Showing papers in "Journal of Synthetic Organic Chemistry Japan in 1984"
TL;DR: In this article, examples of the above-mentioned functional particles are reviewed and discussed, including absorbents, latex diagnostics, affinity bioseparators and drug and enzyme carriers.
Abstract: Functional particles are prepared directly by heterogeneous polymerization, e.g. emulsion polymerization and dispersion polymerization. Modification of existing particles is another method to prepare functional particles. The features of nano- or microparticles such as large specific surface area, high mobility, easy recovery from the dispersion and reversible dispersibility, etc., are utilized for the exhibition of functions. Medical and biochemical applications of particles, including absorbents, latex diagnostics, affinity bioseparators and drug and enzyme carriers, are the most practical ones at present. Optical and opto-electrical functions of particles are attracting attention. Some particles exhibit unique rheological behavior under special conditions and will expand their applications. In this review article, examples of the above-mentioned functional particles are reviewed and discussed.
98 citations
TL;DR: In this article, the relation between molecular structure and liquid crystalline properties is discussed in detail, and the examination of the mesomorphic behavior for the compounds incorporating an angular linkage is important for the study of the relation.
Abstract: This review is concerned with the structure and properties of liquid crystals. We do not discuss lyotropic systems, but only thermotropic liquid crystalline mesophases. Classification, identification method, and structural characteristics of thermotropic liquid crystals are described. Fundamental physical properties such as order parameter, dielectric anisotropy, birefringence and so on are also explained. The relation between molecular structure and liquid crystalline properties is discussed in detail. We showed that the examination of the mesomorphic behavior for the compounds incorporating an angular linkage is important for the study of the relation. The relation between molecular structure and the different physical properties is also reviewed.
94 citations
TL;DR: In this paper, major physico-chemical impacts resulting from the incorporation of fluorine atom into hydrocarbon moiety of organic molecules are briefly described in alternate reference to its unique electronic features and various physical parameters essential with recent structure-activity studies, some of which are discussed respectively as active examples of pesticide developments on the basis of quantitative structureactivity relationship.
Abstract: Firstly, major physico-chemical impacts resulting from the incorporation of fluorine atom into hydrocarbon moiety of organic molecules are briefly described in alternate reference to its unique electronic features and various physical parameters essential with recent structure-activity studies, some of which are discussed respectively as active examples of pesticide developments on the basis of quantitative structure-activity relationship. Then, a number of new or important fluorine chemistry are introduced as useful tool for synthesis of pesticide molecules having fluorine atom. Finally, 24 of selected examples of fluorine containing pesticides of mostly late issue are compiled in view of visualizing the recent R & D trend.
56 citations
TL;DR: The recent advances and trends in the synthesis of useful organofluorine compounds have been reviewed in this paper, focusing on the utility of commercially available fluorine-containing products as building block.
Abstract: The recent advances and trends in the synthesis of useful organofluorine compounds have been reviewed. This article is especially focused on the utility of commercially available fluorine-containing products as building block.Topics are discussed in the following four items : (1) introduction of fluoroalkyl groups in organic molecules using halofluorocarbons, (2) functionalization of fluorine-containing olefins, (3) ring-opening reaction of fluorocyclopropanes to give fluorobutadienes or ketones, and (4) carbon-carbon bond forming reaction of fluorine-containing carbonyl compounds.
36 citations
20 citations
TL;DR: In this article, the utility of dioxopyrrolines in the field of heterocyclic chemistry was discussed, focusing on focusing carbon-carbon bond forming reactions, in which they acted as dienophiles on Diels-Alder reaction and also as enophiles in photocycloaddition reaction yielding hydroindoles and 2- azabicyclo [3. 2. 0] heptanes respectively.
Abstract: This article deals with the synthetic utility of dioxopyrrolines in the field of heterocyclic chemistry, especially on focusing carbon-carbon bond forming reactions, in which they acted as dienophiles on Diels-Alder reaction and also as enophiles on photocycloaddition reaction yielding hydroindoles and 2- azabicyclo [3. 2. 0] heptanes respectively. The latter compounds, strained cyclobutanes, underwent skeletal rearrangements to form various heterocyclic compounds such as hydroindoles, azatropolones, azanorbornenes, azanonanes, dihydropyridones, and dihydropyridines. This methodology was successfully applied to total synthesis of erythrina alkaloids.
19 citations
TL;DR: In this article, an algorithm for enumeration of stereoisomeric structures due to asymmetric carbon, C-C double bond and so on has been developed, where all the possible stereochemical structures for a molecule may be generated on the basis of its topological representation.
Abstract: An algorithm for enumeration of stereoisomeric structures due to asymmetric carbon, C-C double bond and so on has been developed. By using this algorithm, all the possible stereochemical structures for a molecule may be generated on the basis of its topological representation. The identification of each distinct stereoisomeric structure is performed by a modification of Morgan's method.
