甲基对硫磷-D6的合成

报道了一种合成甲基对硫磷-D₆的新方法。以三氯硫磷、氘代甲醇和对硝基苯酚为起始原料,经三次酯化反应合成了目标产物甲基对硫磷-D₆,总收率47.6%,其结构经¹H NMR、 ¹³C NMR、 ³¹P NMR和HR-MS(ESI)确证。     

有机-无机骨架杂化酸碱双功能高硅Y型沸石的制备和结构表征

以甲胺水溶液为改性剂, 高硅Y型沸石可在常温下吸附甲胺(MA)制备有机-无机杂化酸碱双功能高硅Y型沸石材料. X 射线粉末衍射(XRD), 固体²⁹Si魔角核磁共振(¹³C及²⁹Si MAS NMR)表征表明甲胺分子与高硅Y型沸石骨架相互作用导致沸石结构发生变化, 骨架上生成新的Si—N键及Si—OH. 以热重分析(TG/DTG), NH₃, CO₂程序升温脱附(NH₃-TPD和CO₂-TPD)研究杂化Y型沸石的酸碱性质及其经不同温度焙烧后的变化, 结果表明, 杂化后沸石的酸/碱量, 尤其是后者明显增大, 其原因是骨架上生成了新的Si—OH及Si—N键.     

Cd(Ⅱ)和ATP的结合位点的NMR研究

用NMR方法研究了金属镉离子在ATP(嘌呤三磷酸腺苷)上的配位点.测量了不同pH值时由于Cd²⁺的存在而引起的¹H,¹⁵N及³¹P的化学位移和³¹P－³¹P中的偶合常数的变化以及由ATP的存在所引起的¹¹³Cd的化学位移的变化.结果表明,在pH＞4.5的条件下,ATP主要以磷酸根和N₇同时对Cd²⁺配位;在pH值2.5～4.5的条件下,ATP主要以磷酸根和N₁同时对Cd²⁺配位,还存在少量的磷酸根和N₇同时配位的模式;而在酸性非常强的条件下(pH＜2.5),ATP不再与Cd²⁺相互作用。     

水热条件下Y型沸石的转晶行为

系统研究了以KOH为结构导向剂,Y型沸石（HY和NaY）在水热条件下转晶为MER型沸石的行为.MER型沸石是硅铝比（Si/Al）在2~3之间且具有四种尺寸8元环孔道（3.1Å×3.5Å,2.7Å×3.6Å,3.4Å×5.1Å,3.3Å×3.3Å）的硅铝沸石分子筛,在小分子催化以及分离方面具有重要的潜在应用.传统水热法合成高结晶度MER型沸石需要7~10 d,将Y型沸石置于KOH的溶液中,经水热处理可在2 d内生成高结晶度的MER型沸石,而水热处理具有等价摩尔组成的无定形硅铝凝胶则得不到高结晶度MER型沸石的纯相.HY沸石可在100和150℃发生转晶,而NaY则只能在150℃发生转晶.KOH/SiO₂比和H₂O/SiO₂比对Y型沸石的转晶行为有重大的影响,只有在最优KOH/SiO₂比和H₂O/SiO₂比条件下才能生成高结晶度的MER型沸石.该转晶合成法显著缩短了MER型沸石的合成周期,对缩短其它有重大工业应用价值的沸石分子筛的合成周期有重要的借鉴意义.     

席夫碱钼(Ⅵ)配合物的制备及催化大豆油环氧化

以水杨醛和邻氨基酚为起始原料, 合成了N-亚水杨醛基-2-氨基苯酚配体(H₂SAP); H₂SAP与乙酰丙酮钼的无水乙醇溶液反应, 制得席夫碱钼(Ⅵ)配合物MoO₂(SAP)(EtOH); 采用元素分析、红外光谱、紫外光谱、¹H NMR及热重分析对配合物进行了表征. 以MoO₂(SAP)(EtOH)为催化剂, 研究了其催化合成环氧大豆油的催化性能, 考察了氧源种类、反应温度、反应时间及溶剂/助剂等因素对环氧化反应的影响. 结果表明, 以65%(质量分数)叔丁基过氧化氢(65% TBHP)为氧源, 在80℃时反应4 h, 转化率和选择性分别为43.0%和67.2%, MoO₂(SAP)(EtOH)在催化体系中表现出强烈的助剂效应, 当加入强给电子配体咪唑时, 环氧产率显著降低. 同时对该配合物催化环氧化机理进行了初步探讨.     

