新型取代吲哚-3-甲醇类衍生物的合成

以取代吲哚为原料,经维尔斯迈尔-哈克反应制得取代吲哚-3-甲醛,再通过DMSO/NaOH体系制得N-取代吲哚-3-甲醛(3a~3g);3a~3g经Na BH4还原合成了7个未见文献报道的取代吲哚-3-甲醇类衍生物(4a~4g),其结构经~1H NMR,~(13)C NMR和MS表征。     

Analysis of Carbamates as Fluorescent 1-Dimethylamino-naphthalene-5-sulfonate Esters

The fluorigenic labelling of several N-methyl carbamates is carried out using 1-dimethyl-aminonaphthalene-5-sulfonyl chloride (dansyl chloride). Prior to chromatography the carbamates are reacted in aqueous solution with the dansyl chloride. The derivative is extracted from the solution with n-hexane and subsequently spotted on a thin-layer plate for chromatography. For each N-methyl carbamate, two highly fluorescent spots are obtained. One is common to all N-methyl carbamates studied, whereas the other is characteristic of each individual carbamate. N.m.r. and infrared spectroscopic data indicate that the common spot is the methylamine derivative, and the second spot is the derivative from the phenyl moiety of each carbamate. The sensitivity of the method is less than one nanogram and has been successfully applied to the analysis of natural water samples.     

Preparation of Substituted Vinylsilanes from Cinnamyl Carbamates

Reaction of N,N-diethyl cinnamyl carbamate with TBDMSC1 yields the mono-silylated carbamate which, on treatment with butyllithium, reacts with various electrophiles to give the corresponding disubstituted carbamates.     

新型SiBNC陶瓷先驱体——聚硼硅氮烷的合成与表征

以甲基氢二氯硅烷、三氯化硼、六甲基二硅氮烷为起始原料, 采用共缩合的方法合成了一种新型的可溶可熔的SiBNC陶瓷先驱体--聚硼硅氮烷(PBSZ). 该法合成工艺简单, 且合成收率约为91% (w%). 采用元素分析、傅立叶红外光谱、核磁共振波谱、X射线光电子能谱、动态热机械分析、热重分析等对PBSZ的组成、结构和性能进行了表征. 结果表明, 先驱体的主要骨架为-Si-N-B-, 其中, B, N以硼氮六环形式存在, 而C则以Si-CH₃形式存在. 该先驱体熔点为69 ℃, 数均分子量为10802, 分子量分散系数为1.50. 此外, 所合成的先驱体具有优良的成型性, 在80 ℃的N₂气氛中可纺丝得到15～20 μm的有机纤维, 1000 ℃时相应陶瓷产率约为63% (w%).     

层状前体镁铁水滑石及磁性材料的制备及表征

本文提出了利用镁铁水滑石作为磁性材料前体再经高温焙烧制备尖晶石型铁氧体的思路,深入研究了水滑石的制备工艺及结构性能并初步探讨了其焙烧后的磁学性能。由共沉淀法合成了Mg/Fe摩尔比为2,3,4,6的镁铁水滑石,XRD结果表明随镁铁比增大、晶化温度的升高及晶化时间的延长,水滑石的晶体结构规整性增强;热重-差热结果显示镁铁水滑石的分解有两个过程,随着镁铁比增大,水滑石的热稳定性提高。高温焙烧后的镁铁水滑石具有较好的磁学性能。     

1-Norbornyllithium as a Precursor for the Synthesis of Novel Organic 1-Bicyclo[2.2.1]Heptane Derivatives and for the Improved Preparation of 1-Chloro-Bicyclo[2.2.2]octane

An improved strategy for synthesis of 1-chloro-bicyclo[2.2.2]octane is described in which the key compounds 1-norborny substituted ethyl formate(3) or 1-norbornylcarbaldehyde (7) were prepared from 1-norbornyllithium(1). The latter appeared as a useful precursor for the synthesis of various organic bridgehead substituted derivatives.     

