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Showing papers on "Derivative (chemistry) published in 1997"


Journal ArticleDOI
TL;DR: In this article, the authors proposed a catalytic cycle composed of sorption of the reactants in the cavities of polycrystalline host 1, preorganized intracavity reaction, and desorption of product.
Abstract: Anthracenebisresorcinol derivative 1 as an organic network material shows a novel catalysis in the solid state for the acrolein−cyclohexadiene Diels−Alder reaction. The suggested mechanism involves a catalytic cycle composed of sorption of the reactants in the cavities of polycrystalline host 1, preorganized intracavity reaction, and desorption of the product. The host also promotes stereoselective intracavity reactions for alkyl acrylates and cyclohexadiene but, in this case, not in a catalytic manner. Relevance of the present system as a functional organic analog of zeolites is discussed in light of the kinetics of respective elementary processes and the effects of pulverization of the catalyst thereupon as well as X-ray crystal structures.

166 citations


Patent
14 Apr 1997
TL;DR: In this article, a cyclic organic compound is expressed by the formula, and composed, for example, by the use of a naphthoquinone derivative, a Grignard's reagent and a lithiation reagent or diaryl benzoflane.
Abstract: PROBLEM TO BE SOLVED: To improve luminous efficiency as well as brightness, and extend service life by applying the constitution that a cyclic organic compound is contained in the hole injection layer or the luminous layer of an organic electroluminescent element having a plurality of layers of organic compound thin films, containing at least a luminous layer and a hole injection layer between a pair of electrodes. SOLUTION: A cyclic organic compound is expressed by the formula, and composed, for example, by the use of a naphthoquinone derivative, a Grignard's reagent and a lithiation reagent or diaryl benzoflane. Preferably, a hole injection layer is doped into an area formed with an anode, or the compound expressed by the formula is doped into the host substance of a luminous layer having an electron injection layer in an area formed with a cathode. As a result, carriers injected from the cathode are evenly recombined within the luminous layer. In the formula, (x) represents a halogen atom, a cyano group, an alkyl group, an aryl group, an alcoxy group, an aryloxy group, an alkylthio group, a cycloalkyl group, a heterocyclic group and an amino group, and (i) represents an integer between 1 and 28. COPYRIGHT: (C)1998,JPO

146 citations


Patent
11 Dec 1997
TL;DR: In this article, a genetic or chemical fusion protein comprising the Fc immunoglobulin region, derivative or analog fused to the N-terminal portion of the OB protein, is described.
Abstract: The present invention relates to Fc-OB fusion protein compositions, methods of preparation of such compositions and uses thereof. In particular, the present invention relates to a genetic or chemical fusion protein comprising the Fc immunoglobulin region, derivative or analog fused to the N-terminal portion of the OB protein, derivative or analog.

112 citations



Journal ArticleDOI
TL;DR: A new annulation sequence leading to the tetracyclic skeleton of the Lycopodium family of alkaloids is effected by using the tandem cycloaddition-cationic pi-cyclization reaction of an isomünchnone dipole as the key strategic element.
Abstract: A new annulation sequence leading to the tetracyclic skeleton of the Lycopodium family of alkaloids is effected by using the tandem cycloaddition-cationic pi-cyclization reaction of an isomunchnone dipole as the key strategic element. Synthesis of the required alpha-diazo imide precursor involved treating 5-methylcyclohex-2-en-1-one with the organocopper reagent derived from 3-methoxybenzyl chloride in the presence of chlorotrimethylsilane. Ozonolysis of the resulting silyl enol ether followed by a Wittig reaction and conversion to the desired alpha-diazo imide was carried out using standard malonylacylation and diazotization procedures. Treatment of the alpha-diazo imide with rhodium(II) perfluorobutyrate afforded a transient 1,3-dipole which subsequently cycloadded across the tethered pi-bond. The resulting cycloadduct was treated with BF(3).2AcOH to give a rearranged tetracyclic compound derived from a Pictet-Spengler-type cyclization of an N-acyliminium ion. The rearranged product was subsequently converted into a key intermediate previously used for the synthesis of (+/-)-lycopodine.

98 citations


Journal ArticleDOI
TL;DR: From the roots of Isatis indigotica, two new alkaloids named isaindigotidione (ISI) 1 and ISIdigotone 2 were isolated by spectral and X-ray crystallographic analyses.

