联机卡尔曼滤波光度法同时测定混合体系中5种合成食用色素

我国法定可使用的合成食用色素主要有5种。即苋菜红、胭脂红、柠檬黄、日落黄和亮蓝。根据调色需要,它们常被混合配置应用.目前一般采用高效液相色谱和层析分离法分析,但尚缺少可靠的同时测定此5组分的化学计量学方法,Loosbroek曾用卡尔曼滤波光度法鉴     

Homolytic Cyclizations of N-Chloroalkenylamines

Many N-chloroalkylamines with double bond(s) dissociate homolytically to give chlorine atoms and aminyl radicals which undergo intramolecular cyclization reactions. Here, the nature of the aminyl radicals (neutral, protonated, or complexed to metal salts) appears to be important. The reactivity varies strongly from one species to another, and their selectivities can be different towards addition, substitution, abstraction, or dimerization reactions. A good synthetic tool appears to be the “complexed radical”, which is generated under mild conditions. A variety of β-functionalized, substituted, fused, or bridged azaheterocycles with alkaloid part structures thus become easily accessible in high yields, in a regio- and, possibly, stereoselective manner. Many examples are discussed illustrating the synthetic possibilities, limitations, and mechanistic features of this cyclization process.     

Determination of dopamine in synthetic cerebrospinal fluid by SWV with a graphite–polyurethane composite electrode

This work describes an electroanalytical investigation of dopamine using cyclic voltammetry (CV) and the graphite–polyurethane composite electrode (GPU). In CV studies, well-defined redox peaks characterize the oxidation process at the GPU electrode, which is indicative of electrocatalytic effects associated with active sites on the GPU electrode surface. A new analytical methodology was developed using the GPU electrode and square wave voltammetry (SWV) in BR buffer solution (0.1 mol L^–1; pH 7.4). Analytical curves were constructed under optimized conditions (f=60s^–1, E_a=50 mV, E_I=2 mV) and detection and quantification limits of 6.4×10^–8 mol L^–1 (12.1 g L^–1) and 5.2×10^–6 mol L^–1 (0.9 mg L^–1), respectively, were achieved. The precision of the method was checked by performing ten successive measurements for a 9.9×10^–6 mol L^–1 dopamine solution. For intra-assay and inter-assay precisions, the relative standard deviations were 1.9 and 2.3%, respectively. In order to evaluate the developed methodology, the determination of dopamine was performed with good sensitivity and selectivity, without the interference of ascorbic acid in synthetic cerebrospinal fluid, which indicates that the new methodology enables reliable analysis of dopamine.     

Cyclizations via Palladium-Catalyzed Allylic Alkylations [New Synthetic Methods (79)]

The history of ring systems in organic chemistry parallels their synthetic accessibility. Transition-metal-catalyzed cyclizations offer a new opportunity to create carbo- and heterocyclic compounds with great facility. Among these methods, allylic alkylations catalyzed by palladium have proven unusually productive because of the extraordinary chemo-, regio-, and diastereoselectivity and the continuing possibility for the development of enantioselectivity. The rules for ring closure differ from those for non-transition-metal-catalyzed reactions. A major benefit is the ability to generate medium (eight-, nine-, ten-, and eleven-membered) and large rings in preference to normal (five-, six- and seven-membered) rings. With the appropriate substrate, efficient macrocyclizations are possible under conditions of normal concentrations. A second major benefit derives from the complementary stereochemistry of the metalcatalyzed substitution (net retention of configuration) compared to non-metal-catalyzed reactions (inversion of configuration). Further, the requirement for the substrate to conform to the transition-metal template may impose a stereochemical preference in the intermediate that ultimately translates into the thermodynamically less stable organic product regardless of the stereochemistry of the starting material. While more work has focused on carbocyclic synthesis, the possibilities for heterocyclic synthesis are just beginning to be tapped. In addition to forming heterocycles by C? C bond formation, use of a heteroatom as a nucleophile has already proven effective for oxygen and nitrogen, with other nucleophiles awaiting investigation. New dimensions for cyclization via allylic alkylation arise by generating the requisite π-allylpalladium intermediates by methods other than palladium(0)-initiated allylic ionizations. In addition, metals other than palladium will clearly expand the possibilities, but as yet remain untapped.     

