邻甲氧基苯甲醛缩4-苯基-3-硫代氨基脲的合成研究

硫代氨基脲类化合物作为具有光谱生物活性的生物分子,在抗癌、抗菌、抗炎等医药领域发挥了重要作用。本论文采用邻甲氧基苯甲醛和4-苯基-3-硫代氨基脲反应制备邻甲氧基苯甲醛缩4-苯基-3-硫代氨基脲,将邻甲氧基苯甲醛缩4-苯基-3-硫代氨基脲作为配体与[Ru(p-cymene)Cl_2]_2反应制备邻甲氧基苯甲醛缩4-苯基-3-硫代氨基脲配合物,并研究其性质。     

3-（2-羟基-4,5-二甲氧基苯基）丙酸钠的合成

丹参素有良好的药效,它的生物活性可能跟苯基乳酸结构有关,本论文以3,4-二甲氧基苯丙酸为原料,经溴代、水解反应合成了丹参素类似物3-（2-羟基-4,5-二甲氧基苯基）丙酸钠。     

雷洛昔芬中间体4-甲氧基-α-[(3-甲氧基苯基)硫代]苯乙酮含量的反相高效液相色谱测定

采用反相高效液相色谱法,以v(甲醇)v∶(水)=802∶0作为流动相,用C18柱和二极管阵列检测器(DAD,282nm),测定4-甲氧基--α[(3-甲氧基苯基)硫代]苯乙酮的含量。结果表明,4-甲氧基--α[(3-甲氧基苯基)硫代]苯乙酮在0.02～0.90μg内呈良好的线性关系,r=0.99999。该方法灵敏、快速、准确,可用于4-甲氧基--α[(3-甲氧基苯基)硫代]苯乙酮含量的测定。     

硫代双烯镍螯合型红外染料的合成

合成成功三个吸收波长在近红外城（１１００￣１２７５ｎｍ）的硫代双烯镍螯合物，其结构为〔ＲＣＳＣＳＲ〕２Ｎｉ，Ｒ为取代苯基。染料Ａ的Ｒ取代基为：对－Ｎ－乙基－Ｎ－苄基苯胺；染料Ｂ的Ｒ取代基为：对－Ｎ－乙基－Ｎ－（２－甲氧基）乙基苯胺；染料Ｃ的Ｒ取代基为：久洛尼定。     

硫代双烯镍络合物的合成及光热稳定性的研究

为了探究近红外染料的光、热特性,本文合成了一个中性和三个离子型硫代双烯镍络合物,并进行了表征.利用紫外和红外吸收光谱分析染料在溶液和固体状态下对光、热变化的关系,比较了其稳定性.结果表明离子型硫代双烯镍络合物具有更好的光、热稳定性.     

NBS对芳香醚类化合物选择性溴代研究

2-(3,4-二甲氧基苯基)乙酸甲酯与N-溴代丁二酰亚胺(NBS)在摩尔比为1∶1,甲醇为溶剂,室温条件下反应,以94％的收率得到选择性好的芳环单溴代产物2-(2-溴-4,5-二甲氧基苯基)乙酸甲酯.其结构经1H NMR、MS谱确证.用温和的NBS作为溴代试剂避免了传统芳环溴代试剂强腐蚀性及强毒性的缺点,可发展为芳香醚类化合物溴代的一般方法.     

1-(3,4-二甲氧基苯基)环丁烷甲腈的合成

以2-(3,4-二甲氧基苯基)乙腈和1,3-二溴丙烷为原料,在KOH碱性条件下,经过两次亲核取代反应,合成得到目标化合物1-(3,4-二甲氧基苯基)环丁烷甲腈,收率59.3％.产物结构经1H NMR和ESI-MS确证.并对影响产物收率的主要因素进行了考察,确定适宜的反应条件为:物料比n3∶n2=1.2∶1;KOH用量n...     

