1－苯基－3－甲基－4－（6－氢－4－氨基－5－硫杂－2，3－吡嗪）－吡唑啉酮光致变色超分子化合物的合成、结构与性能

通过1－苯基－3－甲基－4－氯乙酰基－吡唑啉酮－5（PMCP）和氨基硫脲（ TSC）缩合，形成了一种含NNS六元杂环的光致变色化合物（PMCP－TSC）。利用元 素分析，MS，”1H NMR，IR和UV光谱进行了表征。通过紫外可见光谱对它的光致 变色性质进行了研究，测出了光致变色反应的动力学常数。并用X线单晶衍射仪测 定了PMCP－TSC变色后的晶体结构，该晶体属单斜晶系，具有P2_1/c空间群，a = 0.105 10(2) nm, b = 0.150 61(3) nm, c = 0.993 70(10) nm, β = 107.890 (10)°, V = 1.496 9(4) nm~3, Z - 4, D_c = 1.417 Mg/m~3, μ = 0.232 mm~(- 1), F(000) = 672, R = 0.033 4, wR = 0.089 6。结构分析表明：其光致变色现 象是由于它在溶剂与光的共同作用下发生了从醇式到酮式的异构化。同时该化合物 经分子间氢键形成二聚体，又通过甲醇与本体分子之间的氢键使化合物形成具有三 维网络结构的超分子化合物。     

锌与7－（2－羧基－4－溴－苯偶氮）－8－羟基喹啉－5－磺酸的显色反应研究及茶叶中锌的测定

本文研究了新显色剂７－（２－羧基－４－溴－苯偶氮）－８－羟基喹啉－５－磺酸与锌的反应条件，试验结果发现在乳化剂ＯＰ存在下，酒石酸介质中新试剂与锌形成稳定配合物，其最大吸收波长为５００ｎｍ，表观摩尔吸光系数为１．１５×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），Ｚｎ￣（２＋）浓度在０～８μｇ／ｍＬ之间符合比尔定律，方法用于茶叶中微量锌的测定结果满意。     

N－芳基－2－乙基－3－羟基－4－吡啶酮的微波合成

用微波辐射从2－乙基－3－羟基－4－吡喃酮和芳胺合成了系列N－芳基－2－ 乙基－3－羟基－4－吡啶酮，并对产物进行了紫外、红外、氢核磁和质谱表征。     

2－（5－Br－2－吡啶偶氮－5－二乙氨基）－酚与铑的显色反应的研究及应用

本文研究了２－（－５－Ｂｒ－２吡啶偶氮－５－二乙氨基）－酚与铑（Ⅲ）的显色反应。在ｐＨ为４．０的邻苯二甲酸氢钾缓冲液介质中，Ｒｈ（Ⅲ）与试剂形成稳定的橙红色络合物，其组成比为１：４，最大吸收波长为４９０ｎｍ，表现摩尔吸光系数为１．３×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）。铑含量在０～４μｇ／１０ｍＬ范围内服从比尔定律。     

镉－硫氰酸根与铵－苯并15－冠－5配合物的合成与结构研究

用凝胶法生长了标题配合物［ＮＨ_４（Ｂ１５Ｃ５）_２］［Ｃｄ（ＳＣＮ）_３］的晶体，并对其进行了红外光谱，元素分析等各项物理性质的测试。经Ｘ射线单晶结构分析得到了配合物的全部晶体学数据：Ｍ_ｒ＝８４１．３１，正交晶系，空间群Ｐ２_１２_１２_１，晶胞常数ａ＝１０．９７０（３），ｂ＝２１．８３４（３），ｃ＝１５．５６３（４），Ｖ＝３７２７（３），Ｚ＝４，Ｄ_ｘ＝１．５０ｇ／ｃｍ￣３，Ｆ（０００）＝１７３６，μ＝７．０９ｃｍ￣（－１），Ｒ＝０．０７０，Ｒ_ｗ＝０．０６３。结构分析结果表明，配阳离子［ＮＨ_４（Ｂ１５Ｃ５）_２］￣＋和配阴离子［Ｃｄ（ＳＣＮ）_３］￣－间靠静电力结合成配合物。     

3－硝基－4－溴－1，8－萘二甲酸酐与己胺的反应

３－硝基－４－溴－１，８－萘二甲酸酐与己胺的反应柳波沈永嘉＊董黎芬（华东理工大学精细化工研究所，上海，２００２３７）关键词合成结构表征１，８－萘二甲酰亚胺１，８－萘二甲酰亚胺是一类良好的荧光发色体，其４位上有供电子基团的衍生物大都具有强烈的荧光，已被...     

