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  • 1970-1974  (16)
  • 1960-1964  (13)
  • 1910-1914
  • 1820-1829
  • Alkaloids
  • Alkenes
  • Polymerization
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 3 (1974), S. 115-120 
    ISSN: 1432-1432
    Keywords: Adenosine Cyclic 2′, 3′-Phosphate ; Polymerization ; 1, 2-Diaminoethane ; Oligonucleotides ; Prebiotic ; Gel Permeation ; Ion Exchange
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Adenosine cyclic 2′, 3′-phosphate has been polymerized at room temperature in the dry state using 1, 2-diaminoethane at alkaline pH as catalyst. The high molecular weight products have been analyzed by several different methods, including ion exchange and gel permeation chromatography and phosphate end-group analysis. Gel permeation chromatography showed that between 3.6% and 8.1% of material higher than the hexamer was formed in 3-, 15- and 40-day reactions. The material from a large-scale, 3-day reaction mixture was first fractionated by ion exchange chromatography and the highest molecular weight material then further fractionated by gel permeation chromatography. End-group analysis on the fractions obtained by this procedure showed that 0.67% of the total reaction mixture was polymer with an average chainlength of 13.4; a trace (0.15%) of higher polymer was also formed, but there was insufficient to determine its average chainlength. The prebiological relevance of these findings is discussed.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 3 (1974), S. 141-150 
    ISSN: 1432-1432
    Keywords: Adsorption ; Clay ; Montmorillonite ; Phosphoramidates ; Polymerization ; Prebiotic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Nucleoside phosphoramidates derived from polyamines containing at least three amine groups are strongly adsorbed by sodium and magnesium montmorillonite clays even from very dilute solutions. Heating the dried clay-phosphoramidate mixture results in the production of small amounts of the dinucleotides.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 3 (1974), S. 57-61 
    ISSN: 1432-1432
    Keywords: Aspartic Acid ; Kaolinite ; Optical Activity ; Polymerization ; Adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary We have been unable to confirm the recent report that kaolinite catalyzes the polymerization of aqueousd- andl-aspartic acid at different rates. In experiments wheredl-Asp was used, no induced optical rotation was found in the reaction solution. No evidence for polymer (or other product) formation was found whenl-Asp-2-14C was used, and products were searched by paper chromatography and X-ray film autoradiography. Asp is adsorbed by kaolinite, but no selectivity for one or the other enantiomer was observed.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 3 (1974), S. 323-330 
    ISSN: 1432-1432
    Keywords: Prebiotic ; Polymerization ; Deoxythymidine-Oligonucleotides ; Deoxythymidine-Triphosphate ; Cyanamide ; 4-Amino-5-Imidazolecarboxamide
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Deoxythymidine 5′-triphosphate in the presence of deoxythmidine 5′-phosphate, cyanamide and 4-amino-5-imidazole carboxamide polymerizes under drying conditions at moderate temperatures (60–90 °C) to yield oligonucleotides of up to four units in length. Enzymatic analysis indicated the majority of these oligomers contained natural 3′–5′ phosphodiester bonds. This reaction offers a possible method for the formation of deoxyoligonucleotides under primitive earth conditions.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    European biophysics journal 1 (1974), S. 55-64 
    ISSN: 1432-1017
    Keywords: Calorimetry ; Circular Dichroism ; Flagellin ; Polymerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The heat effects accompanying the isothermalin vitro polymerization ofPr. mirabilis flagellin on short flagella fragments (seeds) have been measured in phosphate buffer pH 7, at various temperatures employing a batch microcalorimeter. Additionally, at 20
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 13 (1974), S. 781-789 
    ISSN: 0570-0833
    Keywords: Kinetics ; Radical polymerization ; Polymerization ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Low molecular reactions are frequently accompanied by side reactions producing a whole spectrum of by-products whose removal in purification operations generally causes little difficulty because the major and side products usually differ sufficiently in their properties. Hence detailed kinetic studies in low molecular chemistry can claim industrial interest only insofar as they aim to reduce the rate of formation of side products. The situation is completely different in polymer chemistry, where the terms major and side product no longer apply. Instead, one obtains mixtures of similar and/or isomeric molecules which differ so little with regard to molecular weight and structure that resolution into pure substances or isolation of pure substances becomes practically impossible. However, since all partial reactions exert a direct influence on the product spread, i.e. the composition and properties of a product mixture are modified by any change in operating conditions, detailed kinetic analyses embracing all relevant partial reactions are an essential prerequisite for the production of defined polymeric products on any scale. This progress report illustrates the importance of kinetics for radical polymerization with the aid of selected examples.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 2 (1973), S. 303-316 
