某些烷基桥联二茂铁双聚分子的丁酰基化反应

丁酸酐和三氟化硼配合物在二氯甲烷中与双二茂铁基甲烷、2,2-双二茂铁基丙烷、2,2-双二茂铁基丁烷、2,2-双二茂铁基戊烷进行丁酰化反应所得产物,经中性氧化铝柱层析分离提纯,得10种单酰基和二酰基双二茂铁基烷。对这些新化合物进行了元素分析、红外和核磁波谱鉴定。     

(2,2-双二茂铁基丙烷)-6,6′-二酰基取代衍生物的合成与表征

以2,2-双二茂铁基丙烷为原料,在BF3催化下进行两步酰化反应,合成了3种6,6′-不同酰基取代双二茂铁基丙烷,在进行戊酰化时分离到了6,6′-二戊酰基双二茂铁基丙烷,利用元素分析、红外光谱和核磁共振氢谱对合成的化合物进行了表征。     

某些烷基二茂铁与丙酮的缩合

以酰氯为酰化剂，无水三氯化铝为催化剂，二氯乙烷为溶剂，对二茂铁进行酰化反应得到一系列酰基二茂铁，经Clemmenson还原法得到相应的烷基二茂铁，再用浓硫酸一甲醇体系做为催化剂，进行二茂铁与丙酮的缩合反应，经层析分离得到相应的双(烷基二茂铁基)丙烷。通过元素分析，红外光谱，折光率的测定，对目标化合物进行表征，并用循环伏安法研究其电化学性质，同时测试其在复合固体推进剂中的燃速催化性。     

(2,2-双二茂铁基丙烷)-6,6′-二甲酸的合成与表征

用2,2-双二茂铁基丙烷与邻氯苯甲酰氯在AlCl3催化下合成了6,6′-二(邻氯苯甲酰基)双二茂铁基丙烷,然后在叔丁醇钾的存在下解离成相应的(2,2-双二茂铁基丙烷)-6,6′-二甲酸。利用元素分析、红外光谱和核磁共振氢谱对合成的化合物进行了表征。     

(2,2-双二茂铁基丙烷)-6,6''''-二酰基取代衍生物的合成与表征

以2，2-双二茂铁基丙烷为原料，在BF3催化下进行两步酰化反应，合成了3种6，6＇-不同酰基取代双二茂铁基丙烷，在进行戊酰化时分离到了6，6＇-二戊酰基双二茂铁基丙烷，利用元素分析、红外光谱和核磁共振氢谱对合成的化合物进行了表征。     

草酰基双二茂铁衍生物还原反应机理探讨

以草酰氯为酰化剂,对二茂铁和乙基二茂铁分别进行了草酰化反应,得到了草酰基双二茂铁和草酰基-（乙基二茂铁）两种草酰基二茂铁衍生物。将两种草酰基二茂铁衍生物通过Clemmemsen还原法制得到了1,2-（二茂铁）-乙烷和1,2-双（乙基二茂铁）-乙烷;本文试从反应条件分析草酰基二茂铁衍生物还原反应机理,给出了其游离基的反应历程。     

1'-烷基二茂铁甲酸的合成

由二茂铁甲酸甲酯与酰氯RCOCl在三氯化铝催化下进行Friedel-Crafts酰化反应,得到1'-酰基二茂铁甲酸甲酯,继而用克莱门森还原反应将酰化产物还原为相应的1'-烷基二茂铁甲酸甲酯,再用氢氧化钠在乙醇和水的溶液中进行皂化反应,得到1'-烷基二茂铁甲酸.通过元素分析、红外光谱及核磁共振氢谱对合成的化合物进行了表征.     

(2,2-双二茂铁基丙烷)-6-甲酰胺的合成与表征

以2,2-双二茂铁基丙烷作为母体,经过邻氯苯甲酰化制得酰化产物,酰化产物在叔丁醇钾的作用下合成相应的甲酸,该甲酸与三氯化磷作用得到酰氯,并以此合成了一系列的甲酰胺,通过元素分析、红外光谱和核磁共振氢谱对这些化合物的结构进行了表征.     

