Polysiloxane based on hydroxyl-containing monomer. Preparation,properties and biomedical application

Russian Chemical Bulletin - A method for synthesis of hyperbranched polysiloxane based on N-methyl-N-(2,3,4,5,6-pentahydroxyhexyl)-N’-(3-triethoxysilylpropyl)urea is proposed. In water, the...     

Molecular and crystal structure of liquid crystalline p-octyloxyphenyl p′-pentyloxybenzoate

The crystal and molecular structure of p-octyloxyphenyl p′-pentyloxybenzoate C₅H₁₁-O-C₆H₄-C(O)-O-C₆H₄-O-C₈H₁₇, which forms a nematic mesophase upon melting, was determined by X-ray diffraction. There is one system of weak directional intermolecular C-H…π interactions responsible for the formation of the nematic phase in these crystals.     

Perfluoropropylene oxide as a reagent for the synthesis of germanium,titanium, tin,and zirconium fluorides

A new method of preparation of germanium, titanium, tin, and zirconium fluoride alcohol complexes by reaction of the metal oxides with a solution of perfluoropropylene oxide in methanol is developed. The reaction of the complexes obtained with ligands (L = 1,10-phenanthroline or dimethyl sulfoxide) was studied, and the structure of the obtained compounds was determined. A new route to the synthesis of 1-fluorogermatrane is developed.     

Synthesis and structural consideration of 1‐chloro‐N,N′,N″‐tris(pentafluorophenyl)azagermatrane: Azagermatrane with the shortest intramolecular N → Ge bond

Two compounds of a novel‐type azagermatrane, N(CH₂CH₂NC₆F₅)₃Ge‐Hal: HalCl ( 1 ), Br ( 2 ), were prepared via a metathetical reaction of trilithium salt of tetramine, N[CH₂CH₂N(Li)C₆F₅]₃, with corresponding GeHal₄. A single crystal structure of 1 was determined by the X‐ray diffraction study: The compound shows the strongest transannular N_ax → Ge interaction (2.148(7) Å) among other studied azagermatranes. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:738–741, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20476     

Synthesis and structures of new 1,3,6,2-dioxazaborocanes containing substituents in the ocane fragment

New 1,3,6,2-dioxazaborocanes R¹N(CHR³CR⁴R²O)(CHR⁶CHR⁵O)BX (1–11, X = Ph, 4-MeC₆H₄, Me; R¹ = Me, PhCH₂; R², R³, R⁴, R⁵, R⁶ = H, Ph) were synthesized by the reactions of aryl- or methylboronic acids with dialkanolamines. The treatment of (Me₂NCH₂CH₂O)₃B (15) with MeN(CH₂CH₂OH)(CH₂CPh₂OH) afforded 2-[2-(dime-thylamino)ethoxy]-1,3,6,2-dioxazaborocane (12). 2-Fluoro-1,3,6,2-dioxazaborocanes R¹N(CHR³CHR²O)(CH₂CH₂O)BF (13: R¹ = PhCH₂, R² = R³ = H; 14: R¹ = Me, R² = R³ = Ph, threo) were synthesized by the reaction of bis(trimethylsilyl) ethers of the corresponding dialkanolamines with BF₃·Et₂O. The new borocanes can be used for the synthesis of the corre-sponding germanium derivatives PhCH₂N(CH₂CH₂O)₂GeX₂ (16, X = OEt; 17, X = Cl), as exemplified by the reaction of compound 6. The structures of erythro-MeN(CH₂CH₂O)(CHPhCHPhO)BPh (3), threo-MeN(CH₂CH₂O)(CHPhCHPhO)BPh (4), erythro-MeN(CH₂CH₂O)(CHPhCHPhO)B(4-MeC₆H₄) (8), and PhCH₂N(CH₂CH₂O)₂BF (13) were established by X-ray diffraction. The coordination polyhedra of the boron atoms in these complexes can be described as distorted tetrahedra. The boron-nitrogen distances (1.705(7)–1.723(3) Å) provide unambiguous evidence for the presence of the B←N transannular interaction in these compounds. The structures of the resulting borocanes containing phenyl substituents at the carbon atoms of the ocane skeleton were studied by NMR spectroscopy and quantum chemical density functional theory calculations.     

Synthesis,structure, and reactivity of germanium-containing derivatives of substituted diethanolamines

The reaction of dialkanolamines RN(CH₂CH₂O)(CHR’CHR’OH) (R = Me, Ph, PhCH₂; R’ = H, Ph) with tetraethoxygermane gives either 2,2-diethoxy-1,3,6,2-dioxazagermocanes RN(CH₂CH₂O)(CHR’CHR’O)Ge(OEt)₂ or 1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7.7]pentadecanes [RN(CH₂CH₂O) (CHR’CHR’O)]₂Ge depending on the reactant ratio. The chemical behavior of the obtained compounds in substitution reactions at germanium was studied. The product structure was confirmed by elemental analysis data and ¹H, ¹³C, and ¹⁹F NMR spectroscopy. The cyclotrigermanoxane [MeN(CH₂CH₂O)₂GeO]₃ was studied by X-ray diffraction.     

