5(6)-羧基荧光素标记2''-脱氧尿苷的合成

以5-碘-2'-脱氧尿嘧啶为起始原料,5(6)-羧基荧光素为荧光标记物,经6步反应合成了5(6)-羧基荧光素标记的2'-脱氧尿苷,并利用高效液相色谱(HPLC),1H NMR和13C NMR对目标化合物的纯度和结构进行了表征.     

微波作用下1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑的合成及生物活性

采用微波和相转移催化法通过1-苯基-5-(4-苯基-1,2,4-三唑-5-巯基-3-甲硫基)四唑(2)与2-氯乙酰芳胺(3)反应高效、快速地合成了10种尚未见文献报道的1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑. 其结构经 IR, ¹H NMR, ¹³C NMR 和元素分析表征. 生物活性实验结果表明, 该类化合物在较低浓度下部分化合物对小麦芽有很好的促进作用.     

新型含环状α-羟基膦酸酯的N1-(四氢呋喃-2-基)-5-氟尿嘧啶衍生物的合成

通过N¹-(2-呋喃烷基)-N³-羟乙基-5-氟尿嘧啶的Moffatt氧化, 再与亚磷酸酯的加成反应合成得到8个新型含环状α-羟基膦酸酯的N¹-(四氢呋喃-2-基)-5-氟尿嘧啶衍生物, 采用IR, ¹H NMR, ³¹P NMR, MS和元素分析对其结构进行了表征.     

2-氨基-6-氟-9-(4-羟基-3-羟甲基丁基)嘌呤的合成

报道了2-氨基-6-氟-9-(4-羟基-3-羟甲基丁基)嘌呤(1)的合成, 通过对起始原料2-氨基-6-氯-9-(4-乙酰氧基-3-乙酰氧甲基丁基)嘌呤(2)水解脱去乙酰基, 得到2-氨基-6-氯-9-(4-羟基-3-羟甲基丁基)嘌呤(3). 化合物3与三甲胺乙醇溶液在混合溶剂[V(THF)∶V(DMF)＝3∶1]中反应得到相应的氯化铵盐4, 然后与KF在DMF溶剂中反应, 得到化合物1. 产品经UV-vis, IR, ¹H NMR, ¹⁹F NMR和MS表征. 考察了反应温度、氟化试剂等因素对氟化反应的影响, 为6位含氟的嘌呤核苷类化合物的合成提供了一种直接、简易的新方法.     

2-(1-苯基-1H-四唑-5-硫基)-N-芳基乙酰胺的合成及其生物活性研究

采用微波法通过2-氯乙酰芳胺与1-苯基-1H-四唑-5-硫醇反应合成了一系列2-(1-苯基-1H-四唑-5-硫基)-N-芳基乙酰胺. 其结构经 IR, ¹H NMR, ¹³C NMR 和元素分析表征. 生物活性实验结果表明, 该类化合物在较低浓度下对油菜籽和小麦的生长表现出良好的促进作用.     

2-取代苯基-5-(3,4,5-三甲氧基苯基)-1,3,4-噁二唑衍生物的合成及生物活性研究

合成了10个2-取代苯基-5-(3,4,5-三甲氧基苯基)-1,3,4-噁二唑衍生物. 并经过元素分析, IR, ¹H NMR, ¹³C NMR对其结构进行了确认. 初步生物活性测试表明, 部分化合物具有一定抗癌活性.     