17 citations
TL;DR: In this article, the synthesis, the reactions, the physicochemical properties, and the uses of Azy derivatives are described, as well as the synthesis process, reactions, and physicochemical property.
Abstract: Since 1965 we have been studying the synthesis of (2 S) -2- aziridinecarboxylic acid (Azyline, (2S) -Azy) or (2 S, 3 S) -3-methyl-2- aziridinecarboxylic acid ((2 S, 3 S) - 3-MeAzy) derivatives. Azyline is relatively labile compound, however azyline placed in the peptide chain become stable and is very easy to handle. They still retain their reactivity, due to the Azy residue, against the protic reagents such as acids, bases, alcohols or thiols. Thus, Azy derivatives can be widely used for peptide chemistry.This paper describes the synthesis, the reactions, the physicochemical properties, and the uses of Azy derivatives.
17 citations
TL;DR: In this article, the Friedel-Crafts reaction was used to synthesize trifluoropropyl aromatic compounds, followed by its attempted application to the synthesis of anti-inflammatory agents.
Abstract: First, some characteristics that appear when fluorine atoms are incorporated into the biologically active compounds are presented. Then, some examples of fluorine-containing drugs are discussed. Finally, an approach for trifluoropropyl aromatic compounds by the Friedel-Crafts reaction is presented, followed by its attempted application to the synthesis of anti-inflammatory agents.
17 citations
TL;DR: In this article, a review deals with the utilization of elements of rare earth series in organic synthesis, focusing on synthetically useful reactions which are not easily achievable with the reagents of main group and d-block elements.
Abstract: This review deals with the utilization of elements of rare earth series in organic synthesis. Emphasis is made on the synthetically useful reactions which are not easily achievable with the reagents of main group and d-block elements.
16 citations
TL;DR: In this article, the authors reviewed the papers concerned with the syntheses of optically active compounds from the meso compounds and the symmetrical molecules having a prochiral carbon atom.
Abstract: Recently, studies on the chiral synthesis have been extensively stressed upon. There has been progress in cooperation with the development of highly selective reagents. Useful enzymes (e. g. immobilized enzymes), microorganisms, and excellent analytical instruments for spectroscopy and for the chromatography have become available. In this context we reviewed the papers concerned with the syntheses of optically active compounds from the meso compounds and the symmetrical molecules having a prochiral carbon atom. We have dealt only with the compounds possessing functional groups in the same ligands of the symmetrical prochiral molecule.
TL;DR: In this article, a new fluororesin useful for solution type paints with extraordinarily high weather resistance has been developed This resin consists of a novel fluoropolymer specifically designed to be soluble in usual organic solvents and curable at temperatures ranging from room temperature to around 200°C.
Abstract: A new fluororesin useful for solution type paints with extraordinarily high weather resistance has been developed This resin consists of a novel fluoropolymer specifically designed to be soluble in usual organic solvents and curable at temperatures ranging from room temperature to around 200°C.The polymer with a highly alternating sequential structure is synthesized from a fluoroolefin and vinyl ethers by radical copolymerization. The combination of specific types of vinyl ethers provides the polymer with suitable solubility, hardness, flexibility, compatibility with pigments and curability by isocyanates and melamines. The resin formulated as paint can be applied to various substrates by spray, brush or roll coating and cured to yield a finish showing high gloss, enough solvent and chemical resistance, good adhesion to substrates and resistance to weather in expectedly about 20 years.Thus the resin is now finding a wide range of actual applications as high performance paint material for outdoor use.
TL;DR: In this paper, the synthesis and reactions of organometallic compounds having Si-Mtl bond as well as metal free silyl anion species are reviewed in the order of the periodic classification of metal elements.
Abstract: Syntheses and reactions of organometallic compounds having Si-Mtl bond as well as “metal free” silyl anion species are reviewed in the order of the periodic classification of metal elements. With these reagents, silyl groups are successfully introduced into organic substrates by (1) substitution of halogen of alkyl, allyl, aryl, vinyl, and acyl halides, (2) addition to ketone and aldehyde carbonyls, and (3) addition to alkynes, allenes, and conjugated dienes. These reactions are useful for synthesis of versatile organosilicon compounds.
TL;DR: In this article, a review deals with the recent advance in the reactions of the diezie systems containing (1) oxygen atom, (2) sulfur atom,(3) nitrogen atom, and lastly (4) mixed hete roatoms.
Abstract: Heterodienes are useful reagents for constructing a variety of heterocyles by means of [9+2] cycloaddition reaction. This review deals with the recent advance in the reactions of the diezie systems containing (1) oxygen atom, (2) sulfur atom, (3) nitrogen atom, and lastly (4) the mixed hete roatoms.
