N－甲基咪唑与氯高铁血红素取代反应动力学

本文用停流法和分光光度法研究了［Ｆｅ（ｐｏｒ）Ｃｌ］（ｐｏｒ＝原卟啉（ｐｐ）或对应的二甲酯（ｐｐｄｍｅ））与Ｎ－甲基咪唑（Ｎ—ＭｅＩｍ）的亲核取代反应动力学，讨论了反应机理，求得前置平衡的平衡常数（Ｋ）和基元步骤的速率常数（ｋ１），研究了温度对反应动力学的影响，得到平衡步骤的和基元步骤的活化参数     

THE REACTION OF CARBOXYLIC ACID CHLORIDES WITH 2,4-BIS(4-METHOXYPHENYL)-1,3,2,4-DITHIADIPHOSPHETANE 2,4-DISULFIDE

Abstract

Carboxylic acid chlorides react with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4- disulfide to give the intermediates 2a,b; 2'a,b) which are useful as thioacylating agents. Compounds 2 react with amines under mild conditions to give the corresponding thioamides.     

N－甲基咪唑与氯高铁血红素取代反应动力学

本文用停流法和分光光度法研究了[Fe(por)Cl](por=原卟啉(pp)或对应的二甲酯(ppdme))与N-甲基咪唑(N-MeIm)的亲核取代反应动力学,讨论了反应机理,求得前置平衡的平衡常数(K)和基元步骤的速率常数(k1),研究了温度对反应动力学的影响,得到平衡步骤的和基元步骤的活化参数     

微圆盘电极上耦合—级均相反应的稳态电流

在电极袭面反应物浓度均匀的近似假设下,得到了微圆盘电极上暂态可逆反应的一般解.然后利用该一般解得到了微圆盘电极上耦合一级均相反应的可逆电极反应CE、EC、EC′和ECE 的稳态电流计算公式.     

THE REACTIONS OF N3P3CL6 AND RELATED COMPOUNDS WITH DIFUNCTIONAL REAGENTS. COMPARISONS AND CONTRASTS

Abstract

The reactions of N₃P₃Cl₆ with a variety of difunctional reagents are discussed. NMR spectroscopic and X-ray crystallographic investigations are presented.     

碳-氮双键固相光加成的新化学反应研究──吲哚与苄叉苯胺的固相光化学反应

本文研究了苄叉苯胺与吲哚的固相光化学反应,分离出两个新化合物,它们的结构由MS、IR、¹HNMR、UV和元素分析得到了确定,对固相光化学反应历程进行了初步探讨。     

含活泼亚甲基多环芳烃与N—溴代丁二酰亚胺的光化学反应

多环芳烃主要来自煤焦油 ,由于这些化合物电子密度高和对称性好 ,在合成耐热性高分子和液晶高分子等聚合物材料方面优于单环芳烃 ,在高性能染料、涂料、医药和农药的合成上也具有良好的应用前景 ,因此探索煤焦油中富含的多环芳烃的转化和利用是提高煤非燃料利用的有效途径。本文利用ＮＢＳ(Ｎ 溴代丁二酰亚胺 )作为光溴化剂 ,研究了温和条件下ＮＢＳ与几种典型的含活泼亚甲基芳烃的光化学反应 ,通过对芴、二苯甲烷 (ＤＰＭ )和二 (1 萘 )甲烷 (ＤＮＭ)等含活泼亚甲基的多环芳烃进行官能团转化 ,得到活泼的溴代中间体 ,为进一步合成多环芳烃…     

菲涂在颗粒物上与NO_2的反应

本文研究菲涂在硅胶或烟尘上与NO_2的暗反应和光化学反应,藉色谱和GC/MS分析反应产物。暗反应以取代反应为主,主要产物是硝基菲.光反应的产物为2,2′-二甲酰基联苯、亚硝基-2-甲酰基联苯等,在UV辐照下以光氧化裂解为主。菲涂在硅胶上或涂在烟尘上与NO_2的暗反应的明显差异可能是由于吸附在硅胶上的水分子与菲对NO_2的竞争反应。产物的Ames试验指出,无致突性的菲与NO_2反应可较容易地生成有直接致突性的二次污染物,对人体健康更有危害。     

