Conjugated schiff's bases—141: Cycloaddition of heterocumulenes to some 1-oxa-4-azabutadienes

1-Oxa-4-azabutadienes proved to be prone to react with some heterocumulenes after 1,3-cycloaddition patterns yielding various 5,5-disubstituted derivatives of 1,3-diaryl-hydanotoins as it was shown by the chemical and spectroscopic analysis. Relatively high yields, mild reaction conditions and a very weak effect of solvent polarity on the reaction rate suggested a synchroneous mechanism involving 1,2-migration of a substituent.     

Catalytic decomposition of CFCs

Catalytic decomposition of CCI₂F₂ was studied over a number of single and complex metal oxides using a fixed-bed reactor. The ZrO₂–Cr₂O₂ catalyst exhibited the highest activity and CO₂ and CCIF₃ were formed at 350–450°C. Selective decomposition of CCI₂F₂ required the presence of both oxygen and water vapor over the catalyst. Catalytic activity gradually declined with time on stream because of the fluorination of ZrO₂. Treatment of the catalyst with both oxygen and water vapor promoted the removal of fluoride ions in sub-surface layers of the catalyst, which is effective for the recovery of the activity. CCI₂F₂ was decomposed at 300–450°C over AIPO₄. No fluorination of the AIPO₄ catalyst took place after the reaction for 1000 h. CH₂FCF₃, an alternative CFC, was completely decomposed over the mixed catalyst of Ce promoted AIPO₄ and Cr₂O₃ at 400–500°C. Catalytic decomposition is a rational method for destruction of used CFCs.     

Thermal decomposition of quaternary oxazolidinium bases

Thermal decomposition of the quaternary oxazolidinium bases is accompanied by the nucleophilic attack of the hydroxyl group at the C(2) carbon atom of the cycle to afford carbonyl compounds and aminoalcohols.Translated fromizvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 930–934, April, 1996.     

Catalytic decomposition of potassium chlorate

Thermal decomposition of potassium chlorate in the presence of various additives is studied using thermogravimetric analysis and differential thermal analysis. Catalytic effects of metal oxides with comparable surface areas are compared, and the catalytic effects of a number of nonoxide additives are also studied. The nonoxide additives show catalytic activities similar to the corresponding metal oxides. Metal cations and their electron configurations determine the catalytic activity of various compounds. Metal cations with partially filledd shells have the highest activity, transition metal cations with completely emptyd orbitals are moderated active, and metal cations with completely filledd shells or noble gas configurations have minimum activity.     

Catalytic decomposition of dimethyl disulfide

We have studied dimethyl disulfide conversion on heterogeneous catalysts in a flow setup at T=250–350°C and atmospheric pressure. Methyl mercaptan appears to be the main reaction product. The rate of dimethyl disulfide decomposition and its selectivity towards methyl mercaptan in H₂S medium are higher than those in pure helium. Thus the process seems to involve the surface protons formed upon dissociative H₂S chemisorption.     

Conjugated schiff's bases.20 cycloaddition of heterocomulenes to some 1,3-heterodienes involving unusual assistance of methyl group

Highly substituted 1,Δ-diazabutadienes react with aroyl isothiocyanates in a 1,3-dipolar cycloaddition node yielding five-membered thiohydantoin-type heterocycles. The cycloaddition is accompanied by 1,4 shift of hydrogen from a methyl group attached to C2 of the 1,C-diazabutadiene moiety. The mechanism of this reaction is discussed in comparison with similar cycloadditions with aryl isocyanates.     

馏出液的酸度对蒸馏-纳氏试剂分光光度法测定氨氮的影响

分析了馏出液的酸度对蒸馏-纳氏试剂分光光度法测定氨氮的影响及其解决办法。若以硼酸为吸收液,需加入氢氧化钠溶液调节馏出液的pH约为10可消除影响。若以盐酸、硫酸和水代替硼酸作为蒸馏吸收液,则无需调节馏出液的酸度即可得到满意的试验结果。     

Palladium‐mediated copolymerization of diazocarbonyl compounds with phenyldiazomethane

