Homolytical Reaction Peculiarities of Phosphororganic Compounds

Abstract

The influence of the transient cyclic radical structure on the reactivity of unsaturated compounds in the processes of homolytical phosphorylation, and allyl and vinyl-phosphonates in the processes of homolytical perfluoro-alkylation is shown by the MINDO/3 method of quantum chemistry computations. The addition of allylderivatives of amides and esters of carbonic, aminocarbonic and carbamino-acids to phosphocentric radicals yields five-membered cyclic radical structures with NH- and O-heteroatoms in the cycle:     

New Methods of Preparation of Some Polyfunctional Pyrroline Derivatives

The reaction of dicyanomethylene compound 1 with nitrosoarene yields α-imino-β-dicyanomethylidene-α,β-diketobutyric acid anilides 2. Treatment of 2 with various nucleophiles leads to polyfunctional derivatives of pyrroline system 4–7.     

Preparation of Optically Active Compounds by Combination of Chemical and Enzymatic Methods

Many natural products contain γ-lactone moieties. For example, β-methyl-γ-butyl-γ-lactones (quercus lactones) are gradients of aged whiskey, and β-methyl-γ-(3-methyl-2-butenyl)-γ-lactone (eldanolide) is a pheromone of the African sugarcane borer. We synthesized such γ-lactones by hydrolyses of the homoallylic alcohols obtained by addition of aldehydes to the allylic anions generated from ketene dithioacetals or 2-propenyl-1,3-dithiane.     

New Methods for Preparation of Organoselenium and Organotellurium Compounds from Elemental Chalcogens

The review summarizes the results of studies in the field of development of efficient proceduresfor the synthesis of dialkyl chalcogenides, dialkyl dichalcogenides, vinyl and ethynyl chalcogenides, andselenium-, tellurium-, and silicon-containing heterocyclic compounds on the basis of elemental seleniumand tellurium.     

Oxidation of Some Furanoselenium Compounds

The organoselenium fragmentation under oxidative conditions to form a carbon-carbon double bond under very mild condition is well established.¹ So [2, 3] -sigmatropic rearrangements of allylic selenium species are well-known.     

Scalable Preparation of Benzimidazole Compounds

The preparation of benzimidazole compound 7, an ORL‐1 agonist, is described. The four‐step procedure gave the compound 7 in 29% overall yield.     

巯基化合物的电位分析法研究

本文对用直接电位法测试巯基化合物的可行性进行了研究。发现由硫化银，硫化汞等金属难溶盐制成的膜电极对６－巯基嘌呤，高胱氨酸，１，４－二巯基苏糖经合物可产生响应，其斜率为３０－１１０ｍＶ／ｐＣ，电极响应时间，则为十几秒至十几分钏，测试结果具有较好的重现性。因此，该方法可望得到应用。文中还对有关响应机理进行了探讨。     

某些新的氟代有机硅化合物的合成

本文用含硅氢键化合物与含双键的氟化合物的加成反应,制备了一系列未见报导的含氟有机硅化合物。在用氯丙烯与2,2,3,3-四氟丙醇制2,2,3,3-四氟丙基烯丙醚时,对方法进行了改进,提高了产率。本文还报道了含氟有机硅聚合物方面的工作。     

几种硝基苯甲酸卟啉酯类化合物的合成

卟啉化合物在模拟光合作用、探索高效利用太阳能等方面具有重要的理论意义和应用前景^[1]。近年来,人们对共价键相连的“卟啉-醌”类化合物研究较多,而关于“卟啉-硝基”类化合物的报道则较少,硝基具有强吸电子等特性,它作为“卟啉-硝基”类化合物的电子受体有利于分子内发生电子传递,可望是光合作用机理研究中的一类较好的模型化合物。为此,我们设计合成了具有不同性质的供体和不同位置的受体的8种新硝基苯甲酸及苯甲酸卟啉酯类化合物,它们的结构已分别通过质谱、核磁、红外、紫外可见光谱以及元素分析确证,结果见表1、2。     

Synthesis of Some New Fused/Spiroheterocyclic Compounds Incorporating Quinone Compounds

A series of fused and spiro pyrazolones, isoxazolines, pyrimidines, β‐lactams, and thiazolidinones incorporating 4‐amino‐2‐methyl‐5,10‐dioxo‐1,5,10,11‐tetrahydrobenz[g]quinoline 3‐carbonitrile 1 and 4‐amino‐2‐methyl‐5,6,11‐trioxo‐1,4,4a,5,6,11,12,12a‐octahydro‐1,12‐diazanaphthacene 3‐carbonitrile 2. 7,8a‐c, 15,16a‐c, 19,20a‐d, 21,22a‐d , have been synthesised by cyclocondensation addition reaction and cycloaddition reaction of hydrazines, hydroxylamine, urea, thiourea, monochloroacetyl chloride and mercaptoacetic acid with the synthesised 15,16a‐c and 17,18a‐c .     

Preparation for Supramolecular Complexes of Chiral Diols BDPDD,DMBDPD and BINOL with Some Prochiral Compounds

Interaction between chiral diols BDPDD,DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared.It was found that these chiral hosts could include prochiral guests,α，β-unsarurated compounds or pinperazinedione derivatives to give inclusion crystals in different molar ratio.Formations of these supramolecular complexes were characterized by the data of IR and ^H NMR spectra.     