基于硼氢化钾-三氟化硼乙醚还原体系的3,4-二甲氧基苯乙胺合成新方法

以邻苯二酚为原料,经醚化、Vilsmeier反应制得藜芦醛,收率95.2%,藜芦醛与硝基甲烷反应制得了3,4-二甲氧基苯基-β-硝基乙烯,收率高达93.6%,然后利用硼氢化钾-三氟化硼乙醚体系(KBH4/BF3-Et2O)催化还原3,4-二甲氧基苯基-β-硝基乙烯合成3,4-二甲氧基苯乙胺。该方法使用KBH4/F3B-Et2O还原体系,具有反应条件温和、后处理容易、产率较高等特点,适于工业化生产。     

异香豆素类衍生物的卤化烷氧基化反应

以N-溴代丁二酰亚胺(NBS)、N-氯代丁二酰亚胺(NCS)分别为溴代、氯代试剂,醇类化合物作为反应原料及溶剂,实现了异香豆素类衍生物3,4-位的卤化烷氧基化反应.室温(25℃)下即可在3,4-位之间发生加成反应,合成具有潜在药理活性的异色满-1-酮类衍生物.对4-溴-3-甲氧基-3-苯基异色满-1-酮(Ⅳa)的合成反...     

(2,3-二甲氧基-6-甲酰基)苯基-β-D-葡萄糖苷的合成

为了优化和改进糖苷化反应的合成工艺,首先以β-D-葡萄糖为原料,经乙酰化、溴代反应合成了糖供体2,3,4,6-O-四乙酰基-α-D-溴代葡萄糖(Ⅲ);再与2-羟基-3,4-二甲氧基苯甲醛(Ⅳ)经糖苷化反应合成了2,3,4,6-O-四乙酰基-(2,3-二甲氧基-6-甲酰基)苯基-β-D-葡萄糖苷(Ⅴ);最后对化合物Ⅴ进行水解得到了目标化合物(2,3-二甲氧基-6-甲酰基)苯基-β-D-葡萄糖苷(Ⅵ)。结果表明:在合成氧糖苷(Ⅴ)的过程中,采用无水K_2CO_3为缚酸剂,四丁基溴化铵(TBAB)为相转移催化剂,反应收率可达78.9%;化合物Ⅴ水解的最优条件是以甲醇为溶剂、无水K_2CO_3为催化剂。所得到产物经核磁、红外、质谱表征,证明为目标化合物。     

四叔丁基金属酞菁化合物的合成

本文以邻-二甲苯为原料,经烷基化、氧化和脱水缩合合成了4-叔丁基邻苯二甲酸酐,然后将4-叔丁基邻苯二甲酸酐在钼酸铵催化下与尿素、无水金属氯化物作用合成了四叔丁基酞菁铁、钴、镍、镁化合物。对合成产物分别用核磁共振、红外光谱或元素分析确证结构。     

一系列硫代双烯镍近红外染料的合成及性能

该文分别通过安息香路线和二酮路线合成了4种具有不同取代基的硫代双烯镍近红外染料,并考察了染料的物理、光电化学及热稳定性等性质。紫外-可见-近红外(UV-Vis-NIR)吸收光谱测试结果表明,配合物在700～1 100 nm都具有较强的吸收。对化合物的取代基效应及溶剂效应的研究发现:供电子基团导致λmax红移,而吸电子基团导致λmax蓝移,且λmax随着溶剂极性增大而增大。利用循环伏安法和差分脉冲伏安法(CV/DPV)测试了化合物的电化学性质。此外,该文还通过密度泛函理论(DFT)对化合物的HOMO和LUMO能级进行了计算。热失重测试研究表明,合成的化合物具有较好的热稳定性。     

Thermal properties and characteristics of thin layers of nickel dithiolene complexes

Thermal properties of near infra–red–absorbing nickel dithiolene complexes have been examined by thermal gravimetric and differential scanning calorimetry analysis. The nickel complexes with relatively low melting points gave a DRAW disc with better recording characteristics, when they were used as inhibitors of the photofading of thin layers of cyanine dyes. Thin layers of the nickel complexes on polymethylmethacrylate or glass were formed by spin coating and by the radio–frequency reactive ion plating technique. Their reflectance, absorption spectra and optical recording characteristics have been recorded.     

