含联萘基团旋光性聚酰亚胺的合成与性质

从１,１′－联萘－２,２′－二胺出发,合成了旋光性二酐单体及相应的外消旋体：（Ｓ）－,（Ｒ）－和（±）－２,２′－（３,３′,４,４′－四酸二酐）二苯甲酰胺－１,１′－联萘．二酐与二胺单体通过溶液缩聚反应制得一系列旋光性聚酰胺酰亚胺．聚合物具有较好的热稳定性、旋光稳定性、良好的溶解性以及独特的光学性质     

含联萘基团施光性聚酰亚胺的合成与性质

从１,１′－联萘－２,２′－二胺出发,合成了旋光性二酐单体及相应的外消旋体：（Ｓ）－,（Ｒ）－和（±）－２,２′－（３,３′,４,４′－四酸二酐）二苯甲酰胺０１,１′－联萘。二酐与一胺单体通过溶液缩聚反应制得一系列旋光性聚酰胺亚胺。聚合物具有较好的热稳定性、旋光稳定性、良好性的溶解性以及独特的关学性质。     

聚酰亚胺/聚丙烯腈共混黑膜的制备及其结构与性能

采用共混的方法制备聚酰胺酸/聚丙烯腈(PAA/PAN)共混溶液.其中2种PAA溶液分别由二酐(3,3′,4,4′-联苯二酐(BPDA)与均苯四甲酸二酐(PMDA))和二胺(对苯二胺(PDA)与4,4′-二氨基二苯醚(ODA))均聚或共聚而得,N,N-二甲基乙酰胺(DMAc)为溶剂,PAN溶于DMAc中制成溶液后与PAA溶液混合,涂膜后热处理制得聚酰亚胺(PI)/PAN共混薄膜.分析了PAA和PAN在热处理过程中的变化,以及PAN的加入量对共混薄膜的结构与性能的影响.结果表明,在热处理过程中,PAA完成了亚胺化成为PI,而PAN完成了预氧化,形成了稳定的梯形结构,制备出具有良好力学性能、黑色、不透光的薄膜,但是随着PAN含量的增加,体系发生明显的相分离,薄膜力学性能有所下降,(BPDA/PDA/ODA)PI中加入10%的PAN和(PMDA/ODA)PI中加入20%的PAN时能获得具有良好力学性能的黑色、低透光率的薄膜.     

双马来酰亚胺树脂增韧研究（1）新型增韧剂的合成、表征及预聚物制备

合成了一种新的增韧剂双（６－稀丙基对甲酚）甲烷（ＭＢＡＰＣ），用元素分析（ＥＡ）、富里哀红外（ＦＴ－ＩＲ）、质谱（ＭＳ）、核磁共振（Ｈ－ＮＭＲ）等方法进行了表征。同时合成了二苯甲烷型双马来酰亚胺（ＭＤＡ－ＢＭＩ）。首次以ＭＢＡＰＣ增韧ＭＤＡ－ＢＭＩ并用溶液法制备了改性ＭＤＡ－ＢＭＩ预聚物。研究了该预聚物的热性能、溶解性和贮存稳定性。     

含三氟甲基聚酰亚胺的合成与性能研究

通过在4,4′-二氨基二苯醚(4,4-′ODA)单体中引入三氟甲基合成了一种新型二胺单体2-三氟甲基-4,4′-二氨基二苯醚(3FODA),该单体具有良好的溶解性和高的反应活性,使用3FODA替代4,4′-二氨基二苯甲烷(MDA)制备了PMR热固性聚酰亚胺树脂.树脂溶液高浓度低粘度,具有室温下良好的储存稳定性;树脂具有很好的加工性能,成型后的模压件显示了优异的热性能和耐热氧化稳定性,玻璃化转变温度在336~379℃之间;此外树脂具有较好的电性能和较低的吸水率.     

新的二苯并环状溴Wong盐的合成及性质研究

以４，４′－二取代联苯（或４，４′－二取代二苯甲烷）为原料合成了几种新的３，７－二取代二苯并环状溴翁盐。对几种溴翁盐与ＫＢＨ４及与ＮａＮ３的反应进行了研究。结果表明，前一反应主产物为２－溴－４－４′－二聚代联苯（或２－溴－４，４′－二取代二苯甲烷），后一反应的主产物为２－叠氮基－２′－溴－４，４′－二取代联苯（２０ａ－２０ｄ）。通过２０ａ－２０ｄ的热反应合成几种新的多取代咔唑（２１ａ－２１ｄ）。     

6,7—取代—1H—苯并（de）异喹啉—1,3（2H）二酮的合成

从二氢苊出发合成了６－溴－７－氨基２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮，６－甲氧基－７－氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮和６，７－二氨基－２－（２′，４′－二甲基）苯基－１Ｈ－苯并（ｄｅ）异喹啉－１，３（２Ｈ）－二酮，测定了它们的荧光量子产率，讨论了分子内重原子溴和给电子基对化合物荧光性质的影响。     

基于3,5-二胺基-N（N′,N′-正二丁基甲酰胺基苯基）-苯甲酰胺的聚酰亚胺的溶解性、热稳定性和取向性能

用制得的大体积双侧基3,5-二胺基-N（N′,N′-正二丁基甲酰胺基苯基）-苯甲酰胺（DAPDM）,与3,3′-二甲基-4,4′-二氨基二苯甲烷（DMMDA）、3,3′,4,4′-二苯醚四甲酸二酐（ODPA）采用一步法共缩聚制得聚酰亚胺共聚物。采用核磁共振对该共聚物进行了表征,对其溶解性、热稳定性、预倾角进行了分析。结...     

含磷聚酰亚胺纤维的制备及其力学与阻燃性能

采用廉价的三苯基氧膦和混酸合成了一种含磷二胺单体,二（3-氨基苯基）苯基膦氧(DAPPO)。在4,4′-二胺基二苯醚（ODA）、3,3′,4,4′-联苯四酸二酐（BPDA）和均苯四酸二酐（PMDA）聚合体系中引入该单体,制备含磷聚酰亚胺纤维。热失重分析（TGA）结果表明,聚酰亚胺纤维的热稳定性随含磷量的增加而明显提高。当n（DAPPO）：n（ODA）为7：93时,纤维的极限氧指数达到了43,说明纤维的阻燃性能显著提高。     

新醚酮聚酰亚胺

二苯醚分别与对位和间位 硝基苯甲酰氯以及间苯二甲酰氯反应合成了五种醚酮双硝基化合物，经还原生成五种相应的二胺，其中，４，４′ 双（３ 氨基苯甲酰基）二苯醚（ＢＡＤＰＥ）分别与均四苯甲酸二酐（ＰＭＤＡ）、３，３′，４，４′ 二苯甲酮四甲酸二酐（ＢＴＤＡ）和４，４′ 氧化二邻苯二甲酸二酐（ＯＤＰＡ）聚合亚胺化后可生成橙色透明薄膜，其韧性好，拉伸强度高，耐溶剂，并有一定的耐强碱性．它们的Ｔｇ分别为２７３５、２３９和２２４℃，它们的高温氧化稳定性均很好，它与ＢＴＤＡ聚合而成的聚酰胺酸对铝／铝及铜／铜等金属都有极好的胶粘性，亚胺化后胶接强度极高．     

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.     

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.     

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.     

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.     

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.     

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.