介孔磷钨酸铯盐的液相组装及酸性研究

以磷钨酸(H₃PW₁₂O₄₀)和氯化铯(CsCl)为原料, 两亲型三嵌段共聚物F127为模板剂, 按不同的Cs/P比制备了一系列介孔磷钨酸铯盐(Cs_xH_3-xPW₁₂O₄₀, m-CsPW). 通过X射线粉末衍射(XRD)、 场发射扫描电子显微镜(FESEM)、 场发射透射电子显微镜(FETEM)、 N₂吸附-脱附测试和小角X射线散射(SAXS)等手段对所得样品进行了表征. 结果表明, 样品是由纳米微晶组装而成的晶态介孔材料. 以三甲基膦为探针分子, 通过³¹P魔角旋转固体核磁共振波谱(³¹P MAS NMR)测定了样品酸处理前后的酸密度和酸强度. 以5,7-二羟基-4-甲基香豆素的Pechmann缩合反应为模型反应, 考察了样品的酸性质与催化活性之间的关系.     

聚苯基磷酸间苯二酚酯的合成、表征及热性能

采用熔融聚合法, 以间苯二酚、 三氯氧磷和苯酚为原料, 通过两步合成, 制备了阻燃剂聚苯基磷酸间苯二酚酯(PRPP). 用红外光谱(FTIR)、 ¹H, ¹³C和³¹P核磁共振(NMR)、 凝胶色谱(GPC)及热重分析(TGA)等对聚合物的结构、 分子量、 热性能进行了表征. 结果表明, PRPP具有与液态商品间苯二酚双(二苯基)磷酸酯(RDP)相同的组成单元, 其数均分子量为3227, 分子量分布系数M_w/M_n=1.31, 聚合度n≈12; PRPP的起始分解温度与液态RDP相同, 但在高温下PRPP的热稳定性优于RDP, 其分解50%质量的温度提高了235 ℃, 在高温阶段表现出优良的成炭性能.     

四氢呋喃/水体系中以蒸气相传输法合成高硅FER沸石

以X射线衍射(XRD), 红外光谱(FT-IR), 扫描电镜(SEM), 低温氮吸附, ²⁹Si固体核磁共振(MAS NMR)等研究了含FER晶种的Na₂O-SiO₂-Al₂O₃干胶(SDG)在四氢呋喃(THF)/水(H₂O)混合蒸气相中的结晶行为, 同时研究了体系中THF分子和[SiO₄], [AlO₄]基团在结晶前后状态的变化. 结果表明, 在THF/H₂O混合蒸气中以蒸气相传输法(VPT)可合成结晶度较高、结构完美且孔道开放的FER沸石. ¹³C交叉极化固体核磁共振(CPMASNMR)和差热分析(TG-DTG-DTA)等研究证明THF分子作为模板剂, 位于FER笼内. FER晶种和水能促进FER沸石的结晶.     

杂多酸的固载化及其催化合成醋酸脂肪醇酯

本文研究了活性炭对磷钼钨杂多酸的固载化方法 ,结果发现使用蒸发法进行固载 ,当活性炭与磷钼钨杂多酸的质量比为 1∶0 75时 ,所得固载型杂多酸的催化效果最好。利用所制备的活性炭固载杂多酸型催化剂探讨了醋酸与各种一元脂肪醇的酯化反应 ,发现该催化剂对醋酸脂肪醇酯的合成均具有较好的催化效果 ,并且重复使用 4次 ,催化活性仍较高     

