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  • General Chemistry  (2,585)
  • Polymer and Materials Science  (2,009)
  • 2000-2004  (378)
  • 1950-1954  (4,216)
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  • 1
    ISSN: 1434-193X
    Keywords: Triplet recombination ; Electron transfer ; Radical ions ; Photochemistry ; Terpenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The triphenypyrylium tetrafluoroborate (TPT)-sensitized reactions of several terpene donor molecules, including sabinene (1), α-phellandrene (4), α-terpinene (5) and γ-terpinene (6) give rise to significantly different products than reactions induced by other electron-transfer sensitizers, such as 1,4-dicyanobenzene (DCB). The divergent reactions require decidedly different key intermediates; the products obtained with TPT can be explained by dissociative recombination of the intermediate radical-radical cation pair in the triplet state, generating donor-derived biradicals.
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  • 2
    ISSN: 1434-193X
    Keywords: Azides ; Cleavage reactions ; Cycloadditions ; Nitrogen heterocycles ; Polycycles ; Ring expansion ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---2-Alkyl-1-methylquinazolinium hexafluorophosphates 9 are deprotonated by sodium or potassium hydride to afford solutions of 2-alkylidenedihydroquinazolines 10, which were investigated by NMR spectroscopy. Trapping with methanesulfonyl azide (5a) of 10 in situ or subsequent treatment with trifluoromethanesulfonyl azide (5b) gives mixtures of colourless (15) and intensely yellow N-sulfonylimino-1,4-benzodiazepines 16 along with products due to cleavage of the exocyclic double bond of 10, viz. 11 and 13. The ethylidene compound 10b yields the bicyclic products 18 and 19, apparently by complex sequences of reactions that are triggered by removal of the acidic proton at C-2 of 16b and 16f. The structures of the products are based on spectroscopic evidence and X-ray diffraction analyses performed on 15b, 16d, 16e, and 19.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1589-1593 
    ISSN: 1434-193X
    Keywords: Azaallenium ions ; Azaallylium ions ; Iminium ion ; Kinetics ; Linear Free Energy Relationships ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The rate constants for the reactions of the 2-azaallenium ion 1b+, the 2-azaallylium ion 2a+ and the iminium ion 3+ with different nucleophiles were determined by 1H NMR spectroscopy. By correlation with the Linear Free Enthalpy Relationship (LFER) lg k20°C = s (E + N), developed by Mayr and Patz, the electrophilicity parameters E(1b+) = -3.7, E(2a+) ≍ -16 and E(3+) = -10.43 were obtained. They show that the relative reactivities of these ions are approximately 1012:1:106. Quantum chemical calculations (ab initio, DFT) of the methyl anion affinities for the ions 1b+,2a+ and3+ are in agreement with the experimental E values. The X-ray structure of 3+·CF3SO3- is reported for the first time; it shows no strong interaction between the cation and the anion.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1595-1601 
    ISSN: 1434-193X
    Keywords: Oxazoline N-oxide ; Cycloadditions ; Cycloadditions ; Lactams ; Thienamycin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---[3+2] Cycloaddition between a camphor-derived oxazoline N-oxide 9 and the γ,δ-unsaturated enamino ester 11 afforded the single adduct 6. A stereoselective reduction of the enamino ester side chain allowed the control of the absolute configuration of the two additional asymmetric centres. Nitrogen protection and oxidative hydrolysis of the resulting product 13, followed by further functional group manipulations, led to the β-lactam derivative 1, a known precursor of the β-methylthienamycin derivative2a.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1603-1607 
    ISSN: 1434-193X
    Keywords: Boron ; Cyclotrimerizations ; Nitrogen heterocycles ; Macrocycles ; Subphthalocyanines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The regioselective preparation of ortho-substituted subphthalocyanides was achieved employing 3-substituted phthalonitrile derivatives as starting materials. A mechanistic proposal has been outlined.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99525_s.pdf or from the author.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1609-1615 
    ISSN: 1434-193X
    Keywords: Terpenoids ; Natural products ; Total synthesis ; Cyclizations ; Rearrangements ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A new route for the synthesis of 2,7- and 7-functionalized labdanes starts from (R)-carvone (1). 11-Nordrim-7-en-9-one (15) is an appropriate starting material for the total synthesis of hispanone (21), a biologically active furolabdane isolated from the Mediterranean medicinal plant Ballota saxatilis.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1623-1626 
    ISSN: 1434-193X
    Keywords: Iridoid glucoside ; (8S)-Kingiside ; (8S)-Loganin ; (8S)-7-Ketologanin ; Asymmetric synthesis ; Natural products ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The tetraacetyl derivative 8 of the naturally occurring kingiside (8a) was prepared from aucubin (1). Intermediates in the synthesis were (8S)-tetraacetyl loganin (6) and (8S)-tetraacetyl-7-ketologanin (7), whose free (8R)-epimers occur in many different plants (Caprifoliaceae, Loganiaceae). The 13C NMR spectrum allows the structure to be unequivocally identified.
