Well‐controlled radical copolymerization of styrene with 2‐[(perfluorononenyl)oxy] ethyl methacrylate and characterization of its copolymers

The atom transfer radical copolymerization of styrene with 2‐[(perfluorononenyl)oxy] ethyl methacrylate was performed in benzotrifluoride at 100 °C in the presence of 1‐bromoethyl benzene (1‐BrEB), cuprous bromide (CuBr), and α,α′‐bipyridine (bpy; [1‐BrEB]₀/[CuBr]₀/[bpy]₀ = 1/1/3). The experimental results demonstrate that this polymerization proceeded in a living fashion, producing fluorinated random copolymers with narrow polydispersities, controlled molecular weights, and desired unit ratios. The compositions of the copolymers were calculated from ¹H NMR spectra. The monomer reactivity ratios were obtained with the Skeist integral method. The copolymers were characterized by gel permeation chromatography, Fourier transform infrared, and differential scanning calorimetry. The solid surface characteristics of the copolymers were evaluated with contact‐angle measurements. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2670–2676, 2001     

Synthesis of 2-Aryl and 2-Hetaryl Derivatives of 2'-Aminospiro[(1,3-dioxane)-5,5'-thiazolin]-4'-one and Spiro[(1,3-dioxane)-5,5'-thiazolidine]2',4'-dione

2-(Het)aryl derivatives of 2'-aminospiro[(1,3-dioxane)-5,5'-thiazolin]-4'-one or spiro[(1,3-dioxane)-5,5'-thiazolidine]-2',4'-dione are formed by the acid catalyzed interaction of 2-amino-5,5-bis(hydroxymethyl)-4-thiazolinone or its oxo analog 5,5-bis(hydroxymethyl)thiazolidine-2,4-dione with (hetero)aromatic aldehydes.     

新型3-萘基-1,3-噻唑烷-4-酮衍生物的微波促进合成及其抗菌活性研究

利用微波促进的多组分一锅法, 在封管条件下, 以萘胺、芳醛和巯基乙酸为原料, 4-二甲氨基吡啶(DMAP)/N,N’-二环已基碳二亚胺(DCC)为催化剂, 合成了系列新的噻唑烷酮衍生物, 该反应具有时间短、操作简便等优点. 目标化合物通过IR, NMR, MS和元素分析等方法确定结构. 初步测试了化合物对丁香假单胞杆菌黄瓜角斑病菌致病变种、番茄灰霉病菌和黄瓜白粉病菌抑制活性, 结果表明: 部分化合物对黄瓜白粉病菌有显著抑制作用, 但对前两种植物病菌抑制效果不明显.     

Enamine Configuration of 5-Methyl-2-phenyl-4-[（Z）-3-tolylamino-phenylmethylene]pyrazol-3（2H）-one

1 INTRODUCTION In contrast to the old-line academic and practical studies of 1-phenyl-3-methyl-4-benzoyl-5-pyrazo- lone (PMBP) on the metal coordination chemistry[1], the complexes of β-ketoamines derivated from PMBP received little attention due to its complicated com- plexation. However, in recent years, there has a sudden growth of this area as a result of its timely interest in biological activities[2]. Recently, a series of β-ketoamines[3] containing PMBP have been prepared fro…     

A simple and efficient approach for the synthesis of a novel class aliphatic 1,3,4-thiadiazol-2(3H)-one derivatives via intramolecular nucleophilic substitution reaction

In this study, we synthesized a new series of substituted aliphatic 1,3,4-thiadiazol-2(3H)-one derivatives (6-24) in yields ranging from 42 to 70% with an interesting mechanism that involves internal nucleophilic substitution followed by an S_N2-type nucleophilic substitution. First, 1-(4-chlorophenyl)-2-((5-methyl-1,3,4-thiadiazol-2-yl)thio)ethanone (3) was synthesized from the reaction of 5-methyl-1,3,4-thiadiazole-2-thiol (1) with 2-bromo-1-(4-chlorophenyl)ethanone (2) in the presence of potassium hydroxide. Then, 1-(4-chlorophenyl)-2-((5-methyl-1,3,4-thiadiazol-2-yl)thio)ethanol (4) was synthesized by a reduction reaction of this compound using NaBH₄. Finally, 5-methyl-3-alkyl-1,3,4-thiadiazol-2(3H)-one derivatives (6-24), which are the target compounds, were synthesized from the reaction of this compound (4), which is a secondary alcohol with various alkyl halides (5a-n) in the presence of sodium hydride (NaH). This study presents an interesting reaction mechanism related to the synthesis of aliphatic 1,3,4-thiadiazol-2(3H)-one derivatives that is not recorded in the literature.     

