Latest News: Reactions of Group 4 Bis(trimethylsilyl)acetylene Metallocene Complexes and Applications of the Obtained Products

Recently published reactions of group 4 metallocene bis(trimethylsilyl)acetylene (btmsa) complexes from the last two years are reviewed. Complexes like Cp’₂Ti(η²-Me₃SiC₂SiMe₃) and Cp₂Zr(py)(η²-Me₃SiC₂SiMe₃) with Cp’ as Cp (cyclopentadienyl) and Cp* (pentamethylcyclopentadienyl) have been considered (py=pyridine). These complexes can liberate a reactive low-valent titanium or zirconium center by dissociation of the ligands and act as ‘‘masked’’ M^II complexes (M=Ti, Zr). They represent excellent sources for the clean generation of the reactive coordinatively and electronically unsaturated complex fragments [Cp’₂M]. This is the reason why they were used for many synthetic and catalytic reactions during the last years. As an update to several review articles on this topic, this contribution provides an update with recent examples of preparative organometallic and organic chemistry of these complexes, acting as reagents for a wide range of coordinating and coupling reactions. In addition, applications and investigations concerning reaction products derived from this chemistry are mentioned, too.     

1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物的合成及抑菌活性

将邻羟苯基引入1,2,3-三唑结构中, 设计合成了10个1-(4-取代苯基)-4-苯基-5-取代-1,2,3-三唑类衍生物. 首先, 以对位取代的芳胺为原料, 经重氮化、叠氮化、闭环和缩合反应制得1-(4-取代苯基)-4-苯基-5-水杨醛亚胺-1,2,3-三唑类衍生物(3a~3e), 再用硼氢化钠还原制得1-(4-取代苯基)-4-苯基-5-(2-羟基苄基)氨基-1,2,3-三唑类衍生物(4a~4e). 目标化合物的结构经核磁、IR及元素分析确认. 抑菌活性测试表明, 当质量浓度为0.1 mg/L时, 除化合物3e和4e外, 所有化合物对白色念球菌的抑菌率均达95%以上, 对大肠杆菌的抑菌率达85%以上, 具有强抑菌活性, 表明该类化合物在抗菌药物开发方面有重要应用价值.     

Synthesis and characterization of thermally stable poly(ether-azomethine)s derived from 1,1-bis[4-(4-benzaldehyde oxy)-3-methyl phenyl] cyclopentane

A new dialdehyde 1,1-bis[4-(4-benzaldehyde oxy)-3-methyl phenyl] cyclopentane (BBMPC) was synthesized starting from cyclopentanone and O-cresol to give 1,1-bis(4-hydroxy-3-methyl phenyl)cyclopentane (BHMPC); followed by reaction with 4-fluorobenzaldehyde in N, N-dimethyl formamide (DMF), containing anhydrous potassium carbonate. New series of poly(ether-azomethine)s were synthesized from (BBMPC) with different diamines such as 4,4′- diamino diphenyl ether (ODA); 4,4′-diaminodiphenyl methane (MDA); 4-aminophenyl sulfone (SDA); p-phenylene diamines (p-PDA), etc. in N, N’- dimethyl acetamide (DMAc) with 5 wt% LiCl by the solution polycondensation method. Inherent viscosities of these polymers were in the range 0.20 to 0.38 dL/g indicating formation of moderate molecular weights. These polymers exhibited good solubility in various polar aprotic solvents such as N-methyl-2-pyrrolidone (NMP), DMAc, DMF, etc. However some polymers showed partial solubility in DMF and DMAc. X-Ray diffraction pattern of polymers showed amorphous nature. Thermal stability was assessed by 10% weight loss temperature and the degradation temperature of the resultant polymers falls in the ranges from 444-501°C in nitrogen. The glass transition temperature was in the range of 155-205°C. The structure-property correlation among these polyazomethines were studied; in view of their potential applications as high performance polymers.     

1，3-二(三甲基硅基)-2-叔丁基锂与铁(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、钛(Ⅳ)的反应及结构

1，3-二(三甲基硅基)-2-叔丁基锂与氯化镍或四氯化钛反应合成了内消旋的1，3-二(三甲基硅基)-2-叔丁基偶联化合物(1)；与氯化钴和氯化亚铁反应分别生成了二配位的1，3-二(三甲基硅基)-2-叔丁基钴和铁配合物(2，3)。用NMR,元素分析和X-射线衍射对其单晶的结构进行了分析，结果表明：化合物1属三斜晶系；化合物2和3均属单斜晶系，配合物2中心钴为六配位畸变的八面体构型。配合物3与2结构相类似。     

Synthesis and characterization of new cardo polyimides prepared from 5,5-Bis[4-(4-aminophenoxy)phenyl]-4,7-methanohexahydroindane

