3,4—二氢—2H—吡喃—5—醛与脂肪二胺的反应研究

３，４－二氢－２Ｈ－吡喃－５－醛与脂肪二胺在水溶剂中，于低温下反应４８ｈ，得到Ｎ，Ｎ＇－二（２－羟丙基－３－氧代－１－丙烯基）二胺。产物经元素分析，ＩＲ，＾１ＨＮＭＲ和ＭＳ证实。     

二安替比林基─（3，4─亚甲二氧基）苯基甲烷光度法测定微量钒（Ⅴ）

合成了胡椒醛与安替比林的缩合产物─—二安替比林基－（３，４－亚甲二氧基）苯基甲烷（ＤＡＤＭＰＭ），研究了ＤＡＤＭＰＭ与钒（Ⅴ）的显色反应。于磷酸介质中，在Ｍｎ（Ⅱ）和吐温－４０的存在下，钒（Ⅴ）与ＤＡＤＭＰＭ反应生成橙黄色化合物，最大吸收波长λｍａｘ为４７Ｏｍｍ，摩尔吸光系数ε为３．２１×１０５Ｌ·ｍｏｌ－１·ｃｍ－１和２．５７×１０￣５Ｌ·ｍｏｌ－１·ｃｍ－１，钒（Ⅴ）的量在０．２～３．Ｏμｇ／２５ｍＬ及３．０～９．Ｏμｇ／２５ｍＬ间符合比尔定律。可用于中草药中微量钒（Ⅴ）的测定。     

新荧光试剂3─苯基─5─（4′─硝基─2′─羧基苯偶氮）─2─硫代─4─噻唑啉酮的合成及其应用研究

报道了新荧光试剂３－苯基－５－（４′－硝基－２′－羧基苯偶氮）－２－硫代－４－噻唑啉酮（３Ｐ－４ＮＲＡＣＰ）的合成，通过元素分析、红外光谱、核磁共振谱及质谱确证了其结构。在ｐＨ５．６时，它与铜（Ⅱ）形成稳定的荧光螫合物，在γｅｘ／λｅｍ＝３０５ｎｍ／４０５ｎｍ处产生强荧光，其荧光强度与铜（Ⅱ）的浓度在１．５７×１０－１０～１．８９×１０－８ｍｏｌ／２５ｍＬ范围内呈线性关系，灵敏度达１．５７×１０－１０ｍｏｌ／ｇ的铜（Ⅱ）。用此方法测定了杂交米、糯米及香米中的痕量铜（Ⅱ），结果满意。     

一步法合成（R，R）－（＋）－2，3－二甲氧基－N，N，N′，N′－四甲基丁二酰胺

一步法合成（Ｒ，Ｒ）－（＋）－２，３－二甲氧基－Ｎ，Ｎ，Ｎ′，Ｎ′－四甲基丁二酰胺王林，恽榴红，张其楷（军事医学科学院毒物药物研究所，北京１００８５０）四甲基丁二酰胺（ＤＴＢＤ）是制备１，４－二胺类手性配基的重要前体［１］，也是ｌ，２－二醇类外消旋体...     

高分子酰化催化剂：聚4－（3－吡咯啉基）吡啶的合成

以频哪醇为原料，经脱水制成２，３－二甲基－１，３－丁二烯（ＤＭＢ），将其溴加成和溴代后，得到２，３－二溴甲基－１，４－二溴－２－丁烯（ＢＢＭＢＢ），再进行碘代，制得２，３－二碘甲基－１，３－丁二烯（ＢＩＭＢ），然后用４－氨基吡啶进攻ＢＩＭＢ进行Ｎ－烷基化反应，获得一种新型的单体：４－（３，４－二甲叉基吡咯烷基）吡啶（ＤＭＰＰ）。最终，将此单体均聚，合成出一种带有高效酰化催化基团的新型高分子化合物：聚４－（３－吡咯啉基）吡啶（ＰＰＰＹ）。     