1,5-Dimethy-4-[(3-nitro-benzylidene)-amino]-2-pheyl-1,2-dihydro-pyrazol-3-one

1INTRODUCTION Antipyrine(2,3-dimethyl-1-phenyl-5-pyrazolone)and its derivatives exhibit a wide range of biological activities and applications[1~3].Antipyrine shows mi-nimal protein binding and is rapidly and completely absorbed from the gastrointestinal tract and exten-sively metabolized by the cytochrome P450liver en-zymes[4].Estimates of half-life and systemic cleara-nce of antipyrine have been used for the in vivo asse-ssment of hepatic drug oxidation in different spe-cies[5].Owing to…     

2-芳基-5-(4-硝基苯甲酰氨基)-1,3,4-噻二唑的合成

以芳甲酰肼和对硝基苯甲酰氯为主要原料, 合成出了10个酰氨基硫脲化合物5a～5j, 其中有6个(5d, 5f～5j)为新化合物. 在无需任何酸性催化剂条件下, 将制得的酰氨基硫脲在DMF中加热回流直接脱水关环合成出了9个2-芳基-5-(4-硝基苯甲酰氨基)-1,3,4-噻二唑化合物6a～6i, 其中7个(6b～6d, 6f～6i)为新化合物. 利用IR和1H NMR证明了化合物5存在两种异构体. 目标产物的结构通过IR, 1H NMR和元素分析进行了表征.     

A Convenient Preparation of 2-(2-Arylidene)- and 2-(2-Polyhydroxyalkylidene)hydrazono-4-imidazolidinones with Various Heterocyclic Side Chain Substituents at Position 5 as Potential Antiviral and Antitumor Agents

A variety of novel 5-[( Z )-arylidene]-2-[(2-( E )-arylidene)hydrazono]-4-imidazolidinones 1a-c to 4a , b and 5-[( Z )-arylidene]-2-[(2-( E )-polyhydroxyalkylidene)hydrazono]-4-imidazolidinones 5a-c to 7a-c were prepared from the reaction of 5-[( Z )-arylidene]-2-methylmercaptohydantoins 8a-c with 2-( E )-arylidene hydrazones 13a-d and/or 2-( E )-monosaccharides hydrazones 16a-c . The linear structure, and not that of the angular isomer, has been selected for the products. This structure has been confirmed from a model study of the condensation of 5-[( Z )-2-thienylidene]-2-hydrazono-4-imidazolidinone 9a with benzaldehyde and D -galactose, respectively. The acetylation and benzoylation reactions of compounds 1-7 have been studied. All the new compounds were tested for their potential antiviral and antitumor activities.     

Thermal behaviour and mechanical properties of novel RTV silicone rubbers using divinyl-hexa[(trimethoxysilyl)ethyl]-POSS as cross-linker

Divinyl-hexa[(trimethoxysilyl)ethyl]-POSS (DVPS) as an octavinyl-POSS derivative was first prepared. A series of novel polydimethylsiloxane (PDMS)/DVPS hybrid materials as room temperature vulcanized (RTV) silicone rubber were prepared. The chemical incorporation of novel POSS into hydroxyl-terminated PDMS system by hydrolytic condensation reaction was verified by attenuated total reflection (ATR) infrared spectroscopy. Thermal degradation, thermo-oxidative stability and mechanical properties of these novel RTV silicone rubbers were studied by means of thermogravimetric analysis and tensile testing. The results exhibited significantly enhanced effects on the thermal stabilities and mechanical properties as compared to the PDMS polymer prepared with tetraethoxysilane (TEOS). The observed improvements in thermal properties could be attributed to the effective three-dimensional network structures resulting from the structure of DVPS. The thermal decomposition of the RTV silicone rubbers in nitrogen was also monitored by TGA coupled with real-time FTIR, and the degradation residues were also characterized by FTIR. It was found that the POSS cross-linker facilitated the formation of cross-links in the degradation residues. The striking improvement in mechanical properties could be attributed to the synergistic action of the structure of three-dimensional multi-arm cross-linker (vinyl-POSS derivative), the plasticization of self-cross-linking Vinyl-POSS derivative and perfect distribution of vinyl-POSS derivative.     

Complexation of N-tris[(1,2-dicarboxyethoxy)ethyl]amine with Ca(II), Mn(II), Cu(II) and Zn(II) in aqueous solution

In a search for environmentally friendly metal chelating ligands for industrial applications, the protonation and complex formation equilibria of N-tris[(1,2-dicarboxyethoxy)ethyl]amine (TCA6) with Ca(II), Mn(II), Cu(II) and Zn(II) ions in aqueous 0.1?M NaCl solution were studied at 25°C by potentiometric titration. A model for complexation and stability constants of the complexes were determined. With all of the metals, complex formation was dominated by ML^4?. Comparison of TCA6 and six other chelating agents showed TCA6 to be suitable for applications where strong calcium binding is essential.     