A new cardo diamine monomer, 5,5-bis[4-(4-aminophenoxy)phenyl]-4,7-methanohexahydroindane (II), was prepared in two steps with high yield. The monomer was reacted with six different aromatic tetracarboxylic dianhydrides in N,N-dimethylacetamide (DMAc) to obtain the corresponding cardo polyimides via the poly(amic acid) precursors and thermal or chemical imidization. All the poly(amic acid)s could be cast from their DMAc solutions and thermally converted into transparent, flexible, and tough polyimide films which were further characterized by x-ray and mechanical analysis. All of the polymers were amorphous and the polyimide films had a tensile strength range of 89–123 MPa, an elongation at break range of 6–10%, and a tensile modulus range of 1.9–2.5 GPa. Polymers V_c, V_e, and V_f exhibited good solubility in a variety of solvents such as N-methyl-2-pyrrolidinone (NMP), DMAc, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, γ-butyrolactone, and even in tetrahydrofuran and chloroform. These polyimides showed glass-transition temperatures between 274 and 299°C and decomposition temperatures at 10% mass loss temperatures ranging from 490 to 521°C and 499 to 532°C in nitrogen and air atmospheres, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2815–2821, 1999     

1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

Decomposition of 2-[4-(2-chloro-1,1-dimethylethyl)phenyl]-propan-2-yl hydroperoxide catalyzed by sulfuric acid

The decomposition of 2-[4-(2-chloro-1,1-dimethylethyl)phenyl]propan-2-yl hydroperoxide in acetone catalyzed by H₂SO₄ affords 4-(2-chloro-1,1-dimethylethyl)phenol. The kinetics of this reaction at 56°C was studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1612–1613, August, 1999.     

Synthesis and Crystal Structure of a Novel Ethyl 5-(4-(2-Phenylacetamido)phenyl)-1H-pyrazole-3-carboxylate as an Acrosin Inhibitor

The title compound (ethyl5-(4-(2-phenylacetamido)phenyl)-1H-pyrazole-3-carboxy- late, C20H19N3O3) was synthesized by the reaction of Claisen condensation, cyclization, reduction and acylation. The structure was characterized by X-ray diffraction, MS, NMR and IR. It belongs to the monoclinic system, space group C2/c with a = 22.723(9), b = 9.324(4), c = 18.890(8) , β = 114.259(6)°, V = 3649(3) 3, Dc = 1.272 Mg·m-3, Z = 8, Mr = 349.38, μ = 0.087 mm-1, F(000) = 1472, the final R = 0.0615 and wR = 0.1643. The biological test shows that the title compound has a moderate acrosin inhibition activity.     

9,10-双-(对-(甲氧基二缩三乙二醇基)苯基乙炔基)蒽的合成、自组装及其光谱分析

通过Sonogashira偶联等反应,合成了三嵌段化合物9,10-双-(对-(甲氧基二缩三乙二醇基)苯基乙炔基)蒽,通过¹H NMR和基质辅助激光解吸电离时间飞行质谱(MALDI-TOF-MS)对其结构进行了表征。利用差示扫描量热仪(DSC)、偏光显微镜(POM)及小角X射线散射仪(SAXS)等技术手段对其本体自组装行为进行了研究,结果表明,化合物在固态相自组装成近晶A相(SmA相)。光谱分析表明,该化合物继承了二取代蒽类发光材料具有高荧光量子产率(Φ_f)的特点,是一种性能良好的光致发光材料。     

Synthesis, Crystal Structure and Fluorescent Properties of 1-（4-（Dimethylamino）benzylidene）- 4-（naphthalen- 1-yl） Thiosemicarbazide

1 INTRODUCTION Recently, for the fluorescent properties, Schiff base has been more and more important and widely studied in density optical memories, nonlinear op- tics (NLO), organic light-emitting diodes (OLED), polymer LED and electrogenerated chemilumines- cence (ECL)[1~5]. Thiosemicarbazones are a kind of Schiff bases with thiourea and good ligands easily chelating with transition metal ions. Although they have been studied extensively for a long time due to their chemical and b…     

高效液相色谱法研究啶菌噁唑对番茄灰霉病菌麦角甾醇生物合成的影响

啶菌噁唑是我国研制的一种新型农用杀菌剂。本实验建立了高效液相色谱法定量分析灰霉病菌麦角甾醇含量的方法,研究了该药剂对番茄灰霉病菌麦角甾醇合成的抑制作用。结果表明,此方法具有良好的准确度和精密度,回收率为98.8%;相对标准偏差为3.0%,适用于测定番茄灰霉病菌麦角甾醇含量;番茄灰霉病菌菌丝在不同浓度啶菌噁唑和对照药剂戊唑醇处理下,药剂对其麦角甾醇合成具有明显的抑制作用,其中在0.5、10.0mg/L啶菌噁唑作用下,菌丝麦角甾醇含量分别为1.59(±0.126)和0.10(±0.011)mg/g干重菌丝,与DMIs类杀菌剂戊唑醇处理相比,没有显著性差异;与空白对照相比,抑制率分别达到22.44%和95·12%;回归分析表明,药剂处理浓度对数与麦角甾醇含量抑制率的机率值表现出正相关线性关系。     

