Synthesis of N-(ω-trimethylsilylalkyl)purines under conditions of interfacial catalysis

A Method of synthesis of N-(-trimethylsilylalkyl)purines, by alkylation of potassium salts of purine bases by 3-chloropropyltrimethylsilane and chloromethyltrimethylsilanes under conditions of interfacial catalysis, has been developed. Hydroxylation of the N-allyl group by dimethylphenylsilane, which is an alternative pathway of synthesis of silicon-containing purine derivatives, has been accomplished for the first time in the purine series. The structure of the compounds obtained was established by methods of PMR and UV spectroscopy.Latvian Institute of Organic Synthesis, Riga LV-1006. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 654-658, May, 1995. Original article submitted October 25, 1994.     

Synthesis of diverse β-(nitrooxy)-substituted amines by regioselective ring-opening of aziridines under neat conditions

An efficient and regioselective method was developed for the synthesis of β-(nitrooxy)-substituted amine derivatives by ring-opening of different aziridines with Zn(NO₃)₂·6H₂O without using additives or catalyst. A library of β-(nitrooxy)-substituted amine derivatives having a variety of substituents has been synthesized. Excellent regioselectivity, high yields, clean reaction, ease of product isolation, easily accessible reactants, and solvent-free as well as environment friendly reaction conditions are the notable advantages of the present methodology. The nitrooxy derivative was successfully transformed into hydroxy derivative by simple reduction. Gram-scale synthesis demonstrates the potential applications of the present method.     

Complexation of antibiotic levomycetin (Chloroamphenicol) with α-hederin and hederasaponin c under the conditions of electrospray ionization

The complexation of antibiotic levomycetin (chloroamphenicol) with triterpene glycoside α-hederin and hederasaponin C was investigated by electrospray ionization mass spectrometry. The glycosides form complexes with levomycetin in the molar ratio 1: 1. The molecular complex of α-hederin is more stable than the one of hederasaponin C because of the presence of a free carboxyl group in its aglycone fragment. The carboxyl group of hederasaponin C is involved into the formation of a glycosidic bond with the trisaccharide unit and is not available for complex formation.     

Effects of fabrication conditions on the structure and function of membranes formed from poly(acrylonitrile–vinylchloride)

Phase-inversion membranes formed from poly(acrylonitril–co-vinylchloride) (PAN–PVC) have been utilized for encapsulating living cells for transplantation; however, a detailed analysis of the structure and function of the integral skin layer has not been reported. PAN–PVC membranes fabricated under different precipitation conditions were analyzed using microscopic techniques and several functional tests. Structural analysis with scanning atomic force microscopy (AFM) revealed the presence of nodular elements in the skin layer which changed as a function of precipitation conditions. In addition, membrane hydraulic permeabilities, sieving coefficients, and diffusive permeabilities also varied with precipitation conditions. Furthermore, changes in the functional properties could be related to the size of the nodular elements and their accompanying interstitial space. The results provide insight into the fundamental interrelationships that exist between membrane fabrication, the fine surface morphology of the skin layer, and membrane performance.     

Influence of preparation conditions on properties of chemical modified nylon affinity membrane (used for γ-globulin adsorption)

Microporous polyamide membrane (Nylon 6, PA) was modified by add hydrolysis and then coupled with hydroxyethyl cellulose (HEC) to amplify reactive groups and reduce nonspecific interaction with proteins. 1,6-Diaminohexane (DAH) as space arm and phenylalanine (Phe) as ligand were immobilized onto nylon membrane through the activation of s-triazine trichloride (CyCl3). The affinity membrane obtained can be used to adsorb γ-globulin specifically. The optimum conditions of preparing affinity membrane and adsorbing bovine γ-globulin were studied.     

Positron annihilation lifetime spectroscopy of advanced reduced-activation alloy (ARAA) in cold‐worked conditions

Journal of Radioanalytical and Nuclear Chemistry - The defects due to cold-rolling deformation in the advanced reduced-activation alloy (ARAA) have been analyzed using positron annihilation...     

Ruthenium(II)-NHC-catalyzed (NHC = perhydrobenzimidazol-2-ylidene) alkylation of amines using the hydrogen borrowing methodology under solvent-free conditions

Transition Metal Chemistry - New ruthenium(II) complexes with N-heterocyclic carbene ligand were synthesized by transmetalation reactions between silver(I) N-heterocyclic carbene complexes and...     