1－苯基－3－甲基－4－（a－呋喃甲酰基）－5－吡唑酮与中性萃取剂协同萃取镱的研究

研究了１－苯基３－甲基－４－（呋喃甲酰基）－５－吡唑酮（ＨＡ）萃取镱及其分别与丁基辛基亚砜（ＢＯＳＯ）、戊基已基亚砜（ＰＨＳＯ）、乙基十二烷基亚砜（ＥＤＳＯ）、二苯亚砜（ＤＰＳＯ）和ＴＢＰ协同萃取镱的行为。协萃配合物的组成为ＹｂＡ＿３·Ｂ，ＨＡ的萃取平衡常数为—５．６４±０．０４，中性萃取剂的协萃能力比单独萃取时高３～４个数量级，协萃效果明显。     

含氟Y－Ba－Cu－O高温超导体稳定性与结构的研究

应用ＢａＦ２、ＣｕＦ２和ＹＦ３分别部分代换ＢａＯ、ＣｕＯ和Ｙ２Ｏ３制得了一系列带有氟元素的Ｙ－Ｂａ－Ｃｕ－Ｏ高温超导体样品，其中ＢａＦ２代换ＢａＯ的摩尔量可达４５％，样品的零电阻温度为８２．５～９３．５Ｋ。应用ＸＲＤ、ＤＴＡ、ＩＲ和化学方法研究了样品的结构和稳定性。初步实验结果表明，氟元素只有少量进入超导相，但含氟的Ｙ－Ｂａ－Ｃｕ－Ｏ超导体在水蒸气和二氧化碳中的稳定性则大大提高。     

2－乙基－1－（α－呋喃基）－1－戊烯－4－炔－3醇的合成

２－乙基－１－（α－呋喃基）－１－戊烯－４－炔－３醇的合成肖蓉，孙悦（成都科技大学化学系６１００６５）涂君俐（中国科学院成都有机化学研究所，６１００４１）蚊香和电热片是拟除虫菊醋类药剂，也是家庭卫生用药的代表性剂型。如果能开发出挥发性高，在非加热条件...     

1－芳酰基－3－烷基－6－羟基－6－芳基富烯的合成

１－芳酰基－３－烷基－６－羟基－６－芳基富烯的合成焦纶基,董育斌,马玉道（山东大学应用化学研究所,济南,２５０１００）关键词富烯,二茂铁,芳酰化,合成前文［１］曾报道过甲基锂、苯基锂与６,６－二烷基富烯加成物的芳酰化。为进一步探讨取代环戊二烯负离子的...     

6－甲基－2，5－二酮基－吗啉与己内酯的嵌段共聚物的合成与表征

６－甲基－２，５－二酮基－吗啉与己内酯的嵌段共聚物的合成与表征叶卫平，顾忠伟，杨纪元，徐琳，陈先丽（国家计划生育委员会科学技术研究所，北京，１０００８１）侯明山（燕山石化研究院，北京，１０２５４９）关键词生物降解，６－甲基－２，５－二酮基－吗啉，己内...     

Novel synthesis of biodegradable linear and star block copolymers based on ε‐caprolactone and lactides using potassium‐based catalyst

Biodegradable, triblock poly(lactide)‐block‐poly(ε‐caprolactone)‐block‐poly(lactide) (PLA‐b‐PCL‐b‐PLA) copolymers and 3‐star‐(PCL‐b‐PLA) block copolymers were synthesized by ring opening polymerization of lactides in the presence of poly(ε‐caprolactone) diol or 3‐star‐poly(ε‐caprolactone) triol as macroinitiator and potassium hexamethyldisilazide as a catalyst. Polymerizations were carried out in toluene at room temperature to yield monomodal polymers of controlled molecular weight. The chemical structure of the copolymers was investigated by ¹H and ¹³C‐NMR. The formation of block copolymers was confirmed by NMR and DSC investigations. The effects of copolymer composition and molecular structure on the physical properties were investigated by GPC and DSC. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5363–5370, 2008     

