2-单核和双核茂铁基-1,3-二烷基苯并咪唑盐的合成、结构及性质研究

以2-二茂铁基苯并咪唑(2)为原料,合成了1-甲基-2-二茂铁基-3-乙基苯并咪唑碘盐(4)和六氟磷酸盐(5);甲酰化的2,2-双二茂铁基丙烷(6)与邻苯二胺在甲醇作溶剂,回流,碘催化下反应,得到2-[1’-(2-二茂铁基丙烷-2-基)二茂铁-1-基]苯并咪唑(7),以7为原料合成了1-甲基-2-[1’-(2-二茂铁基丙烷-2-基)二茂铁-1-基]-3-乙基苯并咪唑碘盐(9)和六氟磷酸盐(10).电化学分析表明所得的盐化合物中,与苯并咪唑阳离子直接相连的二茂铁的氧化电位相对2和7均产生了较大正移.对化合物4的单晶结构进行了解析,晶体结构中存在π-π堆积.UV-Vis吸收光谱表明所得盐化合物具有光致电荷迁移现象.DSC-TG(差示扫描量热-热重)测试表明碘盐4对高氯酸铵(AP)热分解有较好催化效果.     

Prins缩合反应合成4-丁基-1,3-二氧六环的研究

以1-己烯和多聚甲醛为原料,使用离子交换树脂作为催化剂,利用Prins反应催化合成新型含氧燃料4-丁基-1,3-二氧六环。采用GC-MS和H-NMR手段对合成产物进行分析表征,并以柱层析分离将4-丁基-1,3-二氧六环分离出来,并优化了合成4-丁基-1,3-二氧六环的条件。     

新型苯并咪唑杂多酸盐离子液体的制备及其在催化合成己二酸中的应用

以1-丁基苯并咪唑为起始原料,合成了1-丁基-3-(4-磺酸基丁基)苯并咪唑內盐(1),1-丁基-3-羧甲基苯并咪唑氯盐(2)和1,3-二丁基苯并咪唑溴盐(3);1~3分别与硅钨酸、磷钨酸和磷钼酸在水或者乙醇中反应,合成了5种新型的杂多酸盐离子液体——1-丁基-3-(4-磺酸基丁基)苯并咪唑硅钨酸盐(4a),1-丁基-3-(4-磺酸基丁基)苯并咪唑磷钨酸盐(4b),1-丁基-3-(4-磺酸基丁基)苯并咪唑磷钼酸盐(4c),1-丁基-3-羧甲基苯并咪唑硅钨酸盐(5)和1,3-二丁基苯并咪唑硅钨酸盐(6),其结构经1H NMR,13C NMR和IR表征。并考察了4~6在30%H_2O_2催化氧化环己烯制备己二酸反应中的催化效果。实验结果表明:4b的催化效果最好。在最佳反应条件[环己烯20 mmol,4b 0.16 mmol,n(环己烯)∶n(H2O2)∶n(ILs)=1∶4.4∶0.008]下,己二酸产率71%。     

双核茂铁四氮唑的合成及对高氯酸铵热分解的催化作用

首先以二茂铁为原料合成丙基桥联的双聚二茂铁(DFP), 经甲酰化得到丙基桥联的双聚二茂铁甲醛(DFP-CHO, 1), 再与NH₂OH·5HCl进行缩合反应得到双核二茂铁肟(2), 然后脱水得到丙基桥联双聚二茂铁甲腈(3), 最后在(n-C₄H₉)₃SnCl 的催化作用下与NaN₃进行[2+3]环加成反应, 生成目标产物丙基桥联双聚二茂铁四唑(4); 通过¹H NMR, FTIR和ESI-MS对目标产物的结构进行了表征. 利用差示扫描量热分析(DSC)和热重(TG)分析研究了这2个双聚二茂铁氮杂衍生物的燃速催化性能, 结果表明, 通过添加质量分数为5%的丙基桥联双聚二茂铁氮杂化合物3和4均使高氯酸铵(AP)的热分解温度降至100℃左右.     