2-甲基-2,5′-(乙烯基)-二-8-羟基喹啉锌配合物的合成与荧光特性

设计合成了8-羟基喹啉衍生物3和4以及它们的金属锌配合物5和6,化合物3和4经质谱(MS)、元素分析(EA)、红外光谱(IR)、紫外光谱(UV)、核磁共振氢谱( ¹H NMR)进行表征,并测定了它们的荧光性质,与2-甲基-8-羟基喹啉(λ_max=390 nm)比较表明,化合物3和4的荧光红移80～150 nm;用X射线单晶衍射仪测定了化合物3的晶体结构,晶体属于三斜晶系,空间群P1,a=0.706 87(5) nm,b=0.962 03(6) nm,c=1.221 09(8) nm,α=86.735(4)°,β=87.840(4)°,γ=74.333(4)°,V=0.798 01(9) nm³,Z=2,D_c=1.367 Mg·m^-3,μ=0.089 mm^-1,F(000)=344,wR₁=0.055 2,wR₂=0.158 1。化合物3的晶体结构确认了2-甲基-8-羟基喹啉甲酰化是在5位。测定了化合物5和6的荧光光谱及其荧光寿命,结果表明,化合物5和6发光的峰值为620 nm 和623nm,能够发出橙色的荧光,与2-甲基-8-羟基喹啉锌(λ_max=515 nm)比较,发生了明显的红移。化合物5和6的寿命分别为1.57 ns和1.77 ns,呈单指数衰减。     

芳醛-[5-(3,4,5-三甲氧基苯基)-1,3,4-噻二唑-2-巯基]-乙酰腙衍生物的合成及生物活性研究

采用活性基团拼接法, 以2-巯基-5-(3,4,5-三甲氧基苯基)-1,3,4-噻二唑为原料, 经硫醚化、肼解、腙化反应合成了8个芳醛-[5-(3,4,5-三甲氧基苯基)-1,3,4-噻二唑-2-巯基]-乙酰腙衍生物, 并经过元素分析, IR, ¹H NMR, ¹³C NMR对其结构进行了确认. 初步生物活性测试表明, 部分化合物具有一定的抑菌生物活性.     

新型2H-噻唑[3,2-b][1,2,4]三嗪-3,7-二酮的超声辅助一锅法合成及乙酰胆碱酯酶抑制活性研究

以取代苯甲醛、溴乙腈和6-苄基-3-硫代-3,4-二氢-1,2,4-三嗪-5(2H)-酮为起始原料,在超声辅助下,一锅合成了9个新型6-苄基-2-亚苄基-2H-噻唑[3,2-b][1,2,4]三嗪-3,7-二酮类化合物,结构经_¹H NMR,_¹³C NMR和MS（ESI）表征并对其合成机理进行了初步研究。测试了目标化合物(4a~4i)的体外乙酰胆碱酯酶的抑制活性,其中4a和4d抑制活性最好,有进一步研究的价值。     

N-2-多氟烷基乙基取代1,3,4-噁二唑-2-硫酮及1,2,4-三唑-5-硫酮类化合物的合成和密度泛函理论研究

为改善二唑及三唑类化合物的生物活性, 设计合成了一系列多氟烷基乙基取代的1,3,4-噁二唑-2-硫酮6a～6l及1,2,4-三唑-5-硫酮类化合物9a～9l. ¹H NMR, ¹⁹F NMR, IR和MS谱以及元素分析表征了它们的结构; 实验结果与Materials Studio 3.0中的Dmol3计算模块理论计算表明了唑环上的NH较之CONH中的NH更易进行烷基化反应.     

29Si- und 23Na-Festkörper-MAS-NMR-Untersuchungen an Modifikationen des Na2Si2O5

²⁹Si and ²³Na Solid State MAS NMR Investigations of Modifications of the Sodium Phyllosilicate Na₂Si₂O₅ . The results of ²⁹Si- and ²³Na-MAS NMR investigations on four modifications of the synthetic Na₂Si₂O₅ demonstrate that the α-, β- and δ-modifications are characterized unequivocally by the parameters of the corresponding NMR spectra. The studies on γ-Na₂Si₂O₅ show that this sample contains a large amount of secondary compounds. For α- und β-Na₂Si₂O₅ the the structural details of the silicate sheets are reflected by the ²⁹Si MAS NMR spectra while from the ²³Na MAS NMR spectra conclusions about the coordination number of the sodium atoms can be derived. The ²⁹Si MAS NMR investigations on δ-Na₂Si₂O₅ indicate that the silicate sheet of this modification consist of identical SiO₄-tetrahydra the parameter of which differ from those of α- and β-Na₂Si₂O₅. The ²³Na MAS NMR studies show that in the interlayer space of δ-Na₂Si₂O₅ two nonidentical sodium atoms exists. The NMR results give rise to the suggestion that one of the sodium is surrounded by five and the other one by six oxygen atoms.     

