Imidomethylation of C-nucleophiles using O-phthalimidomethyl trichloroacetimidate and catalytic amounts of TMSOTf

The O-phthalimidomethyl trichloroacetimidate (1), as a latent aminomethylating agent, exhibits high electrophilicity towards a variety of C-nucleophiles in the presence of catalytic amounts of TMSOTf and mild reaction conditions. The nucleophiles include aromatics, alkenes and active methylene compounds 2-11 whereby a phthalimidomethyl group could be introduced to give compounds 12-22. Removal of the phthaloyl group gave the respective amines, β-amino ketones, and β-amino acids. The O-(trichloroacetamido)methyl trichloroacetimidate (35) was also found to be a good amidomethylating agent.     

Copolymers and two-layered composites of poly(<Emphasis Type="Italic">o</Emphasis>-aminophenol) and polyaniline

Electroactive conducting copolymers of aniline (ANI) and o-aminophenol (OAP) and two-layered poly(o-aminophenol) (POAP)/polyaniline (PANI) composites were prepared in aqueous acidic solution by electrode potential cycling. Copolymerization was carried out at different feed concentrations of OAP and ANI on a gold electrode. A strong inhibition of electropolymerization was found at a high molar fraction of OAP in the feed. The copolymers showed good adherence on the electrode surface and gave a redox response up to pH=10.0. Two transitions were observed in the in situ conductivities of the copolymers (as with PANI), but the conductivities were lower by 2.5–3 orders of magnitude as compared to PANI. Electrosynthesis of PANI on POAP modified electrodes showed copolymer formation after reaction initiation and finally formation of a PANI layer at the copolymer/solution interface. The ‘memory effect’ of the bilayer structures of both polymers was discussed in terms of protonation/deprotonation and anion consumption taking place during redox processes of both polymers.     

Röntgenstrukturanalysen von Cyclododekaschwefel (S12) und Cyclododekaschwefel-1-Kohlendisulfid (S12 · CS2) [1]

X-Ray Structural Analyses of Cyclododecasulfur (S₁₂) and Cyclododecasulfur-1-Carbon-disulfide (S₁₂ · CS₂) S₁₂ · CS₂ crystallizes in space group R&3macr;m–D with hexagonal lattice constants a = 1066.8(3), c = 1155.1(4) pm, Z = 3, d_calc. = 2.04 g · cm^?3. The S₁₂ molecules occupy sites of D_3d symmetry with bond distance (d_ss) of 205.4(1) pm, bond angles (α) of 105.80(5) and 106.65(6)º and torsional angle (τ) of 87.20(7)º. The CS₂ molecule interacts only very weakly with the S₁₂ units. S₁₂ crystallizes in space group Pnnm–D with lattice constants a = 472.5(2), b = 910.4(3), c = 1453.2(3) pm, Z = 2, d_calc = 2.045 g · cm^?3. The molecules with mean parameters d = 205.2 pm, α 106.6º, τ 88.0º occupy sites of C_2h symmetry.     

Simultaneous kinetic determination of thiocyanate and sulfide using eigenvalue ranking and correlation ranking in principal component-wavelet neural network

In this work, two toxic compound, sulfide and thiocyanate were determined simultaneously using kinetic spectrophotometry. These anions have shown the catalytic effects on the reaction between iodine and azide. Since the system was nonlinear, a nonlinear model, principal component-wavelet neural network (PC-WNN) was used as the multivariate calibration method. The principal component analysis was used to decrease the dimension of the original matrix. In other words, the scores of the PCs, 5, instead of the original variables, 301, were used as the input for the model. Two methods were used to select the most relevant principal components: eigenvalue ranking and correlation ranking. In this work, eigenvalue and correlation ranking methods have shown better results for thiocyanate and sulfide, respectively, and it can be concluded that these methods are complementary. The WNN has several advantages relative to other types of neural network such as better convergence ability. The data set was divided to calibration, prediction and validation sets. Each set was selected so that the concentrations of the analytes were approximately covered the entire ranges of the analytes. Mean relative error for thiocyanate and sulfide in validation set were 8.5 and 10.6, respectively. Thiocyanate and sulfide can be determined in the range of 60–700 ng ml⁻¹ and 20–400 ng ml⁻¹, respectively. The proposed method was applied for the determination of sulfide and thiocyanate in real samples such as tap, waste and river waters with satisfactory results.     

Facile Desulfurization of Thioamides and Thioureas with Tetrabutylammonium Periodate under Mild Conditions

Summary. Thioamides and thioureas were reacted with tetrabutylammonium periodate at room temperature to afford the corresponding amides and ureas, respectively, under aprotic conditions.     

An efficient and chemoselective method for protection of thiols catalyzed by aluminumdodecatungstophosphate (AlPW12O40), as a highly water tolerant Lewis acid catalyst

Protection of various thiols with diphenylmethanol was achieved in high yields at room temperature using catalytic amounts of AlPW₁₂O₄₀ in CH₂Cl₂. In the presence of this catalyst, protection of SH versus OH was achieved with high chemoselectivity and yields. The catalyst can be easily recovered and reused. Deprotection of DPM thioethers was also achieved using molecular iodine at reflux in CH₂Cl₂ in high yields.     

Effective PET and ICT switching of boradiazaindacene emission: a unimolecular, emission-mode, molecular half-subtractor with reconfigurable logic gates

[reaction, structure: see text] We report a unimolecular system functioning as a combinatorial logic circuit for half-subtractor. The emission characteristics can be modulated by chemical inputs, and when followed at two different wavelengths, two functionally integrated logic gates XOR and INHIBIT are obtained. Both logic gates function in the emission mode, and with very large differences in the signal intensity allowing unequivocal assignment of logic-0 and logic-1.     

Adsorptive stripping voltammetric analysis of 2,4,6-tri(2′pyridyl)-1,3,5-triazine at a mercury electrode

The redox behaviour of adsorbed species of 2,4,6-tri(2-pyridyl)-1,3-5-triazine (TPTZ) at the surface of a mercury electrode was examined using cycling voltammetry. Based on the adsorption and accumulation of TPTZ at the charged mercury surface cathodic adsorptive stripping voltammetry (CSV) is applied for the trace determination of TPTZ using a differential pulse (DP) technique. Experimental and operational parameters for the quantitative analysis of TPTZ are optimized and the detection limit was found to be 3×10^–9 mol/l. The effect of some interferences, e.g. organic compounds, cations and anions, are investigated.     

New insights into ethene epoxidation on two oxidized Ag[111] surfaces

Reaction mechanisms and activation energies for the complete conversion of ethene to ethene epoxide on two recently characterized oxidized Ag{111} surfaces have been determined from density functional theory. On both surfaces, epoxidation proceeds through a two-step nonconcerted mechanism via an oxametallacycle intermediate. The key implications are that both surfaces are active and that epoxidation can take place over a wide O coverage regime.