TL;DR: In this article, a review of enamide cyclization and its application to the synthesis of nitrogen-containing heterocyclic compounds, particularly related to alkaloids, is presented.
Abstract: N-α, β-Unsaturated acylenamines and N-α, β-unsaturated acylanilides, which form a common conjugated six π electron system, are two major types of enamides capable of undergoing smooth cyclization under both photochemical and thermal conditions according to the Woodward-Hoffmann rule. These cyclizations of enamides are found to occur under various conditions, such as nonoxidative (in the absence of oxygen), oxidative (in the presence of oxidizing agent), reductive (in the presence of hydride reagent), and even under asymmetric conditions (under asymmetric circumstance), thus established the enamide cyclization as a useful synthetic weapon widely applicable to the construction of nitrogen-containing heterocyclic compounds, particularly related to alkaloids. Usefulness of this enamide cyclization is proved by the establishment of stereochemical and regiochemical controls of the cyclization by the use of substituent and solvent effects. This review covers rather quick look at the outline of this enamide cyclization and its application to the synthesis of heterocycles.
TL;DR: In this article, a two-phase polycondensation using phase transfer catalysis (PTC) has been used to synthesize various types of condensation polymers such as polyesters, polyethers, polysulfides, carbon-carbon chain polymers, and polyamine derivatives.
Abstract: This article deals with syntheses of various types of condensation polymers by two-phase polycondensation using phase transfer catalysis (PTC). The scope of this article encompasses (i) synthesis of polyesters and their analogs such as aromatic polyesters, polysulfonates, polyphosphonates, and polythioesters by PTC nucleophilic acyl substitution ; (ii) synthesis of condensation polymers such as polyethers, polysulfides, carbon-carbon chain polymers, and polyamine derivatives by the application of PTC alkylation ; and (iii) synthesis of polyesters and their analogs such as polycarbonates, polyesters, and polysulfones by PTC nucleophilic aliphatic substitution. Some factors influencing these PTC polymer syntheses are discussed and comparison of this method with other synthetic methods are also presented.
TL;DR: Synthetic approaches to fluorinated prostaglandin analogs are reviewed and their characteristic biological and chemical properties due to fluorination are briefly discussed in this article, where the authors also discuss the effects of fluorination on prostaglandsin analog.
Abstract: Synthetic approaches to fluorinated prostaglandin analogs are reviewed and their characteristic biological and chemical properties due to fluorination are briefly discussed.
TL;DR: An in vivo evaluation using FPU-20 E as an artificial heart pump for a goat showed it to have superior blood compatibility and durability, and thus may have possible application as a new biomaterial in cardiovascular devices, such as blood pumps in particular.
Abstract: A series of fluorine-containing segmented polyurethanes (FPU) was synthesized from a new fluorinated aliphatic diisocyanate, polyalkylene glycols, and diamines. Electron microscopy showed that FPU have microphase separated structures which may possibly consist of hydrophobic domains of fluorocarbon chains and hydrophilic domains of hydrocarbon chains. FPU-20 E, prepared from polytetramethylene glycol (PTMG) of 1080 in molecular weight and ethylenediamine, exhibited excellent tensile properties as an elastomer and a high degree of in vitro antithrombogenicity. An in vivo evaluation using this material as an artificial heart pump for a goat showed it to have superior blood compatibility and durability, and thus may have possible application as a new biomaterial in cardiovascular devices, such as blood pumps in particular.
TL;DR: In this article, the reactivity of hydroxyl groups in mono-saccharides toward direct acylation is discussed and a method of regioselective modifications (acylation, alkylation, etc) without blocking-deblocking technique via cyclic tin intermediates is described.
Abstract: This article critically reviews the reactivity of hydroxyl groups in mono-saccharides toward direct acylation and describes the method of regioselective modifications (acylation, alkylation, etc) of a hydroxyl group without blocking-deblocking technique via cyclic tin intermediates. O-Acyl migration in mono-O-acyl derivatives of D-glucose and L-arabinose under various conditions is also discussed.
TL;DR: Mixtures of the two polymers degraded at a rate in proportion to poly (ethylene carbonate) content, and degradation rate in the peritoneal cavity was faster than that in subcutaneous tissue in guinea pigs.