Crystal packing in the structures of diethanolamine derivatives

Four distinct hydrogen‐bonding topologies were observed in the structures of six diethanolamine ligands. These compounds are (1R*,2R*)‐2‐[(2‐hydroxyethyl)(methyl)amino]‐1,2‐diphenylethanol, C₁₇H₂₁NO₂, (I), 1‐[(2S)‐2‐(hydroxydiphenylmethyl)pyrrolidin‐1‐yl]‐2‐methylpropan‐2‐ol, C₂₁H₂₇NO₂, (II), 2‐[(2‐hydroxyethyl)(methyl)amino]‐1,1‐diphenylethanol, C₁₇H₂₁NO₂, (III), 1‐{(2‐hydroxy‐2‐methylpropyl)[(1S)‐1‐phenylethyl]amino}‐2‐methylpropan‐2‐ol, C₁₆H₂₇NO₂, (IV), 1‐{[(2R)‐2‐hydroxy‐2‐phenylethyl][(1S)‐1‐phenylethyl]amino}‐2‐methylpropan‐2‐ol, C₂₀H₂₇NO₂, (V), and (1R*,2S*)‐2‐[(2‐hydroxyethyl)(methyl)amino]‐1,2‐diphenylethanol, C₁₇H₂₁NO₂, (VI). In each compound, all `active' hydroxy H atoms are engaged in hydrogen bonding, but the N atoms are not involved in intermolecular hydrogen bonding. In the structures of (I), (II) and (IV)–(VI), molecules are linked into chains by intermolecular O—H...O interactions. These chains are organized in such a way as to hide the hydrophilic groups inside, and so the outer surfaces of the chains are hydrophobic. The structure of (VI) contains two distinct non‐equivalent systems of intermolecular O—H...O hydrogen bonds formed by disordered hydroxy H atoms.     

Novel regular polyimide‐graft‐(polymethacrylic acid) brushes: Synthesis and possible applications as nanocontainers of cyanoporphyrazine agents for photodynamic therapy

An approach to the synthesis of new regular graft‐copolymers polyimide (PI)‐graft‐polymethacrylic acid is elaborated, including (1) synthesis of multicenter PI macroinitiators, (2) controlled ATRP of tert‐butylmethacrylate on the prepared macroinitiators, and (3) protonolysis of tert‐butyl ester groups of side chains of the resulting PI‐graft‐poly(tert‐butylmethacrylate). Experimental conditions for attaining complete conversions of the first and the third stages of the process are determined by means of ¹H NMR and FTIR‐spectroscopy. Polymer products of the first and the second stages of the process, as well as poly(tert‐butylmethacrylate) side chains cleaved from the PI‐graft‐poly(tert‐butylmethacrylate) copolymers by complete decomposition of the PI backbone under alkaline hydrolysis conditions, are characterized by GPC. The kinetics of poly(tert‐butylmethacrylate) chain growth on a PI macroinitiator under ATRP conditions are studied. The results obtained provide evidence for the controlled character of the ATRP process and the regular structure of the synthesized graft‐copolymers. It is shown that PI‐g‐PMAA PI brushes are significantly more efficient intracellular delivery agents for the potential photosensitizer [tetra(4‐fluorophenyl)tetracyanoporhyrazine free base] than are the commonly used PEG‐micelles. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4267–4281     

Design of crystal packings of styryl heterocycles and regularities of [2+2] photocycloaddition in their single crystals 8. Topochemical [2+2] autophotocycloaddition and back reaction in styryl dye of the benzothiazole series

New styryl dye of the 2-benzothiazole series was synthesized. The new dye contains two methoxy groups in the benzene ring and tosylate counterion. The [2+2] photocycloaddition (PCA) of the dye was studied in the polycrystalline film and in single crystal. Two modifications of the dye cocrystallizate with hydroquinone differed in the ratio of components were obtained, and their ability to enter PCA was studied. According to the X-ray diffraction data, molecular cations of the dye form stack packings either of syn-“head-to-tail” type or relatively isolated stacking dimers. In all cases, the ethylene bonds of the adjacent cations are brought together and antiparallel, favoring PCA to form the centrosymmetric rctt-isomer of 1,2,3,4-tetrasubstituted cyclobutane. In two cases, the PCA reaction proceeded as the “single crystal-to-single crystal” transformation. Hydrogen bonds in crystals including hydroquinone molecules strengthen the crystal packing retarding the PCA. The back photoreaction (retro-PCA) was detected: it occurs without single crystal decomposition and results in the accumulation of the initial styryl dye in crystal consisting of the cyclobutane derivative. This is the first example of such a transformation in single crystals.