4，4＇－偶氮二［4－氰基戊酰（对－二甲氨基）苯胺］作为引发剂的嵌段共聚物合成

４，４＇－偶氮二［４－氰基戊酰（对－二甲氨基）苯胺］作为引发剂的嵌段共聚物合成邱醒宇，魏峰，关宏宇，平学真（辽宁大学化学系，沈阳，１１００３６）关键词４，４＇－偶氮二［４－氰基戊酰（对－二甲氨基）苯胺］，多官能团引发剂，自由基聚合７０年代以来，陆续报...     

(R)-N-酰基四氢噻唑-2-硫酮-4-羧酸在DCC存在下与胺的反应

由Ｎ－乙酰四氢噻唑－２－硫酮－４－羧酸（［α］２０Ｄ－１０９．８３°），及Ｎ－苯甲酰四氢噻唑－２－硫酮－４－羧酸（［α］２０Ｄ－１１２．２２°），在Ｎ，Ｎ′－二环己基二亚胺（ＤＣＣ）存在下分别与环己胺、苯胺反应得到光学活性产物（Ｒ）－Ｎ－乙酰四氢噻唑－２－硫酮－４－甲酰环己胺（［α］１７Ｄ－７４．５°），及（Ｒ）－Ｎ－苯甲酰四氢噻唑－２－硫酮－４－甲酰苯胺（［α］１９Ｄ－７．０４°）。用量子化学ＰＭ３方法研究了反应物和产物的电子结构。     

聚(L-天冬氨酸)衍生物-顺铂结合物的制备及体外细胞毒性研究

通过α，β－聚（Ｌ－天冬氨酸）及其衍生物α，β，Ｌ－天冬氨酸和［α，β，Ｌ－（Ｎ－羟乙基）天冬酰胺］共聚物，［α，β，Ｌ－（Ｎ－羟乙基）天冬酰胺］和［α，β，Ｌ－（Ｎ－丁二酸基）天冬酰胺］共聚物为载体，与顺式二氯二氨合铂（Ⅱ）结合，合成了相应高分子－顺铂结合物．研究结果表明，在中性ｐＨ值络合最有效，聚合物－顺铂结合物的体外细胞毒性随结合物浓度增大而增大，但均小于同浓度顺铂毒性．     

聚丙烯酸[2,5-双(对甲氧基苯甲酰氧基)苄酯]及聚甲基丙烯酸[2,5-双(对甲氧基苯甲酰氧基)苄酯]的合成

周其凤等曾报道聚丙烯酸［２,５－双（对甲氧基苯甲酰氧基）节酯］［１］和聚甲基丙烯酸［２,５－双（对甲氧基苯甲酰氧基）苄酯］［２］的合成．但后来的研究发现,在合成单体的条件下出现的一种未见报道的异常反应［３］使产物成分复杂化,因此当时报道的聚合物可能不是聚丙烯酸［２,５－双－（对甲氧基苯甲酰氧基）苄酯］或聚甲基丙烯酸［２,５－双（对甲氧基苯甲酰氧基）苄酯］,而可能是共聚物．针对这一问题,我们重新设计了合成路线以避免发生上述副反应,成功地合成了丙烯酸或ａ－甲基丙烯酸［２,５－双－（对甲氧基苯甲酰氧基…     

对硝基二苯胺的一个新制法

对硝基二苯胺的一个新制法韦长梅，周建峰（淮阴师范专科学校化学系，江苏省２２３００１）对硝基二苯胺（ｐ－Ｎｉｔｒｏｄｉｐｈｅｎｙｌａｍｉｎｅ）是重要的有机试剂和合成中间体，可用作橡胶稳定剂和染料中间体［１］、合成抗乙酰胆碱能的抑制剂和溃疡抑制剂［２］。...     

3-甲氧基二苯胺-4-重氮盐的制备及其光、热分解性质

３－甲氧基二苯胺－４－重氮盐（ＭＤＤＳ）与甲醛或４，４－二甲氧次甲基二苯醚的缩合物用作阴图ＰＳ版感光剂，Ｈｏｅｃｈｓｔ等公司［１～５］已有很多专利．可能是出于商业利益，关于ＭＤＤＳ的制备方法未见报道．我们［６］从苯胺钾与３－甲氧基氯苯出发，制备了这...     

含氢硅氧烷的硅氢加成反应

含氢硅氧烷的硅氢加成反应师彤，谢择民，王清正（中国科学院化学研究所北京１０００８０）关键词含氢硅氧烷，二乙烯基四甲基二硅氧烷，硅氢加成反应，~1ＨＮＭＲ铂催化硅氢加成的机理~［１，２］、副反应￣［３，４］、聚合物性能￣［３，５］等均有报道，个别文献用粘?..     

