一种新型磷酰胺吗啉代寡鸟苷酸单体的合成及工艺优化

发展了一种以鸟苷为原料的新型磷酰胺吗啉代寡鸟苷酸单体的合成路线。在对碱基上氨基和核糖5’位羟基进行保护的基础上,将核糖环转变为吗啉环,得到保护的吗啉代鸟苷。在吗啉环上进行三苯甲基化反应,并利用Mitsunobu反应对嘌呤6-O位进行修饰;对脱保护后的羟基进行N,N-二甲基氨基磷酰化反应,合成得到目标产物。对Mitsunobu反应和磷酰化反应的条件进行了优化。在优化的条件下,新合成路线的总产率为14.1%。通过LC-MS、¹H NMR和³¹P NMR等技术手段对中间产物和目标产物进行了结构表征。     

Imidazolium ionic liquid as the background ultraviolet absorption reagent for determination of morpholinium cations by high performance liquid chromatography-indirect ultraviolet detection

A novel analytical method was developed for determining morpholinium cations lacking ultraviolet absorption groups.This determination was carried out by high performance liquid chromatographyindirect ultraviolet（HPLC-1UV） detection using imidazolium ionic liquid as background absorption reagents,and imidazolium ionic liquid aq.soln.-organic solvent as mobile phase by a reversed-phase C18 column.The background ultraviolet absorption reagents,imidazolium ionic liquids and organic solvents were investigated.The imidazolium ionic liquid in the mobile phase is not only the background ultraviolet absorption reagent for IUV,but also an active component to improve the separation of morpholinium cations.It was found that morpholinium cations could be adequately determined when0.5 mmol/L 1-ethyl-3-methylimidazolium tetrafluoroborate aq.soln./methanol（80：20,v/v） was used as mobile phase with an IUV detection wavelength of 210 nm.In this study,the baseline separation of Nmethyl,ethylmorpholinium cations（MEMo） and N-methyl.propylmorpholinium cations（MPMo） was successfully achieved in 8.5 min.The detection limits（S/N = 3） for MEMo and MPMo were 0.15 and0.29 mg/L,respectively.This simple and practical method has been successfully applied to the determination of two morpholinium ionic liquids synthesized by the chemistry laboratory.     

Synthesis,Crystal Structure and Biological Evaluation of 4-Chloro-2-(morpholine-4-carbonyl)phenyl-4′-methoxybenzoate as Molluscicidal Agent

The title compound 4-chloro-2-(morpholine-4-carbonyl)phenyl-4'-methoxybenzoate(C19H18ClNO5, Mr = 375.79), a 5-chlorosalicylic acid derivative incorporating morpholine moiety, was conveniently synthesized through two steps and crystallized in the monoclinic space group P21/c with a = 7.8501(10), b = 9.3149(12), c = 25.133(3), V = 1836.2(4)3, Z = 4, Dc = 1.359 Mg/m3, λ = 0.71073, μ(MoKα) = 0.237 mm-1, F(000) = 784, R = 0.0447 and wR = 0.1227 for 3982 independent reflections with I 2σ(I). The dihedral angles formed between 4-methoxybenzene and 5-chlorobenzene rings, the 5-chlorobenzene and morpholine, and 4-methoxybenzene and morpholine rings are 82.55(3), 72.56(5) and 47.68(0)° by X-ray analysis, respectively. Bioassay shows that the title compound has a good molluscidal effect.     

再生丝素/NMMO·H2O溶液的流变性能

使用N-甲基吗啉-N-氧化物的水合物(NMMO·H2O)作为再生丝素的溶剂.可以得到w=0.10～0.25的再生丝素/NMMO·H2O溶液.研究了再生丝素/NMMO·H2O溶液流变性能,讨论了剪切速率、温度和溶液中的再生丝素的含量对再生丝素/NMMO·H2O溶液流变性能的影响.     

4-(4-氨基苯基)-3-吗啉酮的合成

4-(4-氨基苯基)-3-吗啉酮是合成利伐沙班的一个重要中间体,以吗啉酮为原料,利用Buchwald-Hartwig偶联反应制得4-苯基-3-吗啉酮,再经硝化,还原三步反应制备4-(4-氨基苯基)-3-吗啉酮。     

2DNMR鉴定吗啉付产物的结构

本文用~H—NMR,反门控定量~(13)C—NMR,异核丁—分解2D、同核化学位移相关2D、异核化学位移相关2D等技术,鉴定了二种未见报道的吗啉付产物结构。     

三苄基锡吗啉二硫代氨基甲酸盐的合成、表征及晶体结构

利用三苄基氯化锡和吗啉二硫代氨基甲酸钠反应,合成了三苄基锡吗啉二硫代氨基甲酸盐。通过元素分析、红外光谱、核磁共振氢谱和质谱对其结构进行了表征。用X-射线单晶衍射测定了该化合物的晶体结构。化合物为三斜晶系,空间群P1,a=0.98417(16)nm,b=1.08163(19)nm,c=1.3788(2)nm,α=72.850(3)°,β=88.895(3)°,γ=64.231(3)°,Z=2,V=1.2528(4)nm³,D_x=1.469g·cm^-3,μ(MoKα)=1.204mm^-1,F(000)=564,R₁=0.0215,wR₂=0.0531。化合物中,锡原子呈五配位畸变三角双锥构型。     

[Zn(C_6H_(14)N_5O)Cl_3]的合成、表征和晶体结构的测定

本文合成了吗啉双胍合锌配合物。经分析鉴定,锌离子、吗啉双胍、氯离子组成比为1:1:3,分子式确定为[Zn(C_6H_(14)N_5O)Cl_3]。对该配合物的红外光谱、核磁共振氢谱、~(13)C、~(15)N谱进行了研究。获得了该配合物的单晶体,结构研究表明,该晶体属于三斜晶系,空间群为P1,晶胞参数:a=7.696(3)、b=7.773(2)、c=12。074(5)A;α=74.95(3),β=81.29(3),γ=66.89(3)度。晶胞中含有二个[Zn(C_6H_(14)N_5O)Cl_3]分子,锌与吗啉双胍呈单齿配位,每个锌离子除与吗啉双胍中N(3)原子配位外,还有三个氯离子参与配位成四面体构型.     

高性能丙烯酰吗啉基离子凝胶的制备及应用研究

随着柔性电子领域的发展,离子凝胶越来越受到关注。本文使用聚合物单体丙烯酰吗啉（ACMO）在离子液体1-乙基-3-甲基咪唑啉双（三氟甲基磺酰基）亚胺（EMIM TFSI）中进行一步光照聚合得到离子凝胶PAI。表征发现：PACMO与EMIM TFSI之间存在强氢键作用使离子凝胶透明度达93%,且具有良好的自修复性能。离子凝胶断裂伸长率为450%,断裂强度为1.9 MPa,对不同的基底材料都有高黏附能力。作为柔性应变传感器应用时,离子凝胶表现出高灵敏度,在长循环测试中稳定性高。不仅如此,废弃的离子凝胶还可以进行回收或重新铸型后循环使用,具有绿色无污染的特点。