Preparation and properties of aromatic polyamides and polyimides derived from 3,3-bis [4-(4-aminophenoxy) phenyl] phthalide

3,3-Bis[4-(4-aminophenoxy)phenyl]phthalide ( II ) was used as a monomer with various aromatic dicarboxylic acids and dianhydrides to synthesize polyamides and polyimides, respectively. The diamine II was derived by a nucleophilic substitution of phenolphthalein with p-chloronitrobenzene in the presence of K₂CO₃. Polyamides IV _a-g having inherent viscosities of 0.77–2.46 dL/g were prepared by the direct polycondensation of diamine II with diacids III _a-g using triphenyl phosphite and pyridine as condensing agents. The polyamides were readily soluble in a variety of solvents such as N, N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidinone (NMP) and afforded transparent and flexible films from the polymer solutions. These polymers had glass transition temperatures (T_gs) in the 227–307°C range and 10% weight loss temperatures occurred up to 450°C. Polyimides VI _a-e based on diamine II and various aromatic dianhydrides V _a-e were synthesized by the two-stage procedure that included ring-opening, followed by thermal or chemical conversion to polyimides. Most of the polyimides obtained by chemical cyclodehydration procedure were found to soluble in DMF, NMP, o-chlorophenol, and m-cresol. The T_gs of these polyimides were in the 260–328°C range and showed almost no weight loss up to 500°C under air and nitrogen atmosphere. © 1994 John Wiley & Sons, Inc.     

4-二氰亚甲基-2,6-二甲基-4H-吡喃衍生物的合成及其 荧光效应

两种新的4-二氰亚甲基-2,6-二甲基-4H-吡喃衍生物及对应的聚酰胺酸被合成和表征。该聚酰胺酸在普通有机溶剂中具有良好的可溶性。报道了这些生色团衍生物的光强度、量子产率和发射波长,以及生色团共价键合所形成的聚酰胺酸膜具有比对应的生色团单体更强的荧光效应。     

Synthesis and Crystal Structure of （Z）-Methyl-3-methoxy-2-{2-[（4-（E-3-p-tolylacryloyl）phenoxy）methyl]phenyl}acrylate

The title compound,(Z)-methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)-methyl]phenyl}acrylate,was synthesized and determined by X-ray single-crystal diffraction. The crystal belongs to the triclinic system,space group P1 with a = 8.0157(8),b = 12.5748(13),c = 13.3768(14) ,α = 64.770(2),β = 75.720 (2),γ = 89.784(2)°,μ = 0.085 mm-1,Mr = 442.49,V = 1174.1(2) 3,Z = 2,Dc = 1.252 g/cm3,F(000) = 468,T = 294(2) K,R = 0.0603 and wR = 0.1498 for 2644 observed reflections with I 2σ(I). X-ray diffraction analysis reveals that the single crystal contains strong non-classical hydrogen bonds. The preliminary bioassay showed that the title compound exhibits inhibitory activity against the Pseudoperoniospora cubensis and Rhizoctonia solani at the test concentration of 200 mg/L.     

Syntheses and properties of aromatic polyamides and polyimides derived from 9,9-bis[4-(p-aminophenoxy)phenyl]fluorene

9,9-Bis[4-(p-aminophenoxy)phenyl]fluorene ( II ) was used as a monomer with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides to synthesize polyamides and polyimides, respectively. The diamine II was derived by a nucleophilic substitution of 9,9-bis(4-hydroxyphenyl)fluorene with p-chloronitrobenzene in the presence of K₂CO₃ and then hydro-reduced. Polyamides IV _a-g having inherent viscosities of 0.73–1.39 dL/g were prepared by the direct polycondensation of the diamine II with various aromatic diacids using triphenyl phosphite and pyridine as condensing agents. All the aromatic polyamides were amorphous and readily soluble in various polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, and N-methyl-2-pyrrolidone. Transparent and flexible films of these polymers could be cast from the DMAc solutions. These aromatic polyamides had glass transition temperatures in the range of 283–309°C and 10% weight loss occurred up to 460°C. The polyimides were synthesized from diamine II and various aromatic dianhydrides via the two-stage procedure that included ring-opening poly-addition in DMAc to give poly(amic acid)s, followed by thermal or chemical conversion to polyimides. The poly(amic acid)s had inherent viscosities of 0.62–1.78 dL/g, depending on the dianhydrides. Most of the aromatic polyimides obtained by chemical cyclization were found to be soluble in NMP. These polyimides showed almost no weight loss up to 500°C in air or nitrogen atmosphere. © 1993 John Wiley & Sons, Inc.     