94 citations


Journal ArticleDOI
TL;DR: In this paper, the synthesis of expanded radialenes and expanded C60-C70 fullerene derivatives is described, which are precursors to C60substituted poly(triacetylenes) (PTAs, Fig. 1) and expanded radialene (Fig. 2) is described.
Abstract: The synthesis of (E)-hex-3-ene-l, 5-diynes and 3-methylidenepenta-1, 4-diynes with pendant methano[60]-fullerene moieties as precursors to C60-substituted poly(triacetylenes) (PTAs, Fig. 1) and expanded radialenes (Fig. 2) is described. The Bingel reaction of diethyl (E)-2, 3-dialkynylbut-2-ene-1, 4-diyl bis(2-bromopropane-dioates) 5 and 6 with two C60 molecules (Scheme 2) afforded the monomeric, silyl-protected PTA precursors 9 and 10 which, however, could not be effectively desilylated (Scheme 4). Also formed during the synthesis of 9 and 10, as well as during the reaction of C60 with thedesilylated analogue 16 (Scheme5), were the macrocyclic products 11, 12, and 17, respectively, resulting from double Bingel addition to one C-sphere. Rigorous analysis revealed that this novel macrocyclization reaction proceeds with complete regio- and diastereoselectivity. The second approach to a suitable PTA monomer attempted N, N′-dicyclohexylcarbodiimide(DCC)-mediated esterification of (E)-2, 3-diethynylbut-2-ene-l, 4-diol (18, Scheme 6) with mono-esterified methanofullerene-dicarboxylic acid 23; however, this synthesis yielded only the corresponding decarboxylated methanofullerene-carboxylic ester 27 (Scheme 7). To prevent decarboxylation, a spacer was inserted between the reacting carboxylic-acid moiety and the methane C-atom in carboxymethyl ethyl 1, 2-methano[60]fullerene-61, 61-dicarboxylate (28, Scheme 8), and DCC-mediated esterification with diol 18 afforded PTA monomer 32 in good yield. The formation of a suitable monomeric precursor 38 to C60-substituted expanded radialenes was achieved in 5 steps starting from dihydroxyacetone (Schemes 9 and 10), with the final step consisting of the DCC-mediated esterification of 28 with 2-[1-ethynyl(prop-2-ynylidene)]propane-1, 3-diol (33). The first mixed C60-C70 fullerene derivative 49, consisting of two methano[60]fullerenes attached to a methano[70]fullerene, was also prepared and fully characterized (Scheme 13). The Cs-symmetrical hybrid compound was obtained by DCC-mediated esterification of bis[2-(2-hydroxy-ethoxy)ethyl] 1, 2-methano[70]fullerene-71, 71-dicarboxylate (46) with an excess of the C60-carboxylic acid 28. The presence of two different fullerenes in the same molecule was reflected by its UV/VIS spectrum, which displayed the characteristic absorption bands of both the C70 and C60 mono-adducts, but at the same time indicated no electronic interaction between the different fullerene moieties. Cyclic voltammetry showed two reversible reduction steps for 49, and comparison with the corresponding C70 and C60 mono-adducts 46 and 30 indicated that the three fullerenes in the composite fullerene compound behave as independent redox centers.

89 citations


Journal ArticleDOI
TL;DR: In this paper, the reaction of the iron(II) picket fence porphyrin derivative [Fe(TpivPP)(NO2] with NO has been examined.
Abstract: The reaction of the iron(II) picket fence porphyrin derivative [Fe(TpivPP)(NO2)]- (Nasri et al. J. Am. Chem. Soc. 1991, 113, 717) with NO has been examined. The result is a new hexacoordinated iron...

88 citations


Journal ArticleDOI
TL;DR: The absolute stereochemistry of the New Zealand shellfish toxin gymnodimine has been determined by X-ray crystal structure analysis of the p-bromobenzamide derivative 3 of gymnodamine as mentioned in this paper.

84 citations



Patent
Anthony J. Allen1
17 Apr 1997
TL;DR: In this paper, an intralinked polyamidoamine which is nonthermosetting and endcapped is presented, which is the reaction product of a dicarboxylic acid or dicaramido acid derivative, a polyamine, an endcapping agent, and an intrainker.
Abstract: An intralinked polyamidoamine which is nonthermosetting and endcapped. This intralinked polyamidoamine is the reaction product of a dicarboxylic acid or dicarboxylic acid derivative, a polyamine, an endcapping agent, and an intralinker.

