Reactions of Epoxides Prepared from Some Monoterpenes with Acetic Anhydride on Aluminosilicate Catalysts

Reactions of epoxides prepared from -, -pinenes and camphene with acetic anhydride on aluminosilicate catalysts (clay K-10, zeolite ) were investigated affording various products of skeleton rearrangements: mono- and diacetates with five- and six-membered rings, and also with norbornane and pinane cores.     

Isomerization of Xylenes in the Presence of Pt-Containing Catalysts Based on Halloysite Aluminosilicate Nanotubes

Pt-containing catalysts based on halloysite aluminosilicate nanotubes and ZSM-5 zeolite were synthesized. The structure of the materials was confirmed by low-temperature nitrogen adsorption/desorption and by transmission electron microscopy. The activity and selectivity of the synthesized catalysts based on micromesoporous supports in isomerization of the xylene reforming fraction was studied on a flow-through laboratory installation with a fixed catalyst bed in the temperature interval 360–440°С at elevated hydrogen pressure. The influence exerted by the textural characteristics of the support and acidity of the materials on the catalyst activity in isomerization of o- and m-xylenes and of ethylbenzene with the aim of obtaining p-xylene was studied.     

2,3-联烯醇及其衍生物的反应

2,3-联烯醇是一类含1,2-二烯官能团和羟基的化合物, 具有很高的反应活性, 它及其衍生物是一类重要的联烯化合物. 概述了2,3-联烯醇及其衍生物的反应, 包括2,3-联烯醇在过渡金属催化下的自身异构环化反应、钯催化的偶联反应、钌催化的环羰基化反应、不同条件下不同方式的扩环反应、亲电试剂参与的反应、分子内环加成反应、自由基反应等和2,3-联烯醇衍生物在零价钯催化下基于亚甲基-π-烯丙基钯中间体生成联烯或1,3-共轭二烯的区域选择性反应, S_N2'类型的加成-消除反应, 二价钯催化下的分子内环化反应以及重排反应等.     

Mixed Anhydrides of Carboxylic and Trifluoroacetic Acids as Acylating Agents: I. Reactions of 3,5-Di-tert-butylbenzoyl Trifluoroacetate with tert-Butylphenols

The rate and pathway of reactions of 3,5-di-tert-butylbenzoyl trifluoroacetate with tert-butylphenols depend on the number and position of bulky substituents determining the extent of steric shielding of the phenolic hydroxyl.     

Reacton of Representative 2-Acyl-1,3-dithianes with Alkylating and Acylating Agents

2-cyclohexanoyl-1,3-dithiane 2, a representative 2-acyl-1,3-dithianes, reacts with various alkylating and acylating agents affording masked polycarbonyl coumpounds.     

Synthesis and Reactions of Some New Quinazoline Derivatives for In Vitro Evaluation as Anticancer and Antimicrobial Agents

A novel series of N,O,S heterocyclic compounds incorporated at position‐3 of a quinazolin‐4(3H)‐one moiety were synthesized through a p‐phenloxy binding including oxadiazolethione pyridazinetrione, thiazolidinedione, benzothiazindione, and quinazolinedione. New carbamates, urea derivatives, and Mannich bases were also prepared for the purpose of in vitro anticancer cell lines evaluation and cytotoxic activity. The key intermediate 2‐(4‐chlorophenyl)‐3‐(4‐hydroxyphenyl)quinazolin‐4(3H)‐one was prepared from the reaction of 4H‐benzo [d][3,1]oxazin‐4‐one and a nitrogenous nucleophilic compound, 4‐aminophenol. Some of the newly synthesized compounds showed significant cytotoxic activity.     

Synthesis of Indole 2,3-Epoxypropyl Derivatives and Their Reactions with Amines

Indole derivatives with a 2,3-epoxypropyl substituent attached to nitrogen were synthesized. In reactions with primary and secondary amines these compounds afforded the corresponding 1,2-aminoalcohols.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 243–246.Original Russian Text Copyright © 2005 by Suzdalev, Babakova.     

金催化剂及其在有机反应中的应用研究进展*

本文综述了金催化剂在选择氧化、选择加氢、不对称醇醛缩合、C-N键生成等多相和均相催化反应中的应用研究,并讨论了各种影响金催化剂催化活性的因素,最后展望了金催化剂的应用前景.     

Convenient Methodology for Some Heterocyclization Reactions with Thioxopyrimidine Derivatives

Russian Journal of Organic Chemistry - A simple and efficient method for derivatization of the pyrimidine nucleus is developed. The readily available 6-amino-2-thioxo-2,3-dihydropyrimidin-4(1H)-one...     

4-Aryl-2,4-dioxobutanoic Acids and Their Derivatives in Reactions with Diazoalkanes

By treating 4-aryl-2,4-dioxobutanoic acids or their alkyl esters with diazomethane alkyl 4-aryl-2-methoxy-4-oxo-2-butenoates and 1-R-3-aroyl-4-methoxy-4-methoxycarbonyl-4,5-dihydropyrazoles were prepared. O-Alkyl derivatives and substituted pyrazoles were also obtained by reaction of 4-aryl-2,4-oxo-butanoic acids aryl amides with diazomethane and diazoethane.     

过渡金属催化肟类化合物的反应研究进展

按照反应类型的不同,对近年来过渡金属催化肟类化合物反应的研究进展进行了综述,主要包括酮肟的还原酰化反应,肟类化合物的催化偶联反应,胺化反应以及肟类化合物与炔烃的环化反应.     