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  • 8
    ISSN: 1434-193X
    Keywords: Tetrakis(dimethylamino)naphthalenes ; Basicity ; Hydrogen bonds ; Cyclicvoltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---For comparison to the recently described 2,3,6,7-tetrakis(dimethylamino)naphthalene (1) the three isomers 2,3, and 4 were synthesized. The basicities of this group of isomers are strongly dependent upon the different mutual orientations of the pairs of dimethylamino substituents: only the isomers 3 and, partially, 4, both with dimethylamino groups in adjacent peri-positions of the naphthalene, are strong “proton sponges”. For the isomers 1 and 2 with the same number and kind of twofold dimethylamino substituents in neighbouring ortho-positions, however, no significant basicity increase is observed. To explain this difference between the two groups of isomers it is suggested that in the ortho-pairs of 1 and 2 the C-N bonds diverge considerably, leading to an increased N···N distance and consequently to less stable [N···H···N]+ hydrogen bonds in contrast to the parallel C-N bonds in the peri-substituted isomers 3 and 4. X-ray crystal structure analyses of the bases and of some of the salts derived therefrom were solved and are discussed. Cyclic voltammetry indicates that 1 to 4 are strong electron donors, reacting easily to radical cations or dications which with suitable acids have been obtained as salts.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1677-1683 
    ISSN: 1434-193X
    Keywords: Radicals ; Cyclizations ; Pyridinethione ; Tetrahydrofurans ; Asymmetric synthesis ; Thiazolethione ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The trisubstituted functionalized tetrahydrofurans 10, 11, 16, 18, and 19 were photochemically prepared from 2,3-syn- and 2,3-anti-configuredN-(3-benzoyloxy-5-hexen-2-oxy)thiazole-2(3H)-thione anti-6, pyridinethiones 7, anti-8, and BrCCl3. The formation of tetrahydrofurans was achieved by an efficient and highly regioselective alkoxyl radical cyclization (5-exo-trig). The 2,3-anti substituted intermediates 9 and 12 cyclize stereoselectively whereas a 2,3-syn-configured O-radical affords both possible diastereomeric addition products in equal amounts. The cyclized tetrahydrofuryl methyl radicals were trapped with the bromine atom donor BrCCl3 to afford the bromomethyl-substituted cyclic ethers 10, 11, 18, and 19 in excellent yields. The utility of this reaction was stressed by conversion of one of the newly prepared tetrahydrofurans in a two-step synthesis into (+)-allo-muscarine (+)-20.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99590_s.pdf or from the author.
