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  • 1960-1964  (18)
  • 1860-1869
  • Dyes/Pigments  (7)
  • Reaction mechanisms  (6)
  • Alkenes  (5)
  • 1
    ISSN: 0570-0833
    Keywords: Willgerodt-Kindler reaction ; Ketones ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ketones react with sulfur and NH3 or amines at room temperature to produce Δ3-thiazolines, 5-alkylidene-Δ3-thiazolines, Δ3-imidazoline-5-thiones, hexathiacycloheptane derivatives, α,α′-dioxodisulfides, bis-(1-aralk-1-yl) disulfides, or thiocarboxamides, depending on the coreactant and on the reaction conditions. It was recognized that the formation of all of these numerous types of compounds can be explained basically by primary thiolations and geminal dithiolations, which in conjunction with their reverse reaction (desulfurization) and the assumption of a thioreductone equilibrium permit a new interpretation of the course of the Willgerodt-Kindler reaction of alkyl aryl ketones.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 2
    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.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 3 (1964), S. 93-101 
    ISSN: 0570-0833
    Keywords: Organometallic catalysts ; Catalysis ; Reaction mechanisms ; Lithium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic investigations of the polyreaction of isoprene with organolithium compounds as initiators in n-heptane as solvent indicate the following sequence of reactions: 1. formation of an adduct between a monomeric form of the organolithium compound and the isoprene and 2. reaction of this adduct with an associated form of the organolithium compound with insertion of the isoprene. The adduct formation is considered to be due to chemisorption, and proof of such chemisorption of a monomer (ethylene) is also demonstrated for a homogeneous Ziegler-type catalyst. All the reactions can be formulated in the form of cyclic structures with electron-deficient character. Postulation of such ring structures explains the surprising values obtained for the frequency factors and equilibrium constants.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 3 (1964), S. 408-416 
    ISSN: 0570-0833
    Keywords: Reactive dyes ; Dyes/Pigments ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new groups of reactive dyestuffs have been developed. One group (Levafix® dyes) comprises compounds which contain —SO2NH—CH2—CH2—OSO3H or —CH2—N(alkyl)-CH2—CH2—OSO3H as reactive groups. The dyes of this group react with cellulose fibers to form cellulose ethers, e.g. R—SO2NH—CH2—CH2—O—cellulose. The substances in the second group (Levafix-E® dyes) consist of the amides formed from 2,3-dichloroquinoxaline-6-carboxylic acid and dyestuffs containing primary or secondary amino groups.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0570-0833
    Keywords: Kinetics ; Dipolar cycloaddition ; Cycloaddition ; Heterocycles ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Criteria for the mechanism of 1,3-dipolar cycloadditions which lead to 5-membered rings are provided by the stereoselectivity observed with cis-trans isomeric dipolarophiles, by the effect of solvent and substituents on the rate constants, by the activation parameters, and by orientation phenomena. A concerted addition, which can also be described in terms of molecular orbitals and in which the two new σ-bonds are formed simultaneously, although not necessarily at equal rates, offers the best explanation of the experimental facts.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 6
    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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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 723-735 
    ISSN: 0570-0833
    Keywords: Phenol oxidation ; C-C coupling ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of well-known phenol oxidation reactions for the preparation of compounds arising from C—C and C—O coupling has recently received increased attention. A selection from the large number of products obtainable by oxidation of mono- and polyhydric phenols and a discussion of the reaction mechanisms indicate the scope of this method. The formation of hydroxyphenylquinones and orceine dyes from resorcinol derivatives is explained. The synthesis of natural products by way of phenol oxidations is briefly discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 20-23 
    ISSN: 0570-0833
    Keywords: Reactive dyes ; Dyes/Pigments ; Reactive dyes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Compounds and dyes containing vinylsulfonyl groups or groupings which readily yield vinylsulfonyl groups possess a marked ability to add onto many compounds containing active hydrogen under alkaline conditions. They also react with natural substances of high molecular weight, e.g. wool and cellulose, which contain amino- or hydroxyl groups. These reactions lead to the formation of strong covalent bonds between the reactants. As a result of this finding, reactive dyes for nitrogenous and cellulose fibers have been developed.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0570-0833
    Keywords: Polycondensation ; Dyes/Pigments ; Bunte salts ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dyes which contain only thiosulfate residues as water-solubilizing groups are readily polycondensed on cellulose under mild conditions in the presence of condensing agents such as sodium sulfide to give insoluble, high molecular-weight dyes. This type of fixation leads to wash-fast dyeings and, in contrast to reactive dyes, involves no reaction with the fiber. The preparation and application of the dyes are described.