Reaction of Perrhenate with Phthalocyanine Derivatives in the Presence of Reducing Agents and Rhenium Oxide Nanoparticles in Biomedical Applications

A novel alternative route to access rhenium(V)−phthalocyanine complexes through direct metalation of metal-free phthalocyanines (H₂Pcs) with a rhenium(VII) salt in the presence of various two-electron reducing agents is presented. Direct ion metalation of tetraamino- or tetranitrophthalocyanine with perrhenate (ReO₄⁻) in the presence of triphenylphosphine led to oxidative decomposition of the H₂Pcs, giving their respective phthalonitriles. Conversely, treatment of H₂Pcs with ReO₄⁻ employing sodium metabisulfite yielded the desired Re^VO−Pc complex. Finally, reaction of H₂Pcs with ReO₄⁻ and NaBH₄ as reducing agent led to the formation of rhenium oxide (Re_xO_y) nanoparticles (NPs). The NP synthesis was optimised, and the Re_xO_y NPs were capped with folic acid (FA) conjugated with tetraaminophthalocyanine (TAPc) to enhance their cancer cell targeting ability. The cytotoxicity profile of the resultant Re_xO_y−TAPc−FA NPs was assessed and found to be greater than 80 % viability in four cell lines, namely, MDA−MB-231, HCC7, HCC1806 and HEK293T. Non-cytotoxic concentrations were determined and employed in cancer cell localization studies. The particle size effect on localization of NPs was also investigated using confocal fluorescence and transmission electron microscopy. The smaller NPs (≈10 nm) were found to exhibit stronger fluorescence properties than the ≈50 nm NPs and exhibited better cell localization ability than the ≈50 nm NPs.     

Azines and Their Acyclic Derivatives as Transferers of One-carbon Fragment in Reactions with Pyrazolones

Enehydrazine derivatives have been obtained by the reaction of 6-phenyl-1,2,4-triazine 4-oxide with pyrazolones 2, which on further heating with pyrazolones 2 are converted into the corresponding symmetrical or unsymmetrical derivatives of dipyrazolylmethane. Enehydrazine derivatives of 1,3-dimethyl-5-nitrosouracil and 1,3-dimethylimidazolidine interact with 3-methyl-1-phenyl-5-pyrazolone (2a) with the formation of dipyrazolylmethane derivative. On interacting compound 2a or 3-methyl-1-(p-nitrophenyl)-5-pyrazolone with 3,6-diphenyl-1,2,4-triazine 4-oxide 12 the corresponding 4,4'-bispyrazolones are formed, but the interaction of compound 12 with 3-(p-nitrophenyl)-1-phenyl-5-pyrazolone leads to dipyrazolylmethane derivative. Dipyrazolylmethane derivative is obtained on heating of fervenulin 4-oxide, 2,4-dihydroxy-5-nitropyrimidine, and 1,3,5-triazines: 6-azauracil, 5-azauracil, azacytosine, and 2,4-diamino-s-triazine with pyrazolone 2a.     

Reactions of Tris(Perfluoroalkyl)Difluorophosphoranes and Their Derivatives with Nucleophilic Reagents

Abstract

This paper is concerned with the reactions of (R_f)₃PF₂ and (R_f)₃PO with N-, 0-, C-nucleophiles and fluoride ion. Either the replacement of one or two perfluoroalkyl radicals by different functional groups or the addition of reagent to electrophilic phosphorus occurs. These phosphinic oxides and phosphoranes readily add fluoride-ion with the expansion of phosphorus coordination: the former produces phosphoranes OP a new type (R_f)₃P(F)O_?Cs₊, while the latter stable substituted fluorophosphates of general formula M ₊[(R_f)₃ PF₃]_?. Based on these salts it was possible to synthesize aryldiazonium tris(perfluoroalkyl)trifluorophosphates, whose thermal decomposition leads to the formation of substituted fluorobenzenes with high yields. The reaction is a convenient modification of the Shieman methd. The approaches of the synthesis of phosphoranes containing simultaneously both perfluoroalkyl groups and nonfluorin-ated radicals are developed due to the reactions of tris-(perf luoroalkyl)dif luorophosphoranes with the lithium-organic compounds. The replacement of either fluorine atom or perfluoroalkyl radical by the nonfluorinated group depends on the lithium reagent nature:     

Synthesis of Methyl p-Alkoxyphenylcarbamates and Some Their Reactions

Alkylation of methyl p-hydroxyphenylcarbamate with allyl bromide and 1,4-dibromobutane leads to formation of the corresponding methyl p-alkoxyphenylcarbamates. Reactions of methyl p-allyloxyphenylcarbamate with benzaldehyde, p-methoxybenzaldehyde, p-nitrobenzaldehyde, and p-chlorobenzaldehyde oximes in boiling ethanol in the presence of N-chlorobenzenesulfonamide sodium salt yields 3-aryl-5- (p-methoxycarbonylaminophenoxymethyl)-4,5-dihydroisoxazoles. Methyl p-(4-bromobutoxy)phenylcarbamate reacts with morpholine in benzene to give methyl p-(4-morpholinobutoxy)phenylcarbamate.     

Recyclization on Condensation of Alkylhydrazones of 2-Phenacyl-1H-Benzimidazole with Acylating Agents

Cyanoethyl-, ethyl-, and methylhydrazones of 2-phenacyl-1H-benzimidazole undergo recyclization on condensation with aroyl chlorides or dimethylformamide with the formation of 5-(o-aroyl-aminoanilino)pyrazoles or 1-(5-pyrazolyl)-1H-benzimidazoles. The reaction with aroyl chlorides occurs selectively only with the corresponding cyanoethylhydrazone.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 372–378, March, 2005.