    ISSN: 1432-1432
    Keywords: Polymerization ; Phosphorylation ; Adenosine Cyclic 2′,3′-phosphate ; Oligonucleotides ; Amines ; 2-Aminoethanol ; Amino Acids ; Prebiotic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary When adenosine cyclic 2′,3′-phosphate is evaporated from solution in the presence of simple catalysts such as aliphatic diamines at alkaline pH, and maintained in a dry state at moderate temperatures (25-85°C), self-polymerization to give oligonucleotides of chainlength up to at least 6 is observed. The products contain an excess of [3′→5′]-linkages over [2′→5′]-linkages. The effects of different catalysts and reaction conditions on the efficiency of the reaction are described. The prebiological relevance of these reactions is discussed.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Naunyn-Schmiedeberg's archives of pharmacology 279 (1973), S. 371-380 
    ISSN: 1432-1912
    Keywords: Serotonin ; Dopamine ; Noradrenaline ; Alkaloids ; Synaptosomes ; Brain Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effect of some tetrahydroharmane derivatives on the synaptosomal uptake of monoamines was studied. 1,2,3,4-Tetrahydroharmane (TH), which can be viewed as an analog of tryptamine, inhibited 5-hydroxytryptamine (5-HT), noradrenaline (NA) and dopamine (DA) uptake, but TH was about 10 times less potent than tryptamine. 6-Hydroxy-1,2,3,4-tetrahydroharmane (6-HTH), a 5-HT analog, was slightly more potent an inhibitor of 5-HT uptake than TH, but as catecholamine uptake inhibitors these compounds were equipotent. Harmane-1,2,3,4-tetrahydro-3-carboxylic acid had no effect. Salsolinol and salsolidine, tetrahydroisoquinoline derivatives, were less potent than the harmane derivatives. It is to be concluded that also tetrahydroharmane derivatives have an affinity to the amine “pump” similarly to that of the tetrahydroisoquinolines, which are the corresponding analogs of catecholamines. These kinds of compounds are important because of the possibility that they may be formed in physiological conditions as condensation products of biogenic amines and aldehydes, e.g. acetaldehyde, which is an intermediate of ethanol metabolism.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Naunyn-Schmiedeberg's archives of pharmacology 279 (1973), S. 361-370 
    ISSN: 1432-1912
    Keywords: Serotonin ; Histamine ; Blood Platelets ; Alkaloids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The effect of 5-hydroxytryptamine (5-HT), tryptamine (T), 6-hydroxy-1,2,3,4-tetrahydroharmane (6-HTH), and 1,2,3,4-tetrahydroharmane (TH) on the accumulation of radioactive 5-HT and histamine, was studied in rabbit blood platelets. 6-HTH and TH inhibited the uptake of the labelled amine, but they were weaker inhibitors than 5-HT or T. All four compounds inhibited the accumulation of radioactive histamine in the granules as well as in the whole cells, but the latter effect is not the consequence of inhibition of granular accumulation. It is concluded that the methylene bridge, which is the most important structural difference between the harmanes and the tryptamines, does not abolish the affinity of the molecule to the uptake receptor at the platelet membrane. However, since the inhibitory potency was lower than that of the parent amines, one cannot be certain as to whether or not the conformation present in the harmane derivatives offers the best fit for the receptor.
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  • 10
    ISSN: 0570-0833
    Keywords: Addition polymerization ; Polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerizability of compounds such as 1,l-disubstituted ethylenes, aldehydes, ketones, isocyanates, and five- and six-membered ring compounds is determined largely by thermodynamic considerations. The transition from non-polymerizability to polymerizability, correspondlng to a change in the sign of ΔG, is often quite sharp. Factors which generally make the free energy of polymerization more negative, and which therefore favor polymerization, are low temperature, high pressure, and high monomer concentration. Additional driving force is sometimes available if the monomer is in the supercooled (glassy) state rather than the crystalline state, or if the polymer crystallizes on formation. Alkyl substituents have an unfavorable effect on polymerizability; halogen substituents have a favorable effect. Many monomers which do not homopolymerize for thermodynamic reasons will copolymerize with a second monomer to the extent of forming copolymers containing 50 or even 66 mol per cent of the first monomer.