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  • 10
    ISSN: 1434-193X
    Keywords: Thioketones ; Thiocarbonyl ylides ; Cycloadditions ; Cycloreversions ; Sulfur heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reactions of diaryl thioketones with diazomethane at room temperature afford 4,4,5,5-tetraaryl-1,3-dithiolanes; the scope of this surprising 2:1 interaction has been studied for decades (Schönberg Reaction). The clue to the mechanism was our observation that the stoichiometry is 1:1 at -78 °C, and 2,5-dihydro-2,2-diaryl-1,3,4-thiadiazoles are formed as primary [2+3] cycloadducts. They lose N2 at -45 °C in first-order reactions generating diaryl thioketone S-methylides which can be intercepted by thioketones (→1,3-dithiolanes), multiple CC bonds, or acids HX. In the absence of trapping reagents, the elusive intermediates either dimerize furnishing 2,2,3,3-tetraaryl-1,4-dithianes or give rise to 2,2-diarylthiiranes by electrocyclization. Beyond thiobenzophenone and diazomethane, our main model reaction, the studies involve fluorene-9-thione, 4,4-dimethoxy- and 4,4-dichlorothiobenzophenone. The ring of 2,5-dihydro-2,2-diphenyl-1,3,4-thiadiazole (8) is opened by LDA at -78 °C and derivatives of anion 12 are obtained. - In summa: The Schönberg reaction consists of two 1,3-dipolar cycloadditions, linked by a 1,3-dipolar cycloreversion.
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  • 11
    ISSN: 1434-193X
    Keywords: Conjugation ; Boron ; Sensors ; Cyclic voltammetry ; Polymers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---New electropolymerizable aromatic compounds (i.e. pyrrole, thiophene, aniline) bearing boronic acid and ester substituents have been synthesized and their electrochemical behavior has been investigated. Functionalized polythiophene and polypyrrole films could be anodically generated in acetonitrile, whereas the polyaniline derivative was electroformed in an acidic aqueous solution. The electrochemical responses of some of these materials were changed when fluoride ions were added to the electrolytic solutions. The strongest modifications, caused by binding of fluoride by the immobilized boron, were observed for the polypyrrole derivative in hydroorganic media.
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  • 12
    ISSN: 1434-193X
    Keywords: Heterocycles ; Zinc ; Palladium ; Catalysts ; Sulfur ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Organozinc halides derived from Grignard reagents behave differently in their reaction with ethyl (±±)-(2RS,3SR)-tetrahydro-4-methylene-2-phenyl-3-(phenylsulfonyl)furan-3-carboxylate (3) according to the hybridisation of the carbon ligand. During the development of short multi-component reactions for the synthesis of diverse functionalized ethyl 2,5-dihydrofuran-3-carboxylates it was discovered that aryl and vinyl zinc halides undergo clean reaction with 3 in the presence of Pd(PPh3)4. In contrast, when alkyl zinc halides are reacted with 3 in the presence of Pd(PPh3)4, reductive desulfonation of 3 is observed. Remarkably, in the absence of a transition metal catalyst, the allylic substitution of 3 with alkyl zinc halides proceeds cleanly and in moderate to good yield.
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  • 13
    ISSN: 1434-193X
    Keywords: Self-assembly ; Vapor-pressure osmometry ; Resorcin[4]arenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Resorcin[4]arene tetracarboxylic acids 5,6 (A) and resorcin[4]arene tetrapyridines 2,3 (P) self-assemble in chloroform solution to form stable heterotopic AP dimers. Data from NMR titration and dilution experiments, as well as from vapor-pressure osmometry (VPO), indicate that the AP dimer is formed with an association constant greater than 107 M-1. Solid-solution extraction experiments are indicative of the formation of a 2:1 trimer (A2P), while self-associated homotopic species (A2 and A3) can be detected by NMR and VPO. Analysis of the heterotopic noncovalent assembly process over a range of compositions shows that these other species are much less stable than the AP heterodimer, which is the exclusive species at an A/P concentration ratio of 1:1 (〉 99.7% of the total at 10 mM).