柄型金属有机化合物（Ⅰ）──硅桥联二（1－茚基）和四氢茚基钛化合物的合成及结构

通过１，３－二（１－茚基）四甲基二硅氧烷的双锂盐与ＴｉＣｌ４·２ＴＨＦ反应制得硅桥联二（１－茚基）钛化合物（Ｍｅ２ＳｉＯＳｉＭｅ２）［Ｉｎｄ］２ＴｉＣｌ２（１），对其催化氢化得到相应的四氢茚基化合物（Ｍｅ２ＳｉＯＳｉＭｅ２）［ＩｎｄＨ４］２ＴｉＣｌ２（２）。对化合物１和２的单晶进行了Ｘ射线衍射结构分析，它们的晶体都属单斜晶系，Ｐ２１／ｎ空间群。     

1,2-二乙炔基四苯基乙硅烷与1,2-二乙炔基四甲基乙硅烷的共聚及其光解

１，２－二乙炔基四苯基乙硅烷与１，２－二乙炔基四甲基乙硅烷在催化剂铑（Ⅰ）络合物［氯化三－（三苯基膦）铑］的作用下得到一种新的含硅共聚物。实验证明此共聚物的主链是有规交替结构。研究了固体薄膜及其溶液的光解作用，并测定了ＳｂＦ５蒸气处理后的共聚物薄膜的导电性。     

1,2-双(四甲基环戊二烯基)四甲基二硅烷与六碳基钼的反应

１,２－双（四甲基环戊二烯基）四甲基二硅烷与正丁基锂作用生成（四甲基二硅撑）双（四甲基环戊二烯基负离子盐）,后者随即与六碳基钼反应形成１,１’－（四甲基二硅撑）双（四甲基环戊二烯基铝负离子盐）－（Ｍｅ２ＳｉＳｉＭｅ２）［Ｍｅ４ＣｐＭｏ（ＣＯ）３－Ｌｉ＋］２（ Ｉ）, Ｉ与冰醋酸作用,随即分别与ＣＣｌ４, ＮＢＳ及Ｉ２反应,生成相应的铝卤化合物（Ｍｅ２ＳｉＳｉＭｅ２）［Ｍｅ４ＣｐＭｏ（ＣＯ）３Ｘ］２［Ｘ＝Ｃｌ（１）,Ｂｒ（２）,Ｉ（３）］．Ｉ与ＣＨ３Ｉ反应,在钼原子上发生烃基化,得到产物（Ｍｅ２ＳｉＳｉＭｅ２）［Ｍｅ４ＣｐＭｏ（ＣＯ）３Ｍｅ］２（４）;Ｉ与单质Ｉ２直接反应,生成脱硅桥产物Ｍｅ４Ｃｐ（ＣＯ）３Ｉ（５）．经元素分析、 ＩＲ及１Ｈ ＮＭＲ表征了化合物 １－５的结构．     

Synthesis of soluble aromatic polyesteramides by stepwise copolycondensation of bisphenols and aromatic diamines with diphenyl chlorophosphate in pyridine

The reaction promoted by diphenyl chlorophosphate (DPCP) in pyridine was successfully applied to the preparation of soluble aromatic copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, bisphenols, and a wide range of mol % aromatic diamines. Dropwise addition of a mixture of bisphenols and diamines (more favorably of bisphenols and then diamines) to the mixture of dicarboxylic acids activated by DPCP led the reactions homogeneously even with high mol % of diamines to produce copolymers of good solubility. This improved copolymer solubility was roughly estimated by sequence distribution of polyamide and polyester units in the copolymers, which was studied in a model reaction and in the copolycondensations by simultaneous and stepwise addition of bisphenols and diamines.     

Sulfur-containing polymers. II. Preparation and properties of polycarbamoylsulfenamides

Polycarbamoylsulfenamides have been prepared by interfacial and solution polycondensation of chlorocarbonylsulfenyl chloride with diamines. In preparing the polycarbamoylsulfenamides, the following types of diamines were used: primary aliphatic diamines, a mixed primary-secondary aliphatic diamine, primary aromatic diamines, and secondary aromatic diamines. The properties of the resulting polymers depended primarily on the kind of diamines used. Transparent, tough films were obtained from the polymer based on N,N′-dimethyl-4,4′-diaminodiphenylmethane. The photochemical decomposition of the polymers has been studied.     

Synthesis and characterization of novel aromatic polyamides derived from two heterocyclic diamines

Two diamines were synthesized as new aromatic monomers. A series of novel aromatic polyamides (aramids) were also synthesized by direct and indirect polycondensation of these diamines with various aromatic dicarboxylic acids. These aramids have inherent viscosities of 0.43-0.84 dl/g and were obtained in quantitative yield.     

Synthesis of polyenamines by vinylogous nucleophilic substitution polymerization of 1,6-diethoxy-1,5-hexadiene-3,4-dione with diamines

Novel polyenamines with inherent viscosities in the 0.2–1.1 range were synthesized by the vinylogous, nucleophilic substitution polymerization of 1,6-diethoxy-1,5-hexadiene-3,4-dione with aromatic and aliphatic diamines in polar aprotic solvents at room temperature. The most effective polymerization medium was hexamethylphosphoramide for preparing high-molecular-weight polymers from aromatic diamines. The dilute solutions showed a marked decrease in viscosity with time. The aromatic polyenamines began to lose weight around 200°C under thermogravimetric analysis in air and nitrogen.     

