Syntheses,Spectroscopic Studies,and Crystal Structures of Me2Sn(O2PPh2)2, Ph2Pb(O2PMe2)2, and Ph2Pb(O2PPh2)2

Me₂Sn(O₂PPh₂)₂ ( 1 ), Ph₂Pb(O₂PMe₂)₂ ( 2 ), and Ph₂Pb(O₂PPh₂)₂ ( 3 ) have been synthesized by the reactions of Me₂SnCl₂ or Ph₃PbCl with the corresponding diorganophosphinic acid in methanol. X‐ray diffraction studies show that the diorganophosphinate groups behave as double bridges between the metal atoms leading to polymeric ring‐chain structures with M₂O₄P₂ (M = Pb, Sn) eight‐membered rings. The organic groups bonded to the metal atoms are in trans‐position in the resulting octahedral arrangement around the metal atoms. The IR and the mass spectra were reported and discussed.     

Magnesium lactate mixed with EVA polymer/paraffin as an EPR dosimeter for radiation processing application

The dosimetric characteristics of γ-radiation-induced defects in magnesium lactate (ML) rods (3.5 mm×10 mm) formulated by mixing ML with molten mixtures of paraffin wax and EVA copolymer have been investigated using electron paramagnetic resonance (EPR). The EPR spectrum of irradiated ML rods was characterized by a quartet signal with the spectroscopic splitting g-factor of 2.0048±0.0003 at 0.4 mT. The useful dose range of the rod dosimeter was 100 Gy to 80 kGy. The mass attenuation coefficient, μ/ρ, and the mass energy-absorption coefficient, μ_en/ρ, versus energy in the range of 10 keV to 20 MeV indicate that the prepared ML dosimeter is typically adipose tissue equivalent overall this energy range. The overall combined uncertainties (at 2σ) associated with routine dose monitoring in the dose range of 0.1–10 kGy and 10–80 kGy were found to be 6.14% and 6.36%, respectively.     

Pore Scale Modeling of Reactive Transport Involved in Geologic CO<Subscript>2</Subscript> Sequestration

We apply a multi-component reactive transport lattice Boltzmann model developed in previous studies for modeling the injection of a CO₂-saturated brine into various porous media structures at temperatures T = 25 and 80°C. In the various cases considered the porous medium consists initially of calcite with varying grain size and shape. A chemical system consisting of Na⁺, Ca²⁺, Mg²⁺, H⁺, CO₂^°(aq){{\rm CO}_2^{\circ}{\rm (aq)}}, and Cl⁻ is considered. Flow and transport by advection and diffusion of aqueous species, combined with homogeneous reactions occurring in the bulk fluid, as well as the dissolution of calcite and precipitation of dolomite are simulated at the pore scale. The effects of the structure of the porous media on reactive transport are investigated. The results are compared with a continuum-scale model and the discrepancies between the pore- and continuum-scale models are discussed. This study sheds some light on the fundamental physics occurring at the pore scale for reactive transport involved in geologic CO₂ sequestration.     

Reaction of 2-carboxy-1-methylindole-3-acetic acid anhydride with amines and with S-methylisothiosemicarbazide

2-Carboxy-1-alkylindole-3-acetic acid anhydrides (I) condensed with S-methylisothiosemicarbazide in DMF to form 5,11-dihydro-6-methyl-2-methylthioindolo[3′,2′:4,5]pyrido[1,2-b]-s-triazol-5-one (II). Compound II underwent ring opening on refluxing with sodium hydroxide solution to give IV. The anhydride I reacted with primary amines in benzene to give 2-carboxy-1-alkylindole-3-acetanilide derivatives (VI) which yielded l-methylindole-3-acetic acid by decarboxylation followed by hydrolysis. Compound II oxidised to the diketo compound X which could be prepared by the hydrolysis of the azomethine derivative IX with acetic acid-hydrochloric acid mixture. Compound II reacted with benzyl chloride to yield the dibenzyl derivative XII, condensed with p-chlorobenzaldehyde to form the 11-p-chlorobenzylidene derivative XI and coupled with arenediazonium salt to give the 11-arylhydrazone derivatives XIII.     

