L-酒石酸正己酯的合成

以甲苯作溶剂,对甲苯磺酸作催化剂,L-酒石酸、正己醇为原料合成了手性选择体——L-酒石酸正己酯。确定最隹反应条件为：L-酒石酸100mmol,n(L-酒石酸)：n(正己醇)=1：2．8,甲苯45mL,对甲苯磺酸0．30g,回流反应．53min,酯化率在99％以上,收率达83％。     

D-酒石酸正庚酯的合成

以D-酒石酸与正庚醇为原料,在对甲苯磺酸催化下合成了手性拆分剂D-酒石酸正庚酯,通过正交实验确定优化反应条件为:D-酒石酸100 mmol,n(D-酒石酸)∶n(正庚醇)=1.0∶2.6,对甲苯磺酸0.5 g,甲苯50mL,回流反应约1 h,酯化率99%,收率在93%以上。其结构经IR确证。     

手性仲丁胺的制备拆分和光学纯度的测定

为了获取仲丁胺的两种光学纯对映异构体，采用D-或L-酒石酸作为拆分试剂， 经过多次结晶，分别得到S-(+)-仲丁胺·乙-(+)-酒石酸盐和R-(-)-仲丁胺·D-(-) -酒石酸盐晶体，从而成功实现了其分离．产物的光学纯度通过用光活性(R)-联萘 酚磷酰氯衍生成(R)-联萘酚磷酰胺后，经^31P NMR测定，o_p_＞99％，拆分剂D-或 L-酒石酸经过强酸型阳离于交换树脂(001×7×7型)方便回收，回收率＞80％．     

KI催化酯交换合成碳酸二正辛酯的研究

研究了碳酸二甲酯与正辛醇酯交换合成碳酸二正辛酯（DOC）的反应，比较了卤化钾与系列碳酸钾复合催化剂的性能，考察了物料配比、反应温度、反应时间诸因素对该反应的影响，得出了该反应的最佳工艺条件．结果表明，KI具有较好的催化活性和选择性；在最佳反应条件（常压、反应温度140℃、反应时间为4h、n（DMC）：n（n-OctOH）=1：4、催化剂用量为总重1．25％。）下，DMC的转化率为83．7％，DOC的收率为70．0％，DOC的选择性为83．7％，甲基辛基碳酸酯（MOC）的收率为13．7％．     

用GC-FID和GC-TOF-MS方法分析α-硫辛酸中有机溶剂残留量

采用GC-TOF-MS鉴定残留有机溶剂,以HP-5毛细管柱为分离柱,FID为检测器,正辛醇为溶剂,外标法进行定量。乙醚、异丙醚的线性范围分别为34．4～344．0μg／mL（r=0．9999）,23．0～230．0μg／mL（r=0．9999）;方法精密度和稳定性试验RSD（n=6）均〈1％;平均回收率范围98．1％～100．7％,RSD0．75～2．7％;检出限分别为0．1,0．08μg／mL。     

二(2-乙基己基)磷酸与酒石酸衍生物复合萃取拆分扁桃酸外消旋体

本文研究了扁桃酸对映体在含二(2-乙基己基)磷酸(D2EHPA)与酒石酸衍生物复合手性选择剂的正辛醇-水两相体系中的萃取分配行为,考察了酒石酸衍生物的种类和初始浓度、D2EHPA的初始浓度、扁桃酸的初始浓度、萃取温度对分配系数和分离因子的影响.结果显示,复合手性选择剂能提高分配系数和分离因子,D2EHPA与D-酒石酸衍生物的复合手性选择剂与L-扁桃酸对映体比与D-扁桃酸对映体形成更稳定的非对映体复合物;且D2EHPA与二对甲基苯甲酰酒石酸(DTTA)的复合手性选择剂的手性选择性大于D2EHPA与二苯甲酰酒石酸(DBTA)的复合手性选择剂;同时,扁桃酸的初始浓度、萃取温度对分配系数和分离因子的影响较大.     

二硫代二乙二醇水基抗磨剂的合成及性能研究

以硫磺、硫化钠、2-氯乙醇为起始原料合成了二硫代二乙二醇。以乙醇为溶剂,硫化钠187mmol,n(2-氯乙醇)：n(硫磺)：n(硫化钠)=1．8：1．2：1．0,回流反应30min,二硫代二乙二醇(其中硫醚硫含量为39．54％)产率达88．5％。含二硫代二乙二醇85．7％的水基抗磨剂具有优良的极压性(PB=804N),但抗磨性不理想(D30min^196N=0．72mm)。     

用H2O2氧化苯乙烯合成苯甲酸

摘要：以30％H2O2做为氧化剂,钨酸钠与含O双齿有机配体(草酸)形成的络合物为催化剂,在无有机溶剂、无相转移剂的条件下,研究了苯乙烯氧化制苯甲酸的反应。研究结果表明,最佳反应条件为：苯乙烯100．0mmol,n(钨酸钠)：n(草酸)：n(苯乙烯)：n(30％H2O2)=2．0：3．2：100．0：440．0,于92℃反应24h,苯甲酸收率98．6％。用GC—MS跟踪了氧化过程中4种主要物质苯乙烯、1-苯基邻二醇、羟基苯乙酮及苯甲酸含量随反应时间的变化关系,提出了其主要氧化机理为苯乙烯经过环氧化反应、水解生成生成1-苯基邻二醇,1-苯基邻二醇再氧化为羟基苯乙酮、最后氧化为苯甲酸。     

丙烯酸十八酯的合成新方法

以十八醇和丙烯酸为原料,在不加带水剂的条件下合成了丙烯酸十八酯。用正交实验确定了最佳合成工艺：十八醇108g(0．4mol),n(十八醇)：n(丙烯酸)=1．0：1．2,对甲苯磺酸1．0％(催化剂,以醇酸总质量计),对苯二酚0．7％(阻聚剂,以醇酸总质量计),反应温度135℃,反应时间6h,酯化率在92％以上。产物结构经元素分析,IR和^1H NMR表征。     

N-[4-(磺酰胺)苯基](甲基)丙烯酰胺的合成

以对氨基苯磺酰胺、丙烯酰氯(或甲基丙烯酰氯)为原料合成了N-[4-(磺酰胺)苯基]丙烯酰胺(ASPAA)和N-[4-(磺酰胺)苯基]甲基丙烯酰胺(ASPMAA),其结构经^1H NMR,IR和元素分析表征。合成ASPAA的最佳条件：对氨基苯磺酰胺13．76g(80mmol),n(对氨基苯磺酰胺)：n(丙烯酰氯)=1．0：1．1,n(丙烯酰氯)：n(NaHCO3)：1．00：1．14,0℃～2℃反应3h,反应液倾入10倍体积的的甲醇-水[V(甲醇)：V(水)=1：10]中析出产物,收率在60％以上。合成ASPMAA的最佳条件：对氨基苯磺酰胺6．88g(40mmol),n(对氨基苯磺酰胺)：n(甲基丙烯酰氯)=1.00：1．05,n(三己胺)：n(甲基丙烯酰氯)：1．0：1．0,在0℃～2℃滴加甲基丙烯酰氯后先在室温下反应1h,然后在60℃反应1h,反应液倾入700mL石油醚中析出产物,收率50％～60％．     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.