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  • 14
    ISSN: 1434-193X
    Keywords: Sulfoxides ; β-Amino sulfones ; Mannich type reaction ; Lithium perchlorate ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The LiClO4-mediated one-pot reaction of aldehydes with (trimethylsilyl)dialkyl amines and the lithium salt of sulfoxides or sulfones, affords the corresponding β-(dialkylamino) sulfoxides and β-(dialkylamino) sulfones in high yields. The aminosulfoxidation reaction of aliphatic or aromatic aldehydes lacks diastereoselectivity, but the diastereomeric sulfoxides can be separated by HPLC or column chromatography for further use.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1741-1744 
    ISSN: 1434-193X
    Keywords: Bridged pyranose derivatives ; Ring enlargement ; Carbenes ; Glycosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Addition of dichlorocarbene to the glycal (±±)-2 followed by cyclopropyl-allyl rearrangement leads to the chloro-2H-pyran (±±)-4. Oxidation of (±±)-4 and reduction of the obtained hydroxypyranone (±±)-5 gave the methyl pyranoside (±±)-6. The relative configuration of (±±)-6 was established by X-ray structural analysis of the corresponding acetate (±±)-7. The synthesis of the optically active starting materials (+)-2 and (-)-2 is also reported.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1745-1758 
    ISSN: 1434-193X
    Keywords: CMP-Neu5Ac analogues ; Enzyme inhibitors ; Substrate analogues ; Transition state analogues ; Transferases ; Carbohydrates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Quinic acid was transformed into phosphitamides 16, 25, and 36, which could be readily linked to 5′-O-unprotected cytidine derivative 17. Ensuing oxidation of the obtained phosphite triesters with tBuO2H and hydrogenolytic de-O-benzylation furnished the corresponding phosphate diesters 18, 26, and 38. Base catalyzed removal of acetyl protecting groups, and methyl ester hydrolysis furnished CMP-Neu5Ac analogues 1d, 1e, and 2. Quinic acid was also transformed into 1,2-unsaturated diallyl α-hydroxymethyl-phosphate derivatives (R)- and (S)-46, which on reaction with cytidine phosphitamide 47 afforded the phosphite triesters. Subsequent oxidation with tBuO2H and then treatment with NEt3 gave phosphate diester derivatives (R)- and (S)-48. Deallylation, acetyl group removal, and methyl ester hydrolysis furnished (R)- and (S)-3, respectively. Treatment of (R)- and (S)-48 with DBU as a base led to acetic acid elimination, thus yielding, after de-O-allylation, acetyl group cleavage, and ester hydrolysis, diene derivative (E)-4. Donor substrate analogues 1d and 1e exhibited good α(2-6)-sialyltransferase inhibition (Ki: 2.0·10-4 and 2.0·10-5 M). However, transition state analogues (R)-, and particularly (S)-3 showed excellent inhibition properties (Ki: 1.6·10-6 and 2.7·10-7 M).
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1759-1765 
    ISSN: 1434-193X
    Keywords: Cyclitols ; Aminocyclitols ; Glycosidase inhibitors ; α-Mannosidase inhibitors ; Deoxygenation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Three deoxy derivatives 2-4 of the α-mannosidase inhibitor mannostatin A (1) were synthesized, and their inhibition of Jack bean α-mannosidase was evaluated in order to elucidate the roles of each of the three hydroxyl groups of the inhibitor. The 1- and 2-deoxy derivatives 2 and 3 retained some inhibitory activity, although reduced by a factor of about 100 relative to the parent, whereas it was completely lost with the 3-deoxy derivative 4. Structure and activity relationships are discussed in the light of these findings.