    Type of Medium: Electronic Resource
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  • 10
    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.
    Additional Material: 11 Ill.
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  • 11
    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.
    Additional Material: 2 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 1 (1962), S. 41-45 
    ISSN: 0570-0833
    Keywords: Dyes/Pigments ; Rutile structure ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Until the present time, new color pigments have been developed by isotypic and homotypic mixed-phase formation. This paper deals primarily with heterotypic mixed-phase formation for the preparation of new colored and white pigments with the rutile structure. Dioxides and difluorides crystallizing in the rutile lattice-form were chosen as host-lattices for the mixed-phase formation. Hosts of the general formula AB2 can accommodate, as guests, in the form of solid solutions, oxides and/or fluorides with different structures. Characteristically, the mean statistical cation-radius lies between 0.55 and 0.98 Å, with single radii between 0.46 and 0.98 Å. Relative quantities are so chosen that the cation to anion ratio of 1:2 prescribed by the host lattice, as well as electroneutrality, is maintained.
    Additional Material: 6 Ill.
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  • 13
    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.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 0570-0833
    Keywords: Elimination ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In bimolecular β-elimination (E 2 mechanism), several bonds are ruptured or formed in one concerted reaction step. However, the various aspects of bond-making or -breaking need not be completely synchronous. In the E 2 transition state for elimination HX, rupture of the C—X bond may be more advanced than that of the C—H linkage, or vice versa. Factors influencing the relative extents of rupture of these two bonds at the transition state are discussed, and the consequences of non-synchroneity in one sense or the other are developed from theory and illustrated from experiment. This treatment provides an understanding of the Hofmann-vs.-Saytzeff orientation problem.
    Additional Material: 1 Ill.
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  • 15
    ISSN: 0570-0833
    Keywords: Azo dyes ; Dyes/Pigments ; Oxidative coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New findings in the field of oxidative coupling reactions are reported. These involve: extension of this type of reaction to amidrazone system displaying (vinylogous) tautomerism and to unsymmetrical diarylhydrazines; elucidation of the coupling mechanism for these arylhydrazines and for the amidrazone systems previously described; the properties of some dyes, complexed with heavy metals, and the synthesis of tetraazapentamethine and penta-azapentamethine dyes.
    Additional Material: 1 Tab.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 1 (1962), S. 382-393 
    ISSN: 0570-0833
    Keywords: Electrophilic reactions ; Reaction mechanisms ; Substitution ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The results obtained in recent years from investigations into the mechanisms of electrophilic substitution reaction at sp3-hybridized carbon atoms are reviewed.
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 1 (1962), S. 532-537 
    ISSN: 0570-0833
    Keywords: Polyacrylonitrile ; Fibers ; Azatrimethinecyanines ; Dyes/Pigments ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Like all basic dyes, azatrimethinecyanines possess a good dyeing affinity for acrylic fibers. Compounds with isolated nitrogen atoms in the trimethine chain show insufficient light fastness, whereas good to excellent fastness to light is displayed by compounds having neighboring nitrogen atoms in the chain. Thus, a working hypothesis stating that the light fastness of trimethinecyanines on acrylic fibers is improved by progressive replacement of methine groups by nitrogen atoms has been partially confirmed.
    Additional Material: 3 Tab.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 1 (1962), S. 568-572 
    ISSN: 0570-0833
    Keywords: Trichloropyrimidyl dyes ; Dyes/Pigments ; Dichloropyrimidyl dyes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several examples are used to show that the reactivity of dichloro- and trichloropyrimidyl dyes and the sensitivity of their dyeings to hydrolysis are determined by the nature of the bridge unit between the chromophore and the reactive system. The tendency of the dyeings to hydrolyze in acid and, more particularly, in alkaline media increases with increasing reactivity of the dyes. In alkaline media, dyeings made with dyes containing oxygen bridges are cleaved mainly between the reactive system and the chromophore, while in dyeings made with dyes containing imino or methylimino bridges, the linkage between the reactive system and the cellulose is hydrolyzed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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