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  • 1995-1999  (42)
  • 1960-1964  (15)
  • 1915-1919
  • 1910-1914
  • 1905-1909
  • 1890-1899
  • 1800-1809
  • Alkenes
  • Fibers
  • Polymerization
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    European food research and technology 209 (1999), S. 389-392 
    ISSN: 1438-2385
    Keywords: Key words Gelation ; Polymerization ; Whey proteins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract  The influence of protein concentration on the properties of gels obtained by a two-stage heating process was determined. In the first stage, whey protein dispersion (3–10%) was heated at pH 8.0, and in the second stage it was diluted to 3% protein, adjusted to pH 7.0 and heated again. Increased protein concentration in the first stage of polymerization resulted in the gels obtained in the second stage having a lower phase angle, increased storage modulus and increased hardness. Increased protein concentration also resulted in gels with an increased optical density, which suggests thathigher protein concentration leads to more and larger aggregates. Gels obtained from dispersions preheated at a higher protein concentration had higher permeability coefficient (B gel) values. The increase in B gel suggests that the higher protein concentration increased the size of the aggregates, which in a second stage of heating formed a gel matrix with a larger pore size.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical chemistry accounts 102 (1999), S. 285-292 
    ISSN: 1432-2234
    Keywords: Key words: Ethylene insertion ; ab initio MO calculations ; Sm complexes ; Polymerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract. Ethylene insertion into the Sm–C bond of H2SiCp2SmCH3, a model reaction of an olefin polymerization propagation step, has been studied by ab initio molecular orbital methods. The small electronegativity of the Sm atom makes the Sm–C bond ionic, the methyl group being negatively charged by −0.75. The reaction passes through a loose ethylene complex with a binding energy of 15 kcal/mol and then a tight four-centered transition state with an agostic interaction between the Sm atom and one of the methyl CH bonds. A small activation energy of 14 kcal/mol is required to pass through this transition state, indicating that this is an easy reaction. Compared with the reactions with group 4 cationic silylene-bridged metallocenes the activation energy is higher and the reaction is less exothermic. The origin of these differences is discussed. The results of molecular mechanics calculations on regio- and stereoselectivities in the insertion reaction of propylene are also reported.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1611-4663
    Keywords: Coriolus versicolor ; Na2SO3-HCHO-AQ pulping effluent ; Polymerization ; Lignosulfonate ; Laccase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A strain of the fungusCoriolus versicolor was inoculated periodically into potato dextrose agar (PDA) slants containing the effluent to enhance the natural ability to grow in the effluent. The acclimated strain grown in the 50% effluent-containing PDA slant and the original strain were employed to treat the effluent. The acclimated strain could grow in a higher concentration of the effluent than the original unacclimated one. Both the original and acclimated strains improved the dispersing ability of the effluent, especially the acclimated strain because of its higher laccase secretion. The dispersing ability of the SFP effluent was improved to a level comparable to a commercial lignosulfonate product because it was strongly polymerized by the fungus. During the fungal treatment, more than 50% of the sugars were removed from the effluent, thereby increasing the purity of the SFP lignin product.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1435-1536
    Keywords: Key words Reaction kinetics in microgravity ; Colloidal silica spheres ; Polymerization ; Transmitted-light intensity ; Dynamic light scattering
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Polymerization reactions of colloidal silica spheres via the hydrolysis and dehydration processes of tetraethyl orthosilicate with ammonia and a tiny amount of water in ethyl alcohol have been studied in microgravity by the parabolic flights of a MU-300 rear-jet aircraft. Induction periods and polymerization rates are determined by fast-scanning transmitted-light-intensity measurements and the fast-scanning dynamic light-scattering method. Direct observation of the reaction mixtures is also made with a charge-coupled device video camera. Reproducible and reliable data are obtained in microgravity compared with those in gravity. Increases in the induction times and decreases in the polymerization rates are observed in microgravity compared with those in gravity. One of the main reasons for these observations is the fact that the translational Brownian movement of the reactants and/or product spheres is free from downward translational movement in microgravity. Very weak convection of the reaction suspensions in microgravity is another important factor.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1435-1536
    Keywords: Key words Allyldimethyldodecylammonium bromide ; Liquid crystals ; Polymerization ; Polymerizable surfactant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Allyldimethyldodecylammonium bromide was polymerized by γ-ray irradiation in both hexagonal and cubic mesophases, and the conversion–time curves were obtained. The maximum conversion was about 35%, and the polymer remained in the liquid-crystalline structure formed by the nonpolymerized monomers. The influence of polymerization on the distribution of water in the different types related to the hydrophilic surfaces of microstructures was studied using Fourier transform infrared spectroscopy. The incomplete polymerization was explained by steric constraints in the liquid-crystalline structures.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 277 (1999), S. 203-209 
    ISSN: 1435-1536
    Keywords: Key words Microemulsions ; Vinylacetate ; Acrylic acid structure ; Polymerization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The composition ranges over which microemulsions are formed in systems containing vinyl acetate, acrylic acid, water with nonylphenol ethoxylated with 25 mol ethylene oxide monomaleate as surfactant were studied. Conductometric and refractometric investigations have shown the existence of some aqueous/organic, bicontinuous and organic/aqueous microemulsions. The types of precursor microemulsions influence the conversion of monomers. In the presence of a crosslinking agent, diethylene glycol bis maleate, hydrogels are formed whose water absorption depends on the composition of the initial microemulsions. The kinetics of water absorption suggests the modification of polymer network structures as a function of the crosslinked monomer content and the ratio of organic to aqueous phases.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 91-96 