Patent
19 Jun 1997
TL;DR: In this article, insulin preparations of superior chemical stability, comprising human insulin or an analogue or derivative thereof, glycerol and/or mannitol, and 5 to 100 mM of the halogenide are disclosed.
Abstract: Insulin preparations of superior chemical stability, comprising human insulin or an analogue or derivative thereof, glycerol and/or mannitol, and 5 to 100 mM of the halogenide are disclosed.

Journal ArticleDOI
TL;DR: An expeditious methodology for the synthesis of β-(1 → 4)-3-deoxythiodisaccharides (3- deoxythiocellobiose) has been developed and is based on the stereoselective Michael addition of 2,3,4,6-tetra-O-acetyl-1-thio-β-d-glucose to levoglucosenone.

Journal ArticleDOI
TL;DR: Water samples from the Nishitakase River in Kyoto, Japan, especially taken at sites below sewage plants, show significantly high mutagenicity in the Ames test, and PBTA-1 is a newly identified potent mutagen, inducing 1,200,000 revertants of Salmonella typhimurium YG1024 per microgram in the presence of S9 mix.
Abstract: Water samples from the Nishitakase River in Kyoto, Japan, especially taken at sites below sewage plants, show significantly high mutagenicity in the Ames test. In the present study, mutagens in the river water were adsorbed to 24 g of blue rayon, extracted, and separated by HPLC on ODS columns. Five mutagenic compounds (I-V) were isolated, and they accounted for 21%, 17%, 11%, 12%, and 6%, respectively, of the total mutagenicity of the blue rayon-adsorbed materials. With compound I obtained from adsorbate to 24 g of blue rayon as a marker, a large quantity (1.1 mg) of mutagenic compound I was isolated by Sephadex LH-20 column chromatography and HPLC on ODS columns from material adsorbed to 27 kg of blue cotton. X-ray crystal analysis was carried out with the debrominated derivative of compound I. Based on this X-ray crystallography data and the UV, mass, and 1H-NMR spectra of both the derivative and compound I, the structure of compound I was determined to be 2-[2-(acetylamino)-4-[bis(2-methoxyethyl)amino]-5-methoxyphenyl]-5-amino - 7-bromo-4-chloro-2H-benzotriazole (PBTA-1). PBTA-1 is a newly identified potent mutagen, inducing 1,200,000 revertants of Salmonella typhimurium YG1024 per microgram in the presence of S9 mix.

Journal ArticleDOI
TL;DR: The 3′-C-allyl furanose 4 has been used as a precursor for synthesis of the novel 2′-O,3′- C-linked bicyclic thymine nucleosides 15, 16, 20 and 25 and is incorporated into oligodeoxynucleotides.
Abstract: The 3′-C-allyl furanose 4 has been used as a precursor for synthesis of the novel 2′-O,3′-C-linked bicyclic thymine nucleosides 15, 16, 20 and 25. The three bicyclic β-nucleosides 15, 20 and 25 have been incorporated into oligodeoxynucleotides. One of these nucleosides, dioxabicyclo[3.3.0]octane derivative 25, induces increased thermal stability of duplexes towards complementary RNA.


Journal ArticleDOI
TL;DR: In this article, two different trivalent europium (Eu 3+ ) complexes, Europium(dibenzoylmethanato) 3 (bathophenanthroline) [Eu(DBM) 3 bath] and EuropIUM(diametrizolamide 3 (monamide 3 phen), with different ligands for emission-layer materials, have been fabricated.

Journal ArticleDOI
TL;DR: The tris(2,2‘-bipyridine)ruthenium(II) complex (Ru(bpy)32+) derivative monomer was copolymerized with N-tert-pentylacrylamide and N-dodecyl acrylamides.
Abstract: The tris(2,2‘-bipyridine)ruthenium(II) complex (Ru(bpy)32+) derivative monomer was copolymerized with N-tert-pentylacrylamide and N-dodecylacrylamide. These copolymers, p(tPA-Ru) and p(DDA-Ru), for...

Patent
01 Apr 1997
TL;DR: In this paper, a pharmaceutical composition for oral administration in which a fumagillol derivative is stabilized and exhibits remarkable antiangiogenesis activity in oral administration was presented, and the formulation was described.
Abstract: The present invention relates to a pharmaceutical composition for oral administration in which a fumagillol derivative is stabilized and exhibits remarkable antiangiogenesis activity in oral administration.

