STRUCTURAL RULES OF TRANSITIONMETAL CARBONYL COMPOUNDS

In this article we have proposed two topological rules to account for the electronic structures of transition-metal carbonyl compounds. The second rule is applied to those which have polyhedral metalhc skeletons with triangular faces and their derivates, while the first rule is applied to all the others We have used these two rules to analyze 261 structure-known compounds with the number of metal atoms from 2 to 12, and the results show that the two rules are in good agreement with the experimental facts. Furthermore, we have also derived from the second rule a formula which can be used to account for the electronic structures of closedpacking carbonyl compounds and which is the same as that given by Ciani and his coworkers.     

REACTIONS OF DERIVATIVES OF PHOSPHORUS ACIDS WITH CARBONYL COMPOUNDS ACTIVATED BY ELECTRONEGATIVE GROUPS

Abstract

The Arbuzov reaction results in the synthesis of various phosphonic esters and is of great importance for the further development of the chemistry of organophosphorus compounds. Investigations of recent decades have shown that, besides halogen-containing organic compounds, different types of organic compounds of the electrophilic type which do not contain halogen atoms are capable of entering this reaction. Reactions with carbonyl compounds are especially interesting. This report presents the results of reactions of derivatives of tricoordinated phosphorus (trialkyl phosphites, amidophosphites, ester anhydrides, isocyanate phosphites) with carbonyl compounds. Special emphasis was placed on studying the reactions with carbonyl compounds activated by some electronegative groups. The regularities and mechanisms of these reactions were investigated depending on the structure of the carbonyl compounds, the derivatives of tricoordinated phosphorus and the reaction conditions.     

A NEW METHOD FOR THE PREPARATION OF CARBONYL DIAZO COMPOUNDS

Azo compounds are very important in organic chemistry. In resent years, some notoworthy studies show that azobenzene derivatives possess very good optic remembering and photoelectric properties, optical switching and image storage by means of azobenzene liquid crystal film.^1,2 We have reported some new methods for the Azo compounds³. In this paper, We describe a new oxidation system KCIO₃/H₂SO₄ catalyzed by FeSO₄ to synthesis diazo compounds (ArN=NCON=NAr) in short time and good yield for the first time.     

REACTIONS WITH PHOSPHACUMULENES: SYNTHESIS OF PYRAN DERIVATIVES FROM THE REACTION OF N-PHENYLIMINOKETENYLIDENE TRIPHENYL-PHOSPHORANE WITH α,β-UNSATURATED CARBONYL COMPOUNDS

Abstract

2-Benzylidene-1,3-indanedione (2), 4-benzylidene-1,2-diphenyl-3,5-pyrazolidenedione (4) and/or 5-benzylidenebarbituric acid (6) can be converted by reaction with N-phenyliminoketenylidene triphenylphosphorane (1) into pyransubstituted phosphoranes 3, 5 and 7. The structure of the new cyclic imino-phosphoranes 3, 5 and 7 was confirmed on the basis of elemental analysis and spectral studies. Moreover, when Wittig reaction was carried out on the pyran compound 7, using p-nitrobenzaldehyde, the new olefin 8 was isolated.     

REDUCTION OF CARBONYL COMPOUNDS TO THE CORRESPONDING ALCOHOLS WITH ISOPROPANOL ON DEHYDRATED ALUMINA UNDER MICROWAVE IRRADIATION

ABSTRACT

The reduction of different types of aldehydes and ketones were performed in the presence of isopropylalcohol (as solvent and hydride source) under microwave irradiation. It is proved that dehydrated Woelm chromatographic alumina supported KOH catalyses these transformations. Regioselectivity was observed in the reduction of cinnamaldehyde and chemoselectivity was observed in the reduction of carbonyl in the presence of nitro group.     

