Reactions with Carbo(heterylhydrazonoyl) Halides. I. Chemistry of Carbo(3-phenylpyrazol-5-yl-hydrazonoyl) Chlorides

The Carbo(3-phenylpyrazol-5-yl-hydrazonoyl) halides 1a , b react with active methylene compounds to yield the 1-(3-phenylpyrazol-5-yl)-pyrazole derivatives 2a – k (Scheme 1). The acyclic intermediates 3a , b could be isolated from reaction of 1a , b with acetylacetone, thus establishing the substitution mechanism for these reactions. Compounds 1a , b reacted with carbon disulfide, phenyl isothiocyanate, methyl cyanide, and with p-chlorobenzaldehyde to yield the corresponding heterocyclic derivatives 5 – 8 , respectively (Scheme 2). The behaviour of compounds 2 with hydrazine hydrate is reported.     

Beta-decay of 71Co and 73Co

A decay spectroscopy study of the neutron-rich cobalt isotopes has been performed using fragmentation of a ⁸⁶Kr³⁶⁺ beam and the new LISE2000 spectrometer at GANIL. For ⁷¹Co and ⁷³Co, the -delayed radiation has been observed for the first time, and the half-lives were found to be 79(5) ms and 41(4) ms, respectively. Features of the decay are discussed qualitatively in terms of nuclear models.     

Stereoselective synthesis of dihydrothiadiazinoazines and dihydrothiadiazinoazoles and their pyrolytic desulfurization ring contraction

Intramolecular base catalyzed C-C bond formation led to exclusive stereoselective syntheses of trans-6,7-dihydro-5H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazines, trans-7,8-dihydro-6H-[1,2,4]triazino[3,4-b][1,3,4]thiadiazin-4-ones, and trans-3,4-dihydro-2H-[1,3,4]thiadiazino[2,3-b]quinazolin-10-one. trans-6,7-Dihydro-5H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazines isomerize slowly in CDCl₃ and more rapidly in DMSO-d₆ into the corresponding cis-stereoisomers. The other trans-6,7-dihydro-[1,3,4]thiadiazines isomerize also in DMSO-d₆ into the corresponding cis-stereoisomers. Pyrolytic conversion of these heterocyclic condensed dihydrothiadiazines into their corresponding pyrazolo[5,1-b][1,2,4]triazoles, pyrazolo[5,1-c][1,2,4]triazin-4-ones and pyrazolo[4,3-b]quinazolin-9-ones via desulfurization ring contraction is described.     

New Methacrylate Copolymers Based on the Benzofurane Ring: Synthesis,Characterization, Monomer Reactivity Ratios and Biological Activity

The free radical copolymerization of (5-bromo-1-Benzofuran-2-yl)(phenyl)-O-methacrylketoxime (BPMKO) with 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate(AOEMA) has been carried out in 1, 4-dioxane at 65°C ± 1 and was analyzed by Fourier transform infrared, ¹H-NMR, ¹³C-NMR and gel permeation chromatography. Elemental analysis was used to determine the molar fractions of BPMKO and AOEMA in the copolymers. The monomer–reactivity ratios were calculated according to the general copolymerization equation using Kelen-Tüdõs and Finemann-Ross linearization methods. The reactivity ratios indicated a tendency toward random copolymerization. The polydispersity indices of the polymers were determined by gel permeation chromatography and suggested a strong tendency for chain termination by disproportionation. The thermal behaviors of copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The glass-transition temperature of the copolymers increased with increasing BPMKO content in the copolymers. All the products showed moderate activity against different strains of bacteria and fungi.     

SYNTHESIS OF SPIRO [1,3-BENZODIOXOLE-2,4′-(3′H) QUINAZOLINES]

Abstract

In the present investigation, the authors could obtain a new series of spiranes (1) through the reaction of the high potential quinone tetrachloro-o-benzoquinone with 2-aryl-3-phenyl-3H-quinazoline-4-thiones. Thus, 2,3-diphenyl- (2a), 2-p-tolyl-3-phenyl- (2b) and 2-p-anisyl-3-phenyl- (2c)-3H-quinazoline-4-thiones react readily with tetrachloro-o-benzoquinone, in boiling toluene, to give the corresponding spiro-1,3-benzodioxole-2,4′-(3′H)-quinazolines (1a-c), respectively.     

