Reaction of salts of nitroaminotetrazoles with alkyl iodides

The reaction of salts of 5-nitroaminotetrazole, 1- and 2-methyl-5-nitroaminotetrazole, and 2-ethyl-5-nitroaminotetrazole with alkyl iodides is studied. It is established that salts of 2-methyl- and 2-ethyl-5-nitroaminotetrazole are alkylated at the nitroamine group while salts of 1-methyl-5-nitroaminotetrazole are alkylated at the second nitrogen atom of the tetrazole fragment with the subsequent splitting off of the methyl group at the 1-position of the tetrazole ring and further alkylation of the nitroamine group. It is shown that salts of 5-nitroaminotetrazole are initally alkylated at the second nitrogen atom of the tetrazole fragment and then at the nitroamine group. It is hypothesized that the initial alkylation of salts of 1-methyl-5-nitroaminotetrazole and 5-nitroaminotetrazole at the second nitrogen atom of the tetrazole fragment results from their nitroimino tautomeric form.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1090–1093, August, 1986.     

N-nitration of 1(2)-substituted 5-aminotetrazoles with tetranitromethane

1(2)-Methyl-5-aminotetrazoles and 2-(-cyanoethyl)-5-aminotetrazole are nitrated by tetranitromethane in the presence of bases with the formation of salts of the corresponding 5-nitroaminotetrazole derivatives. In contrast to this, decyanoethylation takes place in nitration of 1-(-cyanoethyl)-5-aminotetrazole by tetranitromethane with the formation of 5-nitroaminotetrazole salt. The structure of the 2-methyl-5-nitroaminotetrazole salts (using the 2-methyl-5-nitroaminotetrazole potassium salt) was confirmed by x-ray structural analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1067–1071, August, 1991.     

Electrochemical reduction of N-nitroaminotetrazoles

The electrochemical reduction of 5-nitroamino- and 2-methyl-5-nitroaminotetrazoles at the first wave potential consumes six electrons, while the reduction at the second wave potential consumes eight or nine electrons. The preparative reduction of 2-methyl-5-nitroaminotetrazole at the second wave potential leads to 2-methyl-5-aminotetrazole and ammonia. A mechanism is proposed for these reactions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 944–946, July, 1992.     

5-Nitroaminotetrazole as a building block for extended network structures: Syntheses and crystal structures of a number of heavy metal derivatives

The lead, mercury, copper and silver derivatives of 5-nitroaminotetrazole (5-H₂NATZ) were obtained by the reaction between the metal nitrate and potassium 5-nitroaminotetrazolate. The lead and mercury complexes were crystallized and characterized by single crystal X-ray diffraction. The lead complex has a polymeric structure formed by (PbO₂)_n chains and anions of 5-NATZ, where each lead atom is surrounded by ten oxygen atoms. The mercury salt is constructed from neutral (Hg–NATZ)_n chains, where the mercury atom has a linear coordination. The influence of chemical hardness and charge distribution on the reactivity and coordination properties of 5-NATZ was estimated based on density functional calculations. The thermal stability of the salts was also studied.     

A container adsorption study of cadmium using109Cd spiking and liquid scintillation counting

¹⁰⁹Cd may be used as a radiolabel in tracer studies of Cd(II) because of the ease and efficiency with which it may be counted by liquid scintillation counting. It has been found that ppm solutions of Cd²⁺, spiked with¹⁰⁹Cd, may be stored for at least 200 d, in either amber glass or polypropylene containers, without measurable container adsorption, at pH's of 5 or less. At pH's above 5, there is some evidence of container adsorption, particularly in the case of polypropylene containers. Amber glass is recommended if pH's between 5 and 7 must be used for storage.     