REACTIONS OF THE RHODIUM TRIFLUOROACETATE DIMER WITH NUCLEOSIDES AND NUCLEOTIDES

Abstract

Complexes of rhodium trifluoroacetate with adenosine (ado), adenosine-5′-momophosphate (AMP), cytidine (cyd), guanosine (guo) and inosine (ino) have been prepared from aqueous or methanolic solutions. They were characterized by elemental analysis, magnetic susceptibility measurements, mass spectra, infrared, visible and nuclear magnetic resonance spectroscopies. In some cases their formation was followed by NMR prior to isolation. They all proved to be diamagnetic and in every compound contain two ligand molecules per rhodium dimer except for the ado complex where the ratio is 1:1. In the solid state it was found that adenosine interacts with the metal via the N(1) and N(7) atoms, its nucleotide through N(7), whereas in the case of cyd, guo and ino their exocyclic oxygen atoms take part in coordination. Solution study seem highly interesting since in some cases more than one species appear.     

D-葡萄糖D-果糖与硼的有机物形成配合物的稳定性研究

葡萄糖异构酶加速葡萄糖与果糖的平衡,平衡时果糖含量为42％左右,体系中加入一些硼酸盐,果糖的含量提高到80％左右,究其原因可能是由于葡萄糖和果糖与硼酸盐形成不同稳定性的配合物。虽然Roy,Conner,Daris,Belcher,Lorand等都已报导了这些配合物的稳定常数,概括结果分歧较大。Belcher曾首次报导了硼酸与D-果糖的配位数为     

Kishner-Wolff改良法——Ⅹ.邻芳族羟基羰基化合物的还原

研究了邻芳族羟基羰基化合物的Kishner-Wolff改良法还原,并讨论了它们的反应机制.萘酚系羰基化合物5与6中的R为H或C₆H₅(5a、6a、6b)时,还原后得高得率的正常还原物;如R为C₆H₅CH₂,C₆H₆CH₂CH₂(5b、5c、6c),则除得正常还原物外,还得含氮环化物;如R为CH₃、CH₃CH₂、CH₃CH₂CH₂、(CH₃)₂CH(5d～g),则同时得正常还原物及含氮环化物,增加R中碳原子数,似乎使正常还原物减少,而含氮环化物增加.当R为CH₃(CH₂)₆(5h),则仅得含氮环化物.苯酚系羰基化合物7中的R为烷烃基或芳族基时,均得高得率的正常还原物.     

REACTIONS OF THE SUBSTITUTED THIOUREAS WITH PLATINUM COMPOUNDS

Abstract

Thiourea and its derivatives easily form the complexes with compounds of Cu^II, Fe^III, Pt^IV etc. By the formation of complexes as a rule redoxprocess proceeds to give an appropriate thiourea disulphide. It has been shown, that redoxprocess goes on prejudice on the derivatives of thiourea in that case when the thion-thiol tautomerism is possible.     

以二甘醇相连的双卟啉金属配合物的合成和X-射线光电子能谱的研究

本文通过二甘醇二氯化物和不对称四苯基卟啉的反应合成了新的二甘醇相连的双卟啉金属配合物。合成的双卟啉金属配合物有(3)(Cu-Cu),(4)(Co-Co)和(5)(Cu-Co),它们的结构经IR、UV、NMR和XPS确证。     

卟吩复合体的电子结构

本文用EHMO法对卟吩及其复合体的电子结构进行了计算。由卟吩复合体的差示电荷分布的分析表明, 在卟吩复合体中卟吩分子属于两性电子施受体, 分子中有固定的施体中心和受体中心部位。体系在相对取向角φ为45°时能量最小。两个分子相对旋转一周要克服四重势垒, 势垒高度为～0.09 eV。本文把简并态微扰理论推广运用于两个分子组成的复合物体系, 并由此定量地解释了卟吩与其复合体之间存在的能级对应现象。     

含酮基吸附剂对莱鲍迪甙A的吸附选择性研究

合成了一系列具有不同骨架结构的中极性含酮基大孔吸附树脂，研究了树脂极性与骨架结构的关系，讨论了树脂对甜菊糖中两种主要糖甙甜菊甙及莱鲍迪甙Ａ的吸附能力和吸附选择性，并设计通过树脂柱的动态色层法从甜菊甙含量高的甜菊糖中成功地分离出高莱鲍迪甙Ａ糖产品．     

SEPARATION OF SOME AROMATIC CARBONYL COMPOUNDS BY THIN LAYER CHROMATOGRAPHY OF THEIR ISONICOTINOYL HYDRAZONE DERIVATIVES

Abstract

The separation of 13 isonicotinoyl hydrazones derived from some isomeric aromatic carbonyl compounds by thin layer chromatography is described. Methods for separating and identifying the components of complex mixtures of these hydrazones are discussed.     