    ISSN: 1434-193X
    Keywords: Alkenes ; Electrophilic additions ; β-Sultones ; sec-Alkyl chlorosulfate ; 2-Chloro-1-alkanesulfonic acid ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -An exploratory study has been made on the reaction of a number of non-branched alkenes in [D]chloroform as an aprotic solvent, using chlorosulfuric acid as reagent both in the presence and the absence of [D8]1,4-dioxane as complexing agent. Reaction of cyclopentene (1a) with 1.1 mol-equiv. of chlorosulfuric acid in [D]chloroform in the presence of 2.2 mol-equiv. of [D8]1,4-dioxane at 0 °C yielded quantitatively 1,2-cyclopentanesultone (2a). Under similar reaction conditions, the linear alkenes 1b-g afforded the corresponding β-sultones 2b-g. The ClSO3H-dioxane complex acted as a sulfonating reagent with the alkenes to yield the corresponding β-sultones in a syn cycloaddition of SO3 to the Carbon-Carbon double bond. In the absence of [D8]1,4-dioxane the reaction of the linear alkenes 1a-1k in [D]chloroform with chlorosulfuric acid at -40 °C led to the formation of the sec-alkyl chlorosulfates 5a-i, which were formed after initial protonation of the alkene by the strongly acidic ClSO3H. Cyclopentyl chlorosulfate (5a) in [D]chloroform at 0 °C was quantitatively converted into 1,2-cyclopentanesultone (2a). The sec-alkyl chlorosulfates 5b-i at 0 °C gave rise to a mixture of the internal trans- and cis-β-sultones 2b-m. Reaction of 1-octene (1g) with both acetyl sulfate (6a) and trifluoroacetyl sulfate (6b) as reagent in [D]chloroform at -20 °C directly afforded the products 1,2-octanesultone (2g), and the (E) and (Z) isomer of 2-octene-1-sulfonic acid (4g).
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1434-1948
    Keywords: Palladium ; Bidentate nitrogen ligands ; Carbohydrates ; Alkenes ; Enantioselectivity ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral N,N-chelates of formula 6-Me-pyridine-2-CH=N-R (1) and R-N=CH-CH=N-R (2) (R = 6-deoxy-α-D-glucoside or 6-deoxy-α-D-mannoside residue) and their palladium(0) complexes [Pd(N,N-chelate)(olefin)] (I) were prepared. Symmetrical type 2 ligands induced higher enantioselectivity in the coordination of prochiral olefins. The ability of a type 1 chelate to promote a stereoselective process was also assessed, i.e. dimethylfumarate inserted into the Pd-Me bond formed upon methylation of a type I complex with 50% ee. Finally, a water-soluble Pd0 complex was also prepared by deprotecting the alcoholic functions on the sugar residue, and its molecular structure determined through X-ray diffractometry.
    Additional Material: 2 Ill.
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  • 9
    ISSN: 1434-193X
    Keywords: Fluorine ; vic-Difluorination ; Fluoroalkenes ; Xenon difluoride ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vic-Difluorination proceeds by the reaction of fluoroalkenes with xenon difluoride to afford the corresponding fluorinated compounds. From the reaction with polyfluoroalkenes, the products are obtained in high to excellent yields. In this reaction, the fluorine atom substituent of alkene stabilizes the cation intermediate and suppresses side-reactions such as rearrangement.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1999 (1999), S. 2249-2255 
    ISSN: 1434-193X
    Keywords: Alkenes ; Eliminations ; Halogens ; Laser chemistry ; Photolysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dehydrochlorination of 1,2-dichloropropane (DCP) was conducted by thermal elimination and CO2 laser-induced dielectric breakdown, which was induced by focusing the 10.6 μm lines of a CO2 TEA laser. Thermal dehydrochlorination proceeded by a four-centered mechanism at 〉 425 °C and by a surface-catalyzed radical process at 〈 400 °C. The product distribution of the breakdown-induced reaction at 〈 400 °C resembled that of high temperature thermal elimination and the corresponding temperature was estimated to be 〉 2000 °C.
    Additional Material: 4 Ill.
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  • 11
    ISSN: 1434-193X
    Keywords: Alkenes ; Methylthiomethyl sulfone ; Carbenoids ; Hetero-substituted carbanions ; Vinyl sulfides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The reaction of methylthiomethyl p-tolyl sulfone with alkyl sulfones when lithiated gives regioselectively vinyl sulfides in high yields in the presence of Ni(acac)2 or Fe(acac)3.
    Additional Material: 2 Ill.
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  • 12
    ISSN: 1434-193X
    Keywords: Hydrogen transfer ; Zirconium ; Alkenes ; Isobutylzirconocene chloride ; Lewis acid catalysis ; Lewis acid catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -The hydrozirconation reaction of monosubstituted alkenes with iBuZrCp2Cl can be significantly accelerated by catalytic amounts of various Lewis acidic metal compounds, most notably AlCl3, Me3SiI, and Pd complexes, such as Li2PdCl4 and Cl2Pd(PPh3)2.Supporting information for this article is available on the WWW under -http://www.wileY-Vch.de/contents/jc_2046/1999/99042_s.pdf or from the author.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 13
    ISSN: 1434-193X
    Keywords: Alkenes ; Chirality ; Longicorn beetle ; Pheromones ; Psacotheahilaris ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: -Both the enantiomers of (Z)-21-methyl-8-pentatriacontene (1), the major component of the female-produced contact sex pheromone of the yellow-spotted longicorn beetle (Psacotheahilaris), were synthesized by starting from the enantiomers of citronellol (2)
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 1434-193X
    Keywords: Alkenes ; Epoxidation ; Manganese ; Porphyrins ; Catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of MnIII porphyrins progressively halogenated in the β-pyrrolic positions was employed to catalyse the epoxidation of cis-stilbene by iodosylbenzene, and to study the role of the electronic effects on the stereoselectivity of this process. A gradual improvement in the stereoselectivity on increasing the number of β-halogen atoms was observed. The role of steric effects upon the epoxidation was also investigated by placing ortho-substituents in the meso-phenyl rings, and it was found that steric effects are more important than electronic effects toward the stereoselectivity of this process. These results can be rationalised by proposing a competition between a nonstereoselective electrophilic pathway of addition and a stereospecific pathway of oxygen insertion, the former being disfavoured by electron-withdrawing substituents. Alternatively, the formation of an open intermediate between the MnV oxene and the substrate could be suggested, where the stereoselectivity ought to be determined by the competition between closure of the epoxide ring and rotation around the C-C bond. In this case, the enhanced stereoselectivity given by our polyhalogenated porphyrins might be attributed to an acceleration of the epoxide ring closure caused by the electron-withdrawing effect of the halogen substituents.