POLYMERIC SURFACTANTS BASED ON OLEIC ACID III. Copolymerization of Sodium Acrylamidostearate and Oleic Acid in a Lamellar Liquid Crystal

Copolymerization of sodium acrylamidostearate (NaAAS) and oleic acid was performed in the lamellar liquid crystal (LLC) formed by NaAAS, oleic acid and water, in the absence of N.N’-methylenebisacrylamide (MBAA) and in the presence of MBAA, respectively. In the absence of MBAA, after the polymerization the lamellar structure remained, and the disorder of the lamellar liquid crystal was, to some extent, enhanced. Surface tension, small-angle X-ray diffraction, viscosity, and fluorescence methods were used to study the properties of the linear copolymer. The linear polymeric surfactant behaves like     

Liquid crystals alignment with PbS nanosculptured thin films

Lead sulphide (PbS) nano-sculptured thin films (nSTFs) are prepared for the first time using glancing angle deposition technique by physical vapour deposition process. An anisotropic morphology is obtained, which provides an orientational effect. Due to this anisotropic nature of PbS nSTF an attempt has been made to check its effect on the alignment of nematic liquid crystals (LCs). Two different LC devices were fabricated, that is, anti-parallel aligned or electrically-controlled birefringence and hybrid twisted nematic. It is noticed that in both types of devices, good alignment is obtained with high extinction and contrast. A significant effect of these alignments on the electro-optic properties of the LC is reported such as the threshold voltage, response time and contrast ratio.     

Intermolecular interactions in (arene)chromium carbonyl compounds: prediction of chiral crystal packing from racemate structure

Six X-ray crystal structures are reported, all containing substituted triphenylmethanol derivative 4 either alone or as its mono or bis(chromium tricarbonyl) complexes. All four chromium complexes studied crystallize with two independent molecules in the crystallographic asymmetric unit. It is demonstrated that from the X-ray crystal structure of the acentric racemic (+/-)-(1pR,1' 'R)(1pS,1' 'S)-[Cr(CO)(3)(eta(6)-t-BuC(6)H(3)(CMeOMe)CPh(2)OH)], (+/-)-3, it is possible to deduce the 4-fold helical structure of the chiral (-)-(1pR,1' 'R) isomer, (-)-3. The bimetallic derivatives demonstrate the ability to control intermolecular interactions by the positioning of relative stereochemistry.     

Syntheses of Some 3—[1′（1′H）—Substituent—pyrazol—5′—yl] benzo [5,6] coumarins

3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described.     

Synthesis and preliminary investigations of the siRNA delivery potential of novel, single-chain rigid cationic carotenoid lipids

The success of nucleic acid delivery requires the development of safe and efficient delivery vectors that overcome cellular barriers for effective transport. Herein we describe the synthesis of a series of novel, single-chain rigid cationic carotenoid lipids and a study of their preliminary in vitro siRNA delivery effectiveness and cellular toxicity. The efficiency of siRNA delivery by the single-chain lipid series was compared with that of known cationic lipid vectors, 3β-[N-(N',N'-dimethylaminoethane)carbamoyl]-cholesterol (DC-Chol) and 1,2-dimyristoyl-sn-glyceryl-3-phosphoethanolamine (EPC) as positive controls. All cationic lipids (controls and single-chain lipids) were co-formulated into liposomes with the neutral co-lipid, 1,2-dioleolyl-sn-glycerol-3-phosphoethanolamine (DOPE). Cationic lipid-siRNA complexes of varying (+/-) molar charge ratios were formulated for delivery into HR5-CL11 cells. Of the five single-chain carotenoid lipids investigated, lipids 1, 2, 3 and 5 displayed significant knockdown efficiency with HR5-CL11 cells. In addition, lipid 1 exhibited the lowest levels of cytotoxicity with cell viability greater than 80% at all (+/-) molar charge ratios studied. This novel, single-chain rigid carotenoid-based cationic lipid represents a new class of transfection vector with excellent cell tolerance, accompanied with encouraging siRNA delivery efficiency.