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  • 18
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1767-1772 
    ISSN: 1434-193X
    Keywords: Circular dichroism ; Conformation analysis ; s-Triazines ; Chiral auxiliaries ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---CD data of the optically pure 2-[(R)-1-(9-anthryl)ethylamino]-4-chloro-6-[(R)-1-(1-naphthyl)ethylamino]-1,3,5-triazine, 2[(R)-1-(9-anthryl)ethylamino]-4,6-bis[(R)-1-(1-naphthyl)ethylamino]-1,3,5-triazine, 2,4-bis[(R)-1-(9-anthryl)ethylamino]-6-chloro-1,3,5-triazine are presented. The analysis of the CD spectra by means of the nonempirical DeVoe approach has afforded the complete conformational characterisation of the three s-triazine derivatives, allowing us to establish how the conformation of these derivatives depends on the nature of the substituent 1-arylethylamino groups.
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  • 19
    ISSN: 1434-193X
    Keywords: Cycloadditions ; Carbenes ; Nitrones ; Nitrilimines ; Pyrazolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of tert-butylalkynyl chromium Fischer carbene complex 1 with nitrones 2 affords β-enamino-ketoaldehydes 4 by the light-promoted rearrangement of the corresponding [3+2] cycloadduct carbene complexes 3. On the other hand, [3+2] cycloaddition of chiral nonracemic Fischer alkenyl carbene complexes 19 with nitrilimines 10 yields enantiomerically pure Δ2-pyrazolines with high regio- and diastereoselectivity.
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  • 20
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Zinc ; Transition structures ; QM/MM computations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Trimethylsilyl substitutions of the fenchyl alcohols [(1R,2R,4S)-exo-(2-Ar)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, Ar = 2-methoxyphenyl (1) and Ar = 2-(dimethylaminomethyl)phenyl (2)] yield the chiral ligands 3 [Ar = 2-methoxy-3-(trimethylsilyl)phenyl] and 4 [Ar = 2-(dimethylaminomethyl)3-(trimethylsilyl)phenyl]. Increased reactivities and enantioselectivities in diethylzinc additions to benzaldehyde are obtained from 3 (63% ee R) and 4 (93% ee S), relative to 1 (26% ee S) and 2 (73% ee S). X-ray crystal structures of 3 and of its methylzinc complex 3-Zn reveal out-of-plane bending of the methoxy groups as major geometrical consequences of the trimethylsilyl substitutions. Analyses of QM/MM ONIOM μ-O transition-structure models for 1, 2, 3, and 4 show that trimethylsilyl-induced distortions of methoxy and of dimethylaminomethyl groups explain the observed increased enantioselectivities.
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  • 21
    ISSN: 1434-193X
    Keywords: Palladium ; exo-π-Allylpalladium complexes ; Allylic alkylation ; Spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The palladium(0)-catalyzed alkylation of 2,3-bis(acetoxymethyl)bicyclo[2.2.1]hepta-2,5-diene 1 with malonate-type enolates as nucleophiles is investigated. A monoalkylated product is formed first, and undergoes (depending on the nucleophile used) a second intramolecular reaction leading to spirocyclopropane-annulated bicyclo[2.2.1]heptene derivatives 5. The formation of endo spirobicyclic cyclopropanes adducts as major isomer is rationalized by assuming formation of an intermediate exo-(π-allyl)palladium complex.
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  • 22
    ISSN: 1434-193X
    Keywords: Ketones ; Reductions ; Micelles ; Cobalt ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Operationally simple and environmentally benign procedures have been developed to selectively reduce different α,β-unsaturated ketones, 4,4-dimethylcyclohex-2-ene-1-one (1), isophorone (2), benzylideneacetone (3), chalcone (4) by NaBH4 or by the system NaBH4 + CoCl2. Alternative reaction media to the extensively used MeOH have been explored, and new procedures take advantage of the acceleration and chemoselectivity induced by water or by aqueous micellar solutions. It was possible to selectively and quantitatively afford pure products of 1,2 and of 1,4 reduction as well as the totally reduced compounds (yield and selectivity 〉 90%) by simple changes in the experimental conditions.