4-[（Furan-2-ylmethylene）-amino]-1,5- dimethyl-1,2-dihyl-1,2-dihydo-pyrazol-3-one

1 INTRODUCTION Antipyrine (2,3-dimethyl-1-phenyl-5-pyrazolone) and its derivatives exhibit a wide range of biological activities and applications[1～3]. Antipyrine shows mi- nimal protein binding and is rapidly and complete- ly absorbed from the gastrointestinal tract and exten- sively metabolized by the cytochrome P450 liver en- zymes[4]. Estimates of half-life and systemic clear- ance of antipyrine have been used for the in vivo as- sessment of hepatic drug oxidation in different spe- c…     

Polyelectrolyte complexes of soluble poly-2-[(methacryloyloxy)ethyl]trimethylammonium chloride and its hydrogels with poly(acrylic acid)

The complex formation of poly-2-[(methacryloyloxy)-ethyl]trimethylammonium chloride (PMADQUAT) with poly(acrylic acid) (PAA) of different molecular weights has been studied in aqueous solutions by potentiometric, viscometric, turbidimetric and FTIR spectroscopic methods. The formation of insoluble non-stoichiometric polyelectrolyte complexes has been shown. The stability of polyelectrolyte complexes in solutions of different pH and ionic strength has been evaluated. The formation of polyelectrolyte complexes between hydrogels of PMADQUAT and linear PAA of different molecular weights has been studied. It was shown that the molecular weight of PAA considerably affects the kinetics of interaction as well as the final state of gel-polymer complex.     

Crystal Structures of Fluoride and Chloride Complexes of Tris[（2-benzimidazolyl）methyl]amine

The crystal structures of fluoride and chloride complexes of tris[（2-benzimidazolyl）methyl]amine 1 were characterized by X-ray crystallography. 1 adopts （73 symmetrical geometry and cone-like conformation so as to allow its three NHs to associate with the anions through hydrogen bonds. Despite the different sizes of the anions, the two crystals are unexpectedly isostructural. The binding ability of the anions of 1 in solution was also studied by using of UV-vis spectroscopy.     

(5-氨基-[1,3,4]噻二唑-2-基)-丙酸乙酯的合成工艺改进

以丁二酸酐为起始原料,经醇解和酰化反应制得丁二酸单乙酯酰氯(3);3经甲烷磺酸催化与氨基硫脲环合合成了重要药物中间体——(5-氨基-[1,3,4]噻二唑-2-基)-丙酸乙酯,其结构经~1H NMR,IR和MS确证。运用正交试验对环合反应条件进行优化。最优反应条件为:3 132 mmol,n(氨基硫脲)∶n(3)∶n(甲烷磺酸)=1∶3∶3,于110℃反应3 h,总收率51.3%。     

Synthesis and Antifungal Bioactivity of Methyl 2-Methoxyimino-2-{2-[(substituted benzylidene)aminooxymethyl]phenyl}acetate and 2-Methoxyimino-2-{2-[(substituted benzylidene)aminooxy-methyl]phenyl}-N-methylacetamide Derivatives

Ten methyl 2‐methoxyimino‐2‐{2‐[(substituted benzylidene)aminooxymethyl]phenyl}acetate and 2‐methoxy‐ imino‐2‐{2‐[(substituted benzylidene)aminooxymethyl]phenyl}‐N‐methylacetamide derivatives were synthesized. Structures of the new compounds were characterized by IR, ¹H NMR and GC‐MS data. These compounds at 10 µg/mL were tested in vitro against five pathogenic fungi, namely, Sclerotonia, Botrytis cinerea Pers, Gibberella zeae, Rhizoctorua solani and Pyricularia oryzae. Compounds G₅ , G₆ , G₇ and G₈ showed potent antifungal activities against Botrytis cinerea Pers, G₇ against Gibberella zeae and G₇ , G₈ against Rhizoctorua solani, respectively.     

一锅法合成4-(5-芳基-1,3,4-噻二唑-2-氨甲基)苯酚衍生物

以2-氨基-5-芳基噻二唑衍生物和对羟基苯甲醛为原料,经亲核加成/脱水、还原两步一锅法合成了一系列新的4-(5-芳基-1,3,4-噻二唑-2-氨甲基)苯酚衍生物,反应具有时间短、后处理简单等优点.采用元素分析,NMR,IR以及质谱等多种谱学技术对产物进行了详细表征.     

1,3,5-三[(4’-乙炔基苯基)乙炔基]苯的合成

设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.     

The Synthesis and Fungicidal Activities of 2,6-Bis[(3-aryl)-s-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]pyridines

In search of better bioactive compounds, a series of novel 2,6-bis[(3-aryl)-s-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]pyridines 2 were synthesized in high yields by the cyclization of 3-aryl-4-amino-5-mercapto-1, 2, 4-triazoles 1 with 2,6-pyridine dicarboxylic acid. 2 exhibited good fungicidal activities against Cerospora beticola sacc.     

Synthesis of 1,3-Bis[(3-aryl)-S-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]benzenes

1,3-bis[(3-aryl)-s-triazolo[3,4-b]-[1,3,4]thiadiazole-6-yl]benzenes 2 were synthesized in high yields by the reaction of 3-aryl 4-amino-5-mercapto-1,2,4-triazole 1 with m-phthalic acid.