    Additional Material: 4 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 2 (1972), S. 1-9 
    ISSN: 1432-1432
    Keywords: Polymerization ; Amino Acids ; Primitive Earth ; Chemical Evolution ; Prebiotic Condensation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Chemical evolution on the primitive earth must have involved the condensation ofα-amino acids to peptides under a variety of conditions. Subjecting a mixture of methane, ammonia, and water to an electric discharge in the presence of free amino acids yields small peptides. The dehydration-condensation may have taken place via ammonium cyanide, the hydrogen cyanide tetramer, or aminonitriles. The experiments may be considered genuinely prebiotic and significant in the context of chemical evolution.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 11 (1972), S. 200-214 
    ISSN: 0570-0833
    Keywords: Elimination ; Stereochemistry ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Earlier evidence led to the view that in bimolecular olefin-forming eliminations the anti steric course is generally preferred over the syn. Recent experiments, however, show that in some common bimolecular elimination reactions, notably those involving onium bases, syn- and anti-eliminations proceed side by side, the former preferentially leading to the trans- and the latter to the cis-olefins.
    Additional Material: 4 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 11 (1972), S. 596-606 
    ISSN: 0570-0833
    Keywords: Bond theory ; Alkenes ; Alkynes ; Alkene ligands ; Alkyne ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular orbital (MO) and valence bond (VB) descriptions of the bonding in metalolefin and -acetylene complexes are examined in relation to their ability to explain the known properties of these complexes. It is concluded that whereas there are difficulties with the valence bond description, the molecular orbital description can satisfactorily explain all the known properties of these complexes and has the necessary versatility to enable it to be readily applied to any series of metal-olefin or -acetylene complexes. It is further shown that olefin and acetylene complexes can be usefully divided into two main classes: those that resemble the platinum(II)-complexes (class S), and are either square-planar or octahedral with essentially free rotation about the metal-olefin bond; and those that resemble platinum(0)-complexes (class T) and are either trigonal planar or trigonal bipyramidal and in which there is no rotation about the metal-olefin or -acetylene bond.
    Additional Material: 4 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 11 (1972), S. 974-978 
    ISSN: 0570-0833
    Keywords: Photopolymerization ; Polymerization ; Ketones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present article deals with the primary photochemical reactions of carbonyl compounds commonly used as photoinitiators. It is shown that radical formation results mainly from three processes, i.e. hydrogen abstraction, β-cleavage, and α-cleavage. The difference in the suitability of the radicals for chain initiation is discussed.
    Additional Material: 1 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 11 (1972), S. 964-973 
    ISSN: 0570-0833
    Keywords: Proton-active compounds ; Electron-rich alkenes ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proton-active substances react with certain electron-rich olefins with cleavage of the central C=C double bond to give compounds that can be formally regarded as insertion products of nucleophilic carbenes. If they satisfy certain structural conditions, they isomerize with β elimination to give open-chain compounds. Both CH-acidic compounds and compounds containing NH or OH groups can undergo this reaction. The mechanisms are discussed, and the importance of the intermediate products to biochemistry (thiamine, tetrahydrofolic acid) is indicated.
    Additional Material: 3 Tab.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 10 (1971), S. 776-786 
    ISSN: 0570-0833
    Keywords: Polymerization ; Polyethylene ; Vanadium ; Chromium ; Catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the present progress report literature data concerning homogeneous catalyst systems based on vanadium and chromium are reviewed and complemented by a combined study of the magnetic properties and the polymerization activity of such systems. The results show that vanadium forms active species as V (III) and as V (II), but chromium only as Cr (II); models are suggested for the polymerization process.  -  A comparison with heterogeneous systems (Phillips catalyst) allows the establishment of some general principles concerning the activity of the catalyst and the properties of the polymers.
    Additional Material: 10 Ill.
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  • 17
    ISSN: 0570-0833
    Keywords: Phenolic bases ; Alkaloids ; Condensation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Provided they contain quaternary nitrogen, simple phenolic bases can undergo oxidative condensation under conditions similar to those of biogenesis to form alkaloids of the isoquinoline series with good yields. By means of such oxidative condensations, more than sixty alkaloids of various structural types have become more easily obtainable. Of the numerous possible condensations of the intermediate mesomeric radicals only those which lead to naturally occurring alkaloids give good yields and few by-products. The results suggest that oxidative condensations of quaternary bases are also involved in the biosynthesis of alkaloids in the plant cell.