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  • 23
    ISSN: 1434-193X
    Keywords: C-Glycosides ; Conformation analysis ; Molecular dynamics ; Selectins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The conformational behavior of the C-glycosyl analogue of sialyl-α-(2→3)-galactose, synthesized as a glycosidase inhibitor, has been studied using a combination of NMR spectroscopy (J and NOE data) and molecular dynamics calculations. The obtained results show that the population distribution of conformers with respect to the orientation about the pseudo-glycosidic linkages is mainly controlled by steric interactions. This is in contrast to findings made for O-glycosides. In these natural compounds, the conformational behavior about the glycosidic linkage Φ is mainly governed by the exo-anomeric effect.
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  • 24
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1815-1820 
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Palladium-catalysed couplings ; Palladacycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Chiral C2-symmetric N-benzylazetidines have been conveniently prepared from optically pure anti-1,3-diols without loss of enantiomeric purity. N-Debenzylation led to the corresponding N-unsubstituted azetidines, which were then subjected to palladium-catalysed coupling reactions with aryl bromides to afford chiral N-arylazetidines. (R,R)-N-Benzyl-2,4-dimethylazetidine has been employed in the synthesis of a new cyclopalladated complex, which can be used, for instance, as a chiral recognition agent for phosphorus ligands.
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  • 25
    ISSN: 1434-193X
    Keywords: Cyclizations ; Spiro compounds ; Nucleosides ; Isomerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Syntheses of the spiro nucleosides 2′-deoxyhydantocidin 3a and its 1′-epimer 3b are described. The newly developed route involves a Horner-Wadsworth-Emmons condensation of the phosphonate 16 with the erythrose derivative 15 affording a mixture of six isomers which was fully assigned by NMR spectroscopy. The mixture was directly converted into the final compounds in an efficient base-catalyzed cyclization reaction. A base-catalyzed interconversion between the two isomers was observed.
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  • 26
    ISSN: 1434-193X
    Keywords: Benzodiazepines ; Heterocycles ; Azeto[1,2-a]-1,5-benzodiazepines ; Cyclizations ; Cycloadditions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of o-phenylenediamine (4) with one, two or three equivalents of p-substituted 3-dimethylaminopropiophenone hydrochlorides 5a-e was studied. 4-Aryl-2,3-dihydro-1H-1,5-benzodiazepine derivatives 6a-e were obtained in good yields, along with the 1:2-adducts 7c-e and the unexpected 1:3-adducts rac-8c-e. The type of adduct formed is determined by the molar ratio of the reactants 4 and 5 and by the nature of the substituent in the para position of the propiophenone 5.
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  • 27
    ISSN: 1434-193X
    Keywords: Cup-shaped PAHs ; Host-guest compounds ; Host-guest chemistry ; Cyclizations ; Semiempirical calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Cyclotrimerisation of benzo-polycyclic bromostannylalkenes 8a-d with Cu(NO3)2·3H2O in THF affords benzotri(benzonorbornadienes) 3a-d as a mixture of the syn and anti isomers. The ratio of syn to anti is close to the 1:3 statistical value in most cases (i.e. in cyclotrimers 3a,b,d), but highly in favour of the anti isomer in 3c, where steric hindrance by the methoxy groups plays an important role in the stereochemistry of the cyclotrimerisation. The substrates for the cyclotrimerisation, i.e. the bromostannyl alkenes 8a-d, were prepared from bromoalkenes 7a-d by treatment with base (LDA) and quenching with trimethyltin chloride. In turn, bromoalkenes 7a-d were prepared from alkenes 5a-d by radical bromination-elimination. The reaction conditions used were designed to minimise Wagner-Meerwein rearrangements that would lead to unwanted bromo isomers. The cup-shaped syn cyclotrimers 3a-d exhibit high electron density within the cavity as determined by AM1 semiempirical calculations of their electrostatic potential surfaces and are valuable substrates for supramolecular chemistry. As an example, it is shown that fullerene C60 is drawn into solution in acetonitrile by complexation with both the syn and anti trimer of benzonorbornadiene 3a.
