N—［1－（2－吡咯烷酮基）甲基］丙烯酰胺类的聚合及其水凝胶

Ｎ—［１－（２－吡咯烷酮基）甲基］丙烯酰胺类的聚合及其水凝胶于淑艳，李福绵（北京大学化学系，北京，１００８７１）关键词Ｎ－［１－（２－吡咯烷酮基）甲基］丙烯酸胺、氧化－还原引发体系、超高分子量、平衡吸水率Ｎ一【ｌ一（２一毗咯烷酮基）甲基］丙烯酸胺（Ｐ...     

N－（N＇，N＇－二甲氨基甲基）丙烯酰胺－过硫酸钾引发丙烯酰胺聚合的研究

Ｎ－（Ｎ＇，Ｎ＇－二甲氨基甲基）丙烯酰胺－过硫酸钾引发丙烯酰胺聚合的研究潘松汉，唐康泰，王贞，王真智中国科学院广州化学研究所，广州，５１０６５０关键词Ｎ－（Ｎ＇，Ｎ＇－二甲氨基甲基）丙烯酰胺、反应动力学、氧化还原体系、相对分子质量及分布为了制备高质量...     

硝酸镧与N，N－双（苯并三唑甲基）－［2，2］及N－三唑甲基－［2，2］配合物的合成、性质和结构

合成了Ｌａ（ＮＯ＿３）＿３与Ｎ，Ｎ－双（苯并三唑甲基）－［２，２］［Ｌ（Ｉ）］及Ｎ－三唑甲基－［２，２］［Ｌ（Ⅲ）］的配合物单晶，测定了结构，并进行了元素分析、红外光谱及热分析表征。Ｌａ￣（３＋）离子均与［２，２］环中六个杂原子及三个ＮＯ离子配位，稍偏离环平面，三个ＮＯ离子分别位于环平面的两侧。初步讨论了［２，２］环所连接支链对配合物结构及其热稳定性的影响。     

金属离子与卟啉的嵌入反应动力学研究──Ⅶ．一元酸根催化Cu(Ⅱ)与溴化间－四(N－乙酸甲酯基－3－吡啶基)卟啉的配位反应

研究了在３５±０．１℃、离子强度０．５ｍｏｌ／Ｌ（ＫＣｌ）条件下，甲酸根、乙酸根、丙酸根和丁酸根分别催化Ｃｕ（Ⅱ）离子与四溴化间－四（Ｎ－乙酸甲酯基－３－吡啶基）卟啉（Ｈ２Ｔβ－Ｎ－ＡＣＭｓｐｙＰＢｒ４）的反应动力学及其机理，该类反应对卟啉和Ｃｕ（Ⅱ）离子均为一级反应，反应动力学方程为：ｄ［ＣｕＰ＾４＋］／ｄｔ＝ｋ｛１．０＋ｂ［Ａ＾－］）／（１．０＋Ｋ３，４．［Ｈ＾＋］＾２｝［Ｃｕ＾２＋］［Ｐ］Ｔ     

水溶性聚合物和两亲聚合物：聚（丙烯酰胺－co－丙烯酸钠）－g－聚（β－胺基丙酸）接枝共聚物

合成了端丙烯酰胺基聚（β－胺基丙酸）大分子单体，用端基滴定法和１Ｈ－ＮＭＲ法测定了大分子单体的分子量，用＾１＾３Ｃ－ＭＮＲ和氢氧化钠水解法测定了支化度，在水溶液中用硫酸亚铁／异丙苯过氧化氢氧化还原引发体系引发丙烯酰胺，丙烯酸钠与聚（β－胺基丙酸）大分子单体的共聚反应，合成了聚（丙烯酰胺－ｃｏ－丙烯酸钠）－ｇ－聚（β－胺基丙酸）用１Ｈ－ＮＭＲ和滴定法测定了接枝共聚物的组成。溶液性质的数据表明，与部分     