催化加氢制备3,4-亚甲二氧基苯胺

3,4 亚甲二氧基硝基苯在95%乙醇溶剂中用雷尼镍催化加氢制备了3,4 亚甲二氧基苯胺。对催化剂用量和活性稳定性进行了研究,讨论了溶剂用量、温度、压力等因素对加氢反应的影响。结果表明最佳工艺参数为:雷尼镍∶乙醇∶3,4 亚甲二氧基硝基苯=0.15∶6∶1(质量比),反应温度40℃,氢压0.45～0.50MPa,搅拌速度450r/min,反应至不再吸氢为止,产品收率在97%以上,纯度为98%。     

Square-planar d8 metal push–pull dithiolene complexes: Synthesis and characterization of [Pd(Me2pipdt)(dmit)]

Experimental and theoretical results on the novel [Pd(Me₂pipdt)(dmit)] complex (1) based on the push Me₂pipdt (1,4-dimethyl-piperazine-3,2-dithione) and pull dmit (1,3-dithiolo-2-thione-4,5-dithiolato), show that an unbalanced electron distribution at the dithiolene core occurs. The presence of a solvatochromic absorption at low energy, shifted to higher frequency when compared to the corresponding nickel case, points out that these complexes are potential second-order non-linear chromophores, whose properties are tunable with the metal.     

Vergleich der thermischen,photochemischen und massenspektrometrischen Fragmentierung von Schwefelheterocyclen mit cis-Dithioethylenstruktur

Comparison of the Thermal, Photochemical and Mass Spectrometric Fragmentation of Sulphur Heterocycles with cis-Dithioethene-Structure The mass spectrometric primary fragmentation of 3-methylthio-1,4,2-dithiazines 1 , 1,4-dithiins 2 , 2,3-dihydro-1,4-dithiin-2-ones 4 , 1,3-dithiole-2-ones 5 , 2-imino-1,3-dithioles 6 and 1,3-dithiole-2-thiones 7 is compared with their thermolytical and photochemical reaction. In the mass spectra an intense peak of the dithiete radical ion is observed, if in the compounds an energetically favourable neutral molecule is preformed: in 1 methyl rhodanide, in 3 ethene, in 4 ketene, in 5 carbon monoxide and in 6 hydrogen cyanide. The substances 1, 3–6 – with the restriction by 3 – yield photochemically the dithiete, too. The photolysis of dithiazines 1 is wave length dependent. Mass spectrometrically, thermally and photochemically the dithiins 2 form thiophenes. The dithiolethiones 7 decompose mass spectrometrically and thermally into carbon disulfide, sulfur and ethynes, but photochemically they form tetrathiafulvalenes. The fragmentation of the compounds 1–6 is analogous in mass spectrometry and photolysis; 2, 3, 5 and with reservation 1 show similar mass spectrometric, thermal and photochemical reactivity. Possible reasons for these analogies are discussed. The dithietes, generated by photolysis of the compounds 1, 4, 5 or 6 react with iron penta-, nickel tetra-, molybdenum hexa- and tungsten hexacarbonyl in preparative scale to the corresponding dithiolene complexes.     

A nitrogen rich Ni(II)–dithiolate system exhibiting acid–base behavior: Synthesis,supramolecular structure and spectroscopy of [Bu4N]2[NiII(ppdt)2] (ppdt = pyrido[2,3-b]pyrazine-2,3-dithiolate)

The compound [Bu₄N]₂[Ni(ppdt)₂] (1) (ppdt = pyrido[2,3-b]pyrazine-2,3-dithiolate) has been synthesized, starting from pyrido[2,3-b]pyrazine-2,3-dithiol, nickel chloride and tetrabutylammonium bromide in methanol. Compound 1 crystallizes in P2₁/c space group (monoclinic system). Its crystal structure is characterized by interesting C–H?S and C–H?N supramolecular weak interactions. Its solution state has been described with acid–base (protonation–deprotonation) behavior, that has rarely been investigated for a metal–dithiolene system. Compound 1 is first instance of a metal–dithiolene compound that has three ring nitrogen on each dithiolate ligand. The pH dependent changes in the charge-transfer absorption band are attributed to the protonation on an imine nitrogen of the ppdt ligand. The complex is electrochemically quasi-reversible with an oxidation potential of E_1/2 = +0.46 V vs. Ag/AgCl in methanol.     