一种新的用于彩色相纸的青成色剂的合成研究

２，４－二氯－３－乙基－６－氨基苯酚与具有防扩散功能的基团连接合成一种新的彩色相纸用青成色剂Ｎ－〔２－羟基－３，５－二氯－４－乙基〕苯基－２－〔２，４－二（１，１－二甲丙基）苯氧基〕丁酰胺。产物经ＨＮＭＲ、ＩＲ、ＭＳ和元素分析测定证实了其结构。     

季铵盐相转移催化合成N-异丙基二碳酰亚胺的研究

以季铵盐为催化剂，相转移催化合成Ｎ－异丙基－１－异丙基－４－甲基二环［２，２，２］－５－辛烯－２、３－二碳酰亚胺（ＴＭＲ）。讨论影响这一反应的主要因素，得出比较适宜的反应条件。通过ＩＲ、ＭＳ和１ＨＮＭＲ分析，证实产物的结构即为ＴＭＲ。     

含磺酰胺桥基偶氮染料的合成及应用研究

本文合成出３，３‘－二氨基－４，４’－二甲基氧基－Ｎ，Ｎ‘－二苯磺酰乙二胺，３，３’－二氨基－４，４‘－二氨基－Ｎ，Ｎ’－二苯磺酰已二胺和４，４‘－二氨基－Ｎ，Ｎ’－二苯磺 二胺三只新中间体。用该中间体合成四种直接黑色染料，并用于丝绸及皮革染色，获得了较好结果。     

新型磷-氮阻燃剂N,N′-双(2-氧-5,5-二甲基-1,3,2-二氧磷杂环己烷)-2,2′-间苯二胺的合成研究

以氯氧化磷、新戊二醇、间苯二胺等为原料合成了未见文献报道的Ｎ，Ｎ′－双（２－氧－５，５－二甲基－１，３，２－二氧磷杂环己烷）－２，２′－间苯二胺（二新戊二醇间苯二胺双膦酸酯），探讨出最佳工艺条件，并通过ＦＴＩＲ、１ＨＮＭＲ、元素分析验证了产物结构。     

含草酰胺桥的新型铜（Ⅱ）─镍（Ⅱ）双核配合物的合成和磁性研究

本文合成和表征了两种新的杂双核配合物：［Ｃｕ（ｏｘｄｎ）Ｎｉ（ｔｍｎ）＿２（ＣｌＯ＿４）＿２（１）和［Ｃｕ（ｏｘｄｎ）Ｎｉ（ｔｍｄ）＿２］（ＣｌＯ＿４）２（２），ｏｘｄｎ代表Ｎ，Ｎ＇－双（３－氨丙基）草酰胺根阴离子；ｔｍｎ为Ｎ．Ｎ．Ｎ＇－四甲基乙二胺；ｔｍｄ表示１．３－丙二胺。测定了配合物（１）的变温磁化率（４～３００Ｋ），其数值用最小二乘法和从自旋哈密顿算符Ｈ＝－２ＪＳ＿１·Ｓ＿２导出的磁方程拟合，求得交换积分Ｊ＝－１１８．８ｃｍ￣（－１）。文中还用Ｋａｈｎ理论解释了这种反铁磁自旋交换作用。     

Characterization and Electrical Properties of Some Hydrochloric Acid-Doped Aniline and 2-Amino-Pyridine Homopolymers and Copolymers

The synthesis of (group I) hydrochloric acid-doped poly(aniline-co-toluidine), poly(aniline-co-thiophene), poly(aniline-co-o-phenylenediamine), and poly(aniline-co-2-aminopyridine) as well as their hydrochloric acid-doped homopolymers of polyaniline, poly-m-toluidine, poly-o-phenylene diamine, and poly-2-aminopyridine and the synthesis of (group II) hydrochloric acid-doped poly (2-aminopyridine-co-o-phenylene diamine) and its hydrochloric acid-doped homopolymers of poly 2-amino pyridine and poly-o-phenylene diamine have been carried out via a chemical oxidation process using ammonium and potassium persulphate as chemical initiators. The synthesized homo- and copolymers were characterized by ultraviolet-visible spectroscopy (UV-VIS), infrared spectroscopy (IR), and thermal analysis. The variation of the electrical conductivity (σ, S cm^?1) with the reciprocal of the absolute temperature (1000/T, K) at different frequencies (1–1000 kHz) for hydrochloric acid homopolymers and copolymers is illustrated.     