Preparation of Stereodefined Secondary Alkyllithium Compounds

We have developed a practical stereoretentive iodine/lithium‐exchange process that allows the stereodefined preparation of cis‐ and trans‐cycloalkyllithium compounds from their corresponding stereodefined iodides. Quenching with electrophiles offers stereospecific access to both cis‐ (up to 96 % cis) and trans‐cycloalkyl derivatives (up to 99 % trans). A detailed study of the thermodynamic stabilities, stereochemical behavior, and reactivities of axially and equatorially substituted cyclohexyllithium reagents is reported. Ab initio calculations demonstrate that the formation of oligomeric cyclohexyllithium structures is pivotal for explaining the observed stereochemical preference.     

Organoboron Compounds: Effective Antibacterial and Antiparasitic Agents

The unique electron deficiency and coordination property of boron led to a wide range of applications in chemistry, energy research, materials science and the life sciences. The use of boron-containing compounds as pharmaceutical agents has a long history, and recent developments have produced encouraging strides. Boron agents have been used for both radiotherapy and chemotherapy. In radiotherapy, boron neutron capture therapy (BNCT) has been investigated to treat various types of tumors, such as glioblastoma multiforme (GBM) of brain, head and neck tumors, etc. Boron agents playing essential roles in such treatments and other well-established areas have been discussed elsewhere. Organoboron compounds used to treat various diseases besides tumor treatments through BNCT technology have also marked an important milestone. Following the clinical introduction of bortezomib as an anti-cancer agent, benzoxaborole drugs, tavaborole and crisaborole, have been approved for clinical use in the treatments of onychomycosis and atopic dermatitis. Some heterocyclic organoboron compounds represent potentially promising candidates for anti-infective drugs. This review highlights the clinical applications and perspectives of organoboron compounds with the natural boron atoms in disease treatments without neutron irradiation. The main topic focuses on the therapeutic applications of organoboron compounds in the diseases of tuberculosis and antifungal activity, malaria, neglected tropical diseases and cryptosporidiosis and toxoplasmosis.     

Quantitative and Qualitative Analysis of Three Classes of Sulfur Compounds in Crude Oil

Owing to the environmental hazards arising from sulfur‐containing combustion products, strong legal regulations exist to reduce the sulfur content of transportation fuels down to a few ppm. With the ongoing depletion of low‐sulfur crude oil reservoirs, increased technological efforts are needed for crude oil refining to meet these requirements. The desulfurization step is a critical part of the refining process but partly suffers from the recalcitrance of certain species to sulfur removal and the inability to quantitatively understand the behavior of individual compound classes during the process. We herein present a new and simple approach for the parallel quantification of three different classes of sulfur species present in crude oils by LC separation and on‐line detection and quantification by ICP‐MS/MS. This approach will help to estimate the amount of recalcitrant species and thus facilitate the optimization of desulfurization conditions during fuel production.     

Biological Studies of Some Perfluorophenyl Antimony Compounds

Perfluoroorganoantimony(III) (R_f)_nSbCl_{3? n} and -antimony(V) (R_f)_nSbCl_{5? n} (n = 1,2,3, R_f = C₆F₅) compounds are screened for the first time for biological activity. The compounds exhibited significant in vitro antitumor activity against MCF-7 (human breast cancer) cell line and antibacterial activity against three pathogenic bacteria: Pseudomonas aeruginosa, Staphylococcus aureus, and Klebsiella pneumoniae. They also showed antifungal activity against Aspergillus flavus and Aspergillus niger as well as insecticidal activity against cockroach (Periplanata americana), housefly (Musca domestica), Tobacco caterpillar (Spodoptera litura), and spider mite (Tetranychus urticae). These studies suggest a better biocidal activity for the pentafluorophenyl antimony halides compared to the corresponding phenyl analogues.     

一些二茂铁苯基亚胺化合物的合成与表征

通过回流对应的二茂铁苯胺和芳香醛的混合物的同样路径合成了一系列新颖的二茂铁苯基亚胺化合物(5~12)。当暴露于空气时化合物5~12稳定,不发生任何分解。所有化合物均用¹H、¹³C NMR,MS,IR,UV-Vis和元素分析表征。还报导了化合物N-(3-bromo-2-hydroxylbenzylidene)-4-ferrocenylimine(10)的单晶结构,其结晶属单斜晶系P2₁/c空间群。     

The Photooxidation of Some Anthryl Phosphorus Compounds

Abstract

The photo-oxidation of anthryl phosphorus compounds occurs via a Type II process. All products observed can be accounted for by involving a 9, 10-endoperoxide, which may subsequently fragment, resulting in cleavage of the phosphorus moiety from the anthracene nucleus.     

一些二茂铁苯基亚胺化合物的合成与表征

通过回流对应的二茂铁苯胺和芳香醛的混合物的同样路径合成了一系列新颖的二茂铁苯基亚胺化合物(5~12)。当暴露于空气时化合物5~12稳定,不发生任何分解。所有化合物均用¹H、¹³C NMR,MS,IR,UV-Vis和元素分析表征。还报导了化合物N-(3-bromo-2-hydroxylbenzylidene)-4-ferrocenylimine(10)的单晶结构,其结晶属单斜晶系P2₁/c空间群。     

α-Ferrocenylalkylation of Some Biologically Active Compounds

Russian Journal of Organic Chemistry -