Asymmetric Synthesis and Crystal Structure of a Bioactive Morpholine Derivative

A novel morpholine derivative was synthesized by Michael addition/internal nucleophilic substitution of 4-（L）-menthyloxy（1R,2S,5R）-butenolide with phenyl-glyalcohol under mild condition, and its structure was determined by X-ray diffraction. The target compound belongs to orthorhombic, space group P212121 with a = 5.7729（7）, b = 11.5032（14）, c = 25.161（3）A, Mr = 319.35, Z = 4, V = 1670.8（4）A^3, Dc = 1.270 g/cm3, μ（MoKα） = 0.094 mm^-1, F（000） = 680, Flack = 0.01（2）, R = 0.0398 and wR = 0.0914.

An ionic 2D inorganic-organic hybrid of tris[((1H-tetrazol-5-yl)methyl)morpholine] dodecatungstophosphate(Ⅴ) pentahydrate:Synthesis X-ray crystal structure and spectroscopic characterizations

A unique ionic hybrid material[C_6H_(12)N_5O]_3[(PO_4)W__(12)O_(36)]·5H_2O has been synthesized from the reaction of((1H-tetrazole-5- yl)methyl)morpholine andα-H_3[(PO_4)W_(12)O_(36)]·21H_2O.It has successfully been characterized by elemental analysis,IR and ~1H NMR spectroscopies,TGA and single-crystal X-ray diffraction method.The title compound is constructed from the three [C_6H_(12)N_5O]^+ cations andα-Keggin[(PO_4)W_(12)O_(36)]^(3-) polyoxoanion.The most remarkable structural feature of this hybrid can...

Synthesis, Crystal Structure and Biological Activities of 2-(4-Fluorophenyl)-2-oxo-1-(1H-1,2,4-triazol-1-yl) ethyl morpholine-4-carbodithioate

The title compound, 2-（ 4-fluorophenyl ） -2-oxo-1-（ 1H-1, 2,4-triazol-1-yl ） ethyl morpholine-4-carbodithioate, was synthesized and its structure was confirmed by means of IR, MS, 1 H NMR and elemental analysis. The single crystal structure of the title compound was determined by X-ray diffraction. The preliminary biological test showed that the synthesized compound possesses some biological activities.

Solid-phase Synthesis of-Haloaldehydes from Polymer-supported 4-(Phenylseleno)morpholine

Polystyrene-supported 4-(phenylseleno)morpholine was synthesized and could be used as an efficient ?selenenylating agent for saturated aldehydes. ?Haloaldehydes were prepared by reaction of polystyrene-supported ?selenoaldehydes with bromine or sulfuryl chloride in good yield and high purity.

Solid-phase Synthesis of Unsaturated β-Dicarbonyl Compounds from Polymer-supported 4-(Phenylseleno)morpholine

The solid-phase synthesis of unsaturated ?dicarbonyl compounds has been reported.

Dissociative Photoionization of Heterocyclic Molecule-Morpholine under VUV Synchrotron Radiation

The radiation damage of biomolecules, in particular with aliphatic compound, has been extensively studied. Morpholine is a typical six-membered aliphatic heterocyclic compound. In the present work, photoionization and dissociation of the morpholine monomer and subsequent fragmentations have been investigated by synchrotron vacuum ultraviolet photoionization mass spectrometry and theoretical calculations. The vertical ionization energy of morpholine monomer is 8.37±0.05 eV, which agrees reasonably well with a theoretical value 8.41 eV of morpholine. Experimentally observed fragmentation of morpholine (m/z=87 amu) gives rise to m/z=86 amu, m/z=57 amu, and m/z=29 amu. Based on experimental and theoretical results, it is found that the m/z=86 amu is produced by losing H atom, the m/z=57 amu is formed by the elimination of CH2O with a ring-opening process, the m/z=29 amu is generated by further dissociation of the fragment m/z=57 amu (C3H7N)+ by the elimination of C2H4. This finding would provide valuable insight into the photo-damage of aliphatic compounds, which may be related to living cells and other biological system.