α‐Bis and α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polymers by atom transfer radical polymerization using 1,1‐bis[(4‐dimethylamino)phenyl]ethylene as tertiary diamine initiator precursor and functionalizing agent

The quantitative syntheses of α‐bis and α,ω‐tetrakis tertiary diamine functionalized polymers by atom transfer radical polymerization (ATRP) methods are described. A tertiary diamine functionalized 1,1‐diphenylethylene derivative, 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1), was evaluated as a unimolecular tertiary diamine functionalized initiator precursor as well as a functionalizing agent in ATRP reactions. The ATRP of styrene, initiated by a new tertiary diamine functionalized initiator adduct (2), affords the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3). The tertiary diamine functionalized initiator adduct (2) was prepared in situ by the reaction of (1‐bromoethyl)benzene with 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) in the presence of a copper (I) bromide/2,2′‐bipyridyl catalyst system. The ATRP of styrene proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene derivative (3) with predictable number‐average molecular weight (M_n) and narrow molecular weight distribution (M_w/M_n) in a high initiator efficiency reaction. The polymerization process was monitored by gas chromatography analysis. Quantitative yields of α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polystyrene (4) were obtained by a new post ATRP chain end modification reaction of α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3) with excess 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1). The tertiary diamine functionalized initiator precursor 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) and the different tertiary amine functionalized polymers were characterized by chromatography, spectroscopy and non‐aqueous titration measurements. Copyright © 2012 Society of Chemical Industry     

Structure–stability correlation of copolyimide membranes derived from aliphatic/alicyclic/aromatic diamine and aromatic dianhydrides

New polyamic acids with ‐A‐B‐A‐C‐ type periodic sequence of monomeric units (A derived from a diamine, B from benzophenone‐3,3′,4,4′‐tetracarboxylic dianhydride, and C from benzene‐1,2,4,5‐tetracarboxylic dianhydride) are prepared and transformed into polyimide membranes that are examined by various methods in order to investigate the influence of diamine units (aliphatic, alicyclic, or aromatic) on the morphology, thermal stability, and mechanical properties of membranes. Small‐ and wide‐angle X‐ray scattering and Atomic force microscopy show amorphous character of all membranes except for those containing hexane‐1,6‐diamine units. Thermogravimetric analysis reveals a decrease in the initial decomposition temperature from 551/501 °C to 437/395 °C (for N₂/O₂ atmosphere) when going from membranes with aromatic to those with aliphatic diamine units. Dynamic mechanical analysis shows quite high initial storage modulus (2100–3300 MPa) for all membranes at frequencies of 1, 10, and 20 Hz. The properties of prepared copolymeric polyimide are promising for a wide range of their potential technological applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45227.     

Zur Stereochemie von N,N′-Bis-[3-(o-ethoxyphenoxy)-2-hydroxy-propyl]-ethylendiamin

Stereochemistry of N,N′-Bis-[3-(o-ethoxyphenoxy)-2-hydroxy-propyl]-ethylendiamine N,N′-Bis-[3-(o-ethoxyphenoxy)-2-hydroxy-propyl]-ethylene diamine ( 5 ), synthesized from racemic 1,2-anhydro-3-O-(o-ethoxyphenyl)-glycerol ( 1 ) and ethylene diamine ( 2 ) or N,N′-dibenzyl ethylene diamine ( 3 ) crystallized in two fractions with different melting points. Both of these analytically pure products gave identical two spot tl-chromatograms on achiral phases. Attempts were made to resolve the mixtures which proved to consist of configurative but not constitutive isomers. Optically pure products were synthesized from chiral precursors.     