    Additional Material: 1 Ill.
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  • 15
    ISSN: 1572-8935
    Keywords: Anionic ; Polymerization ; Hydrogenation ; Head-to-head ; 2,3-Dimethyl-1,3-butadiene ; Polypropylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Poly(2,3-Dimethyl-1,3-butadiene) (PDMB) with varying contents of 1,4-and 1,2-structures has been anionically synthesized using either n-butyllithium or sec-butyllithium as an initiator. The addition of tetrahydrofuran could enhance the rate of synthesis and effect the microstructure. The Tm was higher for PDMB with a lower content of 1,2-structure, and the Tg was lower. This PDMB was then hydrogenated with a nickelocene/n-butyllithium catalyst system leading to the formation of HPDMB. The trans 1,4-structure unit was more difficult to hydrogenate due to its steric hindrance. Repetitive hydrogenation was necessary in order to achieve a high degree of hydrogenation. The hydrogenated PDMB is an amorphous elastomeric material. The Tg’s were found to decrease with an increase in the degree of hydrogenation, concurrent with a gradual disappearance of the Tm’s. Since a HPDMS with a low content of 1,2-structure resembles a head-to-head polypropylene, our data suggest that the Tg of an atactic head-to-head polypropylene lie between −30 and −35 °C.
    Type of Medium: Electronic Resource
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  • 16
    ISSN: 1432-072X
    Keywords: Key words Anaerobic alkane oxidation ; Sulfate-reducing bacteria ; Cyclodextrin ; Alkenes ; Fatty acids ; Alkane activation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Natural relationships, improvement of anaerobic growth on hydrocarbons, and properties that may provide clues to an understanding of oxygen-independent alkane metabolism were studied with two mesophilic sulfate-reducing bacteria, strains Hxd3 and Pnd3. Strain Hxd3 had been formerly isolated from an oil tank; strain Pnd3 was isolated from marine sediment. Strains Hxd3 and Pnd3 grew under strictly anoxic conditions on n-alkanes in the range of C12–C20 and C14–C17, respectively, reducing sulfate to sulfide. Both strains shared 90% 16 S rRNA sequence similarity and clustered with classified species of completely oxidizing, sulfate-reducing bacteria within the δ-subclass of Proteobacteria. Anaerobic growth on alkanes was stimulated by α-cyclodextrin, which served as a non-degradable carrier for the hydrophobic substrate. Cells of strain Hxd3 grown on hydrocarbons and α-cyclodextrin were used to study the composition of cellular fatty acids and in vivo activities. When strain Hxd3 was grown on hexadecane (C16H34), cellular fatty acids with C-odd chains were dominant. Vice versa, cultures grown on heptadecane (C17H36) contained mainly fatty acids with C-even chains. In contrast, during growth on 1-alkenes or fatty acids, a C-even substrate yielded C-even fatty acids, and a C-odd substrate yielded C-odd fatty acids. These results suggest that anaerobic degradation of alkanes by strain Hxd3 does not occur via a desaturation to the corresponding 1-alkenes, a hypothetical reaction formerly discussed in the literature. Rather an alteration of the carbon chain by a C-odd carbon unit is likely to occur during activation; one hypothetical reaction is a terminal addition of a C1 unit. In contrast, fatty acid analyses of strain Pnd3 after growth on alkanes did not indicate an alteration of the carbon chain by a C-odd carbon unit, suggesting that the initial reaction differed from that in strain Hxd3. When hexadecane-grown cells of strain Hxd3 were resuspended in medium with 1-hexadecene, an adaptation period of 2 days was observed. Also this result is not in favor of an anaerobic alkane degradation via the corresponding 1-alkene.
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 47 (1998), S. 470-474 
    ISSN: 1612-1112
    Keywords: Affinity chromatography ; Polymerization ; Imprinted polymer networks ; Colloid ; Silica
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The article covers the methods that are currently available for the preparation of molecularly imprinted polymers. The disadvantages of the conventional grinding of bulk polymerized blocks of imprinted polymer are first identified. The newer methods are divided into four sections: suspension polymerization; modified surfaces; polymer colloids and finally miscellaneous techniques such as the use of linear polymers. Each alternative method is compared with the grinding method and the relative advantages and disadvantages identified.
    Type of Medium: Electronic Resource
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  • 18
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Alkenes ; Epoxides ; Retention index
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Retention indices or five 1-alkenes, seven branched alkenes and five cycloalkenes and the corresponding epoxides were determined at two temperatures on a fused-silica capillary column coated with cyanopropyl methyl siloxane to interpret their chromatographic behaviour. The standard deviation was 0.2 index units.