Alpha-nitro ketone synthesis using N-acylbenzotriazoles

[Reaction: see text]. Readily available N-acylbenzotriazoles 2a-l (derived from a variety of aliphatic, (hetero)aromatic, and N-protected alpha-amino carboxylic acids) smoothly convert primary 3a-c and alpha-functionalized primary nitroalkanes 3d into the corresponding alpha-nitro ketones 5a-p in yields of 39-86% (average 63%).     

Darstellung und schwingungsspektren von trimethylzinndiorganothiophosphinaten Me3SnOSPR′R″ (R′R″ = Me2, MePh,Ph2). Die kristallstruktur von Me3SnOSPMe2

A series of trimethyltin diorganothiophosphinates Me₃SnOSPR′R″ (R′R″ = Me₂, MePh, Ph₂) was prepared from (Me₃Sn)₂O and R′R″PSCl in cyclohexane solution. A close study of the vibrational spectra is given; ³¹P NMR and mass spectra are also reported. The structural investigation of Me₃SnOSPMe₂ by means of X-ray diffraction (R 5.2%, 1697 observed independent reflexions) shows the compound to consists of chains, in which planar SnMe₃ units and tetrahedral OSPMe₂ groups are linked by the O- and S-atoms of the thiophosphinate.     

Synthesis,characterization and metal chelating properties of silica-physisorbed and chemisorbed-2,5-dioxypiperazine

2,5-Dioxypiperazine (DOPZ) was covalenty bonded as a chelating compound to chloropropyltrimethoxysilane (Si–Cl) for the formation of a new chemisorbed silica [Si–(CH₂)₃–DOPZ]. Physisorbed silica-loaded-2,5-dioxypiperazine [Si–DOPZ] was also synthesized via a physical adsorption approach. Elucidation of the chemisorption and physisorption of 2,5-dioxypiperazine onto silica was confirmed on the basis of 70 eV electron impact mass spectrometric (70 eV EI-MS) mode of ionization via a direct insertion probe (DIP) as a promising technique for providing characteristic fragment ion peaks. The metal probe testing method and elemental analysis were applied to determine the surface coverage values and these were found to be 0.179 and 0.160 mmol g⁻¹ for [Si–(CH₂)₃–DOPZ] and 0.251 mmol g⁻¹ for [Si–DOPZ]. [Si–(CH₂)₃–DOPZ] was characterized by high stability in acidic and buffer solutions, pH 1–7, compared to [Si–DOPZ]. Differential scanning calorimetry studies (DSC) for the modified silica were performed to evaluate the various thermodynamic and kinetic parameters of the thermal degradation processes, and these have been enumerated. The results obtained by both EI-MS and DSC are very similar in many respects. Metal chelation and stoichiometric properties of chemically modified silica were evaluated on the basis of the metal binding capacity, distribution coefficient and separation factor for a series of metal ions. The evaluated results refer to the high metal chelating properties of [Si–(CH₂)₃–DOPZ] for cadmium(II), lead(II) copper(II) and mercury(II). These four [Si–(CH₂)₃–DOPZ]–metal complexes were also synthesized and the identified stoichiometric ratios were found to be 1:2 based on the nitrogen and metal analysis. EI-MS via 70-eV ionization was also used as a potential method for further confirmation of the metal complex formation based on structure and fragmentation elucidation. DSC studies of these four metal complexes were also performed and evaluated.     

Expedient acylations of primary and secondary alkyl cyanides to alpha-substituted beta-ketonitriles

Primary and secondary cyanides are efficiently acylated with N-acylbenzotriazoles 3a-f (derived from a variety of acids) to afford the corresponding alpha-substituted beta-ketonitriles 5a-r in 67-96% yields.     

Efficient conversion of sulfones into beta-keto sulfones by N-acylbenzotriazoles

Acyclic sulfones 4a-f and alicyclic sulfone 7 react with readily available N-acylbenzotriazoles 3a-g (derived from aliphatic, aromatic, and heteroaromatic carboxylic acids) to provide the corresponding beta-keto sulfones 5a-n and 8a-c, respectively, in good to excellent yields.