟基。

Therefore esterification crosslinked reactionbetween polyearboxylic acid and wood can be quantitatively determined.According toexperiment results of stereoscopic configuration choices by crosslinking agents,crosslinkingreaction between model of reaction intermediate and wood,and the intermediate characteristic incrosslinking reaction,crosslinking reaction intermediate was proofed.We can infercrosslinking reactions between polycarboxylicacid and wood want through a mechanism of twosteps reaction process,the first cyclic anhydrides were formed as intermediates by dehydratingbetween hydroxyls in polycarboxylic acids,second esters were occurred by substitution reactionbetween wood hydroxyls and cyclic anhydrides.

从而可全面定量表征木材与多元羧酸类化合物的酯化交联反应；依据交联剂立体构型选择性、反应中间体模型物与木材的交联反应和交联反应中间体的波谱特征实验结果，证实了交联反应中间体，因此可以推测：多元羧酸类化合物与木材化学组分的交联反应是经历两步反应的机理，首先多元羧酸中相邻羧基的羟基之间脱水形成五元环酸酐中间体，然后木材的羟基与酸酐发生亲核取代反应形成酯。

To our knowledge, reverse phase of high performance liquid chromatography was firstly developed to analyze the metabolites of 7-tocopherol with ideal results. Meanwhile, Gas chromatography/Mass chromatography were used to analyze the structures of unknown metabolites of 7-tocopherol and a main unknown metabolite was identified as a side chain ω- hydroxylate of 7-tocopherol.The kinetic results of of 7-tocopherol reacted in the S9 of male SD-rat liver showed that the optimal time was 45 min; the optimal concentration of S9 5 mg/ml; the optimal concentration of NADPH 1 mM; and the optimal concentration of 7-tocopherol 8 μg/ml. The result of γ-tocopherol metabolized in the S9 of male SD-rat was the best; male Brazil turtle better; and male cobia worst.

本试验首次确立了γ-生育酚代谢物的RP-HPLC分析方法，结果理想且重现性好；用GC／MS对γ-生育酚的未知代谢物结构进行分析，判断其中一种主要的代谢物为γ-生育酚侧链初级羟基化代谢物；γ-生育酚在雄性SD-大鼠肝S9的代谢动力学表明，本实验条件下代谢反应的最佳时间为45min，S9浓度为5mg／ml，NADPH浓度为1mM，γ-生育酚浓度为8μg／ml；发现γ-生育酚在雄性SD-大鼠肝S9中代谢最高，雄性巴西龟次之，雄性军曹鱼最低。

The results showed polymeric diaryliodonium salts were effective aryl ion transfer reagents. Thirdly, a new type polymer supported hypervalent iodine reagents poly { [4-Hydroxy iodo] styrene} has been developed. It was an effective oxidative reagent, and could be applied to the one pot synthesis of 4-arylthiazoles.

然后，我们以聚苯乙烯羟基对甲苯磺酰氧基碘苯为原料，成功制备了一类新型聚合物高碘试剂—聚苯乙烯负载的炔基碘盐，并研究了其作为炔基转移试剂的有效性：(1)该试剂可对硫、氮、硒等负离子进行亲电炔基化反应，合成炔基亚砜、0，0-二烃基二硫代磷酸炔基酯、1-苯乙炔基苯并噻唑以及炔基硒醚。

Two coordination polymers composed of in situ synthesized ligand deriving from isophthalic acid through the hydroxylation on the 2-position have been synthesized under hydrothermal conditions.

利用铜离子的氧化还原性质，以铜离子和间苯二甲酸在水热条件下反应使配体发生羟基化衍生成2，6-二羧基苯酚，并组装出2个含衍生配体的配位聚合物。

The structure of the product was characterized by IR and 1H NMR.It indicated that the double bonds in ester were sulphonated and then converted into the corresponding saturated hydrocarbon ester sulphonate after hydrolysis.

对产物用红外光谱和核磁共振 1H谱进行的结构分析结果显示，油酯的不饱和双键发生了磺化反应，生成了饱和的羟基磺酸盐。

Treatment of sucrose alkyl 4,6-orthoacetate hexaacetates I with water or alcohol in the presence of an acid catalyst afforded derivatives of sucrose acetates by selectively blocking specific hydroxyl group in sucrose and acetyl migration.

4，6-原乙酸蔗糖六乙酸酯在酸催化下水解和醇解，选择性地保护了蔗糖分子中的某些羟基，并通过乙酰基由C~4→C~6迁移的异构化反应合成了一系列蔗糖乙酸酯。

The results of FT-IR 1H-NMR indicate the structure of polyester, and the 13C-NMR analysis of three quaternary carbon showed the existing of hyperbranched struscture, MALDI-TOF MS showed the hyperbranched polyester structure, the degree of branching of the polyesters determined by 13C-NMR being 0.408. The esterification reaction kinetics followed a second-order equation and the reaction rate was controled by the concemtration of carboxyl group and hydroxyl group,-d/dt=K.

以IR、1H-NMR证实了聚酯结构的存在，13C-NMR谱图上3种季碳的特征峰有力证实了超支化分子结构的存在，MALDI-TOF MS证明了超支化聚酯的成功合成，并计算超支化聚酯的支化度为0.408；探讨并建立了超支化聚酯的缩聚反应动力学方程－d/dt=K，该缩聚反应属于二级反应，反应速率由羟基浓度和羟基浓度共同决定。

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。