Tribological Behaviors of S,B-Containing Morpholine Derivatives as Additives in Rapeseed Oil

Two novel ashless and non-phosphorus S, B-containing morpholine derivatives, MBOC and MBOD, were prepared and their tribological behaviors in rapeseed oil （RSO） were evaluated using a four-ball tester. Thermal degradation tests were conducted to identify their thermal stabilities using a thermo-gravimetric analyzer. The worn surfaces of the steel balls were investigated by scanning electron microscopy （SEM）. The results indicated that the additives possessed high thermal stabilities and good load-carrying capacities. Moreover, they both had good anti-wear and friction reducing property at a relatively high concentration （1.5 m%） and under all test loads. The results of XPS analyses illustrated that the prepared compounds as additives in RSO could form a protective film containing inorganic sulfide, sulfate, oxidized compounds and organic nitrogen-containing compounds on the metal surface during the sliding process.

Studies of Oxide Layers Grown at 260°C on A106 B Carbon Steel in Aqueous Medium with Ethanolamine or Morpholine

The water chemistry of the secondary coolant in the majority of Nuclear Power Plants is controlled by AVT (All Volatile Treatment), wherein volatile amines are used to maintain the alkaline pH required for minimizing the corrosion of structural materials which one of them is Carbon Steel. In this treatment, ammonia, morpholine and ethanolamine are commonly used as conditioning reagents. In this context, experiments were carried out by exposing carbon steel A106 B samples in a simulated secondary coolant in order to study the nature of the oxide films. The tests were performed in a static autoclave at 260°C using two media: I) hydrazine + morpholine and II) hydrazine + ethanolamine during different exposure periods up to ≈1020 h. The oxide film characterization was mainly studied using Scanning Electron Microscopy and X-ray diffraction. A chemical descaling procedure was used to obtain the material weight loss (W) of samples, the adherent and released oxide. The XRD analyses, for all exposures studied, showed that magnetite was the corrosion product formed in the films grown in both media. The material weight loss, after descaling, could be fitted by a law of the type W = ktn, up to 1020 h of exposure tested, resulting in n = 0.42, k = 6.24 for films grown in medium I) and n = 0.39, k = 6.08 for films grown in medium II) respectively (W is in mg/dm2 and t in h). The higher corrosion product release measured in the medium with morpholine could be important in power plant operation.

Studies on the Oxazaborolidine-catalyzed Enantioselective Reduction of 3-Morpholin-4-yl-1-phenyl-1-propanone with Density Functional Theory

Density functional theory (DFT) has been applied to study the enantioselective reduction of 3-morpholin-4-yl-1-phenyl-1-propanone with borane catalyzed by (S)-4-benzyl-5,5- diphenyl-1,3,2-oxazaborolidine at the B3LYP/6-31G* level. All molecular species involved in the four reaction steps have been fully optimized and the structural parameters are provided, and the micro process of reaction was also investigated. The catalyst-alkoxyborane adduct formed in step III exhibits a B-O-B-N tetra-atomic ring. Reaction coordination calculations show that BH3 can react with 3-morpholin-4-yl-1-phenyl-1-propanone spontaneously, resulting in the need of 2 mol BH3 in the reaction.

NON-ISOTHERMAL KINETICS OF THERMAL DECOMPOSITION OF A NOVEL ANTITUMOR AGENT 4-{5-[3,4-DIMETHYL-5-(3,4,5-TRIMETHOXYPHENYL)THIOPHEN-2-YL]-2-METHOXYPHENYL}MORPHOLINE

The thermal decomposition of a new antitumor agent,4-{5-[3,4-dimethyl-5-(3,4,5-trimethoxyphenyl)thiophen-2-yl]-2-methoxyphenyl}morpholine was studied by Differential Scanning Calorimetry(DSC)and Thermogravimetry(TG)/Derivative Thermogravimetry(DTG)methods at a flow rate of nitrogen gas of 120 mL/min,The kinetic parameters were obtained from the analysis of the corresponding curves by Kissinger's method,Ozawa's method and the integral method,The results indicate that the apparent activation energy and pre-exponential constants of the decomposition reaction are 106.67 kJ/mol and 10^6.19s^(-1),respectively.