Poly(p‐phenylene methylene)‐based block copolymers by mechanistic transformation

The synthesis of poly(p‐phenylene methylene) (PPM)‐based block copolymers such as poly(p‐phenylene methylene)‐b‐poly(ε‐caprolactone) and poly(p‐phenylene methylene)‐b‐polytetrahydrofuran by mechanistic transformation was described. First, precursor PPM was synthesized by acid‐catalyzed polymerization of tribenzylborate at 16 °C. Then, this polymer was used as macroinitiators in either ring‐opening polymerization of ε‐caprolactone or cationic ring‐opening polymerization of tetrahydrofuran to yield respective block copolymers. The structures of the prepolymer and block copolymers were characterized by GPC and ¹H NMR investigations. The composition of block copolymers as determined by ¹H NMR and TGA analysis was found to be in very good agreement. The thermal behavior and surface morphology of the copolymers were also investigated, respectively, by differential scanning calorimetry and atomic force microscopy measurements, and the contribution of the major soft segment has been observed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

SYNTHESIS AND POLYMERIZATION OF 2-OXO-3-METHYLENE-5, 6-DIPHENYL-1,4-DIOXAN

A new cyclic monomer, 2-oxo-3-methylene-5, 6-diphenyl-1, 4-dioxan, was synthesized. Thestructure of the intermediates and the monomer were determined by IR,~1H NMR,~(13)C NMR andelemental analysis. This new monomer is different from other cyclic monomers in this series,it isa solid (mp 108--109℃)and not very reactive, but still can undergo free radical ring-openingpolymerization. The free radical polymerization was carried out at 130℃. The structure of theresulting polymer was discussed and charaterized by IR, ~1H NMR, ~(13)C NMR and elementalanalysis. The molecular weight of the polymer was estimated by viscosity determination.     

Synthesis of amphiphilic biodegradable glycocopolymers based on poly(ε‐caprolactone) by ring‐opening polymerization and click chemistry

Amphiphilic, biodegradable block glycopolymers based on poly(ε‐caprolactone) (PCL) with various pendent saccharides were synthesized by combination of ring‐opening polymerization (ROP) and “click” chemistry. PCL macroinitiators obtained by ROP of ε‐caprolactone were used to initiate the ROP of 2‐bromo‐ε‐caprolactone (BrCL) to get diblock copolymers, PCL‐b‐PBrCL. Reaction of the block copolymers with sodium azide converted the bromine groups in the PBrCL block to azide groups. In the final step, click chemistry of alkynyl saccharides with the pendent azide groups of PCL‐b‐PBrCL led to the formation of the amphiphilic block glycopolymers. These copolymers were characterized by ¹H NMR spectroscopy and gel permeation chromatography. The self‐assembly behavior of the amphiphilic block copolymers was investigated using transmission electron microscopy and atomic force microscope, spherical aggregates with saccharide groups on the surface were observed, and the aggregates could bind reversibly with Concanavalin A. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3583–3594, 2009     

Novel synthesis of biodegradable amphiphilic linear and star block copolymers based on poly(ε‐caprolactone) and poly(ethylene glycol)

Biodegradable, amphiphilic, diblock poly(ε‐caprolactone)‐block‐poly(ethylene glycol) (PCL‐b‐PEG), triblock poly(ε‐caprolactone)‐block‐poly(ethylene glycol)‐block‐poly(ε‐caprolactone) (PCL‐b‐PEG‐b‐PCL), and star shaped copolymers were synthesized by ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) methyl ether or poly(ethylene glycol) or star poly(ethylene glycol) and potassium hexamethyldisilazide as a catalyst. Polymerizations were carried out in toluene at room temperature to yield monomodal polymers of controlled molecular weight. The chemical structure of the copolymers was investigated by ¹H and ¹³C NMR. The formation of block copolymers was confirmed by ¹³C NMR and DSC investigations. The effects of copolymer composition and molecular structure on the physical properties were investigated by GPC and DSC. For the same PCL chain length, the materials obtained in the case of linear copolymers are viscous whereas in the case of star copolymer solid materials are obtained with low T_g and T_m temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3975–3985, 2007     

Synthesis of four‐armed poly(ε‐caprolactone)‐block‐poly(ethylene oxide) by diethylzinc catalyst