Synthesis of ω-(2-oxocyclododecyl)alkanoic acids by alkylation of cyclododecanone with ω-haloalkanoic esters under conditions of phase-transfer catalysis

(-(2-Oxocyclododecyl)alkanoic acids have been obtained by alkylation of cyclododecanone with alkyl 3-bromopropionate, 5-iodopentanoate, and 11 -bromoundecanoate under conditions of phase-transfer catalysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2521–2523, December, 1995.     

Impact of environmental conditions on the sorption behavior of radionuclide 63Ni(II) onto hierarchically structured γ-MnO2

A novel hierarchically structured γ-MnO₂ has been synthesized using a simple chemical reaction between MnSO₄ and KMnO₄ in aqueous solution without using any templates, surfactants, catalysts, calcination and hydrothermal processes. As an example of potential applications, hierarchically structured γ-MnO₂ was used as adsorbent in radionuclide ⁶³Ni(II) treatment, and showed an excellent ability. The effects of pH, ionic strength, temperature, humic acid (HA) and fulvic acid (FA) on the sorption of radionuclide ⁶³Ni(II) to hierarchically structured γ-MnO₂ have been investigated by using batch techniques. The results indicated that the sorption of ⁶³Ni(II) on γ-MnO₂ is obviously dependent on pH values but independent of ionic strength. The presence of HA/FA strongly enhances the sorption of ⁶³Ni(II) on γ-MnO₂ at low pH values, whereas reduces ⁶³Ni(II) sorption at high pH values. The sorption of ⁶³Ni(II) on γ-MnO₂ is attributed to inner-sphere surface complexation rather than outer-sphere surface complexation or ion exchange. The thermodynamic parameters (ΔH ⁰, ΔS ⁰, ΔG ⁰) are also calculated from the temperature dependent sorption isotherms, and the results suggest that the sorption of ⁶³Ni(II) on γ-MnO₂ is a spontaneous and endothermic process.     

Salen-Cu(Ⅱ)@MIL-101(Cr) as an efficient heterogeneous catalyst for cycloaddition of CO_2 to epoxides under mild conditions

A double active center system, namely Salen-Cu(Ⅱ)@MIL-101(Cr), was successfully synthesized via the"ship in a bottle" approach, which acted as a bifunctional material for both capture and conversion of CO_2 in a single process. For the first time, Salen-Cu(Ⅱ)@MIL-101(Cr) catalyst was developed for the synthesis of propylene carbonate from CO_2 and propylene oxide under room temperature and ambient pressure with a yield of 87.8% over 60 h. Furthermore, the reaction mechanism was also discussed.     

Dispersity and kinetic characteristics of dissociation of mono- and hemiaquo adducts of copper N,N′-ethylenebis(acetylacetoniminate) under nonisothermal conditions

Using optical microscopy and thermogravimetry, we have established that determination of the kinetic characteristics of dissociation for the monoaquo adduct of copper N,N-ethylene-bis(acetylacetoniminate) with particle size 0.5–2 mm is hindered by self-dispersal processes. Using a piezoquartz microbalance, we have obtained the kinetic parameters for thermolysis for a phase whose crystal sizes are substantially smaller than the minimal size after self-dispersal of a block of a large crystal (0.5–2 m). For thermolysis of the hemiaquo adduct not accompanied by self-dispersal, the kinetic characteristics of the process for phases of dispersity 0.5–2 mm and 0.5–2 m are comparable.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 3, pp. 226–231, May–June, 1992.     

Ruthenium(Ⅲ) chloride as an efficient catalyst for the synthesis of perimidine derivatives under mild conditions

Various biologically important perimidine derivatives have been synthesized efficiently from various ketones and naphthalene1,8-diamine by using a catalytic amount of RuC13 (1 mol%). This method is a very simple and high yielding reaction for the synthesis of perimidine derivatives.     

Steady-state γ-radiolysis of aqueous methyl ethyl ketone (2-butanone) under postulated nuclear reactor accident conditions

The steady-state γ-radiolysis of aqueous solutions containing 1×10⁻³ mol dm⁻³ methyl ethyl ketone (MEK) has been studied at a dose rate of 0.12 Gy s⁻¹, 25°C and an initial pH of 10. Experiments were conducted in air-, Ar- or N₂O-purged aqueous solutions, or in Ar-purged solutions with added tert-butanol. MEK, its radiolytic products, and the change in pH resulting from MEK decomposition were analysed as a function of time (or total absorbed dose). The main initial step for the radiolytic decomposition of MEK is the H abstraction from MEK by OH, produced by γ-radiolysis of water, to form MEK radical. In the absence of O, the main decay path of the MEK radical appears to be dimerization to , -dimethyl-2,5-hexanedione. In the presence of oxygen, the MEK radical reacts primarily with O to form the MEK peroxyl radical. This radical ultimately results in a series of progressively smaller oxidation products. The formation of organic acids, and eventually CO₂, reduces the pH of the solution. This paper presents the experimental data and proposes the MEK decay kinetics and mechanism.     

