A highly efficient synthetic route to ketones through sequential coupling reactions of grignard reagents with s-phenyl carbonochloridothioate in the presence of nickel or iron catalysts

The sequential coupling reactions of Grignard reagents with $\text{S}$phenyl carbonochloridothioate in the presence of nickel(II) or iron(III) catalysts provides a very mild and straightforward route to symmetrical and unsymmetrical aliphatic and aromatic ketones.     

Synthesis of marrubiin

The synthesis of marrubiin has been achieved starting from the keto lactone (II) which was prepared stereoselectively from the known keto ester (XI).     

The electron-impact induced fragmentation of substituted 4-styrylquinolines

The fragmentation of 4-styrylquinoline (I), 4-(p-nitrostyryl)-quinoline (II), 4-(p-chlorostyryl)-quinoline (III), 4-(p-hydroxystyryl)-quinoline (IV), 4-(p-methoxystyryl)-quinoline (V), 4-(p-dimethylaminostyryl)-quinoline (VI) and 4-(p-cyanostyryl)-quinoline (VII) under electron-impact in the mass spectrometer is reported. The role and the influence of substituents on the fragmentation scheme is discussed. The loss of the substituents from the molecular ion is correlated with LCAOMO quantities.     

Encapsulating bis(beta-ketoiminato) polyethers. Volatile, fluorine-free barium precursors for metal-organic chemical vapor deposition

The synthesis, characterization, and incorporation in volatile metal-organic chemical vapor deposition (MOCVD) precursors of a new class of linked beta-ketoiminate-polyether-beta-ketoiminate ligands is presented. These ligands are designed to encapsulate alkaline-earth cations having low charges and large ionic radii. Barium complexes having the general formula Ba[(RCOCHC(R')N)2(R")] (R = tert-butyl or CF3; R' = tert-butyl, methyl, or CF3; R" = -(CH2CH2O)4CH2CH2- or -(CH2CH2O)5CH2CH2)-) were prepared and characterized by 1H and 13C NMR spectroscopy, elemental analysis, and mass spectrometry. Single-crystal X-ray diffraction analysis of 2,2,5,25,28,28-hexamethyl-9,12,15,18,21-pentaoxa-4,25-diene-6,24- diimino-3,27-pentacosadionatobarium(II) reveals a monomeric, nine-coordinate, tricapped trigonal prismatic coordination geometry. Single-crystal X-ray structural analysis of 1,1,1,24,24,24-hexafluoro-4,21-ditrifluoromethyl-8,11,14,17- tetraoxa-3,21-diene-5,20-diimino-2,23-tetracosadionatobarium(II).2DMSO reveals a monomeric, ten-coordinate, distorted tetracapped trigonal prismatic coordination geometry. Volatility data are presented for these barium complexes, demonstrating viability as MOCVD precursors. In addition, it is demonstrated that thin epitaxial films of BaTiO3 can be grown on (001) MgO by low-pressure MOCVD techniques using one of these barium complexes and Ti(dipivaloylmethanate)2(isopropoxide)2 as precursors.     

AB Initio calculations and vibrational spectra of CH3SC≡CH and CH3SC≡CSCH3

Methylthio- (MTE) and bis-methylthioethyne (BMTE) molecules are calculated by the SCF MO method (geometry optimization, basis set 6–31G*/MP2). The calculated internal rotation barriers of methyl groups are 7.12 kJ/lmole for MTE and 12.86 kJ/mole for BMTE (both groups are simultaneously rotated). The s-gosh-orientation of the thiomethyl fragments corresponds to a stable conformation of BMTE. The estimated values of the s-cis- and s-trans-barriers of mutual rotation of SCH₃ groups about the axis of the C≡C bond are 13.61 and 12.54 kJ/mole, respectively. Conformationally sensitive MOs and vibration frequencies are established. An analysis of the experimental IR absorption and Raman spectra and the calculated vibrational spectrum makes it possible to conclude that in the liquid phase the BMTE molecules also have an s-gosh-conformation. Translated fromZhumal Strukturnoi Khimii, Vol. 39, No. 4, pp. 602–609, July–August, 1998.     

Regioselective uncatalysed hydrophosphination of alkenes: a facile route to P-alkylated phosphine derivatives

The synthesis of alkylarylphosphines is easily carried out by hydrophosphination of unactivated alkenes under mild thermal activation; gram scale amounts of products can be prepared by this simple methodology.     

Synthesis and Structure of the New Ammonium Indium Phosphate (NH4)In(OH)PO4

A new ammonium indium phosphate (NH₄)In(OH)PO₄ was prepared by hydrothermal reaction in the In₂O₃-NH₄H₂PO₄-NH₃/OH system (T=200°C, autogenous pressure, 7 days). The formula (NH₄)In(OH)PO₄ was determined on the basis of chemical and thermal analysis (TG/DSC), X-ray powder diffraction and IR-spectroscopy. (NH₄)In(OH)PO₄ crystallizes in the tetragonal system with space group P4₃2₁2 (No. 96); a=9.4232(1) Å, c=11.1766(1) Å, V=992.45(2) ų; Z=8. The crystal structure was refined by the Rietveld method (R_w=6.35%, R_p=5.10%). The second-harmonic generation study confirmed that structure of (NH₄)In(OH)PO₄ does not have a center of symmetry. The cis-InO₄(OH)₂ octahedra form helical chains, parallel to the c-axis. The In-O-In bonds are nearly equidistant. The chains are interconnected by phosphate tetrahedra and create tunnels containing the NH₄⁺ ions along the c-axis. (NH₄)In(OH)PO₄ is isostructural with RbIn(OH)PO₄.     

Phthalocyanines and related compounds: XXXVIII. Synthesis of symmetric taurine- and choline-substituted phthalocyanines

Procedures have been developed for the synthesis of a series of metal complexes derived from water-soluble anionic and cationic octa-4,5-carboxyphthalocyanine-taurine and choline conjugates.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 11, 2004, pp. 1907–1911.Original Russian Text Copyright © 2004 by Mikhalenko, Soloveva, Lukyanets.For communication XXXVII, see [1].This revised version was published online in April 2005 with a corrected cover date.     

Photodegradation of a 1,3,4-thiadiazole-urea herbicide. Isolation,characterization, X-ray crystal structure and synthesis of photoproducts

The photodegradation of 1,3-dimethyl-1-(2-(3-fluorobenzylthio)-1,3,4-thiadiazol-5-yl)urea as a thin film and in solution is described. The two photoproducts from thin-film photolysis were characterized by spectral and synthetic methods. The X-ray crystal structure of one of the photoproducts is also reported. The rearrangements were shown to involve an S-to-N benzyl migration, followed by a sulfur-oxygen substitution.