异环二取代二茂铁衍生物的合成

从芳基二茂铁的汞化产物中首次分离出四种异环二取代产物 1-氯汞基-1'-芳基二茂铁。1-氯汞基-1'-芳基二茂铁与碘作用得到四种相应的碘代产物。氯汞基二茂铁及1-氯汞基-1'-芳基二茂铁经[ClRh(CO)~2]~2 催化偶联反应制得联二茂铁和三种1'、1''-二芳基联二茂铁。以上化合物的组成与结构经元素分析、IR 和^1H NMR确证, 其中10种为新化合物。     

哒嗪酮-类肟醚菊酯衍生物的合成研究

从2-叔丁基-4,5-二氯哒嗪酮出发,以两种方法合成了中间体2-叔丁基-4-氯-5-(4-溴甲基苯氧)哒嗪酮(3)。3与肟反应合成了含哒嗪酮的苄基肟醚类化合物4a～4l。在相转移催化条件下,3与芳香醛肟反应得到单一的产物4,与芳香酮肟反应则生成4和5的混合物。文中讨论了反应物的空间效应、亲核试剂对该反应区域选择性的影响,并论证了产物的构型。     

1-二茂铁基甲基-2-二茂铁基-3-烷基苯并咪唑盐的合成、晶体结构及性质研究

以二茂铁甲醛为原料,在对甲苯磺酸催化下,与邻苯二胺缩合得到1-二茂铁基甲基-2-二茂铁基苯并咪唑(2),化合物2与碘代烷进行烷基化反应得到1-二茂铁基甲基-2-二茂铁基-3-烷基苯并咪唑碘盐(3,4),并通过阴离子交换反应得到1-二茂铁基甲基-2-二茂铁基-3-烷基苯并咪唑六氟磷酸盐(5,6)及双三氟甲磺酰亚胺盐(7,8).利用1H NMR,13C NMR,IR,MS,HRMS及元素分析对所有产物进行结构表征.化合物5的单晶结构表明该化合物通过分子间氢键作用自组装成了沿c轴无限延伸的一条链状超分子结构.电化学分析表明化合物3～8中的Fe1与Fe2由原来的一组氧化还原峰分离成了两组氧化还原峰.UV-Vis吸收光谱曲线表明所有产物具有光致电荷迁移现象.DSC-TG(差示扫描量热-热重)曲线显示所得碘盐化合物对高氯酸铵(AP)热分解有较好的催化效果.     

钯催化下三正丁基杂环基锡和酰氯及取代芳烃偶联反应的研究

本文研究了在Pd(PPh3)2Cl2(1)催化下的三正丁基-2-呋喃基锡(6a), 三正丁基-2-噻吩基锡(6a), 三正丁基-2-(N-甲基)吡咯基锡(6c)和菊酰氯(5), 肉桂酰氯(7)的交联反应。发现除了三正丁基-2-(N-甲基)吡咯与5的不寻常反应得到2, 5-二取代的吡咯衍生物外, 其余反应皆以70～87%的产率得到交叉偶联产物。本文同时还报道了钯催化下有机锡试剂与取代卤代芳烃反应, 高收率地得到了不对称的杂环基芳烃和双杂环化合物。在合成的交联产物中, 化合物2, 8, 9, 15, 16与17均为新化合物。     

N-丁基-4-[乙基-(3-甲基苯基)氨基]丁酰胺的合成

以γ-丁内酯为起始原料,经开环氯化和酰化反应制得N-丁基-4-氯丁酰胺(2);2与N-乙基间甲苯胺经N-烷基化反应合成了N-丁基-4-[乙基-(3-甲基苯基)氨基]丁酰胺,总收率74.6%,纯度97.6%,其结构经1H NMR和MS(ESI)确证。     

吉非替尼的合成新工艺研究

以6-羟基-7-甲氧基喹唑啉-4-酮(1)为起始原料,在离子液体催化下与N-(3-氯丙基)吗啉(2)醚化,然后经氯代再与3-氯-4-氟苯胺进行亲核取代反应,得到目标产物吉非替尼,三步反应总收率为68.7%。通过改变反应物配比、离子液体用量和反应温度,得到了关键中间体3的优化制备工艺条件:n(1)∶n(2)=1.0∶1.2;离子液体四氟硼酸1-甲基-4-丁基咪唑鎓用量为原料1的质量的5%;95℃下反应5h。在此条件下,醚化收率约93.6%。该路线具有反应条件温和、分离简单、路线短和总收率较高的特点,为吉非替尼的工业化生产提供了实验依据。     

Chiral ferrocene amines derived from amino acids and peptides: synthesis, solution and X-ray crystal structures and electrochemical investigations