STUDY ON THE COORDINATION COMPOUNDS OF RARE EARTHS WITH DIPEPTIDE-COORDINATION OF RARE EARTHS WITH DL-ALANYL-ALANINE

In this paper protonation constants of the title lisand and stability constants of its coordination compounds with rare earths have been determined by potentiometric titration at 25±0.1℃ and ionic strength of 0.10mol.dm~(-3)NaClO_4. The coordination of rare earths with DL-alanyl-alanine has been discussed. The stability of the coordination compound shows "tetrad effect". The position for yttrium shifts from its usual Bo-Er region to the vicinity of Tb.     

A FLUORESCENCE STUDY OF THE INTERACTION OF INDOLIC COMPOUNDS WITH SYNTHETIC POLYELECTROLYTES

Abstract— –The interaction of indole derivatives with synthetic polyelectrolytes was investigated using UV absorption and fluorescence spectroscopy. The presence of both sodium poly(styrene sulfonate) (PSS) and sodium polyvinyl sulfonate) (PVS) inhibits the fluorescence quenching of 1-pyrene sulfonic acid by tryptamine. The effect is more marked for PSS than for PVS. There was no polyelectrolyte effect on the quenching by tryptophan. It was also found that aromatic polyelectrolytes strongly quench the fluorescence of indole derivatives of opposite charge by a static mechanism. This is accompanied by a new absorption in the red extreme of the UV spectrum of the mixtures. The systems investigated were tryptamine-PSS and polyvinyl benzyl trimethylammonium chloride) with the anions of indole-3-alkanoic acids. Equilibrium constants for the binding of the indole derivatives to the polyelectrolytes were determined. The fluorescence of zwitterionic tryptophan is not affected by the presence of the polyelectrolytes.     

THE KINETICS AND MECHANISM OF THE REACTION OF TRICOORDINATE PHOSPHORUS COMPOUNDS WITH SULFENATE ESTERS

Abstract

The kinetics and mechanism of the reaction of tricoordinate phosphorus compounds, Ar_nP(OCH₂CF₃)_3-n with arylsulfenate esters, ArSOCH₂CF₃, are reported. Product analysis, kinetic order, activation parameters, Hammett data and solvent effects are the criteria used to elucidate the two step mechanism involving arylthiophosphoranes as intermediates.     

超声辐射下某些含官能团化合物与二氯卡宾的反应

超声辐射在有机反应中的应用日趋广泛。我们曾报道了超声辐射与相转移催化相结合产生二氯卡宾和二溴卡宾的方法及其与烯烃加成反应的结果。该法比单纯使用相转移催化剂或超声辐射更为可取。本文进一步将它用于二氯卡宾与某些含官能团化合物的反应,考察超声辐射的影响。反应是在固-液两相条件下进行的,即以粉末状氢氧化钠为碱,氯仿过量兼作溶剂。结果表明,超声辐射对各类化合物反应的影响有相当明显的差异。     

OXIDATION OF α-METHYL OR α-METHYLENE GROUPS IN CARBONYL COMPOUNDS WITH AMMONIUM CHLOROCHROMATE

This paper reports a new method for oxidizing the α-methyl orα-methylene groups in carbonyl compounds into 1,2-dicarbonyl compoundsby ammonium chlorochromate(ACC).     

A CLEAN CONVERSION OF CARBONYL COMPOUNDS TO OXIMES USING SILICA GEL SUPPORTED HYDROXYLAMINE HYDROCHLORIDE

The efficient condensation of carbonyl compounds with hydroxylamine hydrochloride under solvent free conditions is described.