1,4—双（氯甲基）—2—甲氧基—5—壬氧基苯的均聚和共聚研究

以１，４－双（氯甲基）－２，５一二甲基苯（ＢＣＭＤＭＢ）和１，４－双氯甲基－２－甲氧基－５－壬氧基苯（ＢＣＭＭＯＮＯＢ）为单体，采用脱氯化氢法，合成了聚（２，５－二甲基）对亚苯基亚乙烯（ＰＤＭＰＶ）和聚（２－甲氧基－５－壬氧基）对亚苯基亚乙烯（ＰＭＯＮＯＰＶ）；并对ＢＣＭＤＭＢ和ＢＣＭＭＯＮＯＢ的共聚进行了研究。结果表明，适宜的反应条件为：碱与单体的摩尔比为２０∶１，在室温下聚合时间为３０ｈ，碱的ｐＨ＝１４时产率最高。用ＩＲ、１Ｈ－ＮＭＲ、ＵＶ—Ｖｉｓ对聚合物进行了表征。     

甲烷直接芳构化反应的研究Ⅰ．负载Mo基催化剂在无氧条件下的催化性能

研究了催化剂制备方法、Ｍｏ含量、预处理条件和反应条件对在无氧条件下ＨＺＳＭ－５负载的Ｍｏ基催化剂上甲烷直接芳构化反应的影响，及积炭和烧炭再生对催化剂性能的影响．发现Ｍｏ含量为３．５～４％时催化剂活性最高，生成苯的速率高达１．２×１０－３ｍｏｌ·ｇ－１·ｓ－１．降低空速和提高反应温度均有利于甲烷的直接芳构化．随着反应的进行，乙烯的选择性不断提高，苯的选择性则不断降低．ＸＰＳ结果表明，反应后催化剂表面积炭，且研磨法制备的催化剂中Ｍｏ６＋被还原成不具活性的金属态Ｍｏ０．卡宾中间体（Ｍｏ＝ＣＨ２）可能是甲烷芳构化反应的起始物．     

铝镁柱联粘土的制备及表征

以铝镁双金属离子低聚物为交联剂，制备了复合柱联膨润土催化剂（简称为Ａｌ－Ｍｇ－ＰＩＬＣ）。详细考察了Ｍｇ／Ａｌ比、Ａｌ／土比等因素对合成产品性能的影响。借助于ＸＲＤ、ＢＥＴ、ＤＴＡ表征手段，结合轻柴油裂解，三甲基苯转化反应，探讨催化剂表面酸性。结果表明，铝镁复合柱直径小于的相应值，所得柱联粘土表面总酸量较少，强酸比例增大。经３５０℃脱附后，其吡啶吸附量可保持２５℃下吸附值的７％左右，而Ａｌ－ＰＩＬＣ只保留２．５％。进一步证实了交联剂的改进对柱联粘土催化剂性能的影响。     

甲烷直接芳构化反应的研究Ⅰ.负载Mo基催化剂在无氧条件下催化性能

研究了催化剂制备方法，Ｍｏ含量，预处理条件和反应条件对无氧条件下ＨＺＳＭ－５负载的Ｍｏ基催化剂上甲烷直接芳构化反应的影响，及积炭和烧炭再生对催化剂性能的影响，发现Ｍｏ含量为３．５～４％时催化剂活性最高，生成苯的速率高达１．２×１０＾－３ｍｏｌ．ｇ＾－１．ｓ＾－１，降低空速和提高反应温度均有利于甲烷的直接芳构化，随着反应的进行，乙烯的选择性不断提高，苯的选择性则不断降低，ＸＰＳ结果表明，反应后催化剂     

Lewis酸催化1,4-脱水-2,3-二-氧-(对迭氮基苯甲基)-α-D-核糖的选择性开环聚合反应

在低温下用三氟化硼乙醚催化１，４－脱水－２，３－二－氧－（对迭氮基苯甲基）－α－Ｄ－核糖（ＡＤＡＢＲ）的阳离子选择性开环聚合反应，首次合成了具有１，５－开环α－结构的聚合物。单体ＡＤＡＢＲ由１，４－脱水－α－Ｄ－核糖在ＤＭＦ溶剂中与对溴甲基迭氮基苯反应获得。聚合物的结构由比旋光度、１Ｈ－ＮＭＲ和１３Ｃ－ＮＭＲ及ＩＲ谱确认。用五氟化锑为催化剂则得到了同时含有α－呋喃单元和β－吡喃单元混合结构的聚合物。研究了催化剂及其用量、聚合反应时间对聚合反应的影响，讨论了聚合反应机理。为研究１，４－脱水－２，３－二－氧－（对迭氮基苯甲基）－α－Ｄ－吡喃核糖的聚合活性以及便于测试迭氮基的含量对聚合物光刻性能的影响，还初步研究了单体ＡＤＡＢＲ与１，４－脱水－２，３－二－氧－苯甲基－α－Ｄ－吡喃核糖（ＡＤＢＲ）的共聚反应。从共聚物的结构分析可以认定共聚物具有１，５－α－结构，并且单体１，４－脱水－２，３－二－氧－苯甲基－α－Ｄ－吡喃核糖在实验条件下具有较高的活性。     