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  • 19
    ISSN: 1434-1948
    Keywords: Palladium ; Platinum ; Bidentate nitrogen ligands ; p-Quinone ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Compounds of the type M(N∩N-κN)(nq)2 and M2(μ2-N∩N)(μ2-pbq)2, in which nq = 1,4-naphthoquinone, pbq = 1,4-benzoquinone, and N∩N is a monodentate or bridging ligand of the α-diimine type, were obtained from reactions of Pd(dba)2 in toluene with the 3,3′-annelated-2,2′-bipyridines: 4,5-diazafluoren-9-one (dafo) and 4,5-diazafluorene (dafe) in the presence of the appropriate p-quinone. In the corresponding reactions with 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 2,2′-bipyrimidine (bpym), N,N′-dicyclohexyl-1,4-diaza-1,3-butadiene (chex-dab), bis[N-(o,o′-diisopropyl)phenylimino]acenaphthene (o,o′-iPr2-bian) and 5,6-dihydro-1,10-phenanthroline (dh-phen) only complexes of the type M(N∩N-κ2N)(Q) were formed (Q = nq, pbq). The structures of the complexes have been established by NMR in solution and by X-ray diffraction in the solid state; crystal structures of Pd(bpy-κ2N)(η2-pbq) (1) Pd(dafo-κN)(η2-nq)2 (14) and Pd2(μ2-dafo)(μ2,η2:η2-pbq)2 (16) have been determined. Of the ligands, dafo and dafe are the only ones apt to form complexes containing a monodentate or bridging N∩N ligand. This behaviour is ascribed to the geometrical constraints of dafo and dafe; the annelation by one carbon atom at the 3,3′-positions in these ligands causes an increase in bite angle from approximately 77° to 82°.
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  • 20
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 1759-1762 
    ISSN: 1434-193X
    Keywords: Alkenes ; Cycloadditions ; Cage compounds ; Ab initio calculations ; Double-bond pyramidalization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The twofold bridged sesquinorbornenes 2 and 6 were prepared using sequential [4 + 2] cycloadditions of benzoquinone with 1,5-dihydropentalenes 1 and 5. These syntheses were improved using dilution conditions or a more reactive substituted benzoquinone. Results from semiempirical and ab initio DFT calculations indicated remarkably high pyramidalization angles (φ = 46-47°) for the central C-C double-bond atoms. The chemical reactivity with triplet and singlet oxygen, dimethyldioxirane and N-methyl-1,2,4-triazoline-3,5-dione supports these structural assignments.
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  • 21
    ISSN: 1434-193X
    Keywords: Alkenes ; Ketones ; O-O activation ; Palladium ; Zeolites ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simple ammonia complexes {cis-[PdCl2(NH3)2], [Pd(NH3)4]Cl2 or [Pd(NO2)2(NH3)2]} with copper(II) chloride and LiCl or PdII (or Pd0) inserted into zeolite (faujasite Y or mordenite Z)/CuII-LiI-Cl- precursors in anhydrous ethanol catalyse the oxidation of terminal olefins to methyl ketones by dioxygen. One oxygen atom is incorporated into the olefinic substrate, while the other is involved in a cooxidation process of the solvent leading to the formation of water. With 1-octene and ethanol, octan-2-one can be obtained selectively (up to 99 %), acetaldehyde and diethyl acetal being the main cooxidation products. Chorohydridopalladium species are key intermediates in the isomerization of 1-alkenes; it appears that the introduction of NH3, NO2- or zeolite ligands reduces the extent of isomerization and subsequently the formation of isomeric ketones (octan-3-one and octan-4-one). Although homogeneous catalysis cannot be ruled out, the improved selectivities and variations of selectivity and conversion with different zeolites suggest that a “ship-in-a-bottle” catalysis may be important.
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  • 22
    ISSN: 1434-1948
    Keywords: Hydrogenations ; Parahydrogen ; Platinum ; Alkynes ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of hydrogenation of alkynes catalyzed by the [(PR3)2PtHX]/SnX2 system (PR3 = PPh3, PMePh2; × = Cl, Br) has been studied by means of parahydrogen-induced polarization of 1H spectra (PHIP). Dihydride intermediates confirming the stepwise hydrogenation at room temperature were observed when the reaction was run in acetone. The obtained 1H-PHIP spectra, together with NMR data for related species, are consistent with the formulation of these intermediates as cis-[H2Pt(PR3)(SnX3)(σ-alkenyl)(acetone)], where the σ-alkenyl ligand originates from an insertion reaction of the alkyne (1-phenyl-1-propyne, 1-phenyl-1-butyne, diphenylacetylene, 3,3-dimethylbutyne). At elevated temperatures, the hydrogenation in acetone proceeds as a cis-synchronous transfer of the two hydrogen atoms of parahydrogen to the substrate molecule. A mechanism for this synchronous hydrogenation is suggested.
    Additional Material: 4 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2775-2784 
    ISSN: 1434-193X
    Keywords: Heterocycles ; Cycloadditions ; Diatomic carbon ; Sulfones ; Alkenes ; Polycycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Chloro-1,4-benzodithiin 1,1,4,4-tetraoxide 11 is a reactive dienophile that forms Diels-Alder adducts with a number of dienes. Adducts 17a-j undergo facile dehydrochlorination to give 2,3-substituted 1,4-benzodithiin tetraoxides 18a-j, which react further with another molecule of diene (the same or a different one) affording the “double” adducts 19-23. Upon reductive desulfonylation with sodium amalgam, the latter are transformed to tetrasubstituted polycyclic olefins 24-27. These olefins correspond to the cycloadducts that would theoretically have been formed by the cycloaddition of diatomic carbon with two molecules of diene, reacting in a Diels-Alder fashion.