Photoreaction of benzofuroxan

Benzofuroxan 5 , upon irradiation using a high pressure mercury lamp with a Pyrex filter in acetonitrile containing a little water, afforded 1H-azepine-2,7-dione 6 . The initial stage of this reaction would be formation of a highly reactive intermediate possessing two nitrile oxide functions. On the other hand, when compound 5 was irradiated using a low pressure mercury lamp in acetonitrile containing a little water, it afforded 6H-furazano[4,5-c]carbazole 3-oxide 11 and compound 6 . The structure of compound 11 was determined by an X-ray structural analysis. In the presence of an aromatic hydrocarbon, the formation of compound 11 was decreased and that of compound 6 was increased. Mechanistic studies on the photoreaction suggest that the photosensitized formation of compound 6 with the aromatic hydrocarbon may be carried out by the reabsorption of the fluorescence of it near 365 nm and the presence of it may quench the formation of compound 11 .     

Chemical and Chromatographic Behavior of Pseudohypericin and Isopseudohypericin,and the Occurrence of Isopseudohypericin in Saint John’s Wort (<Emphasis Type="Italic">Hypericum perforatum</Emphasis>) Extracts

Summary. Isopseudohypericin is formed from pseudohypericin in an alkaline, alcohol/water environment. The conditions for this conversion are specified, showing that these two compounds are in equilibrium at pH values of 5–10; pseudohypericin is stable below pH 5, and isopseudohypericin is stable above pH 10. It is also shown that the HPLC behavior of isopseudohypericin is dependent on the pH of the mobile phase: pH determines both the retention time and the UV-Vis spectrum characteristics of the corresponding peak analyzed using a diode array detector. Finally, different extraction conditions yield extracts containing different proportions of isopseudohypericin: it is suggested that this isopseudohypericin may be an artefact of extraction conditions and/or it may correspond to the compound cyclopseudohypericin, discussed by other experts but never formally characterized.     

Hydrazine-based polyimides and model compounds

The reaction of hydrazine hydrate with aromatic anhydrides may give either N-amino imides or cyclohydrazides. The conditions that favor the formation of N-aminoimides, in which the imide contains respectively a 5- and 6-membered ring, are discussed. These compounds may be reacted with aromatic anhydrides to give N-N-linked imides. The properties of a number of model compounds and polymers are described, and it is shown that those compounds which have alternating 5- and 6-membered imide rings give the maximum oxidative stability in air at 400°C.     

Synthesis and electrochemical Reduction of 2,2′-diaryl-5,5,5′,5′-tetramethyl-3,3′-bi(pyrrol-3-ylidene)-4,4′(5<Emphasis Type="Italic">H</Emphasis>,5′<Emphasis Type="Italic">H</Emphasis>)-dione 1,1′-dioxides

2,2′-Diaryl-5,5,5′,5′-tetramethyl-3,3′-bi(pyrrol-3-ylidene)-4,4′(5H,5′H)-dione 1,1′-dioxides containing a carboxy, alkoxycarbonyl, or carbamoyl group in the para position of one or both benzene rings were synthesized. These compounds may be regarded as cyclic dinitrones with conjugated C=C bond. Mild aminolysis of carboxy groups in the title compounds may be used to introduce dinitrone fragments into oligonucleotide or polypeptide structures. Electrochemical reduction of the resulting amides involves reversible oneelectron transfer in the first step at a near-zero potential, which makes it possible to use the title compounds as electrochemically active labels in applied bioorganic electrochemistry.     

Quasi-equilibrium adsorption gravimetry of water on MFI- and ‘FER’-type zeolites and on an AFI-type aluminophosphate

Water adsorption at temperatures of 286 and 296 K on silicalite-I, ZSM-5 (Si/Al=16), ZSM-48 (Si/Al=50) and AlPO₄-5 is followed by gravimetry with a quasi-equilibrium continuous adsorptive introduction. The results show that all of these samples are characterized by a continuous distribution of strongly energetic water adsorption sites (from 60 to 120 kJ·mol^?1) for which the adsorption is irreversible at the experimental temperature. This probably justifies the presence of hysteresis on desorption at very low relative pressure values. Adsorption of water in these systems firstly occurs by site. This is then followed by cluster formation and it is suggested that it is the ability of the adsorbent to build up these clusters within the microporous structure which determines intracrystalline uptake. It is put forward that the zeolites, silicalite-I and ZSM-5, do not accommodate cluster formation within its microporous network. However, an external flexible microporous structure, containing Lewis sites, may be present for large crystals. This flexible secondary structure may then be able to opened (swelled) at high relative pressures. On the other hand, for the aluminophosphate AlPO₄-5, it is believed that a change in the aluminium coordination on the formation of a crystal hydrate together with capillary condensation results in a large step in the adsorption isotherm, which is itself preceded by a smaller step, revealing a brutal densification of the adsorbed phase.     

