Local analyticity for the [`(?)]\overline \partial -Neumann problem in completely decoupled pseudoconvex domains-Neumann problem in completely decoupled pseudoconvex domains

In this paper we prove local analyticity of solutions to the -Neumann problem up to the boundary of rigid, completely decoupled pseudoconvex domains with real-analytic boundary. These are domains that are locally of the form Imw > Σ |h _k (z _k )|² with eachh _k holomorphic and vanishing only at 0. As in those earlier papers, we use purelyL ² methods and must construct a special holomorphic vector fieldM and then use carefully balanced polynomials inM to localize high powers ofT = ∂/∂t effectively, wheret = Rew.     

Unique continuation theorems for the\bar \partial - Operator and applications

We formulate a unique continuation principle for the inhomogeneous Cauchy-Riemann equations near a boundary pointz ₀ of a smooth domain in complex euclidean space. The principle implies that the Bergman projection of a function supported away fromz ₀ cannot vanish to infinite order atz ₀ unless it vanishes identically. We prove that the principle holds in planar domains and in domains where the problem is known to be analytic hypoelliptic. We also demonstrate the relevance of such questions to mapping problems in several complex variables. The last section of the paper deals with unique continuation properties of the Szegő projection and kernel in planar domains. Research supported by NSF Grant DMS-8922810.     

Aryl-bis(triorganylphosphine)nickel phenoxides

Compounds of general formulatrans-ArNi(PR₃)₂OAr' (R = Et, cyclohexyl; Ar = 2-MeC₆H₄, 2-FC₆H₄; Ar' = 4-FC₆H₄, 4-NO₂C₆H₄) were synthesized by the reaction of Ar'OK with cationic nickel complexes generated by treatment of ArNi(PR₃)₂Cl with TlBF₄. Syntheses of 4-fluorophenoxide complexes, ArNi(PR₃)₂OC₆H₄F-4, additionally give some quantities oftrans-[ArNi(PR₃)₂OC₆H₄F-4][HOC₆H₄F-4] adducts. Exchange reactions MeC₆H₄Ni(PEt₃)₂OC₆H₄F-4 + XC₆H₄OH 2-MeC₆H₄Ni(PEt₃)₂OC₆H₄X + 4-FC₆H₄OH were studied in THF. The equilibrium is shifted to the right as the acidity of ArOH increases. A linear relationship between lgK _eq and pK _a of XC₆H₄OH in DMSO was found. A conclusion concerning the strong polarization of the Ni-O bond was made on the basis of an analysis of the chemical shifts of fluorine atoms in 2-MeC₆H₄Ni(PEt₃)₂OC₆H₄F-4.Translated fromIvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2271, November, 1995.     

Prediction of aqueous solubility of drugs and pesticides with COSMO-RS

The COSMO-RS method, originally developed for the prediction of liquid-liquid and liquid-vapor equilibrium constants based on quantum chemical calculations, has been extended to solid compounds by addition of a heuristic expression for the Gibbs free energy of fusion. By this addition, COSMO-RS is now capable of a priori prediction of aqueous solubilities of a wide range of typical neutral drug and pesticide compounds. Only three parameters in the heuristic expression have been fitted on a data set of 150 drug-like compounds. On these data an rms deviation of 0.66 log-units was achieved. Later, the model was tested on a set of 107 pesticides, which have been critically selected based on two experimental data sources and by a crosscheck with an independent HQSAR model. On this data set an rms of 0.61 log-units was achieved, without any adjustments to the structurally extremely diverse pesticides. This result verifies the ability of this extended COSMO-RS to predict aqueous solubilities of drugs and pesticides of almost arbitrary structural classes. The new method is COSMO-RSol.     

The Route of Alkylation of 5-Substituted 1,3,4-Thiadiazoline-2-thiones

The reaction of 5-anilino(toluidino-, morpholino)-1,3,4-thiadiazoline-2-thiones at 80°C with allyl bromide and benzyl chloride in alcohol, acetonitrile or DMF in the presence of KOH and also with phenoxymethyloxirane in alcohol in the absence of base gives the corresponding novel allyl-, benzyl-, and 2-hydroxy-3-phenoxypropyl products substituted at the exocyclic S atom. Alkylation of the indicated thiones with benzyl chloride at 150-153°C in DMF in the presence of KOH occurs similarly. Under these conditions, allyl bromide forms alkylation products at the endocyclic N(3) atom as a result of an SN thio-Claisen rearrangement of the initially formed product which is allyl substituted at the exocyclic S atom.     