    Additional Material: 4 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1998 (1998), S. 2885-2896 
    ISSN: 1434-193X
    Keywords: Alkenes ; Alkynes ; Cycloadditions ; Nitrogen heterocycles ; Tetrazines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Full details on the reactivity of the title compound as 4π component in inverse-type Diels-Alder reactions, including kinetic data, are reported. Donor-substituted alkynes, alkenes, donor-substituted and unsubstituted cycloalkenes, ketene acetals and aminals, as well as several cyclic enol ethers were used as dienophiles in these investigations. A number of 4-mono- and 4,5-disubstituted pyridazines can easily be obtained by this method.
    Additional Material: 5 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    Springer
    Sexual plant reproduction 10 (1997), S. 136-141 
    ISSN: 1432-2145
    Keywords: Key words Ginkgo biloba L. ; Tubulin ; Purification ; Polymerization ; Pollen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Tubulin was purified by a combination of acetone powder preparation, DEAE Sephadex A-50 chromatography, Sephacryl S-300 gel filtration, and Mono Q anion exchange chromatography from the pollen of ginkgo (Ginkgo biloba L.), a typical gymnosperm. The average yield of tubulin is 2 mg per 100 g of pollen grain. The purified tubulin is electrophoretically homogeneous. It seems to be composed of two subunits on SDS-PAGE and is resolved as two major spots on two-dimensional electrophoresis, preliminarily indicating that there are no obvious tubulin isotypes in ginkgo pollen. The apparent molecular weights of the two subunits are about 54 kDa and 52 kDa respectively, estimated from the SDS-PAGE. It was also demonstrated that tubulin from ginkgo pollen is immunochemically related to animal brain tubulin, and the purified tubulin was polymerized to microtubular aggregates in the presence of taxol and GTP in vitro.
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  • 26
    ISSN: 1432-1017
    Keywords: Key words Diacetylenic lipids ; Polymerization ; Microfluorescence ; Filmbalance ; AFM
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract Molecular films from polymeric materials play an important role in basic research as well as in technology. We have synthesized the double chain diacetylenic ammonium lipid N-bis-(10, 12-pentacosadiinoyl)-oxy-ethyl)-N-methyl-amine (ONCO). We have characterized monomolecular films at the air/water interface by means of microfluorescence filmbalance techniques and by atomic force microscopy (AFM). ONCO forms stable monomolecular films that exhibit a fluid-solid phase transition with a transition enthalpy of 90 kJ/mol at 10 °C and neutral pH. The coexistence pressure was found to decrease with decreasing protonation, which is in contrast to the commonly found Coulomb mechanism. A change in the chain packing due to a different nitrogen bond angle is discussed as a possible mechanism. This model is cor-roborated by the finding that crystals at high and at low pH differ in their polymerization properties as measured by microfluorescence.
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  • 27
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1557-1565 
    ISSN: 0009-2940
    Keywords: Carbonylations ; Alkenes ; Palladium ; Asymmetric catalysis ; P and N ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Palladium complexes L2PdX2 containing various group Va ligands and weakly coordinating anions are active catalysts for the carbonylation of olefin substrates. These catalytic systems, though gaining significance in industry for the synthesis of polyketones, are normally characterised by a low chemoselectivity. This derives from the numerous possibilities for initiation and termination reactions which lead to different catalytic cycles and from facile multiple alternating insertion reactions of olefins and carbon monoxide. Based on experiments carried out under conditions of low selectivity and on previously published data, the factors involved in the control of the regio-, chemo- and stereoselectivity for those reactions are discussed, taking current ideas and model studies involving the above palladium complexes into consideration.
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  • 28
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 399-404 
    ISSN: 0009-2940
    Keywords: Disilylamides ; Group 4 Complexes ; Polymerization ; Metallacycles ; Titanium ; Zirconium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of metallacyclodisiladiazanes has been prepared. Lithiated (SiMe2NHtBu)2 (1) reacts with TiCl4 · 2 THF to give (SiMe2NtBu)2TiCl (4). Methylation or fluorination of 4 leads to (SiMe2NtBu)2TiMe2 (8) and (SiMe2MtBu)2TiF2 (9), respectively. The reaction of ZrCl4 · 2 THF with lithiated 1 or [SiMe2NH(4-FC6J4)]2 (2) yields (SiMe2NtBu)2ZrCl2 (5) and [SiMe2N(4-FC6H4)]ZrCl2 · THF (7), respectively. The lithiated ligand [SiMe2NH(2,6-iPr2C6H3)]2 (3) reacts with noncoordinated ZrCl4 to give [SiMe2N(2,6-iPr2C6H3)]2ZrCl2 (6). X-ray structural analysis of 9 showed it to be a fluorine-bridged dimer in the solid state. Compounds 4, 6, 8 and 9 were found to be catalysts for the polymerization of ethylene.
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  • 29
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 231-234 
    ISSN: 0009-2940
    Keywords: Diasteroselective cyclopropanation ; Copper compounds ; Homogeneous catalysis ; Molecular recognition ; Bimacrocycles ; Alkenes ; Macrocyclic ligands ; Heterocycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Concave 1,10-phenanthrolines 1a-c have been used as ligands in the copper(I)-catalyzed cyclopropanation of alkenes 2 with ethyl diazoacetate. The complexes proved to be efficient cyclopropanation catalysts and exhibited an enhanced diastereoselectivity, particularly in the reactions of cyclic alkenes 2b-d. The preferred formation of exo-cyclopropanes 3b-d can be explained by the concave shape of these catalysts.