Polyimides with alicyclic diamines. I. Syntheses and thermal properties

The polyaddition reactions of alicyclic diamines such as 1,4-diaminocyclohexane (1,4-CHDA) or 4,4′-diaminodicyclohexylmethane (DCHM) and configurational isomers of 1,4-CHDA or DCHM with tetracarboxylic aromatic anhydrides in aprotic solvents were carried out to prepare high molecular weight poly(amic acid)s. Through the thermal imidization of poly(amic acid)s, several flexible polyimide films were prepared. Because of the stiffness of the alicyclic moieties in diamines, the resulting polyimides exhibit high glass transition temperatures (220–340°C) almost similar to those for corresponding aromatic polyimides which have phenylene groups in place of cyclohexyl groups, and show good thermal stability. The partial crystallization was observed for polyimides with trans-cyclohexyl moiety during the heating in differential scanning calorimetry and ascertained by wide-angle x-ray diffraction. Thus, the inhibition of the occurrence of charge transfer in polyimides is accomplished by introducing alicyclic diamines in place of aromatic diamines without reducing their thermal stability. © 1993 John Wiley & Sons, Inc.     

New high-temperature polymers. II. Ordered aromatic copolyamides containing fused and multiple ring systems

Symmetrical diamines, containing preformed carbonamide linkages, were prepared by reacting nitrobenzoyl chlorides with aromatic diamines and reducing the dinitro intermediates. The diamines were polymerized with aromatic diacid chlorides to give wholly aromatic ordered copolyamides of exceptionally high thermal stability. Ordered diamines were prepared containing only phenylene units as the aromatic portion, and others containing phenylene and naphthylene or biphenylene groups. Low-temperature solution polymerization of these diamines with isophthaloyl chloride, 4,4′-bibenzoyl chloride, or 2,6-naphthalenedicarbonyl chloride, gave thirteen ordered copolyamides, each containing a naphthylene and/or biphenylene group in its repeating unit. Differential thermal analyses and thermogravimetric analyses showed these polymers to have melting points or decomposition temperatures of from 420 to over 500°C. Films of one of the polymers had a breakdown voltage of 3000 v./mil at 180°C. Fibers of the same composition had tenacities of up to 8 g/den.; a 5.5 g/den. sample retained 85% of its tenacity after 17 hr. at 300°C. and 21% after 9 days.     

Synthesis and characterization of some aromatic polyamides containing double bonds

Ten polyfumaramides based on fumaric acid and aromatic diamines and six polystilbenediamides based on 4,4′-stilbenedicarboxylic acid and aromatic diamines were synthesized and characterized by solubility, viscosity, density, infrared and UV-visible spectroscopy, and thermal analyses. Variation in properties with structure is discussed here.     

New poly(amide-imide) siloxane copolymers by polycondensation

Some new poly(amide-imide) siloxane copolymers have been synthesized by solution polycondensation of some aromatic diamines with siloxanic diacids having preformed imide rings. Two polycondensation techniques were used: polycondensation of aromatic diamines with diacid chlorides and direct polycondensation of aromatic diamines with diacids in the presence of organic phosphites, following the Yamazaki-Higashi phosphorylation technique. In all cases the reactions were carried out using equimolecular amounts of the two monomers, in polar aprotic solvents and inert atmosphere.The obtained compounds were characterized by elemental C, H and Si analysis, solubility tests, IR and ¹H-NMR spectrometry. Thermogravimetric curves were also recorded. All data agree with the proposed structures.     

SYNTHESIS, CHARACTERIZATION OF DIAMIDE-DIIMIDE-DIAMINES BASED ON L-CYSTEINE AMINO ACID AND THEIR EFFECT ON THE THERMAL PROPERTIES OF DIGLYCIDYL ETHER OF BISPHENOL-A (DGEBA)

The curing behavior of diglycidyl ether of bisphenol-A(DGEBA) with aromatic diamide-diimide-diamines having aryl ether,sulfone and methylene linkages was studied by differential scanning calorimetry(DSC).Nine diamide-diimide-diamines of varying structure were synthesized by reacting 1 mole of dianhydride with 2 moles of L-cysteine(S) in a mixture of acetic acid and pyridine(3:2 V/V) followed by activation with thionyl chloride(SOCl_2) and then condensation with excess of diamines.Structural characterizat...     

N-Acylbenzotriazole: convenient approach for protecting group-free monoacylation of symmetric diamines

Monatshefte für Chemie - Chemical Monthly - An efficient green route for monoacylation of aromatic diamines, namely o-phenylenediamine and p-phenylenediamine and aliphatic diamines...