芳酰基芳基偶氮化合物的合成

芳酰基芳基偶氮化合物的合成;芳酰基芳基偶氮化合物;哌啶氮氧自由基;芳酰基芳肼;相转移催化     

相转移催化条件下N-芳酰基-N＇-芳基硒脲衍生物的合成及其晶体结构

硒是人体所必需的14种微量元素之一，硒脲作为有机硒化合物中的重要一类，在抗菌和抗肿瘤方面已显示出了很高的生物活性．关于芳酰基硒脲的合成方法虽然早在1937年就有报道，但是由于反应复杂且控制条件苛刻，故有关芳酰基硒脲的研究至今仍然很少见报道．     

N—芳酰基—N′—（4—安替比林基）硫脲类化合物的合成

N,N′-二取代芳酰基硫脲类化合物具有多种重要的生物活性,如抗真菌、抗病毒及抑制中枢神经系统等,因而对此类化合物的研究已引起人们的广泛兴趣,许多学者进行了这一方面的合成工作。为了进一步研究不同的取代基团对此类化合物生物活性的影响,作     

芳硫基乙酸酯及其氧化产物的色谱行为(Ⅲ)──在反相高效液相色谱中的行为

芳硫基乙酸酯及其氧化产物的色谱行为（Ⅲ）──在反相高效液相色谱中的行为练鸿振,茅力,苗进,徐小青,张正（南京大学现代分析中心,化学系,南京,２１００９３）关键词芳硫基乙酸酯;芳亚磺酰基乙酸酯;芳磺酰基乙酸酯;反相高效液相色谱在现代有机合成中,含硫有机...     

Microwave-assisted synthesis of new pyrimido[4′,5′：4,5]thiazolo[3,2-α] benzimidazol-4（3H）-one derivatives in solvent-free condition

Microwave-assisted synthesis of new 2-arylpyrimido[4′,5′：4,5]thiazolo[3,2-α]benzimidazol-4（3H）-ones from 3-aminothia- zolo[3,2-α]benzimidazol-2-earboxamide and aroyl halides in solvent-free condition is described. In comparison with classical conditions the reactions are faster and the yields are higher under microwave irradiation.     

相转移催化条件下N-芳酰基-N''''-芳基硒脲衍生物的合成及其晶体结构

硒是人体所必需的14种微量元素之一, 硒脲作为有机硒化合物中的重要一类, 在抗菌和抗肿瘤方面已显示出了很高的生物活性[1]. 关于芳酰基硒脲的合成方法虽然早在1937年就有报道[2], 但是由于反应复杂且控制条件苛刻, 故有关芳酰基硒脲的研究至今仍然很少见报道.     

二芳酰基及二芳氧乙酰基芳二硫脲衍生物的合成及植物生长调节活性

用相转移催化法将具有良好植物生长调节活性的取代芳氧乙酸(取代芳酸)与芳二胺反应合成了15个双酰基硫脲类化合物，其结构经元素分析、IR和1H NMR确证。生物活性测试结果表明，多数化合物具有较好的植物生长调节活性，个别化合物的活性尤为显著。     

1,3-双(偶氮介晶基)-1,1,3,3-四甲基二硅氧烷的 合成、2D NMR结构分析和液晶性能

合成了2个(CH3(C6H4)N2(C6H3A)COO(C6H4)OCH2-Si(CH3)2)2O化合物,其中A = H为1,A = CH3为2。经IR、1H NMR和元素分析表征,并用2D NMR1H-1H COSY记录了2个化合物中不同取代基苯环上所有质子的化学位移和相关-自旋偶合常数,对谱线的归属作了指认。通过偏光显微镜和DSC分析,1具有液晶性能,而2没有液晶性能。同时,用AM1方法计算了它们的电子结构,讨论了它们的结构与性能之间的关系。     

Azo Bond Reduction of N,N＇,diaryl Adipyl Bis-azo Compounds with Hydrazine Hydrate

Reduction of a series of N,N'-diaryl adipyl bis-azo compounds using hydrazine hydrate as reductant was investigated. The products were characterized by elemental analysis, IR and 1H NMR methods and confirmed to be N,N'-diaryl adipyl dihydrazine. The results show that hydrazine hydrate can selectively reduce azo bonds with other potential reducible bonds intact in the N,N'-diaryl adipyl bis-azo compounds. The yields are high up to 92% under mild reaction conditions. According to the previous reports, this reduction process was attributed to an indirect reduction mechanism through an intermediate diimide.     

Synthesis and Chemical Shifts Calculation of a-Acyloxycarboxamides Derived from Indane-l,2,3-trione by DFT and HF Methods

α-Acyloxycarboxamides are synthesized from three-component Passerini reaction between indane-1,2,3-trione, isocyanides, and thiophenecarboxylic acids in quantitative yields. The structures of the final products were confirmed by IR, 1H and 13C NMR spectroscopy, mass spectrometry, and elemental analysis. The B3LYP/HF calculations for computation of 1H and 13C NMR chemical shifts have been carried out for the title compounds at the 6-311+G** and 6-311++G** basis set levels within GIAO and CSGT approaches. Predicted 1H and 13C NMR che-mical shifts have been assigned and compared with experimental 1H and 13C NMR spectra and they are supported each other.     