1＇-烷基二茂铁甲酸的合成

由二茂铁甲酸甲酯与酰氯RCOCl在三氯化铝催化下进行Friedel-Crafts酰化反应,得到1＇-酰基二茂铁甲酸甲酯,继而用克莱门森还原反应将酰化产物还原为相应的1＇-烷基二茂铁甲酸甲酯,再用氢氧化钠在乙醇和水的溶液中进行皂化反应,得到1＇-烷基二茂铁甲酸。通过元素分析、红外光谱及核磁共振氢谱对合成的化合物进行了表征。     

2,2-双-(乙基二茂铁)-丙烷(GFP)的合成工艺改进

以乙酰氯为酰化剂,无水三氯化铝为催化剂,二氯甲烷为溶剂,对二茂铁进行酰化反应,得到乙酰基二茂铁,经锌锡齐还原剂还原制得乙基二茂铁。在浓硫酸与甲醇混合溶剂中,由乙基二茂铁与丙酮缩合得到了2,2-双(乙基二茂铁)丙烷(GFP)。目标产物为目前正在广泛应用的高氯酸铵(AP)热分解催化剂。研究结果表明,这种2,2-双(乙基二茂铁)丙烷新合成工艺具有较高的产率。为2,2-双(乙基二茂铁)丙烷(GFP)的广泛应用奠定了基础。     

双二茂铁基醇与二苯甲烷二异氰酸酯合成聚氨酯及性质研究

将含有双二茂铁基的二元仲醇与二苯甲烷二异氰酸酯反应,合成了相应的聚氨酯。并且研究了反应温度对反应产物相对分子质量的影响,确定了较适宜的反应条件。通过元素分析、红外光谱、核磁共振对聚合物的结构进行了表征,使用GPC测定了聚合物的相对分子质量,通过DTA-TG研究了聚合物的热性能,用循环伏安法测定了聚合物的氧化还原性质。     

The synthesis and optical characterization of quinoxalines bearing 2,2′:6′,2″-terpyridine

4′-(4-{2-[6,7-Bis-dodecyloxy-3-(2-p-substituted phenyl-vinyl)-quinoxalin-2-yl]-vinyl}-phenyl)-[2,2′:6′,2″] terpyridine was prepared by the Horner–Wadsworth–Emmons (HWE) reaction of 4-[2,2′:6′,2″]terpyridin-4′-yl-benzaldehyde and quinoxaline derivatives. The absorption and fluorescence maximum of these compounds were observed at 398–443 nm and 484–586 nm, respectively. The compounds were characterized by ¹H NMR spectroscopy and MALDI-TOF-MS, and their recognition properties for metal ions were evaluated using both absorption and emission spectroscopy.     

The synthesis and optical properties of quinoxalines bearing 2,2′:6′,2″-terpyridine

4′-(4-{2-[6,7-Bis-dodecyloxy-3-(2-substituted-phenyl-vinyl)-quinoxalin-2-yl]-vinyl}-phenyl)-[2,2′:6′,2″]terpyridine was prepared by the Horner–Wadsworth–Emmons reaction of 4-[2,2′:6′,2″]terpyridin-4′-yl-benzaldehyde with various quinoxaline derivatives. The absorption and fluorescence maxima of the compounds were observed at 398–443 nm and 484–586 nm, respectively; the compounds offer potential as optical sensors for protons and metal ions.     

Synthesis of novel bipyridyl ligands and application in preparation of polyketone

In this article, novel 2,2′‐bipyridyl derivatives were synthesized and the excellent bipyridyl ligands were chosen as catalyst to apply in the copolymerization of carbon monoxide (CO) and styrene (ST) to prepare polyketone. 4,4′‐Dicarboxyl‐2,2′‐bipyridine(4,4′‐dcpy) was synthesized by use of synthesized 4,4′‐dimethyl‐2,2′‐bipyridine(4,4′‐dmpy). The products (4,4′‐dmpy and 4,4′‐dcpy) were characterized by melting point, NMR, IR, GC‐MS, and elemental analysis. The effects of different ligands and various reaction conditions incuding the usage of ligand, p‐toluenesulfonic acid, solvent, p‐benzoquinone, the CO pressure, and reaction temperature on catalytic activity of the copolymerization were investigated. The catalytic activity of 4,4′‐dmpy, 4,4′‐dcpy and 2,2′‐bipyridine were compared. The results showed that the addition of the electron‐donating substituent can enhance catalytic activity, with the sequence as follows: 4,4′‐ dimethyl‐2,2′‐bipyridine > 2,2′‐bipyridine > 4, 4′‐carboxy 2,2′‐ bipyridine. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 000: 000–000, 2012     