SSZ-53 and SSZ-59: two novel extra-large pore zeolites

The syntheses, structure solutions, and physicochemical and catalytic characterizations of the novel zeolites SSZ-53 and SSZ-59 are described. SSZ-53 and SSZ-59 were synthesized under hydrothermal conditions with the [1-(4-fluorophenyl)cyclopentylmethyl]trimethyl ammonium cation and 1-[1-(4-chlorophenyl)cyclopentylmethyl]-1-methyl azocanium cation, respectively, as structure-directing agents. The framework topology of SSZ-53 was solved with the FOCUS method, and the structure of SSZ-59 was determined by model building. Rietveld refinement of synchrotron X-ray powder diffraction data confirms each proposed model. SSZ-53 and SSZ-59 each possess a one-dimensional channel system delimited by 14-membered rings. Results from transmission electron microscopy, electron diffraction, catalytic experiments (spaciousness index and constraint index tests), and argon and hydrocarbon adsorption experiments are consistent with the proposed structures.     

Spectroscopic studies on 2,3,4,5-tetraphenylpyrylium salts with and without silver (I)-bridged structures

Two novel phenylated pyrylium compounds, silver (I)-bridged 2,3,4,5-tetraphenylpyrylium perchlorate (P1) and its silver (I)-free pyrylium ligand (P2) were prepared from 1,2,3,4-tetraphenylcyclopentadiene to examine their spectroscopic behaviors. The UV/vis absorption and fluorescent emission spectra of P1 and P2, measured in three solvents (acetonitrile, dichloromethane and toluene), reveal that the photophysical behaviors are closely related to silver (I) fragment, and strongly dependent on solvent polarity. In polar acetonitrile, P1 displays longer absorption wavelength and much lower fluorescent emission intensity than P2, although they exhibit much similarity in shape. In contrast, in nonpolar toluene, while P2 shows an apparent absorption band at 338 nm, P1 displays a tail-like line without absorption band observed. All the spectra obtained indicate a better coplanarity and a stronger intra-molecular charge transfer in P1 due to the effect of silver (I) fragment. Additionally, the 1H NMR spectra of P1 and P2, which were recorded under the same conditions, indicate that the silver (I) fragment reinforces pyrylium ring's capacity to localize the formal positive charge within the heterocyclic ring.     

A simpler and greener protocol for the preparation of β-acetylamino ketones by a one-pot reaction of aryl aldehydes, enolisable ketones, acetyl chloride and acetonitrile in the presence of zeolite Hβ as a reusable catalyst

β-Acetylamino ketones have been obtained in a one-pot coupling of an aldehyde with an enolisable ketone, acetyl chloride and acetonitrile in the presence of zeolite Hβ as catalyst at room temperature (26-28 °C). The procedure has the advantages of mild workup, circumvention of high temperature and inert atmosphere. The catalyst was found to be recyclable.     

Use of Tetramethylthiuram Disulfide in Synthesis of Nitrogen-containing Heterocyclic Compounds

We have developed a method for synthesis of aryl isothiocyanates by means of thiocarbamoylation of aromatic amines by tetramethylthiuram disulfide followed by degradation of the intermediate N₍₁₎-aryl-N,N-dimethylthiourea by concentrated HCl. We have shown that thiocarbamoylation of 4-amino-5-ethyl-4H-1,2,4-triazole-3-thiol occurs at the 2 position of the triazole ring, while thiocarbamoylation of 4-amino-3-methyl-6-phenyl-4,5-dihydro-1,2,4-triazin-5-one leads to the dihetaryl-substituted thiourea. We consider the possibility of using N₍₁₎-aryl-N,N-dimethylthioureas as analogs of isothiocyanates in reactions with N-nucleophiles.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 775–780, May, 2005.