Biodegradable, amphiphilic, four‐armed poly(?‐caprolactone)‐block‐poly(ethylene oxide) (PCL‐b‐PEO) copolymers were synthesized by ring‐opening polymerization of ethylene oxide in the presence of four‐armed poly(?‐caprolactone) (PCL) with terminal OH groups with diethylzinc (ZnEt₂) as a catalyst. The chemical structure of PCL‐b‐PEO copolymer was confirmed by ¹H NMR and ¹³C NMR. The hydroxyl end groups of the four‐armed PCL were successfully substituted by PEO blocks in the copolymer. The monomodal profile of molecular weight distribution by gel permeation chromatography provided further evidence for the four‐armed architecture of the copolymer. Physicochemical properties of the four‐armed block copolymers differed from their starting four‐armed PCL precursor. The melting points were between those of PCL precursor and linear poly(ethylene glycol). The length of the outer PEO blocks exhibited an obvious effect on the crystallizability of the block copolymer. The degree of swelling of the four‐armed block copolymer increased with PEO length and PEO content. The micelle formation of the four‐armed block copolymer was examined by a fluorescent probe technique, and the existence of the critical micelle concentration (cmc) confirmed the amphiphilic nature of the resulting copolymer. The cmc value increased with increasing PEO length. The absolute cmc values were higher than those for linear amphiphilic block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 950–959, 2004     

Preparation and characterization of biodegradable poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone) copolymers

A series of poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone) copolymers were prepared with varying feed rations by using two step polymerization reactions. Poly(trimethylenecarbonate)(ε‐caprolactone) random copolymer was synthesized with stannous‐2‐ethylhexanoate and followed by adding p‐dioxanone monomer as the other block. The ring opening polymerization was carried out at high temperature and long reaction time to get high molecular weight polymers. The monofilament fibers were obtained using conventional melting spun methods. The copolymers were identified by ¹H and ¹³C NMR spectroscopy and gel permeation chromatography (GPC). The physicochemical properties, such as viscosity, molecular weight, melting point, glass transition temperature, and crystallinity, were studied. The hydrolytic degradation of copolymers was studied in a phosphate buffer solution, pH = 7.2, 37 °C, and a biological absorbable test was performed in rats. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2790–2799, 2005     

Synthesis and characterization of well‐defined cyclodextrin‐centered seven‐arm star poly(ε‐caprolactone)s and amphiphilic star poly(ε‐caprolactone‐b‐ethylene glycol)s

Per‐2,3‐acetyl‐β‐cyclodextrin with seven primary hydroxyl groups was synthesized by selective modification and used as multifunctional initiator for the ring‐opening polymerization of ε‐caprolactone (CL). Well‐defined β‐cyclodextrin‐centered seven‐arm star poly(ε‐caprolactone)s (CDSPCLs) with narrow molecular weight distributions (≤1.15) have been successfully prepared in the presence of Sn(Oct)₂ at 120 °C. The molecular weight of CDSPCLs was characterized by end group ¹H NMR analyses and size‐exclusion chromatography (SEC), which could be well controlled by the molar ratio of the monomer to the initiator. Furthermore, amphiphilic seven‐arm star poly(ε‐caprolactone‐b‐ethylene glycol)s (CDSPCL‐b‐PEGs) were synthesized by the coupling reaction of CDSPCLs with carboxyl‐terminated mPEGs. ¹H NMR and SEC analyses confirmed the expected star block structures. Differential scanning calorimetry analyses suggested that the melting temperature (T_m), the crystallization temperature (T_c), and the crystallinity degree (X_c) of CDSPCLs all increased with the increasing of the molecular weight, and were lower than that of the linear poly(ε‐caprolactone). As for CDSPCL‐b‐PEGs, the T_c and T_m of the PCL blocks were significantly influenced by the PEG segments in the copolymers. Moreover, these amphiphilic star block copolymers could self‐assemble into spherical micelles with the particle size ranging from 10 to 40 nm. Their micellization behaviors were characterized by dynamic light scattering and transmission electron microscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6455–6465, 2008     

CHLOROSULPHONATION OF 2-ANILINO-1,4-NAPHTHOQUINONE AND SYNTHESIS OF NEWER SULPHONYL DERIVATIVES

Synthesis of 2-anilino-1,4-napthoquinone-3-sulphonyl chloride (2) was achieved from the reaction of the title compound with chlorosulphonic acid. The interesting derivative 2 was used as a building block for synthesis of the sulphonyl derivatives 3–24. All these sulphonyl derivatives were characterized by the physical and spectral data (IR, Mass, ¹H- and ¹³C NMR spectra).