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  • 18
    ISSN: 0570-0833
    Keywords: Stereospecific polymerization ; Polymerization ; Polycyclopentene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of cyclo-olefins, like that of olefins with an internal double bond, is sterically hindered. Within recent years it has become possible to prepare copolymers of these compounds with ethylene, with the aid of anionic coordination Ziegler catalysts. This copolymerization always results in cis-opening of the double bond. Despite the steric hindrance, cyclobutene and cyclopropene have also been homopolymerized, with opening of the double bond. - Rather surprisingly, the best catalysts for homopolymerization of cyclopentene are those which exhibit low activity in the polymerization of ethylene. Ring cleavage occurs with MoCl5/Al(C2H5)3 to give the cis-polypentenamer, whereas WCl6/Al(C2H5)3 gives the trans-polypentenamer. Both polypentenamers exhibit elastomeric properties. - Evidence from infrared spectra and oxidative degradation indicates that the monomer units in the trans-polypentenamer are linked head-to-tail. It is presumably the single bond adjacent to the double bond that is broken. Using X-ray methods at -50 °C, it was possible to determine the crystal structure of the crystalline trans-polypentenamer at about 400% elongation.
    Additional Material: 6 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 3 (1964), S. 245-249 
    ISSN: 0570-0833
    Keywords: Addition ; Alkenes ; Electrophilic reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various structures have been proposed for the intermediates of electrophilic additions onto olefins; these include halonium ions, classical carbonium ions, π-complexes (i.e. nonclassical carbonium ions), and π-complexes with back-coordination. It is shown here that it is impossible to use any one of these entities alone to explain all such electrophilic additions; the electrophile itself determines the nature of the transition state formed. Polar addition of hydrogen halides onto olefins appears to proceed via a classical carbonium ion which does not occur as the free ion but as an undissociated ion pair. Various other mechanisms have been excluded by studies reported here of the stereochemical course of such additions.
    Additional Material: 2 Tab.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 441-458 
    ISSN: 0570-0833
    Keywords: Biosynthesis ; Alkaloids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 21
    ISSN: 0570-0833
    Keywords: Koch carboxylic acid synthesis ; Carboxylic acids ; Alkenes ; Isomerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When straight-chain mono-olefins, from pentene to decene, are subjected to the Koch carboxylic acid synthesis by the addition of CO and H2O or CH3OH in the presence of strongly acidic catalysts, not only the expected secondary acids, but also mixtures of a specific type of tertiary acids or their methyl esters are formed. When the catalysts contain boron trifluoride, the secondary acids are formed in ratios of isomers which are, within the scope of this investigation, independent of the experimental conditions and which agree well with the values calculated from the isomer equilibria of the corresponding n-olefins. Using concentrated sulfuric acid as catalyst, a larger proportion of tertiary acids is obtained than with BF3-catalysis, and amongst the secondary acids, those isomers predominate in which the COOH group is situated near the centre of the molecule.
    Additional Material: 1 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 32-41 
    ISSN: 0570-0833
    Keywords: Polymerization ; Polyethylene ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A two-component organometallic catalyst of composition CH3TiCl3·CH3AlCl2 effects high-speed polymerization of ethylene in the presence of chlorinated hydrocarbons at low temperatures. The catalyst does not undergo any alteration in the process. In contrast to the Ziegler catalysts, the titanium remains quadrivalent. Olefins of low-molecular-weight and with branched structures are produced. It proved possible to isolate the primary products of the polymerization at -50 to -100°C and to elucidate the mode of their formation from a knowledge of their structures. The findings are incompatible with either a cationic or anionic reaction mechanism. A novel type of mechanism is proposed, whereby the catalyst is supposed to have an ionic structure and molecular growth proceeds via π-complex formation of the olefin with the titanium cation. The formation of ethylene/olefin copolymers is also discussed.