Solid‐State NMR Investigations on the Amorphous Network of Precursor‐Derived Si2B2N5C4 Ceramics

Employing a multitude of modern solid state NMR techniques including ¹³C{¹⁵N}REDOR NMR, ¹H–¹³C CP NMR, ¹¹B MQMAS NMR spectroscopic experiments, the structural organization of Si₂B₂N₅C₄ ceramic has been studied. The experiments were executed on double isotope enriched (¹³C, ¹⁵N) and natural isotope abundance Si₂B₂N₅C₄ ceramics. The materials were synthesized by aminolysis and subsequent pyrolysis of intermediate pre‐ceramic polymers that were obtained from the single source precursor TSDE, 1‐(trichlorosilyl)‐1‐(dichloroboryl)ethane (Cl₃Si–CH(CH₃)–BCl₂). The result of the ¹³C{¹⁵N} REDOR NMR spectroscopic experiment shows that carbon atoms are incorporated into the network by bridging to nitrogen, which already occurs during the polymerization step. Furthermore, the combined results of ¹¹B NMR and ¹¹B MQMAS NMR indicate that boron atoms may also be connected to carbon in addition to nitrogen.     

FREE RADICAL RING OPENING POLYMERIZATION OF CYCLIC ACRYLATES

Cyclic acrylates, 2,2- dimethyl-5-methylene-1 , 3-dioxolan-4 -one and 2- phenyl-5-methylene-1,3-dioxolan-4-one, were synthesized successfully. The monomers were characterized by ~1H NMR, ~(13)C NMR, IR and elemental analysis or HRMS. Polymerization of the monomers were carried out at 120℃with di-t-butylperoxide as initiator. The polymers were studied by ~1H NMR, ~(13)C NMR, UV and hydrolysis. The molecular weights of the resulting polymers were estimated by viscosity measurement and the extent of ring opening was estimated also by ~1H NMR and hydrolysis of the polymers and further confirmed by UV spectra.     

A study of the hydrolysis of ZrF<Stack><Subscript>6</Subscript><Superscript>2−</Superscript></Stack> and the structure of intermediate hydrolysis products by <Superscript>19</Superscript>F and <Superscript>91</Superscript>Zr NMR in the 9.4 T field

The high-field ¹⁹F and ⁹¹Zr NMR method is used to study the hydrolysis and polycondensation of hexafluorozirconate ZrF₆²⁻ in aqueous and water-peroxide solutions. During hydrolysis in aqueous solutions only ZrF₆²⁻ and F⁻ ions were observed by NMR, however, in the water-peroxide medium, an intermediate product of hydrolysis ([F₅Zr-OO-ZrF₅]⁴⁻ dimer) was detected. The dimer structure is confirmed by ¹⁹F and ⁹¹Zr NMR. In high fields (¹⁹F NMR frequency > 200 MHz), the fluorine exchange between ZrF₆²⁻ and F⁻ is slow in the ¹⁹F NMR scale and has a multisite character.     

Intramolecular hydrogen bonds C-H?N in bisheterocyclic compounds according to 1H and 13C NMR data

Data of ¹H and ¹³C NMR spectra show that in 2,2??-bipyridyl, 1-vinyl-2(2??-pyridyl)benzimidazole, 1-vinyl-3-vinylsulfanyl-5-(2-furyl)-1,2,4-triazole, and 1-vinyl-5-vinylsulfanyl-3-(2-furyl)-5-vinylthio-1,2,4-triazole exists a weak intramolecular hydrogen bond between the heterocyclic fragments. It causes a downfield shift of the bridging proton signal in the ¹H NMR spectrum by 0.6?C0.7 ppm and an increase in the corresponding direct coupling constant ¹³C-¹H by 1.5?C2.0 Hz. These variations in the spectral parameters can be efficiently used in the conformational analysis for establishing with the use of NMR method which conformers are predominantly populated in the heterocyclic compounds.     