Preparation of TiO2 Sol Using TiCl4 as a Precursor

A titanium dioxide sol with narrow particle size distribution was synthesized using TiCl₄ as the starting material. The sol was prepared by a process where HCl was added to a gel of hydrated titanium oxide to dissolve it. The resulting aqueous titanic acid solution was heated to form titanium dioxide sol. The effects of preparation parameters were investigated. TiCl₄ was slowly added to distilled water at 5°C. Aqueous solution of sodium hydroxide was added to adjust the pH of the system to 8–12. After aging for a period of time, the peptized sol was filtered and sufficiently washed. The filtered cake was repulped in water. Hydrochloric acid was slowly added to the solution with stirring. After condensation reaction and crystallization, a transparent sol with suspended TiO₂ was formed. XRD results show that the crystalline phase was anatase. The suspended TiO₂ particles were rhombus primary particles with the major axis ca. 20 nm and the minor axis ca. 5 nm. The TiO₂ particles prepared at pH 8 had the largest surface area of 141 cm³/g and it was microporous. The compositions of the solution which yielded the smallest suspended TiO₂ particles were TiO₂:HCl (35% HCl) = 1:1 (molar ratio), concentration of TiO₂ = 10%. Hydroxypropyl cellulose with viscosity of 150–400 cps was added as a dispersant. The sol was excellent in dispersibility and long-term stability. Transparent thin films could be obtained through dip-coating glass substrate in the sol. The dip-coating on glass can be less than three times to have one monolayer TiO₂. The transparent TiO₂ thin film had strong hydrophilicity after being illuminated by UV light.     

含硅氨基甲酸酯衍生物的合成,结构及生物活性

通过１－甲硫基亚乙基氨－甲基氨基甲酸酯与二氯亚砜反应，制得一系列新的含硅氨基甲酸酯衍生物．化合物结构经１￣ＨＮＭＲ、元素分析ＩＲ和ＭＳ确证，测定了化合物３ａ的晶体结构．生物测定结果表明，该类化合物对蚊子、粘虫、玉米螟等多种害虫具有优良的杀虫活性，且与母体灭多威相比，在哺乳动物安全性方面有显著提高．     

以油胺-硒化氢复合物为前体的脂溶性量子点的制备

报道了一种以油胺-硒化氢复合物为前体的脂溶性CdSe量子点的制备方法. 将新制备的H2Se气体通入到油胺中, 得到油胺-硒化氢复合物, 以此复合物作为前体, 采用溶剂热合成法制备了CdSe量子点, 并采用荧光光谱、电镜以及X射线衍射对其进行了表征. 结果表明, CdSe量子点为立方晶型, 荧光半峰宽较窄(25~40 nm), 荧光量子产率可达23%, 并且荧光发射光谱从480到610 nm连续可调. 该方法无须使用三烷基膦, 是一种价廉环保的量子点制备方法.     

From C1 to C2: TMSCF3 as a Precursor for Pentafluoroethylation

A highly efficient copper‐mediated aromatic pentafluoroethylation method using TMSCF₃ as the sole fluoroalkyl source is described. The reaction proceeds by a key C₁ to C₂ process, that is, the generation of CuCF₃ from TMSCF₃, followed by a subsequent spontaneous transformation into CuC₂F₅. Various aryl iodides were pentafluoroethylated with the TMSCF₃‐derived CuC₂F₅. This method represents the first practical and efficient method for pentafluoroethylation of aryl iodides using commercially available TMSCF₃ as a pentafluoroethyl precursor.     

吲哚-3-醛-邻硝基苯基半卡巴腙的阴离子识别

利用吲哚~-3~-醛和邻硝基苯基半卡巴肼设计合成了新型含内氢键的阴离子识别受体吲哚~-3~-醛~-邻硝基苯基半卡巴腙.利用核磁共振波谱、质谱和元素分析等手段对该受体进行了表征,利用荧光光谱滴定和核磁共振波谱滴定研究了该受体对Ac O~-,F~-,H_2PO~-_4,Cl~-,Br~-,I~-,HSO~-_4等阴离子的识别性能.结果表明,该受体与Ac O~-,F~-,H_2PO~-_4,Cl~-,Br~-,I~-,HSO~-_4的结合常数和结合比分别是6.98,1∶2;6.85,1∶2;5.40,1∶2;13.51,1∶2;6.34,1∶1;5.40,1∶1;2.88,1∶1.该受体由于具有内氢键,与具有适当体积、碱度的Cl~-很匹配,对Cl~-具有很强的结合能力和很高的选择性.     