酸碱存在下水溶性铑膦配合物的NMR表征及氢甲酰化性能研究

31P(¹H)NMR和¹HNMR研究表明,当NaOH加入到水溶性铑膦配合物HRh(CO)·(TPPTS)₃[TPPTS:P(m-C₆H₄SO₃Na)₃]后,可观察到有少量的OTPPTS[OTPPTS:O=P(m-C₆H₄SO₃Na)₃]出现,但配合物的特征谱峰即使在高浓度的NaOH存在下也基本保持不变,表明NaOH对配合物分子结构的影响较小;当吡啶加入到HRh(CO)(TPPTS)₃中,³¹P(¹H)NMR谱图中出现游离配体TPPTS的³¹P谱峰及若干结构未知的新水溶性配合物的³¹P谱峰,表明吡啶分子将与配合物分子中的配体TPPTS发生配体交换反应.在HRh(CO)(TPPTS)₃中分别加入一定量的HCl,HNO₃,H₂SO₄和H₃PO₄等无机酸时,随着酸量的增加,配合物的³¹P物种含量逐渐下降,而OTPPTS量明显上升,直至配合物³¹P物种完全消失;高浓度乙酸对配合物结构的影响与上述无机酸类似.HRh(CO)(TPPTS)₃的1-己烯氢甲酰化催化反应结果表明,碱存在下可获得较高的正异构醛比值,但催化活性降低;酸存在下所得产物正异构醛比值相对较低且呈淡黄色.     

Aerobic selective oxidation of alcohols to aldehydes or ketones catalyzed by ionic liquid immobilized TEMPO under solvent-free conditions

A selective ionic-liquid immobilized TEMPO/CuCl catalyzed oxidation procedure of alcohols to the corresponding aldehydes and ketones with molecular oxygen under solvent-free conditions was developed. The catalyst was easily recovered and reused in the reaction. Correspondence: Yun-Yang Wei, School of Chemical Engineering, Nanjing University of Science and Technology, 210094 Nanjing, P.R. China.     

Green synthesis of 5-benzylidene rhodanine derivatives catalyzed by 1-butyl-3-methyl imidazolium hydroxide in water

A basic functionalized ionic liquid, 1-butyl-3-methyl imidazolium hydroxide ([bmim][OH]), catalyzed the Knoevenagel condensation of rhodanine with aromatic aldehydes. It proceeded smoothly in water to afford the 5-benzylidene rhodamine derivatives in high yields at room temperature. This new method offers several advantages, such as excellent yields, short reaction times, and simple procedure. The catalyst can be reused at least 5 times without significant loss of activity. Correspondence: Zu-liang Liu, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P.R. China.     

Simultaneous determination of polysaccharides and 21 nucleosides and amino acids in different tissues of Salvia miltiorrhiza from different areas by UV–visible spectrophotometry and UHPLC with triple quadrupole MS/MS

Salvia miltiorrhiza, a traditional Chinese medicine, is a widely used herbal medicine to treat cardiovascular and cerebrovascular diseases. In this study, ultraviolet (UV)–visible spectrophotometry and ultra‐high performance liquid chromatography with triple quadrupole tandem mass spectrometry analytical methods were used for rapid quantification of polysaccharides and 21 nucleosides and amino acids in S. miltiorrhiza to determine 17 samples of different tissues from different areas. Based on the total contents, hierarchical clustering analysis and principal components analysis were performed to classify these samples. The established methods were validated with good linearity, precision, repeatability, stability, and recovery. Chemical analysis revealed a higher content of total analytes in the sample of inflorescence from Nanjing (34.17 mg/g), sample of root and rhizome from Shaanxi (34.13 mg/g) and sample of stem and leaf from Nanjing (31.14 mg/g), respectively, indicating that root and rhizome from Shaanxi and the aerial parts from Nanjing exhibited the highest quality due to their highest content. In addition, contents of nucleosides and amino acids in the aerial parts (14.67 mg/g) were much higher than that in roots and rhizomes (9.17 mg/g). This study suggested that UV–visible spectrophotometry and ultra‐high performance liquid chromatography with triple quadrupole tandem mass spectrometry are effective techniques to analyze polysaccharides, nucleosides, and amino acids in plants, and they provided valuable information for the development and utilization value of the aerial parts of S. miltiorrhiza. This analysis would also provide useful information for the quality control of S. miltiorrhiza.     