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 233-234 
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    Description / Table of Contents: Wetting of metals by waterIn the following own experiments and such of other authors are discussed concerning the balances of wetting of air, water and metal,  -  the explanation of which has hardly been tried so far  - , as they appear to be of importance for the basic research of the corrosion of metals. In view of the fact that their methodic has haidty been used in corrosion research, only the basic trials are demonstrated.Prior to the careful measurings of Bartell and Cardwell only more informative researches on the wetting of metals by water were made by older authors. This article, therefore, starts from the experiments on gold and silver made by Bartell and Cardwell. Own observations on mercury follow, which admit certain qualitative statements on account of the knowledge of the respective surface tension of liquid mercury. As regards other metals, among which platinum shows particularly remarkable results, only preliminary qualitative results can be discussed. They lead to some consequences concerning the question of the sort of combining power of oxygen of air to the surfaces of metals.A survey is given on the indirectly gained values of the surface tension of solid metals. These values yield together with the heats of adsorption obtained on metal catalysers a comparative measure for the different adsorption power on metal surfaces.The conclusions from the observed rivalry between the wetting by water and the adsorption of air are compared with the results of various authors on the adsorption of gases or aequous mediums on metal surfaces. Finally a hypothesis is proposed for the traceadhesion of water (Wasscr-Haftspur-Erscheinung).
    Notes: Im folgenden werden fremde und eigene Untersuchungen über Benetzungsgleichgewichte des Stofftrios: Luft, Wasser, Metall, deren Ausdeutung bisher kaum versucht wurde, zusammenfassend diskutiert, da sie für die Grundlagenforschung der Metallkorrosion von Bedeutung sein dürften. Mit Rücksicht darauf, daß ihre Methodik in der Korrosionsforschung bisher kaum Anwendung fand, werden zunächst die Verfahrens-Grund-Lagen dargelegt.Vor den sorgfältigen Messungen von Bartell und Cardwell wurden nur seitens älterer Autoren mehr orientierende Untersuchungen über die Benetzung von Metallen durch Wasser veröffentlicht. Deshalb wird von den Untersuchungen Bartells und Cardwells an Gold und Silber ausgegangen. Hieran schließen sich eigene Beobachtungen an Quecksilber, welche dank der Kenntnis der in Frage kommenden Grenzflächentensionen des flüssigen Quecksilbers gleichfalls noch gewisse quantitative Aussagen ermöglichen. Uber andere Metalle, von denen Platin besonders bemerkenswerte Erscheinungen lieferte, können nur vorläufige, qualitative Ergebnisse besprochen werden; auch ergeben sich einige Folgerungen zur Frage der Bindungsart von Luftsauerstoff an Metalloberflächen.Nach einem Überblick über indirekt erschlossene Werte der Oberflächentension fester Metalle, die neben den an Metallkatalysatoren erschlossenen Adsorptionswärmen ein Vergleichsmaß für die unterschiedliche „Adsorptionskraft“ von Metalloberflächen ergibt, werden dic Schlußfolgerungen aus der zu beobachtenden Konkurrenz von Wasserbenetzung und Luftadsorption mit Ergebnissen verschiedener Autoren über Adsorption an Metallflächen aus gasförmigem oder wäßrigem Medium verglichen. Schließlich wird für die vom Verfasser früher beschriebene Wasserhaftspurerscheinung eine Hypothese vorgeschlagen.
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    Description / Table of Contents: Phase boundary-lines, especially in their impotance for corrosionTwo phases have a common cleavageplane, whilst three phases touch one another along a boundary line only. Corroesponding to an adsorption in the first case in an adlineation in the second case. Both processes diminish the free energy and herewith the activity of the boundary, so inhibiting the possibilities of corrosion.Local elements, glow cathodes and catalysts consisting of several components are typical systems acting at microscopic boundary-lines. Cavitation is the inverse phenomenon.Macroscopic boundary-lines in partially filled containers, formed by wall, liquor and gaseous phase, are about this especially active, as being mixed with a four-phases-point-system, that results from the heterogeneity of the container wall. Gravity potentials, and electrokinetic potentials have their maximum value in the boundary-lines too.