For the recognition of all but the simplest naturally occurring molecules, electrochemical sensors based on ferrocene will certainly require chiral centers. To advance the necessary chemistry, this work describes the synthesis and properties of ferrocene derivatives of enantiomerically pure amino acids, peptides, and other chiral amines. Ferrocene aldehyde is condensed with amino acid esters to yield the corresponding Schiff bases 2, which are reduced by NaBH4 in methanol to the ferrocene methyl amino acids 3. An X-ray single-crystal analysis was carried out on the phenylalanine derivative 3a (monoclinic space group P2(1), a = 10.301(1) A, b = 9.647(1) A, c = 18.479(2) A, beta = 102.98(2) degrees, Z = 4). Further peptide chemistry at the C terminus proceeds smoothly as demonstrated by the synthesis of the ferrocene labeled dipeptide Fc-CH2-Phe-Gly-OCH3 5 (Fc = ferrocenyl ((eta-C5H4)Fe(eta-C5H5))). We also report the synthesis of the C,N-bis-ferrocene labeled tripeptide Phe-Ala-Leu and its electrochemical characterization. Starting from the enantiomerically pure ferrocene derivative 9, which was synthesized from ferrocene aldehyde and L-1-amino-ethylbenzene, two diastereomers 10 were obtained by peptide coupling with N-Boc protected D- and L-alanine. There was, however, only very little diastereomeric induction if 0.5 equiv of a racemic mixture of alanine were used. This suggests that amino acid activation rather than coupling is the rate-determining step. A combination of NOESY (nuclear Overhauser effect spectroscopy) spectra and molecular modeling furnished detailed insights into the solution structures of 3, 9, and 10 and was used to rationalize their different reactivity.     

Cyclopolycondensations

Fully aromatic polyquinazolinediones of high molecular weight were prepared by the cyclopolycondensation reaction of 4,4′-diamino-3,3′-biphenyldicarboxylic acid with aromatic diisocyanates. The poly(phosphoric acid) solution polymerization techniques yielded tractable poly(urea acid), which was converted to polyquinazolinediones by thermal cyclodehydration at 300–400°C. under reduced pressure. The polyquinazolinediones thus obtained have excellent thermal stability both in nitrogen and in air. The poly(urea acid) is soluble in dimethyl sulfoxide, and films can be cast from the polymer solution of poly(urea acid) (η_inh = 0.8 to 1.8). The films are made tough by being heated in nitrogen or under reduced pressure at 300–400°C. The polymerization mechanism of the cyclopolycondensation reaction was studied, and it was established that the polymerization proceeded through the formation of tractable poly(urea acid), Structure (I), of high molecular weight, followed by cyclodehydration, yielding poly(1,2-dihydro-2-imino-4H-3,1-benzoxazin-4-one), Structure (II). On subsequently being heated this undergoes intramolecular rearrangement along the polymer chain, giving the thermodynamically stable polyquinazolinedione, Structure (III).     

由Diels-Alder反应合成新型热稳定性含硅双马来酰亚胺──合成及表征

由Ｄｉｅｌｓ－Ａｌｄｅｒ反应合成新型热稳定性含硅双马来酰亚胺──合成及表征郝建军,江璐霞,蔡兴贤（四川联合大学材料科学与工程学院高分子材料系,成都,６１００６５）关键词双马来酰亚胺,有机硅,Ｄｉｅｌｓ－Ａｌｄｅｒ反应,合成,表征采用单体扩链增韧［１］...     

Preparation, Curing Reactivity and Thermal Properties of Titanium-doped Silicone Resins

Novel titanium-doped silicone resins were synthesized from low-cost silane monomers and tetrabutyl titanate as raw materials and hydrochloric acid as catalyst, with titanium element as dopant into principal chain of Si-O-Si. The resins were characterized by means of FTIR, 1 H NMR and 13 C NMR spectra, their thermal properties and curing properties were investigated and their corresponding films were determined. The results show that the thermal stability and storage stability of the resins were influenced by the types of silane monomers containing different carbon atomicities of organic group. The thermal stability of the titanium-doped silicone resin with a molar ratio of silane monomer B(n-propyl triethoxysilane) to silane monomer C(n-octyl triethoxysilane) being 1:1 is superior to that of the resin with a molar ratio of silane monomer B to silane monomer C being 1:3. However, the storage stability of the former is inferior to that of the latter.This work also showed that the synthesized titanium-doped silicone resins have the highest thermal stability up to 450―500 °C with an atomicity molar ratio of 1:4 of titanium to silicon in the reactants. But the best storage stability of the resin prepared from the reactants with an atomicity molar ratio of 1:6[n(Ti):n(Si)] was obtained. The effect of the type and content of curing agent on the curing properties of the resin was also studied. Moreover, thermal mechanism and curing mechanism were proposed in this work.     

Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

TiO2纳米棒载Pd催化剂的制备及其对甲酸的电催化氧化

利用水热合成和无机溶胶法,分别制备了具有棒状(TiO2-R)和无规则结构(TiO2-I)的锐钛矿相TiO2,并以之为载体制备得到Pd/TiO2电催化剂.循环伏安测试显示,与无规则TiO2相比,具有棒状结构的TiO2载Pd催化剂对甲酸氧化的电催化性能提高了70%;计时电流测试显示,运行3000 s后,甲酸在棒状TiO2载Pd催化剂上的氧化电流是无规则TiO2载Pd催化剂的16倍.其原因可能与TiO2纳米棒拥有更好的电子传导性且表面拥有较多的活性含氧基团有关,从而能够有效提高催化剂对甲酸氧化的电催化活性和抗毒化性能.     

NaBH4-I2还原法制备N,N'-二甲基间苯二胺

以间苯二胺为原料, 与酰化剂甲酸反应制得中间体N,N'-二甲酰基间苯二胺, 再以NABH4-I2为还原剂合成得到产品N,N'-二甲基间苯二胺, 对合成工艺进行了优化, 并分析了还原机理, 化合物的结构经IR, 1H NMR和MS分析确定. 该法原料易得, 反应条件要求低, 收率高且成本更低.     

Synthesis of poly(butylene terephtahlate) nanocomposites using anionic clays

The synthesis of poly(butylene terephthalate) (PBT) nanocomposites by in situ polymerisation method using an organo-modified layered doubled hydroxide is described. 4-Sulfobenzoic acid potassium salt, sodium dodecyl sulfate and dimethyl 5-sulfo isophthalate sodium salt were used as intercalating compounds to improve clay exfoliation. The thermal and dynamic mechanical properties of the nanocomposites prepared were investigated and compared to those of montmorillonite-type nanocomposites prepared by similar synthetic route. The nanocomposites obtained, independent of the degree of exfoliation, showed better dynamic mechanical properties respect to PBT homopolymer while improvements in thermal stability were achieved when dimethyl 5-sulfo isophthalate was used as intercalating agent, highlighting the importance of the interactions of ionic groups covalently linked to the polymer with the charged clay platelets.     

富马酸奈拉西坦的合成工艺改进

报道了一种合成富马酸奈拉西坦(7)的新工艺。以衣康酸二甲酯和苄胺为起始原料,经Michael加成和分子内环合反应制得1-苄基-5-氧代吡咯烷-3-羧酸甲酯(3); 3经NaBH₄还原得1-苄基-4-羟甲基-吡咯烷-2-酮(4); 4经甲磺酰化反应得1-苄基-5-氧代吡咯烷-3-羧酸甲磺酸酯(5); 5经氨解得奈拉西坦(6); 6与富马酸经成盐反应合成7,总收率78.4%,其结构经¹H NMR确证。     

Nylon surface modification: 2. Nylon-supported composite films

We have developed techniques for the introduction of reactive functional groups to nylon surfaces via site-specific reactions targeting at the naturally abundant amide repeating units on the surface. In this report, we describe the fabrication of nylon-supported composite surfaces using the most efficient modification methods we have developed. N-Alkylation with (3-glycidoxypropyl)triethoxysilane (GPTES) in the presence of potassium tert-butoxide (t-BuOK) leads to surfaces with silica-like reactivity. Subsequent chemical vapor deposition using tetrachlorosilane (SiCl4) and water results in composite films with a thin layer of silica, which was made hydrophobic by reaction with a fluorinated silane reagent. Reduction of the amide groups with borane-THF (BH3-THF) complex leads to a 69% conversion of surface amides to the corresponding secondary amine groups. Alginate was chosen as the model polyelectrolyte for the introduction of a hydrated surface layer. Because of the strong electrostatic interaction between alginate and the amine-enriched nylon surfaces, the adsorption is fast and concentration-independent (within the concentration range studied). The polysaccharide coats the surface homogeneously, without the formation of large aggregates. The amine surfaces obtained by reduction with BH3-THF ((BH3-THF)nylon-NH) and by alkylation with 2-bromoethylamine hydrobromide (BEA-HBr, (EBA-HBr)nylon-NH2) were also used to study gold deposition through electroless plating. Immobilization of a negatively charged metal complex (AuCl4(-)) was achieved through electrostatic interaction. Gold particles disperse preferentially in the bulk of (EBA-HBr)nylon-NH2 films, while they remain confined to the outer surface layer of (BH3-THF)nylon-NH films.