Calculation of partial molar volume of components in supercritical ammonia synthesis system

The partial molar volumes of components in supercritical ammonia synthesis system are calculated in detail by the calculation formula of partial molar volume derived from the R-K equation of state under different conditions. The objectives are to comprehend phase behavior of components and to provide the theoretic explanation and guidance for probing novel processes of ammonia synthesis under supercritical conditions. The conditions of calculation are H₂/N₂ = 3, at a concentration of NH₃ in synthesis gas ranging from 2% to 15%, concentration of medium in supercritical ammonia synthesis system ranging from 20% to 50%, temperature ranging from 243 K to 699 K and pressure ranging from 0.1 MPa to 187 MPa. The results show that the ammonia synthesis system can reach supercritical state by adding a suitable supercritical medium and then controlling the reaction conditions. It is helpful for the supercritical ammonia synthesis that medium reaches supercritical state under the conditions of the corresponding total pressure and components near the normal temperature or near the critical temperature of medium or in the range of temperature of industrialized ammonia synthesis. __________ Translated from Journal of Chemical Industry and Engineering, 57(7):1503–1507 [译自: 化工学报]     

The absolute configuration of the glutarimide antibiotics streptimiodone and 9-methylstreptimidone.

Chemical and spectroscopic studies have established the absolute configuration of the glutarimide antibiotics streptimidone and 9-methylstreptimidone, which can now be represented as the (2R,5S,6E)-structures 14 and 15 , respectively.     

The Epimerization of Trimethylsilyl Ethers During Their Gas Chromatographic Analysis

We are grateful to the donors of the Petroleum Research Fund, administered by the American Chemical Society, to the National Science Foundation and to the Research Board of the University of Illinois for support of this research, to Dr. B. Willhalm for useful comments and to the Department of Organic Chemistry, University of Geneva, for its hospitality (1971/72).     

Chemical shifts for tritons in the ortho,meta and para positions of toluene as determined by tritium NMR spectroscopy

Chemical shifts for tritons in ortho, meta and para positions in toluene have been determined using a 64 MHz tritium NMR spectrometer. The order of shift is meta>para>ortho, whereas the calculated shift order for protons is meta>ortho>para.     

Concerning the chemical shifts of the ring protons of toluene as determined by 1H NMR spectroscopy of deuterated material

Chemical shifts of the ring protons are determined by ¹H NMR of 99% deuterated toluene. At low temperatures the deuterons relax rapidly, yielding sharp ¹H peaks for the ortho, meta and para protons. These are compared with shifts obtained by other methods.     

Chemical composition and antibacterial activity of methanolic extract and essential oil of Iranian Teucrium polium against some of phytobacteria

The antibacterial activity of essential oil and methanolic extract of Teucrium polium was determined against Pseudomonas aeruginosa, Pantoea agglomerans, Brenneria nigrifluens, Rhizobium radiobacter, Rhizobium vitis, Streptomyces scabies, Ralstonia solanacearum, Xanthomonas campestris and Pectobacterium cartovorum by disc diffusion method. Minimum inhibitory concentration and minimum bactericidal concentration were determined by using the serial dilution method. Chemical composition of essential oil and methanolic extract was determined by GC-MS and HPLC. α-Pinene (25.769%) and myrcene (12.507) were of the highest percentage in T. polium essential oil, and sinapic acid (15.553 mg/g) and eugenol (6.805 mg/g) were the major compounds in the methanolic extract. Our results indicate that both methanolic extract and essential oil did not show antibacterial activity against P. aeruginosa. Also the essential oil did not show antibacterial activity against P. cartovorum. In general, both methanolic extract and essential oil showed the same antibacterial activity against R. solanacearum, P. agglomerans, B. nigrifluens and S. scabies.     

Sesquiterpenoids and Their Glycosides from Gynura procumbens

Chemical investigation of the MeOH extract of the leaves of Gynura procumbens (Lour .) Merr . afforded one new sesquiterpenoid, muurol‐4‐ene‐1β,3β,10β‐triol ( 1 ), and two sesquiterpene glycosides, muurol‐4‐ene‐1β,3β,10β‐triol 3‐O‐β‐D ‐glucopyranoside ( 2 ) and muurol‐4‐ene‐1β,3β,15‐triol 3‐O‐β‐D ‐glucopyranoside ( 3 ), together with three known sesquiterpenoids. Their structures were elucidated on the basis of spectroscopic analyses and chemical methods.