Phenyldiazomethane was found to be polymerized by the reaction with palladium‐based initiating systems. Homopolymerization of phenyldiazomethane afforded a polymer, whose main chain consists of phenylmethylene framework (–CHPh–) and azo groups (–N?N–). The incorporation of the azo group was suggested from the results of elemental analyses, and confirmed by Raman spectroscopy. Palladium‐mediated copolymerization of phenyldiazomethane with (E)‐1‐diazo‐3‐nonen‐2‐one or ethyl diazoacetate proceeded to give copolymers having phenylmethylene framework, azo group, and acylmethylene or ethoxycarbonylmethylene framework in the main chain, with a variety of their compositions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1536–1545, 2007     

Synthesis and fluorescence properties of naphthalimide-containing Tröger’s bases

Tröger’s bases based on the naphthalimide fluorophore have been prepared from N-alkyl-4-amino-1,8-naphthalimides. The fluorescence emission intensity of these dyes is highly medium dependent. In cyclohexane, these dyes emit near 440 nm with high quantum yields; addition of cosolvents reduces the fluorescence intensity near 440 nm and leads to increased fluorescence intensity around 480 nm.     

Reactions de decomposition thermooxydante des polymeres d'episulfures

Thermal oxidations of polymers and oligomers of episulphides have been studied between 150 and 250° by measurements of oxygen absorption. Thermal stabilities of oxidation products have also been studied. It has been shown that oligomers (3,6-dithia-octane; 3,6,9,12-tetrathiatetradecane) resemble polythioethylene in their reactivity towards oxygen. Thermal oxidation of the polythioethers is accompanied by degradation caused by the formation of unstable sulphoxide groups.     

Catalytic decomposition of aliphatic peroxy acids

The catalytic decomposition of peroxy acids is studied in various solvents in the presence of manganese, cobalt, chromium, nickel, and copper acetates and cerium benzoate. The catalytic activity of the salts in peroxy acid decomposition decreases in the order Mn²⁺ > Co²⁺ > Ce³⁺ > Cr³⁺ > Ni²⁺ > Cu²⁺. The apparent activation energies of the catalytic decomposition of peroxydecanoic acid range between 45.9 and 88.0 kJ/mol. The reaction medium has an effect both on the apparent rate constant and on the activation energy of the reaction. The reaction mechanism includes the fast formation of a catalyst-peroxy acid intermediate complex, which decomposes to release a catalyst molecule and forms the reaction products. The oxidation state of the metal ion of the catalyst can change. The introduction of compounds capable of forming complexes with metal ions of the catalyst substantially slows down the catalytic decomposition.     

Catalytic decomposition of hydrogen peroxide in alkaline solutions

Catalytic activity of carbon, platinum-supported on high-area carbon, platinum, lead ruthenate, and ruthenium oxide towards hydrogen peroxide decomposition in alkaline solution is investigated using the rotating disk electrode technique. The heterogeneous rate constant for peroxide decomposition on these catalysts is determined from the slope of log(i_L) versus time, where i_L is the diffusion-limiting current corresponding to the concentration of peroxide at a given time. The order of catalytic activity is found to be platinum>lead ruthenate>ruthenium oxide>carbon. A general reaction mechanism for the peroxide decomposition on these catalysts is also proposed.     

Catalytic condensation of ethyl cyclopentanonecarboxylate with Schiff bases

Ethyl cyclopentanonecarboxylate reacts with Schiff bases to give amino keto esters, from which 5,6-benzoquinoline derivatives are synthesized in the presence of hydrochloric acid. Compounds of the enamine type are obtained in the presence of acetic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 683–688, May, 1973.     

Co/Hβ催化剂上N_2O的分解性能研究

采用浸渍法制备了Hβ分子筛负载钴氧化物催化剂。考察了催化剂焙烧温度和钴负载量对催化剂催化分解N2O活性的影响,并采用XRD、NH3-TPD、H2-TPR、SEM等手段对催化剂的理化性质进行表征。结果表明,催化剂中的钴物种主要以Co3O4尖晶石型形态存在;催化剂焙烧温度显著影响其酸性和酸量及氧化还原性能,焙烧温度达到700℃后,催化剂中有难还原的Co-Al-O物种生成。焙烧温度和钴负载量对催化剂的催化活性均有影响,焙烧温度为600℃、钴负载量为10%~15%的催化剂催化活性好,N2O分解温度低,t10、t50和t95分别为325~329℃、364~367℃和406~408℃。