Novel Copolymers of Styrene. 9. Methyl and Methoxy Ring-Substituted 2-Cyano-3-phenyl 2-propenamides

Novel electrophilic trisubstituted ethylene monomers, methyl and methoxy ring- substituted 2-cyano-3-phenyl-2-propenamides, RPhCH=C(CN)CONH₂, where R is 2,3-dimethyl, 2,4-dimethyl, 2,5-dimethyl, 2-(3-methoxyphenoxy), 2-(4-methoxyphenoxy), 3-(4-methoxyphenoxy), 4-(4-methylphenoxy), 2,3-methylenedioxy were prepared and copolymerized with styrene. The monomers were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (5.8–33.8 wt%), which then decomposed in the 500–800°C range.     

甲氧基萘类荧光单体的合成及其光谱研究

以4-溴-1,8-萘二甲酸酐为原料,合成了2种水溶性甲氧基萘类荧光单体,测定了它们的激发光谱和发射光谱.运用密度泛函(DFT)及含时密度泛函(TDDFT)方法预测的荧光发射光谱与实验结果符合得较好.     

A High Yield Method for Preparation of Potential Pesticides : Syntheses of 1-Alkoxy-Ethyl-N N-dialkyl Carbamates

A number of 1-alkoxy-ethyl-N, N-dialkyl carbamates have been prepared by reaction of the corresponding 1-chloro-ethyl-N, N-dialkyl carbamates with alcohols.     

1-Protected 5-amido 1,2,3-triazoles via ruthenium-catalyzed [3+2] cycloaddition of azides and ynamides

Ynamides react with various azides in the ruthenium-catalyzed Huisgen [3+2] cycloaddition reaction. This ruthenium-catalyzed azide-ynamide cycloaddition reaction yields 1-protected 5-amido 1,2,3-triazoles.     

Unexpected Reaction of Oximinoacetoacetate with Amines: A Novel Synthesis of Carbamates

The synthesis of alkyl carbamates by a solvent-free reaction of oximinoacetoacetate and amine at 130°C is reported. A preliminary mechanism to this unexpected reaction is also given.     

一种胺氧化羰化制氨基甲酸酯新催化剂体系

异氰酸酯是重要的有机反应中间体 ,可用于合成聚异氰酯、聚氨酯、聚脲及用于高聚物的粘合剂、杀虫剂、除草剂等[1 ] .一些异氰酸酯在军事上也有重要用途 .目前 ,工业异氰酸酯的生产方法仍为光气法 :ＲＮＨ2 +ＣＯＣｌ2 ＲＮＣＯ + 2ＨＣｌ　　该法普遍存在设备腐蚀、环境污染等问题 ,因而由含氮有机物羰化制取氨基甲酸酯 ,再通过热裂解制取异氰酸酯的环境友好催化过程已受到世界各国的重视[1 ,2 ] .尽管由硝基化合物直接还原羰化制氨基甲酸酯 ,从减少反应步骤的角度考虑更为合理[3～7] ,但该反应存在条件苛刻、催化剂回收困难、多硝基化合物…     

Mono-(BOC)-Protected Diamines. Synthesis of tert-Butyl-N-alkyl-N-(2-aminoethyl)carbamates and tert-Butyl-N-[2-(alkylamino)ethyl] Carbamates

We wish to report preparative pathways to the mono-(BOC)-protected diamines 1a-d and 2a-c.     

Preparation of YSZ Microporous Membranes on Porous a-Alumina with Metal Chlorides as Precursor

A sol-gel process for YSZ membrane prepared with less expensive chemicals, ZrOCI₂·8H₂0 and YC1₃, has been developed. The sol viscosity as a function of concentration, acidity and temperature was brane formation processes were also studied. investigated. And gelation and Based on an optimized procedure memhole and crack-free YSZ membranes with the pore size less than 100 nm have obtained on coarse porous a-alumina.