Silver-silver(I) system in superacid mixtures HF+SbF5

An electrochemical study of silver in superacid medium HF+SbF₅ shows that Ag is not oxidized and that the couple Ag/Ag(I) may be used as a reference electrode in mixtures of HF and SbF₅ containing 30% of SbF₅ (by weight). From potentiometric measurements with a silver electrode, it is shown that AgSbF₆ is slightly soluble and the solubility product is determined (log(K_s/mol²l^?2)=1.1). Evidence for the strong acidity of SbF₅ is demonstrated and it is shown that there are no polymers (such as Sb₂F₁₁^?) in the concentration range 0–3 M of SbF₅.     

Intramolecular metal—double bond interactions : VII. Intramolecular cyclization of alkenyl derivatives of lithium,aluminum, gallium and indium

The intramolecular cyclization reactions of tri-1-hex-5-enyl Group III derivatives and of 1-hex-5-enyllithium have been investigated and it is proposed that the reactions may be depicted as internal addition across the terminal double bonds of the alkenyl species. The cyclization reaction proceeds more readily for the 1-hex-5-enyl derivatives than for any other chain length and is dependent on temperature, concentration and solvent. ¹H NMR data and cryoscopic molecular weight data are presented for several diisobutyialkenyl- and diisobutylalkyl-aluminum derivatives. These data have been interpreted in terms of a direct intramolecular interaction between the metal center and the π-electron system of the olefinic site. The intramolecular cyclization reactions for the 1-hept-6-enyl, 1-oct-7-enyl- and 1-undec-10-enylaluminum derivatives also were investigated and it was found that cyclization occurred only for the 1-hept-6-enyl derivative.     

Density functional theory study of single-wall platinum nanotubes

Single-wall platinum nanotubes (SWPtN) were studied using spin-polarized density functional theory calculations. These nanotubes consist of 5-, 6-, and 8-Pt atoms coiling around the tubular axis forming 3.54–4.73 Å in diameter and 0.7–1.4 nm and infinite in length. Two types of wall structures, square and triangular, were investigated. The results show that triangular nanotubes are more stable. Our results suggest that it is also feasible to synthesize the 5- and 8-atom triangular nanotubes as the 6-atom Pt nanotubes were found experimentally. These SWPtN may provide a new dimension in the catalytic applications of platinum.     

Bond strength and bond angles for hybrid orbitals composed of arbitrary sets of orbital angular momentum quantum number

According to the formulas obtained in the preceding paper, it may be used for all types of the hybridization with any set of azimuthal quantum numbers l, l = 0 through l = 5, and a complete theoretical data of bond angles and bond strengths are shown in this paper.     

Hydrogenation of Cinnamaldehyde on Ir/γ-Al2O3 Catalysts. Influence of the Surface Acidity

The oxidation of methane has been studied in a flow system as a function of the chemical composition of zeolite catalyst using nitrous oxide as oxidant. It is concluded that methanol is a primary oxidation product which may undergo further oxidation to formaldehyde and to carbon oxides. However, it may also undergo conversion over the acidic catalyst to higher hydrocarbons. Reaction with nitrous oxide resulted in the production of carbon oxides, methanol, formaldehyde, C₂ - C₄ , C₅ - C₇ nonaromatics, and aromatics. The effect of Fe₂ O₃ and Al₂ O₃ , with or without, over HZSM5 on products was studied.     