The Synthesis and Biological Activities of N-(3-pyridylmethyl) N ′-(trans-2-thio-4-substitutedphenyl- 5,5-dimethyl-1,3,2-dioxaphosphinane-2-yl)thioureas

A series of novel title compounds were synthesized by the addition reaction of trans 2-isothiocyano-4-substitutedphenyl-5, 5-dimethyl-1,3,2-dioxaphosphinane 2-sulfide to 3-aminomethylpyridine or 2-chloro-5-amino methylpyridine. Their structures were confirmed by ¹H NMR, ³¹P NMR, IR, MS, and elemental analyses. Results of preliminary bioassay showed that all new compounds possess good fungicidal activity and insecticidal activity to some extent.     

COMPETITIVE NMR STUDY OF THE COMPLEXATION OF SOME ALKALINE EARTH AND TRANSITION METAL IONS WITH 12-CROWN-4, 15-CROWN-5 AND BENZO-15-CROWN-5 IN ACETONITRILE SOLUTION USING THE LITHIUM-7 NUCLEUS AS A PROBE

Abstract

⁷Lithium NMR measurements were used to determine the stoichiometry and stability of Li⁺ complexes with 12-crown-4, 15-crown-5 and benzo-15-crown-5 in acetonitrile solution. A competitive ⁷Li NMR technique was also employed to probe the complexation of Mg²⁺, Ca²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Cd²⁺ ions with the same crown ethers. In all cases, the stability of the resulting 1:1 complexes was found to decrease in the order 15-crown-5 > benzo-15-crown-5 > 12-crown-4. Ca²⁺ and Cd²⁺ ions formed the most stable complexes in the series.     

Synthese und Charakterisierung neuer Acetylenkomplexe des Mangans und Rheniums

The reaction of the photochemically-generated tetrahydrofuran complexes Cp′(CO)₂M(thf) (Cp′  η⁵-C₅H₅, η⁵-C₅H₄Me, η⁵-C₅Me₅; M  Mn, Re) with various alkynes R¹C₂R² (R¹, R²  H, Me, Ph) yields are acetylene complexes Cp′(CO)₂MR¹C₂R². These compounds were identified from their IR, ¹H NMR, ¹³C NMR and mas spectra.     

Synthesis of dimethyl 3-perfluoroalkyl-4-(3-oxo-2-triphenyl-phosphoranylidenbutanylidene)-pent-2-enedioate and its cyclization

The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroal-kynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (2) with acetylmethylenetriphenylphosphorane (1) at -5-0℃. Intramolecular elimination of Ph3PO took place when compound 5 was heated in aqueous methanol at 115-120℃ in sealed tube, yielding dimethyl 2-trifluoromethyl-4-methylisophthalate (6a) from 5a and methyl 5-acetyl-4-hydroxy-2-heptafluoropropanylbenzoate (6b) from 5b, respectively. The structures of compounds 5, 6a and 6b were confirmed by IR, MS, 1H NMR, 19F NMR and 13C NMR spectroscopy and elemental analyses. Rection mechanisms for the formation of compounds 5, 6a and 6b were proposed.     

Synthesis of Novel bis-Phosphonate Derivatives by Pudovik Reaction

Synthesis of novel bis-(3-methyl-5-nitro-2-oxo-2,3-dihydro-2λ ⁵benzo[1,3,2]oxazaphosphol-2yl)substituted aryl methanes was accomplished by Pudovik reaction. Addition of equimolar quantities of 2-methylamino-4-nitro phenol (1) and ethanol to PCl₃ afforded cyclic condensation product. On reaction with respective aldehydes followed by treatment with phosphorus(III) monochloride of 1, and on subsequent reaction at reflux temperature, this rearranged from P(III) to P(V) state. Their structures were determined by IR, ¹H NMR, ¹³C NMR, ³¹P NMR, and mass spectral data.