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  • 30
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 291-294 
    ISSN: 0009-2940
    Keywords: Halogenoacetates ; Silver salts ; Solid-state reactions ; Polymerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure of silver chloroacetate was determined by single-crystal X-ray structure analysis. This represents the first salt of a monohalogenoacetic acid with a monovalent metal whose structure was determined with high precision. The salt undergoes a thermally induced solid-state polymerization to polyglycolide under elimination of silver chloride. A probable mechanism for a structure-determined reaction in the solid state is discussed.
    Additional Material: 4 Ill.
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  • 31
    ISSN: 0947-3440
    Keywords: [3 + 2] Cycloadditions ; Organylseleno group transfer ; 2,3-Dihydroselenophenes ; Polysubstituted butadienes ; Selenium ; Alkenes ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (2-tert-Butylseleno)propenenitrile (12a) has been prepared and treated with dimethyl ethynedicarboxylate (3) and methyl propiolate (18) to give the 2,3-dihydroselenophenes 16 and 21, respectively. In contrast, 2-(ethylseleno)-, 2-(methylseleno)- and 2-(phenylseleno)propenenitrile (12b-d) tend to form polysubstituted butadienes 17b-d with 3 by net organoylseleno group transfer from 12b-d to C-2 of 3 following attachment of C-3 of 17 to C-3 of 3. Five-membered selenonium ylides are proposed as intermediates.
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  • 32
    ISSN: 0947-3440
    Keywords: Kinetics ; Azo couplings ; Alkenes ; Allylsilanes ; Enthalpy relationships, linear-free ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions of arenediazonium ions with arenes, alkenes, allylsilanes, allylstannanes, and silyl ketene acetals have been studied in acetonitrile solution. The reactions follow second-order kinetics, and in several cases rate-determining attack of the diazonium ion has been proven by kinetic isotope effect studies (1a + 2b), by the independence of the allylsilane reactivities of the rate of desilylation (1a + 10a, d) and by the independence of the rate constants of the diazonium counterion. A decrease of the rate constant with increasing solvent donor ability (correlation with Gutmann's donor number) was found. The reactions of diazonium ions with π-nucleophiles roughly follow the correlation lgk (20°C) = s (E + N), previously derived for the reactions of carbocations with nucleophiles. With the E parameters derived for diazonium ions, rate constants for azo couplings with aromatic and nonaromatic π-nucleophiles can be predicted with an accuracy of ≈102. On the basis of E, the electrophilic reactivities of diazonium ions can be compared with those of carbocations (Figure 9), and the combination with the nucleophilicity parameters N (Figure 10) gives a first clue on possible azo coupling reactions. Literature reports are discussed within this scheme.
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  • 33
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    Liebigs Annalen 1997 (1997), S. 81-85 
    ISSN: 0947-3440
    Keywords: Halogenocarboxylates ; Solid-state reactions ; Polyesters ; Thermal analysis ; Polymerization ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Heating of the sodium salts of chlorocarboxylic acids leads to exothermic elimination of sodium chloride and oligomerization of the organic backbone of the molecule. Thermochemical data of sodium 2-chloropropionate (1), sodium 3-chloropropionate (2) and sodium 2-chlorobutyrate (3) were derived. The reaction products were characterized by IR and NMR spectroscopy, and the degree of polymerization was determined by gel permeation chromatography (GPC).
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  • 34
    ISSN: 0947-3440
    Keywords: Mannich bases ; Quaternization ; Grob fragmentation ; Alkenes ; Nucleophilic attack ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quaternary β-amino aldehydes and β-amino ketones are cleaved in a Grob-type fragmentation induced by nucleophilic attack of NH2- on the carbonyl group of 3, to yield new carbonyl derivatives 4 and alkenes 5, and unsaturated amides 6, respectively.
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  • 35
    ISSN: 0947-3440
    Keywords: Electron transfer reactions ; Radical additions ; 1,3-Asymmetric induction ; Alkenes ; γ-Lactones ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkyl 2-iodoalkanoates 2, and 2-iodoalkanenitriles 15 were added, with copper powder, to the 1-alkenes 1a, e, f, and h, and to the alkenes 1b, c, d, and g with a 1,2-dialkyl substituted double bond, to give, respectively, γ-lactones and 4-iodoalkanenitriles in very good yields. No solvent was used. The reaction is a free radical addition initiated by electron transfer from copper to the activated iodoalkane. Yields were lower using the respective bromo compounds. In situ formation of the iodo compounds, by addition of stoichiometric amounts of sodium iodide to the reaction mixture, gave improved yields. In the case of the methyl bromomalonates 6, the addition of sodium iodide proved to be unnecessary. The diastereoselectivity of the addition reaction by relative 1,3-asymmetric induction was rationalized by consideration of the steric interactions of the substituents in the transition state which is formed in the process of iodine transfer to the chiral adduct radical.
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  • 36
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    Journal of computer-aided materials design 3 (1996), S. 173-182 
    ISSN: 1573-4900
    Keywords: Nanotechnology ; Fullerenes ; Fibers ; Elasticity ; Fracture ; Simulations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary Motivated by recent observations of bent, collapsed and twisted carbon nanotubes, we investigate their behavior at large deformations. These hollow molecules behave remarkably similar to their macroscopic homologs. They reversibly switch into different morphological patterns, and each shape change corresponds to an abrupt release of energy and a singularity in the stress-strain curve. These transformations, simulated using a realistic many-body potential, are accurately described by a continuum-shell model. In contrast, a response to axial tension proceeds smoothly up to a fracture threshold, beyond which a monoatomic carbon chain unravels between the tube fragments.