Abstract: Poly (ethylene carbonate), poly (propylene carbonate), and poly (ethylene propylene carbonate) were examined as to their biodegradability, permeability, and drug release characteristics.Poly (ethylene carbonate) degraded but poly (propylene carbonate) did not in the peritoneal cavity of rats and the peritoneal cavity and subcutaneous tissue of guinea pigs. Mixtures of the two polymers degraded at a rate in proportion to poly (ethylene carbonate) content. Degradation rate in the peritoneal cavity was faster than that in subcutaneous tissue in guinea pigs.Membranes free from pores were obtained from poly (ethylene carbonate). Permeability of drugs through them depended on lipophilicity indicating role of solubility of the drugs in the membrane material for permeation.Release rate of tegafur from poly (ethylene carbonate) implants was faster than that from poly (propylene carbonate) implants. Blood level profiles were obtained after implantation of implants in rats.Microspheres containing local anesthetics were prepared by a solvent evaporation process and effects of drug content and polymer on release profiles were examined in vitro. Duration of local anesthesia after administration of dibucaine microspheres in guinea pigs was demonstrated.
TL;DR: Synthetic applications of radical cyclization leading to monocyclic, bicyclic, and spirocyclic compounds are summarized in this article, including their high regio-and stereoselectivity.
Abstract: Synthetic applications of radical cyclization leading to monocyclic, bicyclic, and spirocyclic compounds are summarized including their high regio- and stereoselectivity.
TL;DR: In this paper, a combination of a hard Lewis acid and a soft nucleophile is described for the cleavage of C-O, C=C, C-NO2, and C-X bonds.
Abstract: A carbon-heteroatom bond has the hard-soft dissymmetry as well as the charge dissymmetry. Thus, a pertinent combination of a hard acid and a soft nucleophile can cleave the carbon-heteroatom bond. This article describes a number of combination systems of a hard Lewis acid and a soft nucleophile which have been developed for the cleavage of C-O, C=C, C-NO2, and C-X bonds.
TL;DR: In this paper, the authors discuss mainly the optical resolution by liquid chromatography with chiral polymers, including proteins, cellulose and other polysaccharide derivatives, cross-linked polymers with a chiral cavity, optically active polyacrylamides, and poly (triphenylmethyl methacrylate).
Abstract: Optical resolution by liquid chromatography, particularly by high-performance liquid chromatography, has become a useful and important method for resolving enantiomers. In this review, the author discusses mainly the optical resolution by liquid chromatography with chiral polymers. The polymers include proteins, cellulose and other polysaccharide derivatives, cross-linked polymers with chiral cavity, optically active polyacrylamides, and poly (triphenylmethyl methacrylate). Chiral discrimination ability of the polymers depends very much on their second or higher order structure. Mostly, a higher chiral recognition ability is attained when the polymer exist as an order structure. This is a pronounced difference between the polymeric stationary phases and the stationary phases consisting of silica gel and chiral small molecules.
TL;DR: The application of ultrafine metal particles, 10-1000 A in diameter, to organic syntheses are reviewed as reagents and catalysts in this paper, and the features of these particles used in organic synthesis are discussed.
Abstract: Application of ultrafine metal particles, 10-1000 A in diameter, to organic syntheses are reviewed as reagents and catalysts. Ultrafine magnesium particles are effectively reactive to organic compounds with rather poor reactivities such as fluorobenzenes and bromobenzenes, yielding the Grignard reagents. Ultrafine zinc particles also react with less reactive bromobenzenes under mild conditions. Ultrafine particles of palladium, platinum, rhodium, ruthenium, copper, and others show high catalytic activity and selectivity in various organic syntheses. The selective catalytic reactions involve1) hydrogenation of C-C double bonds, nitro groups, and aromatic rings, 2) hydrogenation of dienes to the corresponding monoenes, 3) hydrogenolysis of cystine to cysteine, 4) hydration of acrylonitrile to acrylamide, and 5) hydration of C-C double bond, followed by dehydrogenation of the resulting alcohol. The features of ultrafine metal particles used in organic syntheses are discussed.
TL;DR: In this article, a model reaction of biological aromatic hydroxylation was proposed, where the oxygen atom incorporated into aromatic rings is entirely from molecular oxygen, and the high spin Ni (II) complexes showed very low NiII, III redox potentials +0.24V vs. SCE and react with molecular oxygen to from 1 : 1 Ni (III) -O-2 adducts in aqueous solution.
Abstract: Substituted and unsubstituted dioxo [16] aneN5 (1, 4, 7, 10, 13-pentaazacyclohexadecane-14, 16- dione) form stable 1 : 1 square pyramidal complexes with Ni (II), which posess two deprotonated amide donors in equatorial positions. The high spin Ni (II) complexes show very low NiII, III redox potentials +0.24V vs. SCE and react with molecular oxygen to from 1 : 1 Ni (III) -O-2 adducts in aqueous solution. The oxygen adducts hydroxylate electron- rich aromatic compounds to form phenol derivatives. This is a good model reaction of biological aromatic hydroxylation since the oxygen atom incorporated into aromatic rings is entirely from molecular oxygen.