Preparation and characterization of finely dispersed drugs. 5. Ethyl 3,5-di(acetylamino)-2,4,6-triiodobenzoate

Controlled precipitation of the diagnostic imaging agent ethyl 3,5-di(acetylamino)-2,4,6-triiodobenzoate has been used to produce fine particles of various sizes, morphologies, and degrees of crystallinity, which depended on experimental conditions. In addition, two distinct polymorphic forms of the drug have been fully characterized by single crystal X-ray diffraction studies, and evidence for a third polymorph was also observed. Some of the so prepared dry particles were coated with a thin layer of silica.     

Synthesis and crystal structure of 1,3,5-tris [4-(phenylethynyl)phenyl]benzene

The crystal structure of 1,3,5-tris[4-(phenylethynyl)phenyl]benzene (1) has been investigated. Compound1 represents a model of the repeating unit of the most typical polyphenylene, which contains 1,3,5-trisubstituted benzene rings (chain centers) and acetylenic groups (complex-forming and cross-linking centers) in the main chain. The acetylene groups of neighboring molecules have a tendency to close mutual arrangement, which is favorable for their topochemical interaction. However, the relative conformational rigidity of molecules1 restricts not only the possibility of the optimal adjustment of the reactive sites of neighboring molecules to one another, but also hampers the close packing of molecules in the crystal, which contains channels filled by the solvent molecules (chloroform).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1986–1992, November, 1994.The work was carried out with the financial support of the International Science Foundation and the American Crystallographic Association.     

Trichloroisocyanuric acid as a novel oxidizing agent for the oxidation of 1,3,5-trisubstituted pyrazolines under both heterogeneous and solvent free conditions

Trichloroisocyanuric acid is used as an effective oxidizing agent for the oxidation of 1,3,5-trisubstituted pyrazolines to their corresponding pyrazoles under both heterogeneous and also solvent free conditions with good yields at room temperature.     

Photochemical properties and structures ofN-amino andN-azomethine derivatives of 2,4,6-triphenylpyridinium perchlorates

The molecular structures of the initial compounds and the products of photocyclization involving amino and azomethine groups in perchlorates ofN-amino (1) andN-azomethine (2) derivatives of 2,4,6-triphenylpyridinium cations were studied. Cations1 and2 have an essentially non-coplanar arrangement of the -Ph rings, and the product of photocyclization of2, cation3, is characterized by a flattened structure. It was found that the orientation of the lone electron pair of the N atom with respect to one of the planes of the -Ph rings in molecule1 is more favorable for monocyclization involving the amino group. The structure of molecule2 allows two routes of the photoreaction,viz., O N proton transfer and monocyclization with an -Ph ring. However, the structural features of molecule2 are more favorable for photocyclization.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 296–301, February, 1995.     

Spin Density Distribution in 2,4,6-Triphenylphenoxyl

The distribution of the unpaired electron over the oxygen and the 24 carbon atoms in the free 2,4,6-triphenylphenoxy radical was determined by electron spin resonance spectroscopy and quantum-mechanical approximation methods. The hyperfine splitting was evaluated with the aid of the spectra of triphenylphenoxyls deuterated in some or all of the substituent phenyl groups. The results of the quantum-mechanical approximations were checked by recording the ESR spectra of triphenylphenoxyls labeled with ¹³C in positions 1,2,3, or 4 of the central ring. The spin density distribution permits a first discussion of the ¹⁷O-coupling constants of correspondingly labeled triphenylphenoxyl and other organic free radicals.     

Amino acid end-group in commercial heparin. III. Determination of the number of amino groups of amino acid and hexosamine residues per heparin molecule

The reactions of heparin with 2,4,6-trinitrobenzenesulfonic acid (TNBS) were studied spectrometrically. Seven different commercial heparins were used in this study. The amino groups react with TNBS to form equimolar amounts of trinitrophenylated (TNP) amino groups and bisulfite ions. The TNP-amino groups further react with bisulfite ions to form the monosubstituted anionic sigma complex. The absorption spectrum with two maxima at approximately 350 nm and approximately 420 nm, characteristic of either the TNP-amino groups or the complex, was analyzed for the reaction of TNBS with heparin. It was shown that the reactivities of TNBS with amino groups from α-amino acid and hexosamine residues are greatly different. By combining the results of the reaction kinetics and the reaction of heparin with Sanger's reagent, the number of the α-amino groups and the free amino groups in hexosamine residues were determined. These data have been performed with a range of heparins from different commercial sources, of different activities and physical characteristics. No correlation was found between the free amino contents of these heparins and biological potency. © 1993 John Wiley & Sons, Inc.     

A versatile and practical synthesis of bis(indolyl)methanes/bis(indolyl)glycoconjugates catalyzed by trichloro-1,3,5-triazine

A practical and efficient electrophilic substitution reaction of indoles with a variety of aldehydes was carried out using catalytic trichloro-1,3,5-triazine (10 mol %) in acetonitrile to furnish the corresponding bis(indolyl)methanes in excellent yields. Similarly, sugar derived aldehydes gave hitherto unknown bis(indolyl)glycoconjugates in very good yields.     

2,4,6-Trichloro-1,3,5-triazine Catalyzed Chemoselective Transthioacetalization of Aldehyde Acetals and Oxathioacetals

Summary. A mild and efficient transthioacetalization of aldehyde acetals and oxathioacetals was carried out using 2,4,6-trichloro-1,3,5-triazine as a mild and inexpensive catalyst. Chemoselective transacetalization is impressive as aldehyde O,O- and O,S-acetals are converted into the corresponding S,S-acetals in the presence of ketones or their acetals and oxathiocetals in nearly quantitative yields.     

Molecular Recognition of Nucleic Acid Bases in Water by Hydrogen Bonding of Poly(vinyldiaminotriazine)

Poly(2-vinyl-4,6-diamino-1,3,5-triazine) efficiently binds nucleic acid bases and nucleosides in water by using complementary hydrogen bonding. The binding activity decreases in the order: U, T > A C, G. The corresponding monomer shows virtually no activity, indicating a predominant role of polymer effect for the molecular recognition in water.