Synthesis, Characterization, Spectroscopic Properties of 2-(4-Dimethylaminophenyl)-5-fluoro-6-(morpholin-4-yl)-1H-benzimidazole and its Interaction with Calf Thymus DNA

Dimethylaminophenyl)-5-fluoro-6-(morpholin-4-yl)-1H-benzimidazole(1) has been synthesized and characterized by H-NMR, MS and elemental analysis. UV-Vis spectra of the 1 aqueous solutions at different pH values reveal that compound 1 can combine three protons. Its three protonation constants are determined by spectrophotometry and calculated by non-linear least squares. The results of steady-state fluorescence measurements indicate that a special interaction occurs between compound 1 and calf thymus DNA, of which the binding constant, Kb, is (2.30 ± 0.10)×l04 L/mol. Compound 1 in the concentration range of 10-8 to 1.2×10-6 mol/L could be used for quantitative determination of DNA.

Utilizing morpholine for purely organic room temperature phosphors

In this article,morpholine,a non-conjugated heterocycle,is embedded intoπsystem to construct single-component organic room temperature phosphorescence(RTP)luminogens.The effect of morpholine on intermolecular interaction,crystal packing modes,and RTP performance is investigated systematically.The experimental and theoretical calculation results illustrate the versatility of morpholine in promoting the n-π*transition and intensifying the intermolecular interactions,which not only enhances the generation of triplet excitons,but also suppresses the nonradiative decay of triplet excitons.Impressively,TMPh containing three morpholine units shows an ultralong lifetime of 1.03 s and a visible afterglow up to 10 s.The unique dual delayed emission and long afterglow property allow potential application of morpholine derivatives in data encryption,and the time-dependent color change of afterglow emission is realized after removing the excitation source,providing a high-level data security.This article provides a new perspective for the design of purely organic RTP system without utilization of metal,or even any heavy atoms.

An Unexpected Discovery in the Willgerodt-Kindler Reaction of Acetophenone--the Formation of the 4-（Benzoylthiocarbonyl）morpholine

The Willgerodt-Kindler reaction of acetophenone was studied. Apart from the normal product 4-（benzylthiocarbonyl）morpholine, another product 4-（benzoylthiocarbonyl）morpholine was obtained unexpectedly. The structure of the latter was confirmed by 1R, IH NMR spectra and X-ray diffraction analysis. The mechanism of the reaction was discussed.

均匀沉淀法制备Al_(2)O_(3)负载的铜基催化剂及其催化合成吗啉的研究

以尿素为沉淀剂,通过均匀沉淀法制备了Al_(2)O_(3)负载的铜基催化剂。利用XRD、SEM和H_(2)-TPR等手段对催化剂进行表征,并考察活性组分铜镍摩尔比、载体质量分数和尿素摩尔分数对其催化合成吗啉的影响。结果表明,铜镍摩尔比为3∶1、载体质量占催化剂质量的40%、尿素物质的量占金属硝酸盐物质的量的5.25倍时,所制备催化剂具有最高的催化性能。相比于商品催化剂,均匀沉淀法制备的催化剂具有更低的还原温度、更小的平均粒径、疏松的表面结构和优良的稳定性。

Morpholine Catalyzed One-pot Multicomponent Synthesis of Compounds Containing Chromene Core in Water

A series of dihydropyrano[c]chromene was obtained via condensation of aldehyde, malononitrile and 4-hydroxycoumarin in water catalyzed by morpholine, as a one-pot reaction. The significance of our findings relates to reducing the use of organic solvents, potentially toxic and hazardous materials, as well as its simplicity, good yields, mild conditions, and lower costs.

离子色谱法测定别嘌醇中吗啉残留

目的 建立了别嘌醇中痕量吗啉测定的离子色谱方法。方法 采用IonPac CS12(250mm×4.0 mm)阳离子色谱柱;以8~40 mmol·L^(-1)甲烷磺酸溶液洗脱;流速为1.0 mL·min^(-1);进样量为500μL;柱温为30℃;抑制器为CERS 300(4 mm);抑制电流为161 mA;外标法定量。结果 该方法下,空白溶液和别嘌醇均不干扰吗啉的检测。吗啉在0.001 487~0.014 87μg·mL^(-1)与峰面积呈现良好的线性关系(r=0.9991),加样回收率(n=3)在89.99%~118.00%,定量限为1.487 ng·mL^(-1)。室温条件下,吗啉对照品溶液和加标样品溶液分别在46.5 h、38 h内稳定性良好。结论 建立的方法灵敏、准确、专属性强、耐用性好,可用于别嘌醇中痕量吗啉的检测。