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  • 37
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    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1123-1129 
    ISSN: 0009-2940
    Keywords: Halogenoacetates ; Solid-state reactions ; Polyglycolide ; Thermal analysis ; Polymerization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nine salts of halogenoacetic acids MOOC-CH2—X were prepared and characterized by their thermochemical reactivity. It was found that in seven cases elimination of MX led to polymerization of the organic part of the molecule. The resulting polyester, polyglycolide, could be isolated easily by washing the reaction product with water. It has a distinct porous morphology. The reaction takes place at moderate temperatures (100—200°C).
    Additional Material: 6 Ill.
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  • 38
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    Angewandte Chemie International Edition in English 35 (1996), S. 241-270 
    ISSN: 0570-0833
    Keywords: alkenes ; asymmetric syntheses ; Horner-Wittig reactions ; phosphane oxides ; synthetic methods ; Alkenes ; Asymmetric synthesis ; Horner-Wittig reaction ; Phosphane oxides ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 1959, Horner showed that metalated alkyldiphenylphosphane oxides react with aldehydes or ketones to give alkenes. With this reaction, the diphenylphosphoryl (Ph2PO) group made its entrance into synthetic organic chemistry. In the thirty-six years since that date, extensive research has shown that this olefination, the Horner-Wittig reaction, has unique properties that make it much more than simply the phosphane oxide cousin of the more famous phosphorus-based olefinations - the Wittig reaction (based on phosphonium salts) and the Wadsworth-Emmons reaction (based on phosphonate esters). Early work on the Horner-Wittig reaction concentrated on the reactivity of phosphane oxides and the regioselectivity of their reactions, but more recently the power of the Ph2PO group to control the stereochemistry of alkenes, and to produce “on demand” either stereoisomer in high stereochemical purity, has emerged. From the study of these stereocontrolled Horner-Wittig reactions arose the realization that the Ph2PO group is useful not only for the control of the two-dimensional stereochemistry of alkenes, but also of three-dimensional stereochemistry in general.After a brief introduction to phosphane oxide chemistry, this review will examine the Horner-Wittig reaction, in both its original and “stereocontrolled” varieties. From there, we will move on to an account of the stereoselective construction of molecules containing the Ph2PO group, concentrating on the stereochemical directing effects of the Ph2PO group and on the role of its unique combination of attributes - steric bulk, electronegativity, and Lewis basicity - in controlling these reactions. Finally, we will present what is intended as a practical guide to this chemistry, covering the type of functionalized alkenes that have been made with the help of the Ph2PO group and giving guidelines that we hope will help the organic chemist to make the most of the chemistry the Ph2PO group has to offer.
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  • 39
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    Angewandte Chemie International Edition in English 35 (1996), S. 2442-2469 
    ISSN: 0570-0833
    Keywords: alkenes ; carbonyl compounds ; heterocycles ; McMurry reactions ; titanium compounds ; Alkenes ; Carbonyl compounds ; Heterocycles ; McMurry reaction ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Among the applications of low-valent titanium in organic synthesis, the reductive coupling of carbonyl compounds to produce alkenes (the McMurry reaction) is particularly prominent. Discovered at the beginning of the 1970s, it has been developed and tested repeatedly, for example in numerous syntheses of natural products. This alkene synthesis has become a standard reaction in the repertoire of preparative chemists. However, the possibilities of low-valent titanium are by no means limited to this process: the last few years have brought some spectacular applications of the conventional McMurry reaction (for example the synthesis of taxol) along with a considerable extension of the scope of reductive carbonyl couplings. Thus, diverse heterocycles are now accessible following novel and efficient pathways based on intramolecular cross-coupling of functional groups - some of which were hitherto considered to be inert to titanium. The use of this method for the synthesis of indole and pyrrole alkaloids illustrates the new possibilities. At the same time, considerably simplified methods for conducting McMurrytype reactions have been developed. Examples include the particularly convenient “instant” method, the first ketone-amide coupling reactions requiring only catalytic amounts of titanium salts, and the first application of commercially available titanium powder as a coupling agent. Last but not least, the detailed investigation of diverse classical McMurry reagents has afforded a deeper understanding of the nature and mode of action of low-valent titanium. Revision of some of the current conceptions of the process of reductive carbonyl coupling is thus indispensable.
    Additional Material: 11 Ill.
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  • 40
    ISSN: 1572-8935
    Keywords: Microstructure modifier ; Isomers ; SBS ; Block copolymer ; Polymerization ; Kinetics ; Diethylether
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Diethylether (DEE) was used as a structure modifier during the synthesis of linear styrene-butadiene block copolymers of poly A-block-polyB-block-polyA type (SBS). The microstructures of synthesized polymers were analyzed, and the effect of DEE on polymerization kinetics was studied. Addition of DEE at 2 wt% concentration results in the highest styrene polymerization rate, while addition at 6 wt% concentration gives the highest butadiene polymerization rate. The vinyl content of the polybutadiene portion increases from 14 to 47% with an increase in the DEE concentration from 500 ppm to 10 wt% while thetrans- l,4 andcis-1,4 isomers decrease. For SBS polymer synthesized via a sequential method, the addition of DEE as a structure modifier minimizes the crossover deficiency which would otherwise result in a skewed molecular weight distribution with a higher polydispersity. For SBS polymers made via a coupling method, the coupling efficiency appears to be constant in a range of DEE concentration from 500 ppm to 1 wt% before declining with a further increase in DEE.