气相中碱金属离子与丝氨酸、亮氨酸和赖氨酸五肽复合物的裂解反应简

为了探索金属离子对含有不同侧链的多肽气相解离的影响,采用质谱法研究了碱金属离子Li+,Na+,K+,Rb+和Cs+分别与丝氨酸、亮氨酸和赖氨酸五肽(分别简写为S5,L5和K5)形成的复合物的裂解反应. 质谱定性结果表明,5种碱金属离子均可以在气相中与丝氨酸、亮氨酸和赖氨酸五肽形成配合比为1：1 和2：1的非共价复合物;竞争反应结果表明,随着碱金属离子半径的增加,它们与3种五肽的结合能力逐渐减弱. 质谱定量结果表明,K+与丝氨酸、亮氨酸和赖氨酸五肽复合物的结合常数分别为8.94×104,2.83×104和2.50×103 L/mol,表明K+与五肽复合物的结合强度按照丝氨酸、亮氨酸和赖氨酸的顺序依次减小. 含不同侧链碱金属离子-五肽复合物的碰撞诱导解离结果表明,复合物的碎裂主要发生在骨架上,丝氨酸五肽复合物最易碎裂,亮氨酸五肽复合物其次,赖氨酸五肽复合物则较难碎裂,且3种复合物的侧链断裂情况也呈现明显差异. 此外,研究了Na+与亮氨酸五肽复合物所产生的碎片离子,分析了不同离子之间的来源关系,并以Dunbar的复合物理论模型为依据,推测在碎裂过程中,碱金属离子可能向五肽的碳端或氮端偏移. 质谱碎片分析结果表明,在2：1的非共价复合物中,第一个碱金属离子与五肽上4个酰胺键的羰基结合,第二个碱金属离子与五肽的羧基氧原子结合.     

Investigation of surface anchoring strength and pretilt angle in NLC on rubbed polythiophene surfaces with alkyl chain lengths

A high pretilt angle for the nematic liquid crystal, 4-n-pentyl-4'-cyanobiphenyl (5CB), was observed on rubbed polythiophene (PTP) surfaces having alkyl chains with more than ten carbon atoms. We consider that this is due to a surface-excluded volume effect caused by the long alkyl chains between the LC molecules and the PTP surfaces. The polar anchoring strength in 5CB on rubbed PTP surfaces with long alkyl chains has also been successfully evaluated. The extrapolation length d_e of 5CB increases with increasing alkyl chain lengths above the seven carbons of alkyl chain R7; that is, it may be attributed to the high pretilt angle. An extrapolation length of 5 nm is observed in 5CB for the seven carbons alkyl chain R7 on the PTP surface; this indicates high anchoring strength.     

The synthesis of some derivatives of 4,5,6,6a,7,12-hexahydroisoquinolino [8,l -ab]carbazole

As part of a general project on the chemistry of alkaloid analogues, the synthesis of derivatives 5 , of 4,5,6,6a,7,12-hexahydroisoquinolino[8,l-ab]carbazole, which can be considered as ring D indole analogues of the aporphine skeleton, was investigated. Compounds of this type are of interest on two grounds. Firstly it is conceivable some may occur naturally; and secondly, they may display unusual pharmacological properties, since the side-chain configuration of the tryptophan residue is intermediate between that present in lysergic acid diethylamide and the yohimbine-reserpine type alkaloids.     

Effect of zinc introduction on catalytic performance of ZSM-5 in conversion of methanol to light olefins

The effect of Zn on the catalytic performance of ZSM-5 in the methanol-to-olefin conversion was investigated. The samples were characterised by X-ray diffraction, N₂ adsorption, FTIR, temperature-programmed desorption of ammonia and water, and Py-IR. The experimental results revealed Znmodified ZSM-5 to show a lower selectivity to light olefin at the higher reaction temperature of 520°C but a higher selectivity to light olefin at lower temperatures. As a comparison, the catalytic performance of Ca-modified ZSM-5 for the methanol conversion is also given. From the above results, it is concluded that Zn may play another role in the methanol conversion in addition to tuning the surface acidic property after modification.