察尔汗盐湖卤水中氯化钠浮选剂十二烷基吗啉在氮化碳光催化剂作用下的降解特性

针对察尔汗盐湖氯化钠浮选尾卤中残留的十二烷基吗啉(DMP)难以有效去除的问题,采用多孔状石墨相氮化碳(mpg-C_(3)N_(4))为光催化剂,系统考察盐湖卤水中典型的高浓度无机盐NaCl、KCl和MgCl_(2)等存在条件下对mpg-C_(3)N_(4)光催化降解DMP浮选剂的影响规律与特性。结果表明,卤水中无机盐对降解过程有显著影响,其中高浓度的NaCl对mpg-C_(3)N_(4)的光催化降解特性有促进作用,当NaCl为80 g/L时,DMP的降解速率相对于无NaCl时提升幅度达到20.59%。KCl在低浓度时也能部分促进降解,其中当KCl为25.5 g/L时,DMP的降解速率相对于无KCl时提升幅度为3.71%。但是,体系中存在的MgCl_(2)对mpg-C_(3)N_(4)光催化降解DMP有较大的抑制作用,当MgCl_(2)为65.2 g/L时,DMP的降解速率相对于无MgCl_(2)时抑制率达到44.90%。最后,通过自由基淬灭实验确定光催化降解DMP的主要活性物种为·O-2,其次为·OH。通过对光催化降解前后的产物进行深入对比分析与表征,结果显示经光催化降解后十二烷基吗啉分子中主要基团特征峰几乎完全消失,这表明DMP分子被有效破坏和降解,中间产物及小分子产物大部分也被有效分解矿化。

双模板剂调控SAPO-34对1-丁烯催化裂解的影响

利用水热合成法,通过调控模板剂吗啡啉和四乙基氢氧化铵物质的量比[n(MOR)∶n(TEAOH)]合成出不同SAPO-34分子筛。采用XRD、SEM、NH_(3)-TPD等测试方法对合成样品进行表征,并考察其在1-丁烯催化裂解制丙烯反应中的催化性能。结果表明,双模板剂相比单模板剂制得的SAPO-34分子筛具有不同的酸性和颗粒尺寸,适宜的[n(MOR)∶n(TEAOH)]可以协同SAPO-34分子筛有更弱的酸强度和B酸酸位,从而抑制裂解过程中氢转移反应的发生。当n(MOR)∶n(TEAOH)=2.0∶0.5时可以最大程度的提升丙烯产率和选择性,在1-丁烯催化裂解制丙烯中具有最高的丙烯产率和丙烯选择性,分别为37.03%和45.78%,可以有效应用于1-丁烯催化裂解反应。

Morpholine triflate promoted one-pot,four-component synthesis of dihydropyrano[2,3-c]pyrazoles

A one-pot, four-component reaction of ethyl acetoacetate, hydrazine hydrate, aldehydes, and malononitrile was discussed using Lewis acid catalyst morpholine triflate （MorT） to afford a series of dihydropyrano[2,3-c]pyrazoles, which were generally catalyzed by organic alkalis. Moderate to excellent yields, no chromatographic purification, and evasion of environmentally hazardous solvents in the reaction process make this protocol very useful for academia and industry.

Synthesis, Spectroscopic and Electrochemical Investigations of Two vic-Dioximes and Their Mononuclear Ni（Ⅱ）, Cu（Ⅱ） and Co（Ⅱ） Metal Complexes Containing Morpholine Group

Two vic-dioxime ligands （LxH2） containing morpholine group have been synthesized from 4-[2-（dimethylaminoethyl）] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at -15 ℃. Reaction of two vic-dioxime ligands with MCl2·nH2O （M： Ni, Cu or Co and n=2 or 6） salts in 1 ： 2 molar ratio afforded metal complexes of type [M（LxH）2] or [M（LxH）2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities （Am） in DMF （dimethyl formamide） at 10^-3 mol·L^-1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, ^1H NMR and ^13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.