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.

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.

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.

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.

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。

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。

水合物抑制剂的合成及在超深水钻井液中的应用

天然气水合物的生成危及钻采作业的安全进行,研发性能优异的动力学抑制剂(KHI)与热力学抑制剂复配对抑制超深水条件水合物生成具有重要意义。选用4-丙烯酰吗啉与N-乙烯基吡咯烷酮共聚,合成不同单体配比动力学抑制剂ACN,采用单因素法优化合成条件,采用红外、扫描电镜、凝胶渗透色谱仪等分析产品;采用甲烷水合物模拟测试法(MHS)、四氢呋喃抑制性能评价法(THF)评价抑制性能;优选最佳ACN产品及加量并与其它KHI产品对比,复配适用于超2000 m窄密度窗口钻井液抑制剂,并配制钻井液。研究发现以1%的AIBN为引发剂,反应温度65℃,反应时间6 h为其最佳合成条件,确定2%ACN(4∶6)抑制效果最佳;确定该抑制剂复配方案为2%ACN+1%KHI-1+35%乙二醇+5%NaCl,该抑制剂密度1.078 g/cm^(3),THF法−25℃测其初始结晶时间为32 min;钻井液密度为1.150 g/cm^(3),高温高压滤失量小于17 mL,滚动回收率大于82%,满足该研究钻井液相关性能要求。

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。

以吗啉与环氧乙烷为原料的无催化剂连续快速合成吗啉乙醇工艺研究

针对以吗啉和环氧乙烷为原料合成吗啉乙醇的反应路线收率不高、反应时间长、安全性不好和需使用催化剂的问题,在以SIMM-V2微混合器和不锈钢管组成的微通道反应器中,进行了连续快速制备吗啉乙醇的工艺研究,考察了反应温度、停留时间、体系压力、物料配比和流量等因素对产物收率的影响。结果表明:利用该反应器,在无催化剂条件下和更短的反应时间内可获得与釜式反应器相当的收率;产物收率随着反应温度、停留时间、环氧乙烷配比的增加均呈现先升高再降低趋势,且相互之间会有影响;存在一个较宽泛的反应条件操作窗口,即在给定某一个条件时,可以通过调节其他条件获得相同的产物收率。在典型的反应条件下,如温度为150℃、吗啉与环氧乙烷摩尔比为1∶1.08、停留时间为3 min、总流量为1 mL min、体系压力为2.5 MPa时,吗啉转化率可达99.55%,吗啉乙醇的选择性为97.1%,远高于釜式反应的结果。

超高效液相色谱-串联质谱法同时检测废水中吗啉和吡啶的含量

建立了超高效液相色谱-串联质谱法同时测定头孢克洛废水中吗啉和吡啶的含量。采用C18色谱柱(4.6 mm×100 mm,2.6μm),以5 mmol/L的乙酸铵-甲酸水溶液(A)-乙腈(B)为流动相进行等度洗脱,流速0.6 mL/min,柱温30℃,进样量5μL,定量离子对分别为吗啉88/70.2、吡啶79.9/53,检测模式为多重反应监测(MRM)。该方法简便、准确、灵敏度高,能够同时准确测定吗啉和吡啶的含量。

柱前衍生-高效液相色谱法测定冰乙酸中微量乙酸酐

建立柱前衍生-高效液相色谱(HPLC)联合紫外检测分析方法测定冰乙酸中微量乙酸酐的含量。样品采用吗啡啉为柱前衍生剂,色谱柱为Atlantis T3(250 mm×4.6 mm, 5μm),以磷酸水溶液(pH 3.0)-甲醇(体积比为95∶5)为流动相,流量为1.0 mL/min,柱温为30℃,检测波长为210 nm。乙酸酐的质量浓度在2.60~25.97μg/mL范围内与色谱峰面积线性关系良好,相关系数为0.999 9,检出限为0.8μg/mL,定量限为3μg/mL。平均样品加标回收率为92.8%~99.2%,测定结果的相对标准偏差为0.9%~2.3%(n=6)。该方法可用于冰乙酸中微量乙酸酐的含量测定。

气相色谱法测定3-氟-4-吗啉基苯胺中吗啉的含量

采用气相色谱法测定3-氟-4-吗啉基苯胺中吗啉的含量。具体方法:色谱柱:以5%苯基,95%二甲基聚硅氧烷为固定相的毛细管柱;载气:氦气;流速:2 mL/min;柱温条件:起始柱温40℃,维持时间2 min,以11℃/min速率升温至120℃,以33℃/min速率升温至250℃,维持3 min;进样口温度:200℃;FID检测器温度:240℃;分流比:10∶1;进样量:1μL。经方法学验证,方法专属性强,准确度及灵敏度较高,可用于3-氟-4-吗啉基苯胺中吗啉的含量测定。

丹皮酚吗啉杂合物的合成及抗血小板聚集活性

以丹皮酚为起始原料,在碱性条件下丹皮酚的2-位酚羟基与二溴烷烃经Williamson反应得到中间体丹皮酚溴代烷基醚2a~2e,化合物2a~2e与吗啉经N-烷基化反应得到丹皮酚吗啉杂合物3a~3e。目标化合物3a~3e经过核磁共振氢谱(1H NMR)、红外(IR)和高分辨质谱(HRMS)表征。体外抗血小板聚集活性测试结果表明,所得目标化合物3a~3e对二磷酸腺苷(ADP)所诱导的血小板聚集均具有较强的抑制活性,优于阳性对照药阿司匹林。

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.