SOME REACTIONS OF CHOLESTERYL N-PHENYL-PHOSPHORAMIDIC CHLORIDE AND RELATED COMPOUNDS

Abstract

Cholesteryl N-phenylphosphoramidic chloride has been converted to the corresponding phosphoramidic hydrazide and azide. The former compound was characterised by the preparation of a number of hydrazones, while the latter has been reacted with norbornene, dimethylsulphoxide, and triphenylphosphine. However, the azide did not react with decane, o-anisole, or butylamine. 17-Oxoandrost-5-ene-3β-yl N-phenylphosphoramidic chloride was prepared and was converted to the hydrazide, but a pure sample of the azide could not be isolated. Cholesteryl N-phenyl phosphoramidic triphenylphosphinimine has been reacted with eight carbonyl compounds and the structures of the products investigated. Cholesteryl N-cyclohexylphosphoramidic chloride was converted to the azide and the triphenylphosphinimine; the latter was reacted with acetone and p-nitrobenzaldehyde.

Cholesteryl phosphorodichloridate has been condensed with phenol, p-nitrophenol, and p-methoxyphenol to give the corresponding O-arylphosphorochloridates. The O-phenyl and O-p-methoxyphenyl phosphorochloridates have been converted to the corresponding azides, but the azide from the p-nitrophenyl derivative could not be isolated. The reactions of cholesteryl phosphorodichloridate with diethylamine, hydrazine, and sodium azide have also been examined; and cholesteryl phosphorodichloridothioate has been condensed with aniline and benzylamine.     

光诱导的5,5-二取代二氢吡咯类硝酮与N-溴代琥珀酰亚胺的反应

光化学反应,自由基聚合反应,物质的辐射裂解以及生物体内的癌变过程都涉及自由基中间体,因此对活泼自由基中间体的研究越来越引人注目。而邻位双取代二氢吡咯类硝酮(Nitrone)能有效地捕捉多种类型的活泼自由基,其中5,5-dimethyl-1-Pyrroline N-oxide(DMPO)被广泛应用于自由基研究。然而,对这一重要的活泼自由基捕捉剂与常用的溴化试剂 N-溴代琥珀酰亚胺(NBS)反应的研究至今未见报道。     

硫化氢对二茂铁乙烯基芳酮亲核加成反应的研究

关于二茂铁基与羰基相连的α,β-不饱和劳酮和硫化氢的亲核加成反应,我们曾有过报导。研究表明,由于二茂铁基的影响使该类加成反应与Michael加成反应规则不同。本文继续研究三茂铁基与烯基相连的α,β-不饱和芳酮和硫化氢的亲核加成反应,制得了四种尚未见报导的β-二茂铁基-β-或α-巯基丙酰基芳烃:     

REACTIONS OF TELLURIUM TETRAHALIDES WITH GLYCOLS

Abstract

Tellurium tetrahalides undergo reaction with glycols to yield three different products: O,O'-dioxotrihalotellurates; bis(alkoxy)dihalotellurium (IV) compounds and hexahalotellurates. The course of the reaction appears to be determined primarily by the nature of the glycol. The structure of dichlorobis(cis- 2-hydroxycyclohexyloxy)tellurium(IV) has been determined crystallographically     

含光学活性联二萘酚基团可溶性高分子手性配体的合成及其不对称加成反应

不对称催化是有机化学研究的前沿领域和发展方向．近10年来,手性配体的研究得到了长足的发展,大量的小分子手性配体被报道,其中许多手性配体展示了优异的催化性能．但是由于昂贵的手性配体（金属催化剂）分离、回收和再利用的问题,从而限制了小分子催化剂的应用．因此,解决手性金属催化剂的分离与回收问题是不对称催化研究领域的一个热点问题．为了解决这一关键问题,国内外科学家从负载的角度出发已经成功地发展了众多的研究方法,无机负载法、交联高分子负载法、可溶性高分子负载法、树状大分子负载法等．许多负载的手性金属催化剂已经表现出优异的催化活性和高的对映选择活性．     