Efficient synthesis of β-enaminones and β-enaminoesters catalyzed by gold (I)/silver (I) under solvent-free conditions

An efficient method for the synthesis of β-enaminones and β-enaminoesters using a combination of [(PPh(3))AuCl]/AgOTf as catalyst has been developed. The reaction between 1,3-dicarbonyl compounds and primary amines was carried out under solvent-free conditions with low catalyst loading in good to excellent yields at room temperature.     

Investigation of unanticipated alkylation at the N(π) position of a histidyl residue under Mitsunobu conditions and synthesis of orthogonally protected histidine analogues

We had previously reported that Mitsunobu-based introduction of alkyl substituents onto the imidazole N(π)-position of a key histidine residue in phosphothreonine-containing peptides can impart high binding affinity against the polo-box domain of polo-like kinase 1. Our current paper investigates the mechanism leading to this N(π)-alkylation and provides synthetic methodologies that permit the facile synthesis of histidine N(π)-modified peptides. These agents represent new and potentially important tools for biological studies.     

Microwave-promoted total synthesis of N-(α-hydroxybenzyl)formamides using DMSO/H2O under neutral conditions

A total synthesis route toward N-(α-hydroxybenzyl)formamides by microwave-assisted reaction of dichloroaziridines and aqueous dimethyl sulfoxide is described. The corresponding products were obtained in excellent yields with reduced reaction times. The obtained formamides were characterized by various techniques such as Infra red (IR), Nuclear Magnetic Resonance (NMR) and mass spectroscopy data.     

Remarkable enhancement of aerobic epoxidation reactivity for olefins catalyzed by μ-oxo-bisiron(III) porphyrins under ambient conditions

With μ-oxo dimeric iron(III) porphyrins [(Fe^IIITPP)₂O] as catalyst, isobutylaldehyde as co-reductant, and dioxygen as oxidant, an efficient model system for epoxidation of olefins has been developed. Compared with mono-metalloporphyrins as catalyst, a remarkable enhancement of reactivity was obtained for the present olefin epoxidation system, in which the turnover number (TON) of the catalyst has doubled from about 700 million to 1400 million. Moreover, a plausible mechanism involving both binuclear and mononuclear intermediate has been proposed.     

Manganese(II) salts as efficient catalysts for chemo selective transesterification of β-keto esters under non-conventional conditions

Transesterification of β-ketoesters with various alcohols has been studied under conventional and non-conventional conditions using desktop chemicals such as Mn(II) salts as catalysts. These methods offered transesterification of β-ketoesters in good yields with dramatic rate accelerations and reduced reaction times. The developed protocols under nonconventional methods such as sonication and microwave irradiation are highly promising compared with the existing procedures.     

Thermodynamic evaluation of the stability of the bone-seeking radiopharmaceutical [Lu]Lu(III)–DOTP under simulated blood plasma conditions

The stability and in vivo robustness of [¹⁷⁷Lu]Lu–DOTP as a potential bone-targeting radiopharmaceutical was determined with the aid of thermodynamic blood plasma modeling simulations. Glass electrode potentiometry was employed to measure the stability constants of the complexes of Lu³⁺ with DOTP. Similarly, the complexes of DOTP with a selection of the important physiological metal ions: Ca²⁺, Mg²⁺, and Cu²⁺ were determined, representing the typical interactions that the ligand would encounter upon administration. This made possible the construction of a blood plasma model of DOTP, aiding in establishing the potential susceptibility of the radiopharmaceutical. The ligand binds predominantly to calcium in vivo, accounting for 59.6% of that initially introduced as a component of the Lu–DOTP complex. Furthermore, due to a preference of the DOTP to bind to Cu²⁺ it causes mobilization of the ions in blood plasma, and would therefore indicate a deficiency if the ligand is administered at a concentration of 8.5 × 10⁻⁵ mol dm⁻³. The lutetium-ions are preferentially bound to DOTP, with as much as 98.1% of the Lu³⁺ occupying the ligand under physiological conditions.