Organosoluble and light-colored fluorinated polyimides based on 9,9-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]fluorene and aromatic dianhydrides

A novel fluorinated diamine monomer, 9,9-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]fluorene (II) was prepared via the nucleophilic substitution reaction of 2-chloro-5-nitrobenzotrifluoride with 9,9-bis(4-hydroxyphenyl)fluorene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C. Polyimides V were synthesized from diamine II and various aromatic dianhydrides III _a-f via thermal imidization. These polymers had inherent viscosities ranging from 0.84 to 1.03 dL/g and were soluble in a variety of organic solvents such as NMP, DMAc, DMF, and DMSO, and some could even be dissolved in less polar solvents such as m-cresol, pyridine, and dioxane. Polyimide films V _a-f had tensile strengths of 85–105 MPa, elongations to break of 7–9%, and initial moduli of 2.13–2.42 GPa. The glass transition temperature of these polymers were in the range of 277–331 °C, their 10% weight loss temperatures were in the range of 539–594 °C in nitrogen and above 544 °C in air, and their char yields at 800 °C in nitrogen ranged between 55–65 wt%. Compared with nonfluorinated polyimides VI, V showed better solubility and lower color intensity. Low dielectric constants (2.68–2.85 at 1 MHz) and low moisture absorptions (0.12–0.24 wt%) were also observed. In particular, V _c-f afforded lightly-colored films, which had cutoff wavelengths lower than 385 nm and b* values ranging from 6 to 22.     

Synthesis of （S）-2-（3-Arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）ethoxy]phenyl}propanoic Acids

The synthesis of （S）-2-（3-arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）etho- xy]phenyl}propanoic acids is described. Their structures were confirmed by ^1H-NMR.     

Synthesis and characterization of new polymer systems containing very bulky tris(trimethylsilyl)methyl substituents as side chains

The 4-chloromethyl styrene (CMS) was copolymerized with different styrenic monomers such as methyl styrene, 4-methoxy styrene and α-methyl styrene by free radical polymerization method at 70 ± 1 °C using α,α^′-azobis(isobutyronitrile) (AIBN) as an initiator and the copolymers I, II and III collected respectively. The very bulky tris(trimethylsilyl)methyl {trisyl} substituents were covalently attached to the obtained copolymers with replacement of all the chlorine atoms in CMS units. The polymers, obtained in quantitative yields, were characterized by FT-IR, ¹H NMR and ¹³C NMR spectroscopy; differential scanning calorimetry (DSC) and GPC studies. All the polymers containing trisyl groups showed a high glass transition temperature (in the range 150-190 °C) in comparison with copolymers I-III (in the range 90-95 °C). The increase of the glass transition temperature reflects the substantial increase in rigidity of new polymers bearing very bulky substituents in side chains.     

新荧光增敏法测定人血清蛋白质

合成了新荧光试剂5-(4-羧基苯偶氮)-8-水杨醛缩氨基喹啉(p-CPSAQ),探讨了与人血清蛋白反应的最佳实验条件.在pH=7.0的缓冲体系中,蛋白质的存在使p-CPSAQ的荧光大大增强,据此建立了测定人血清蛋白质的灵敏方法;对人血清白蛋白和γ-球蛋白的线性范围分别为0.1～4.5 mg/L和 0.1～4.0 mg/L;检出限分别为0.028和0.027 mg/L.方法灵敏、快速、选择性好,用于人血清样品中总蛋白的测定,结果满意.     

New poly(amide-imide) syntheses. XII. Preparation and properties of poly(amide-imide)s based on the diimide-diacid condensed from 9,9-bis[4-(4-aminophenoxy)phenyl] fluorene and trimellitic anhydride

A dicarboxylic acid ( I ) was prepared from the condensation of 9,9-bis[4-(4-aminophenoxy) phenyl] fluorene and trimellitic anhydride. A new family of poly(amide-imide)s having inherent viscosities of 0.75-1.04 dL/g was prepared by the triphenyl phosphite activated polycondensation from the diimide-diacid I with various aromatic diamines in a medium consisting of N-methyl-2-pyrrolidone (NMP), pyridine, and calcium chloride. Most of the resulting polymers showed an amorphous nature and were readily soluble in polar solvents such as NMP and N,N-dimethylacetamide. All the soluble poly(amide-imide)s afforded transparent, flexible, and tough films. The glass transition temperatures of these polymers were in the range of 262–325°C and the 10% weight loss temperatures were above 525°C in air. © 1994 John Wiley & Sons, Inc.