混合食用色素的卡尔曼滤波光度分析

本文用联机卡尔曼滤波光度法成功地同时测定了混合合成食用色素样品中五个组分。它们分别是40号红、苋菜红、柠檬黄、日落黄和亮蓝。方法准确、快速,无需予分离。     

Studies of chromium cages and wheels

Studies of two distinct classes of chromium(III) cage complexes are discussed. The first are compact oxo- and carboxylate cages, made by heating precursors to high temperature under a flow of nitrogen. One of these cages, [Cr₁₂O₉(OH)₃(O₂CCMe₃)₁₅], has an S = 6 spin ground state which proves a very interesting subject for study by EPR and MCD spectroscopy. Use of other carboxylates leads to other octa- and dodeca-nuclear complexes. The second class of compounds are homo- and hetero-metallic wheels and chains bridged by fluoride and carboxylates. These include the first heterometallic anti-ferromagnetically coupled ring systems and are being widely studied in areas as diverse as magnetic cooling and quantum information processing. The mechanism by which these unusual cyclic and acyclic structures form is discussed.     

Capto-dative Substituent Effects in Syntheses with Radicals and Radicophiles [New synthetic methods (32)]

The 100 yers old Wurster's salts have long been recognized as compounds with redical cations. Their unusual stabilization derives partly form capto-dative (cd) substitution. This principle is now discussed as one factor of radical stabilization and it is applied to simple methine derivatives. cd-Substitution has synthetically useful applications: cd-substituents on a carbon atom allow its selective dehydrodimerization. Olefines with geminal and thus cross-conjugated cd-substituents are “radicophilic” and permit twofold carbon radical addition. cd-Substituted olefines are useful antioxidants, polymerization inhibitors and are promising agents in the control of biological radical reactions. Generally, many reactions of cd-substituted molecules appear to involve radicals.     

New Possible Applications of Heavy Main-Group Elements in Organic Synthesis

Aside from elements of the 2nd row, and one element of the 3rd row of the periodic system—Si, P, S, and Se, respectively, whose organoelement groups such as Me₃Si and Ph₃P^⊕ have proven useful in numerous organic syntheses—other elements of the 3rd as well as 4th and 5th row (Ge, As, Sn, Sb, Te, Pb, Bi) can also be used as components of synthetically useful organoelement groups, the elements As, Sn, and Pb, in particular, offering certain advntages over the others. Some of these organoelement groups are suitable equivalents for Li- or halogen-substituents attached to carbon; they stabilize carbanionic centers (minimum of this effect at the 3rd-row elements), and owing to their suitability as leaving groups in β-eliminations, also open up interesting synthetic possibilities. The thermally unduced syn- and silica-gel induced anti-elimination of Ph₃Sn, Ph₂Sb, Ph₃Pb, together with β-OH, are novel. With the newly synthesized compounds Ph_nEl—Ch₂—Li (El = Sn, Pb, As, Sb, Bi) and other α- and β-lithiated R_nEl- and Ph₂As(O)-reagents such organoelement groups can be introduced into organic compounds and exploited in organic and organoelement synthesis.     

Recent Applications of α-Metalated Isocyanides in Organic Synthesis

Being both nucleophilic and electrophilic, α-metalated isocyanides can add to polar double bonds, forming heterocycles. They are also synthons for α-metalated primary amines. This article describes recent or improved procedures for their use in organic synthesis: (1) In heterocyclic syntheses to give 2-oxazolines, 2-imidazolines, 2-thiazolines, oxazoles and oligooxazoles, thiazoles, triazoles, imidazolinones, pyrroles, 5,6-dihydro-1,3-oxazines and -thiazines, and (via cycloaddition with nitrones) 2-imidazolidinones. (2) In the field of formylaminomethylenation, for example transformation of estrone methyl ether and a keto sugar into the corresponding α-formylaminoacrylic esters, and the conversion of aldehydes and ketones by 3- and 4-pyridyl-methyl isocyanides into N-(1-pyridyl-1-alkenyl)formamides and their hydrolysis to 3- and 4-acylpyridines. (3) In connection with the use of α-metalated isocyanides as synthons for α-metalated primary amines, the author demonstrates how they may be used for preparation of 1,2- and 1,3-amino alcohols, 1,2-diamines, 2,3-diaminoalkanoic acids and for synthesis of higher amino acids starting from simple amino acids.     

Thin-layer and gas chromatographic separation of the stereoisomers of some synthetic pyrethroids

Summary Analytical conditions were established permitting the enabling separation of the cis-trans stereoisomers of selected synthetic pyrethroids with help of thin-layer and gas chromatography. Using the example of permethrin the possibility of isomeric separation in an oilbased commercial formulationis also illustrated.