Journal ArticleDOI
TL;DR: The first dialkylead(II) species to be structurally characterized is the title lead (II) derivative, obtained as dark blue crystals by treatment of PbCl2 with (TMEDA = N,N,NN, N'N', N'Tetramethylethylenediamine) in tetrahydrofuran and its structure determined by X-ray diffraction as mentioned in this paper.


Journal ArticleDOI
TL;DR: A Diels-Alder adduct of [60] and a tetrathiafulvalene (TTF) derivative is synthesised by direct reaction of [ 60]fullerene with a TTF diene precursor as mentioned in this paper.

Journal ArticleDOI
TL;DR: While the colorless form of the binaphthol-condensed indolylfulgide did not emit fluorescence, its colored form, generated by the UV-light irradiation, emitted fluorescence in toluene at room temperature as mentioned in this paper.
Abstract: While the colorless form of the propyl-substituted, binaphthol-condensed indolylfulgide did not emit fluorescence, its colored form, generated by the UV-light irradiation, emitted fluorescence in toluene at room temperature. Thus, a perfect on/off switching system of fluorescence controlled by the photochromic reaction has been exhibited.


Patent
16 May 1997
TL;DR: In this paper, a method of preparing a fluorescent polymer, whereby an ethylenically unsaturated monomer is copolymerized with a polynuclear aromatic hydrocarbon or a substituted aromatic derivative thereof, such that the resultant polymer is fluorescent.
Abstract: Disclosed is a method of preparing a fluorescent polymer, whereby an ethylenically unsaturated monomer is copolymerized with a polynuclear aromatic hydrocarbon or a substituted aromatic derivative thereof, such that the resultant polymer is fluorescent. Also disclosed are coating compositions containing such fluorescent polymers.


Journal ArticleDOI
TL;DR: A short multigram synthesis of 2′-O-methylpseudouridine and its phosphoramidite derivative is described which avoids the use of protecting groups on the nitrogens, and a binding study of oligonucleotides containing this modification suggest an increased binding affinity to RNA when compared to oligon nucleotides incorporating this modification.
Abstract: A short multigram synthesis of 2′-O-methylpseudouridine and its phosphoramidite derivative is described which avoids the use of protecting groups on the nitrogens. A binding study of oligonucleotides containing this modification suggest an increased binding affinity to RNA when compared to oligonucleotides incorporating 2′-O-methyluridine.


Journal ArticleDOI
TL;DR: In this article, the X-ray crystal structure analysis of 11·(Et2O)2 reveals a nearly planar U-shaped 1-azapentadienyl moiety that exhibits five close contacts to the lithium atom located above the ligand plane.
Abstract: Fluorenyllithium (1) adds to tert-butyl isocyanate to yield 9-(N-tert-butylcarboxamido)fluorenyllithium (3). Its reduction with LiAlH4 followed by aqueous workup leads to the formation of the corresponding dibenzo-N-tert-butylaminofulvene 5. Treatment of 5 with sodium cyanoborohydride furnishes 9-(N-tert-butylaminomethyl)fluorene (6). Deprotonation of the fulvene 5 with n-butyllithium in ether yields the η5-azapentadienyllithium derivative 11. The X-ray crystal structure analysis of 11·(Et2O)2 reveals a nearly planar U-shaped 1-azapentadienyl moiety that exhibits five close contacts to the lithium atom located above the ligand plane. Computational chemistry (PM3) has identified the η5-(1-azapentadienyl)lithium derivative 11 as a global minimum. In solution compound 11 undergoes a dynamic degenerate rearrangement process that is rapid on the 1H NMR time scale. It equilibrates the annulated arene moieties of 11. The Gibbs activation energy of this symmetrization process is ΔG⧧enant = 11.8 ± 0.3 kcal mol-1. ...

Patent
27 May 1997
TL;DR: In this paper, a photodimerizable cinnamic acid-polysaccharide derivative photocurable with high sensitivity and efficiency was proposed. But it was not shown to be photodimable with ultraviolet light irradiation.
Abstract: The invention provides a cinnamic acid derivative having a novel spacer introduced into cinnamic acid which is photodimerizable, a cinnamic acid-polysaccharide derivative photocurable with high sensitivity and efficiency obtainable by introducing the above cinnamic acid derivative into a host polysaccharide such as a glycosaminoglycan, and a photocrosslinked cinnamic acid-polysaccharide derivative obtainable by exposing the same cinnamic acid-polysaccharide derivative to ultraviolet light irradiation.