一种新型2,5-二甲基-2,4-己二烯不对称环丙烷化原位催化体系

以（ － ）１ Ｒ,２ Ｓ２氨 基１ ,２二苯 基乙 醇 作为 手性 源, 与取 代 水杨 醛 缩合 制 备 了系 列 手性 Ｓｃｈｉｆｆ 碱配 体,考察 了该类配体的二价铜配合物及配体与 Ｃｕ（ Ｃ Ｈ３ Ｃ Ｎ）４ Ｃｌ Ｏ４ 组成的原位 体系对２ ,５二甲基２ ,４己二烯与 重氮乙酸 Ｌ薄 荷酯的环丙烷化反应的催化作用． 结果表明, Ｃｕ（Ⅱ） 配合物尽管具有较高的催化活性,但几乎没有光 学选择性,而原 位体系 则表 现出极 高的 催化活 性和 一定的 光学选择性,化学收率为９０３ ％ , 顺 式体ｅ ．ｅ ．值达到３０ ％     

钯-三苯膦催化体系选择氢化顺酐制备琥珀酸酐

开发了一种由顺酐直接加氢高选择性及高转化率制备琥珀酸酐的新方法,研究结果表明：钯三苯基膦催化体系对顺酐加氢具有较高的反应活性．在所考察的反应条件下,此催化剂体系对琥珀酸酐的选择性为１００％,无其他副产物生成．并考察了三苯基膦／钯摩尔比,反应温度,氢气压力,催化剂和顺酐浓度对顺酐催化加氢生成琥珀酸酐的影响．在反应条件为ＰｄＣｌ２＝１２５×１０－３ｍｏｌ／Ｌ,ｎ（顺酐）／ｎ（Ｐｄ）≤２０００,ｎ（三苯基膦）／ｎ（Ｐｄ）＝４,Ｔ＝３７３～３９３Ｋ,２５ＭＰａ的氢压下于乙二醇二甲醚溶剂中反应１ｈ以上,可使顺酐的转化率大于９０％．     

双稀土氟氧化物Sm-La-O-F催化剂的AFM研究

双稀土氟氧化物ＳｍＬａＯＦ具有良好的乙烷氧化脱氢（ＯＤＥ）催化性能，特别是对于Ｓｍ２Ｏ３ＬａＦ３（１∶１摩尔比），在９７３Ｋ，乙烯选择性为８９７％，乙烷转化率为２２１％，是目前报道的具有高乙烯选择性的ＯＤＥ反应催化剂．比表面积和ＸＲＤ测试表明，Ｓｍ２Ｏ３ＬａＦ３催化剂体相是由单一相结构的双稀土氟氧化物Ｓｍ２／３Ｌａ１／３ＯＦ组成，比表面积较小．原子力显微镜（ＡＦＭ）研究表明，该催化剂的表面颗粒排布规整致密，粒径均匀；而其它乙烯选择性较低的催化剂颗粒排布较为松散，颗粒大小不一．     

胺基铪茂催化乙烯/1-辛烯无规共聚合的研究

在亚乙基双（ 茚基） 二胺化茂铪（ｒａｃ Ｃ２Ｈ４（Ｉｎｄ）２Ｈｆ（ＮＭｅ２）２ ,简称１ ,Ｉｎｄ ＝ 茚基,Ｍｅ＝ 甲基） 催化作用下,对乙烯（Ｅ） 与１ 辛烯（Ｏ） 无规共聚合进行了研究．作为比较,利用异亚丙基（ 环戊二烯基）（１ 芴基） 二甲基锆茂催化体系（（ＣＨ３）２Ｃ（Ｆｌｕｏ）（Ｃｐ）ＺｒＭｅ２ ,简称２ ,Ｆｌｕｏ ＝ 芴基,Ｃｐ ＝ 环戊二烯基） 对乙烯／１ 辛烯在相同共聚合条件下进行了共聚合．结果表明,在单体浓度比［Ｏ］／［Ｅ］ 较小时共聚合速率随单体浓度比增加而增加,进一步增加单体浓度比则导致共聚合速率降低．催化体系１／Ａｌ（ｉＢｕ）２Ｈ／［Ｐｈ３Ｃ］［Ｂ（Ｃ６Ｆ５）４］（３） 催化共聚活性比２／ ＭＡＯ高得多．共聚物中辛烯含量随反应单体１ 辛烯含量的增加而增加,两单体竞聚率乘积（ ｒＥ×ｒｏ） 小于１ ,表明聚合物为无规共聚物．相同共聚单体浓度比下１／Ａｌ（ｉＢｕ）２Ｈ／３ 催化共聚物中辛烯含量比２／ ＭＡＯ 共聚物中辛烯含量高,表明前者具有更强的共聚合能力．所得无规共聚物熔点温度、结晶度、本体粘度及密度随共聚物中辛烯含量的增加而显著降低．辛烯含量较高时共聚物呈现明显无结晶行为．差示扫描量热分析显示,同乙烯均聚?     

化学液相沉积与沸石择形催化性能

在经ＳｉＣｌ４化学液相沉积的ＨＺＳＭ－５沸石催化剂上进行了甲茉歧化、Ｃ６烷烃异构体催化裂解和邻二甲苯异构化反应，随着ＳｉＯ２沉积量增加，沸石内表面性质变化不大，而孔径逐渐缩小，甲苯歧化和邻二甲苯异构化反应的对二甲七选择性提高，Ｃ６烷烃异构体中支链烃３－甲基戊烷和２，２－二甲基丁烷的裂解反应转化率下降，实验结果表明，化学液相沉积是改善沸石催化剂对反应物物产物择形性能的一种有效方法。     

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.     

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.     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.