二烯丙基二甲基氯化铵—丙烯酰胺反相乳液聚合的动力学特征研究

采用油酸失水山梨醇酯（ＳＰＡＮ）－壬基酚聚氧化乙烯醚（ＯＰ）复合乳化剂与Ｋ２Ｓ２Ｏ８－Ｎａ２ＳＯ３氧化还原引发剂，进行二烯丙基二甲基氯化铵－丙烯酰胺反相乳液共聚合，测得单体的竞聚率为γＤＡＤＭＡＣ＝０．１４±０．１１，γＡＭ＝５．０５±０．６６；在单体浓度为２５─４５％，引发剂浓度０．０６—０．１％，乳化剂浓度为５—９％，聚合温度３０３Ｋ条件下，得到了共聚反应动力学方程：Ｒｐ＝ｋ［Ｍ］０．６８［Ｉ］１．３１［Ｅ］０．７３，文中对上述结果做了解释．     

Semisynthesis and Biological Evaluation of Taxayuntin 13－［N－Benzoyl－（2’R，3’S）－3’－phenylisoserinate］

ＳｅｍｉｓｙｎｔｈｅｓｉｓａｎｄＢｉｏｌｏｇｉｃａｌＥｖａｌｕａｔｉｏｎｏｆＴａｘａｙｕｎｔｉｎ１３－［Ｎ－Ｂｅｎｚｏｙｌ－（２’Ｒ，３’Ｓ）－３’－ｐｈｅｎｙｌｉｓｏｓｅｒｉｎａｔｅ］ＱｉｎＹＵＥ；ＱｉＣｈｅｎｇＦＡＮＧａｎｄＸｉａｏＴｉａｎＬＩＡ...     

（E）－β，γ－UNSATURATED NITRILES FROM DIMETHYLSULFONIUM CYANOMETHYLIDE AND 9－ALKENYL－9－BORABICYCLO［3，3，1］NONANES

（Ｅ）－β，γ－ＵＮＳＡＴＵＲＡＴＥＤＮＩＴＲＩＬＥＳＦＲＯＭＤＩＭＥＴＨＹＬＳＵＬＦＯＮＩＵＭＣＹＡＮＯＭＥＴＨＹＬＩＤＥＡＮＤ９－ＡＬＫＥＮＹＬ－９－ＢＯＲＡＢＩＣＹＣＬＯ［３，３，１］ＮＯＮＡＮＥＳＮａｎＳｈｅｎｇＬＩ；ＭｉｎＺｈｉＤＥＮＧ；Ｙ...     

N－甲基丙烯酰－N＇－嘧啶哌嗪与过硫酸钾引发体系引发的丙烯酰胺聚合

Ｎ－甲基丙烯酰－Ｎ＇－嘧啶哌嗪与过硫酸钾引发体系引发的丙烯酰胺聚合高青雨，张福莲，杨更须，张举贤（河南大学化学化工系，开封，４７５００１）李福绵（北京大学化学系，北京，１０００８７１）关键词Ｎ－甲基丙烯酰－Ｎ＇－嘧啶哌嗪，可聚合芳香叔胺，氧化还原引发...     

PAP-H2O2-HRP酶促反应产物光谱及电化学研究

前文［１］首次提出了以对氨基酚（ＰＡＰ）为底物的ＰＡＰ－Ｈ２Ｏ２－辣根过氧化物酶（ＨＲＰ）伏安酶联免疫分析新体系,并成功地应用于烟草花叶等植物病毒的血清学检测．在此之前,我们也曾报道过一些伏安酶联免疫分析新体系［２,３］．迄今,还没有人对 ＨＲＰ催化 Ｈ２Ｏ２氧化 ＰＡＰ的酶促反应进行过探讨．Ｐｒａｔｉ等［４］报道了在铜催化作用下,Ｏ２氧化对氨基酚生成３－［（４－个羟苯基）氨基」－４－（２－氨基－５－羟苯基）－６－［（４－羟苯基）亚胺基］－２,４－环己二烯基－１－酮．本文的实验结果与此文献不符． 为…     

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.