Synthesis, experimental and theoretical characterization of tetra dentate N,N'-dipyridoxyl (1,3-propylenediamine) salen ligand and its Co(III) complex

The new tetra dentate dianionic H2PS (N,N'-dipyridoxyl (1,3-propylenediamine)) Schiff-base ligand and its octahedral Co(III) salen complex [Co(PS)(H2O)(CH3OH)]+CH3COO(-) were synthesized, where coordinating atoms of H2PS (N,N,O(-),O(-)) occupied equatorial positions with H2O and CH3OH as axial ligands. The nature of the H2PS and its complex were determined by elemental and spectrochemical (IR, UV-vis, 1H NMR and Mass) analysis. Also, the fully optimized geometries and vibrational frequencies of them together with the 1H NMR chemical shifts of H2PS have been calculated using density functional theory (B3LYP) method. Obtained structural parameters are in good agreement with the experimental data reported for similar compounds. The calculated and experimental results confirmed the suggested structures for the ligand and complex.     

Long-range deuterium isotope effects on (13)C chemical shifts of intramolecularly hydrogen-bonded N-substituted 3-(cycloamine)thiopropionamides or amides: a case of electric field effects

A series of intramolecularly hydrogen-bonded N-substituted 3-(piperidine, morpholine, N-methylpiperazine)thiopropionamides and some corresponding amides have been studied with special emphasis on hydrogen bonding. The compounds have been selected in order to vary and to minimize the N...N distance. Geometries, charge distributions, and chemical shifts of these compounds are obtained from DFT-type BP3LYP calculations. 1H and 13C 1D and 2D NMR experiments were performed to obtain H,H coupling constants, 13C chemical shifts assignments, and deuterium isotope effects on13C chemical shifts. Variable-temperature NMR studies and 2D exchange NMR spectra have been used to describe the rather complicated conformational behavior mainly governed by the ring flipping of the piperidine (morpholine) rings and intramolecular hydrogen bonding. Unusual long-range deuterium isotope effects on 13C chemical shifts are observed over as far as eight bonds away from the site of deuteriation. The isotope effects are related to the N...N distances, thus being related to the hydrogen bonding and polarization of the N-H bond. Arguments are presented showing that the deuterium isotope effects on 13C chemical shifts originate in electric field effects.     

取代芴—9—羧酸酯衍生物的合成

报道了以９，１０－菲醌为起始原料，通过在碱性条件下重排，再经过氯化、酯化及Ｎ杂环取代反应，合成了２０个新的含氮杂环芴－９－羧酸酯类似物，其结构经ＩＲ，＾１Ｈ ＮＭＲ及元素分析所证实。并对其合成方法进行了研究。同时还对合成的新化合物的抗霉菌生物活性进行了简单的测定。     

Solution and solid-state NMR studies of some cadmium-selenone complexes

Cadmium(II) complexes of Imidazolidine-2-selenone (ImSe) and its derivatives have been prepared with the general formula Cd(RImSe)2Cl2 (where R=Me, Et, Pr, etc.). These complexes are characterized by elemental analysis, IR and NMR (1H, 13C, 77Se and 113Cd) spectroscopy. An upfield shift in C=Se resonance of selenones in 13C NMR and in 77Se and high-frequency shifts in N-H resonances in 1H are consistent with the selenium coordination to Cd(II). The 77Se nucleus in Cd(ImSe)2Cl2 is shielded by 38 ppm on coordination, relative to the free ligand. The principal components of the 77Se, 113Cd and 13C shielding tensors for the complexes were determined from solid-state NMR data. Large selenium chemical shift anisotropies were observed for these complexes.     

三烷氧基(β-酯基)乙基锗的合成及性质

生物及临床实验结果表明β-羧基乙基锗倍半氧化物[简式为(GeCH_2CH_2COOH)_2O_3]工具有抗癌等广泛的生物活性,且毒性极低。最近,我们又发现该化合物是一种具有双重性能的放射增敏剂,并合成了末见报道的类似物β-(N-芳基酰胺基)乙基锗倍半氧化物[简式(GeCH_2CH_2CONHAr)_2O_3],研究了其抗癌活性。本文所要报道的新有机锗化合物包括7个三烷氧基(β-酯基)乙基锗化合物[简式(R~2O)_3GeCH_2CHR~1COOR~2]和6个β-三氯锗基丙酸酯类化合物[简式Cl_3GeCH_2CHR~1COOR~2]。     

双酰腙钳形受体分子的合成及阴离子识别研究

在微波辐射下快速、高产率地合成了一系列含有四唑环的双酰腙受体,并对其进行了元素分析、红外以及核磁共振氢谱和碳谱表征.利用紫外-可见吸收光谱及1HNMR考察了其与F-,Cl-,Br-和I-卤素阴离子的相互作用.紫外滴定实验表明4a较4b,4c对F-有更好的识别作用.Job曲线表明,主体4a与F-间形成1∶1型氢键络合物.通过1HNMR滴定及质子溶剂效应进一步证明了该受体分子与阴离子以氢键作用相结合.     

15N NMR spectroscopy of labeled alkoxyamines. 15N-labeled model compounds for nitroxide-trapping studies in free-radical (Co)polymerization

Eight (15)N-labeled derivatives of 1-ethoxy-2,2,6,6-tetramethylpiperidine were synthesized in order to investigate the effects of their structural units on (15)N NMR spectra. A single peak is found for each alkoxyamine. The chemical shift depends extensively on the nature of the alpha carbon atom of the alkoxy group. The remote functional group attached to position 4 of the piperidine ring has a smaller but still significant effect. The results of the (15)N NMR measurements are supported by the detection of the N-H and N-C spin-spin coupling from the (1)H and (13)C NMR. The investigated alkoxyamines are model compounds for the radical-trapping products of styryl, methyl methacryloyl, alpha-methylstyryl, and methyl acryloyl radicals by (15)N-labeled nitroxides. The potential of (15)N NMR spectroscopy to analyze such products is discussed. In addition, it is shown that the (13)C chemical shifts of the alpha carbon atom of the alkoxy group fall in an empty part of the (13)C NMR spectrum, which allows the identification of trapped (macro)radicals via natural abundance (13)C NMR.