Paramagnetic cp/dithiolene complexes as molecular hinges: interplay of metal/ligand electronic delocalization and solid-state magnetic behavior

Paramagnetic, flexible organometallic dithiolene complexes associating cyclopentadienyl (Cp) and dithiolate (dt) ligands, such as CpM(dt), Cp2M(dt), or CpM(dt)2, are investigated in the solid state through their structural and magnetic properties. The degree of delocalization of the spin density between the metal and the dithiolene fragments in a given complex, its varying molecular geometry and frontier orbitals, and the structures adopted in the solid state are intimately correlated and adapt mutually to each other. A variety of magnetic structures follows, from noninteracting spins to dyads, spin chains, spin ladders, or antiferromagnetic ground state, the detailed properties of which are highly sensitive to "minor" molecular modifications.     

Metal complex dyes of nickel with schiff bases

Nickel complexes with Schiff bases 2-(2-pyridylmethyleneamino) phenol (PMAP) and 2-(2-quinolylmethyleneamino) phenol (QMAP) were prepared and the composition of the crystalline complexes was determined by elemental analysis, solubility, UV-Vis, IR and mass spectrometry. It was found that, for the Ni-PMAP complex, two ligands were bonded to one metal ion, giving a neutral complex with one molecule of water probably bonded in the inner sphere of the complex. With QMAP, nickel forms cationic complexes with a metal-to-ligand ratio of 2:2 and two molecules of acetate as anions. The solution properties of Ni-QMAP were investigated at different pH. The chromophoric properties of the complex were enhanced with increase in pH, while stability decreased with time. The application of QMAP as a spectrophotometric reagent for the determination of small amounts of nickel was investigated. Adherence to Beer's law was observed from 0.00 to 5.00 μg/ml at pH 8, the most appropriate pH in respect to sensitivity and acceptable time stability of the complexes. Dyeing properties of both complexes were investigated on polyamide 66 and the influence of the addition of another phenyl ring to the ligand molecule on the dyeing properties of the complex is discussed.     

Tetrathiafulvalene. XIX. Synthese und Eigenschaften elektronenleitender Poly-Dithiolenkomplexe mit Ethylentetrathiolat und Tetrathiafulvalentetrathiolat als Brückenliganden

Tetrathiafulvalenes. XIX. Synthesis and Properties of Electron Conducting Poly-Dithiolene Complexes with Ethylene Tetrathiolat and Tetrathiafulvalene Tetrathiolat as Bridge Ligands [1,3]-Dithiolo[4,5-d]-1,3-dithiol-2,5-dione 7 and 5-(5-oxo[1,3]-dithiolo[4,5–d]1,3-dithiole-2-ylidene)[1,3]-dithiolo[4,5–d]1,3–dithiol-2-one 8 were synthesised from 1,3-dithiole-2-thione-4,5-dithiolat. The ligands react with salts of iron, cobalt, nickel, palladium, platinum and copper to give the polymer complexes 22a–g and 23a–e , respectively. Irradiation of 7 in the presence of iron penta-, dicobalt octa- or nickel tetracarbonyl gives the corresponding dithiolene complexes 21a–c . The amorphous insoluble polymer complexes from types 21, 22 , and 23 have been characterised by i.r.-spectroscopy, susceptibility and conductivity measurements. The nickel complexes have the highest electrical conductivity (σ_RT ∼ 10⁻¹Ω⁻¹cm⁻¹, pellets) with a very low activation energy (0,045 eV, 100–300 K) A high electron delocalization in the direction of the polymer chain and an easy charge transfer from chain to chain is supposed.