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 243-247 
    ISSN: 0570-0833
    Keywords: Ergot alkaloids ; Alkaloids ; Biosynthesis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this article the biogenesis of the ergoline ring in lysergic acid derivatives and the clavines is discussed. T·yptophan and mevalonic acid are the precursors. The N-methyl group is supplied by formate or methionine. Concepts and results dealing with the manner in which the compounds are formed are discussed. Finally, the known biogenetic relationships among the ergot alkaloids are discussed in connection with their biogenesis.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 295-308 
    ISSN: 0570-0833
    Keywords: Emulsion polymerization ; Polymerization ; Polymerization ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionizing radiation induces the polymerization of some vinyl monomers in aqueous emulsion with high radiation yields. With identical emulsion compositions, the kinetics of this reaction and the kinetics of emulsion polymerization induced by water-soluble initiators are very similar. The rate of reaction in emulsion polymerization is about one hundred times greater than in bulk polymerization. The initiation of emulsion polymerization by means of ionizing radiation permits uniform “illumination” of the reacting volume, as well as almost any desired variation in the frequency of initiation during the reaction. The sharp decrease in the overall rate of reaction when initiation is interrupted during emulsion polymerization of styrene induced by γ-rays contradicts the earlier concept of sharply separated reaction zones.
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  • 25
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 341-357 
    ISSN: 0570-0833
    Keywords: Biosynthesis ; Alkaloids ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 26
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 704-714 
    ISSN: 0570-0833
    Keywords: Titanium ; Alkenes ; Polymerization ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At low temperatures, ethylene and α-olefins (Δ1-olefins or 1-alkenes) are rapidly converted into oligomrs by the two-component organometallic catalyst CH3TiCl3·CH3AlCl2. To achieve smooth oligomerizations, aromatic or chlorinated hydrocarbons must be used as solvents. Although the activity of the titanium-carbon bond is enhanced by the aluminum component of the catalyst, the aluminum and its methyl group do not participate in the reaction proper; the latter proceeds exclusively at the titanium-carbon bond. The reaction will olefins can be used as an analytical method for the quantitative determination of the titanium-carbon bond in admixture with the organoaluminum component. It is thus possible to follow the reaction leading to formation of the catalyst from titanium tertrachloride, as well as the processes occurring at the titanium-carbon bond during the oligomerization of olefins. All the observations indicate that the catalyst possesses an ionic structure which is determined by the solvent. It is shown that the initial reaction step probably involves formation of a complex between the olefin and the alkyltitanium cation. The reaction scheme proposed is based on organometallic reactions which are characterized by carbanion and hydride transfers within the olefin-cation complex. This mechanism, which is unusual for Ziegler catalysts, is due to the predominance of hydride transfers.
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 1 (1962), S. 80-88 
    ISSN: 0570-0833
    Keywords: Oxidation ; Palladium ; Catalysis ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of olefins to carbonyl compounds with palladium compounds, especially the oxidation of ethylene to acetaldehyde, is at present carried out on a technical scale. The reaction takes place via a palladium-olefin complex, the formation of which is inhibited by halide ions. Hydrolysis to the carbonyl compound is inhibited by hydrogen ions. The knowledge gained by studying the reaction of olefins with pure solutions of palladium salts allows important conclusions to be drawn concerning the action of technical catalyst solutions containing copper and palladium chloride.
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  • 28
    ISSN: 0570-0833
    Keywords: Pyrrolidone ; Polyamides ; Fibers ; Lactams ; Polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The industrial production of capryllactam (1-azacyclononan-2-one) and of laurolactam (1-azacyclotridecan-2-one) starts with cyclization of acetylene or butadeine to give cyclooctatetraene or cyclooctadiene, or cyclization of butadiene to give cyclododecatriene. Further steps are: oxidation of the cyclic hydrocarbon to the ketone, formation of the oxime, and rearrangement of the latter with sulfuric acid. Pyrrolidone can be prepared from acetylene and formaldehyde by way of butyrolactone. The behavior of the lactams during polycondensation is described and the properties of the resulting fibers are compared with those of the known polyamide fibers.
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  • 29
    ISSN: 0570-0833
    Keywords: Lactams ; Polymerization ; Fibers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: β-Lactams can be prepared by cyclization of β-aimno acid esters. Recently they have become available also from olefins by addition of N-carbonysulfamyl chloride (isocyanatosulfonyl chloride) and from aldehydes by reaction with N-carbonylsulfamyl chloride and ketene. Condensative or anionic polymerization results in polyamides the chains of which contain many more amide groups than the chains of polyamides of the nylon-6 type. Hence the new polymers resemble silk moreclosely. Fibers and films can be prepared from solution.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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