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  • 41
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    Journal of statistical physics 80 (1995), S. 389-404 
    ISSN: 1572-9613
    Keywords: Polymerization ; Markov process ; limit behavior ; stationary distribution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We consider a reversible Markov process as a chemical polymerization model and study the asymptotic behavior (in the thermodynamic limit asN→+∞) of a particular probability distribution on the set ofN-dimensional vectors, thekth component of which is the number ofk-mers. The study establishes the existence of three stages (subcritical, near-critical, and supercritical stages) of polymerization, depending on the value of the strength of the fragmentation reaction. The present paper concentrates on the analysis of the subcritical stage. In the subcritical stages we show that the size of the largest length of polymers of sizeN is of the order logN asN→+∞.
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  • 42
    ISSN: 0570-0833
    Keywords: alkenes ; catalysis ; metallocenes ; polymerizations ; Catalysis ; Metallocenes ; Polymerization ; Polyolefins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Current studies on novel, metallocenebased catalysts for the polymerization of α-olefins have far-reaching implications for the development of new materials as well as for the understanding of basic reaction mechanisms responsible for the growth of a polymer chain at a catalyst center and the control of its stereoregularity. In contrast to heterogeneous Ziegler-Natta catalysts, polymerization by a homogeneous, metallocene-based catalyst occurs principally at a single type of metal center with a defined coordination environment. This makes it possible to correlate metallocene structures with polymer properties such as molecular weight, stereochemical microstructure, crystallization behavior, and mechanical properties. Homogeneous catalyst systems now afford efficient control of regio- and stereoregularities, molecular weights and molecular weight distributions, and comonomer incorporation. By providing a means for the homo- and copolymerization of cyclic olefins, the cyclopolymerization of dienes, and access even to functionalized polyolefins, these catalysts greatly expand the range and versatility of technically feasible types of polyolefin materials.For corrigendum see DOI:10.1002/anie.199513681
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  • 43
    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.
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  • 44
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    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.
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  • 45
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    Angewandte Chemie International Edition in English 3 (1964), S. 460-470 
    ISSN: 0570-0833
    Keywords: Heat resistance ; Fibers ; Polymers ; Materials science ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This survey is principally concerned with papers published since 1959 on hydrocarbon polymers, aliphatic poly(terephthalamide) fibers, poly(hydroxybenzoic acid) films, poly(oxadiazole) fibers, poly(benzimidazole) films, poly(phenyltriazole) films, poly(pyromellitimide) films, and fibers from cyclized poly(acrylonitrile). All these materials have extremely high melting points and satisfactory in-use characteristics at high temperatures.
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  • 46
    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.
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  • 47
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    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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  • 48
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    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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  • 49
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    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.
    Type of Medium: Electronic Resource
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  • 50
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 410-420 
    ISSN: 0570-0833
    Keywords: Oligomers ; Pleionomers ; Polymers ; Fibers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The term “oligomer” is defined, and a survey of methods for the isolation and synthesis of cyclic and linear oligoesters, oligourethanes, oligo(acrylonitriles), and oligoamides is presented. The oligomers serve a valuable function as model substances for the investigation of many properties of the corresponding high polymers. This is shown using several examples (infrared spectroscopy, X-ray spectroscopy, viscosity).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 51
    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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  • 52
    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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 53
    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
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  • 54
    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.
    Type of Medium: Electronic Resource
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  • 55
    ISSN: 0570-0833
    Keywords: Elastomers ; Fibers ; Polyurethanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Highly elastic polyurethanes suitable for fiber production can be obtained by various synthetic routes based on diisocyanate polyaddition processes. Macrodiisocyanates obtained from long chain diols and diisocyanates are allowed to react with polyamines during fiber formation (chemical spinning process) or the macrodiisocyanates are treated in solvents (e.g. dimethylformamide) with polyamines to give highly viscous, spinnable solutions of polymer. Both methods yield highly elastic polymers with wide-mesh network structures. The production of polyurethane fibers and their structures and physical properties are described.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 56
    ISSN: 0570-0833
    Keywords: Copolymers ; Fibers ; Vinylidenedicarbonitrile ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinyldendicarbonitrile (Vinylidene cyanide) on free redical catalyzed copolymerization shows a much stronger tendency to form 1:1 alternating copolymers than acrylonitrile. While bulk poly(vinylidene cyanide) fails to crystallize, despite its molecular symmetry, several alternating copolymers are readily crystallizable, notably those containing butadiene, isoprene, isobutylene, or vinylidene chloride. Fibers have been prepared from a number of the higher melting copolymers and examined for physical properties. Fibers from the vinyl acetate and vinyl chloride copolymers show expectional elastic behavior both when dry and wet. The fiber from the vinylidene cyanide |vinyl acetate alternating copolymer (Darvan® nytril fiber) is only moderately oriented and is characterized by exceptional softness and excellent elastic recovery and resilience, both when dry and wet.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 57
    ISSN: 0570-0833
    Keywords: Long periods ; Polyethylene ; Fibers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Meridional reflections appearing in small-angle X-ray diffraction diagrams of drawn polyethylene are caused by a nearly periodic arrangement of crystalline and disordered regions. The long period, which is determined by the average distance between two consecutive crystallites, depends on the method of preparing the sample. The time and temperature dependences of the positions of the small-angle reflections have been investigated. The growth of the long period of unoriented bulk polyethlene and polyethylene single crystal follows the same time dependence as that of stretched films. However, characteristic differences were obseved in the relationship between density and long period; they are attributed to the fact that in single crystals and in material crystallized from the melt, the chains are folded at the boundaries of the crystallites, whereas this in not the case in stretched polyethylene.
    Additional Material: 25 Ill.
    Type of Medium: Electronic Resource
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