A REGIOSPECIFIC SYNTHESIS OF 1-HETEROCYCLIC SUBSTITUTED 1,2,4-TRIAZOLES VIA ADDITION REACTION OF 1,2,4-TRIAZOLE WITH FUNCTIONALIZED CARBODIIMIDE

ABSTRACT

The reaction of 1,2,4-triazole with functionalized carbodiimide 2 or 6 under solid K₂CO₃ provide a convenient and regiospecific route to 1-(2-imidazolonyl)-1,2,4-triazole 4 or 1-(2-quinazolonyl)-1,2,4-triazole 8.     

REACTIONS OF XENON DIFLUORIDE WITH ORGANO-SULPHUR MOLECULES

Abstract

Xenon difluoride readily reacts with various organo-sulphur compounds. In general, three types of products were isolated, the course of the reactions depending on the structure of the organo-sulphur substrate. Alkyl-phenyl substituted sulphides, 3,3-dibromothiochroman-4-one and thiochroman-4-ol reacted to form α-fluoro substituted products, 2,5-diphenyltetrahydrothiopyran-4-one, thiochroman-4-one and 3-bromothiochroman-4-one formed dehydrogenated products, while diphenyl-sulphide, dibenzothiophene and 10-thioxanthenone reacted to form sulphoxide and sulphone. The reaction mechanism and the reaction pathways, which are shown on the Scheme, will be discussed.     

固相配位化学反应研究 LV.FeCl_2·4H_2O,CoCl_2·6H_2O,NiCl_2·6H_2O,CuCl_2·2H_2O与邻菲咯啉的低热固相化学反应研究

邻菲咯啉(Phen)与过渡金属离子在液相中的反应速度很快,瞬间即可完成,形成稳定的配合物。过渡金属氯化物在水溶液中反应时,一般是以水合离子[M(H_2O)_6]~(2+)的形式参加反应。而在固相中参加反应物质的形式是其物质本身的凝聚态分子。因此,尽管是同一反应物,但在固相,液相反应中,参加反应物质的形式不同,可能产生两种不同的反应结果。为了比较固、液相反应的差别,寻找固相反应的规律性。我们研究了FeCl2_·4H_2O,CoCl_2·6H_2O,NiCl_2     

S-(1-二茂铁烷基)硫代乙醇酸与胺的反应——一类新型二茂铁衍生物的合成与性质研究

Ratajczak等研究了S-(1-二茂铁烷基)疏代乙醇酸的合成与反应(?)Ugi等将它们与羟胺反应,合成了一种有用的手性模板试剂。最近,Czech等用键合载体液相色谱对它们进行了光学拆分研究。本文报导了此类化合物与胺的反应,合成了一类新的化合物(?)二茂铁烷基)硫代乙醇酸胺。     

STUDIES ON CYCLOADDITION REACTIONS OF VINYLPHOSPHONATES WITH NITRONES

Cycloaddition reactions of vinylphosphonates with nitrones were studied. A series of 4-phosphonyl-3-aryl-N-arylisoxazolidines were synthesized by the reaction of vinylphosphonates with nitrones. The structure of 3a was confirmed by X-ray single-crystal diffraction.     

STEREOSELECTIVE REACTIONS OF CHIRAL AMINES WITH RACEMIC CHLOROPHOSPHINES

Racemic chlorophosphines react stereoselectively with chiral l-phenylethylamines or amino acid esters to give diastereomerically enriched aminophosphines 3, which were isolated as diastereomerically pure crystalline borane complexes. Oxidation, thionation, the reaction with methyl iodide provide optically active derivatives of aminophosphines. (R,S)- and (S,S)-stereomers of phosphinic acid amides were separated by crystallization and a flash-chromatography. The stereochemical properties of phosphorus acid amides were investigated. The mechanism of asymmetric induction at the trivalent phosphorus atom was rationalized.