The synthesis and characterization of heterocyclic azo dyes derived from 5-N,N-dialkylamino-2,2′-bithiophene couplers

Heterocyclic azo dyes were synthesized by diazotation of several substituted anilines and coupling with 5-N,N-dialkylamino-2,2′-bithiophenes to give 4-phenylazo-5-N,N-dialkylamino-2,2′-bithiophenes. This reaction contrasts with the behavior of 5-alkoxy-2,2′-bithiophenes towards aryldiazonium salts which provides 5-phenylazo-5-alkoxy-2,2′-bithiophenes. The thermal stability of the derivatives was evaluated using thermogravimetric analysis and their solvatochromic behaviour was investigated in several solvents of different polarity. The experimental results indicate that the heterocyclic azo dyes could be used as thermally stable, solvatochromic probes.     

Synthesis of a novel hexaarylbiimidazole with ether groups and characterization of its photoinitiation properties for acrylate derivatives

A novel photoinitiator 2,2′‐bis‐(2‐chlorophenyl)‐4,4′,5,5′‐tetra‐[3‐(2‐hydroxylmethyl‐2‐triethylene glycol monoethylene ether‐ethane‐1‐oxy)‐phenyl]‐1,2′‐biimidazole (BCTE‐HABI) was synthesized from 3,3′‐dimethoxy benzoin. Ultraviolet spectra, fluorescence spectra, ESR, photodilatometer, and photo‐DSC measurements indicate that its photoinitiating activity for acrylate derivatives is better than 2,2′‐bis‐(2‐chlorophenyl)‐4,4′,5,5′‐tetraphenyl‐1,2′‐biimidazole (o‐Cl‐HABI), which is one of the most widely studied and used derivatives of HABI. POLYM. ENG. SCI., 46:474–479, 2006. © 2006 Society of Plastics Engineers.     

The effect of chemical structure of derivatives of 1,1-bis(4-hydroxyphenyl)-2,2-propane on the antiplasticization of polycarbonate

The antiplasticizing effect of ester derivatives of bisphenol A: 1,1-bis(4-hydroxyphenyl)-2,2-propane diacetate (DAPP), 1,1-bis(4-hydroxy-3,5-dichlorophenyl)-2,2-propane diacetate (DACPP), 1,1-bis(4-hydroxy-3,5-dibromophenyl)-2,2-propane diacetate (DABPP), 1,1-bis(4-hydroxy-3,5-dichlorophenyl)-2,2-propane dibenzoate (DBCPP), 1,1-bis(4-hydroxy-3,5-dichlorophenyl)-2,2-propane di-2,4-dichlorobenzoate (DCBCPP) on polycarbonate was investigated. Obtained results indicate that antiplasticizing abilities of these compounds depend on the number of polar groups in the molecule, as well as on the possibility of tight filling the free volume by the molecules in polymer–antiplasticizer system.     

Alfred Werner revisited: the coordination chemistry of anions

A series of macrocyclic receptors were designed to probe the influence of four factors, hydrogen bonding, charge, dimensionality, and topology, on anion binding. Monocyclic and bicyclic polyammonium and polyamide receptors were synthesized from either 2,2'-diaminodiethylamine derivatives (dien) or 2,2',2'-aminoethylamine (tren) building blocks, plus aromatic or heterocyclic spacers. Supramolecular complexes of these hosts with three simple anion topologies were probed: spherical (halides), trigonal planar (nitrate), and tetrahedral (sulfate). Results indicate a number of corollaries with transition-metal coordination chemistry in terms of binding concepts such as the chelate effect and dual valencies, as well as geometries for anion complexes that are strikingly similar to those observed in transition-metal coordination chemistry.