Analysis of cationic and amphoteric surfactants: V. structural analysis of the amphoteric surfactants obtained by the reaction of 1-(2-Hydroxyethyl)-2-alkyl-2-imidazoline with sodium monochloroacetate

Structural analysis of the amphoteric surfactants obtained by the reaction of l-(2-hydroxyethyl)-2-alkyl-2-imidazoline (HEAI) with sodium monochloroacetate has been carried out. These amphoteric surfactants were hydrolyzed under aqueous alkaline media, followed by acid hydrolysis to afford fatty acid and diamine derivatives. The resulting diamine derivatives were identified by the isolation and their syntheses, and were quantitatively analyzed by gas chromatography. Based upon the results of these analyses, it has been found that the reaction products can be divided into two typical types. The reaction products have simpler compositions than those of ethyl acrylate. However, these amphoteric surfactants are characterized by the presence of appreciable amounts of hydrolysis products of amides, soap and free diamine derivative XI.     

Hydrolysis of polyurea under high pressure of carbon dioxide

A chemical decomposition of polyurea (PUA) by hydrolysis under high pressure of carbon dioxide (CO₂) was proposed. The hydrolysis of PUA was carried out at 190 °C for 2 h under 7.0 MPa of CO₂ in the presence of water. The hydrolysis reaction gave white residual solid and water soluble compound. The white residual solid was characterized to be degraded PUA by FT-IR spectrum and elemental analysis. ¹H-NMR spectra of the water soluble compound revealed that the hydrolysis of PUA produced diamine only from repeating unit of PUA, which was a component of PUA. This hydrolysis gave the corresponding diamine for quantitative yields.     

磷-氮系膨胀型阻燃剂1,2-二(2-氧代-5,5-二甲基-1,3-二氧-2-磷杂环己基-2-亚氨基)乙烷及其同系物的合成

以三氯氧磷、乙二胺、新戊二醇或二溴新戊二醇为原料合成了两种磷氮系阻燃剂１,２－二（２－氧代－５,５－二甲基－１,３－二氧－２－磷杂环己基－２－亚氨基）乙烷和１,２－二（２－氧代－５,５－二溴甲基－１,３－二氧－２－磷杂环己基－２－亚氨基）乙烷,产品经ＩＲ、１ＨＮＭＲ和元素分析确定。同时研究了反应溶剂、反应温度和催化剂对产物收率的影响     

Synthesis and resolution of 1,11-diamino-dibenzo[d,f][1,3]dioxepine: A route to new asymmetric ligands and their complexes

Reaction of 2-iodo-3-nitrophenol with methylene iodide and Ullmann intramolecular coupling of the produced 1,1′-[methylenebis(oxy)]bis[2-iodo-3-nitro]benzene afforded 1,11-dinitro-dibenzo[d,f] [1,3]dioxepine, characterized by single crystal X-ray analysis. The title diamine was obtained by reduction of the nitroderivate with hydrazine hydrate. Resolution of the enantiomers of the novel C₂-symmetric ligand can be easily obtained by use of tartaric acid. A test on the coordinating ability of the diamine has produced a complex examined by X-ray diffraction analysis.     

Silarylene-containing poly(ether-amide)s obtained by Yamazaki–Higashi phosphorylation technique: use of bis(4-(4-aminophenoxy)phenyl)ethylmethyl silane

Aromatic poly(ether-amide)s (PEAs) based on -(R₁,R₂)diphenylsilane- and oxyether units were synthesized by direct polycondensation of a diamine and two dicarboxylic acids. For this, the diamine bis(4-(4-aminophenoxy)phenyl)ethylmethylsilane was obtained by reduction of the respective dinitro compound, which was synthesized by nucleophilic aromatic halogen displacement from 1-fluoro-4-nitrobenzene with bis(4-hydroxyphenyl)ethylmethylsilane in basic medium. New silicon-containing aromatic diamine and the PEAs were characterized by elemental analysis, FT-IR, ¹H, ¹³C and ²⁹Si NMR spectroscopy and the results were in agreement with the proposed structures. The incorporation of aliphatic units such as methyl and/or ethyl groups on the silicon atoms affected positively the solubility of the PEAs in organic polar solvents. When their thermal and optical properties were compared with two PEAs of similar structure, containing phenyl groups bonded to the silicon atoms, it was observed a decrease of the glass transition temperature and transmittance values, maintaining a high thermal resistance.