    Notes: Zwei Phasen haben eine gemeinsame Grenzfläche, während drei Phasen sich nur entlang einer Grenzlinie berühren. Der Adsorption im ersten Falle entspricht eine Adlineation im zweiten Falle. Beide Vorgänge setzen die freie Energie und damit die Aktivität der Grenze herab, hemmen also Korrosionsmöglichkeiten.Lokalelemente, Glühkathoden und Mehrstoff-Katalysatoren sind typische Systeme, die an mikroskopischen Grenzlinien zur Wirkung kommen. Kavitation bildet die inverse Erscheinung hierzu.Makroskopische Grenzlinien an teilgefüllten Behältern, die durch Wandung, flüssigem Inhalt und gasförmiger Phasegebildet werden, sind darüber hinaus besonders aktiv, da sie von einem Vierphasen-Punktsystem durchsetzt sind, das infolge er heterogenität der Behälterwand resultiert.Gravitationspotentiale und elektrokinetische Potentiale haben ebenfalls in den begrenzenden Linien ihren maximalen Wert.
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    Source: Wiley InterScience Backfile Collection 1832-2000
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    Materials and Corrosion/Werkstoffe und Korrosion 1 (1950), S. 432-432 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 362-365 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Description / Table of Contents: Dissolving-speed of iron in 0,1n-hydrochloric acid1For polished test pieces of iron the increased dissolving-speed in 0,1n-hydrochloric acid in the first seconds is due to the effect of a surface-oxyde.Tests with iron pieces without surface-oxyde (reduction in hydrogen, no touching of the reduced sample with air) show an increasing of the initiating dissolving-speed as well in aqueous as in etheric hydrochloric acid, which may be explained by an increased reactivity of active iron-atoms of the surface. At coarse-field aerated test-pieces the effect of the surface-oxyde is smaller than the increased activity of the surface.The diagram of solubility of polished (surface-oxyde) samples is distinctly different to that field (surface activity) test-piecees.
    Notes: 1Bei geschliffenen Eisenproben wird die erhöhte Auflösungsgeschwindigkeit in 0,1n HCl in den ersten Sekunden auf die Wirkung eines Oberflächen-oxydes zurückgeführt.2Versuche mit Eisenproben ohne Oberflächenoxyd (Reduktion in Wasserstoff, keine Berührung der reduzierten Probe mit Luft) zeigen sowohl in wässeriger als auch in ätherischer Salzsäure eine Erhöhung der Anfangs-Lösungs-geschwindigkeit, die durch eine erhöhte Reaktionsfähigkeit aktiver Eisenatome der Oberfläche zu erklären ist. Bei grobgefeilten belüfteten Proben tritt die Wirkung des Oberflächenoxydes gegenüber der erhöhten Aktivität der Oberfläche in den Hintergrund.3Der Charakter der Lösbarkeits-kurven der geschliffenen (Oberflächenoxyd) bzw. gefeilten (Oberflächenaktivität) Proben ist deutlich verschieden.
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 401-404 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 406-406 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 404-405 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materials and Corrosion/Werkstoffe und Korrosion 1 (1950), S. 433-437 
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    Materials and Corrosion/Werkstoffe und Korrosion 1 (1950), S. 441-441 
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    Materials and Corrosion/Werkstoffe und Korrosion 1 (1950), S. 442-443 
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    Materials and Corrosion/Werkstoffe und Korrosion 1 (1950), S. 443-444 
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    Materials and Corrosion/Werkstoffe und Korrosion 1 (1950), S. 452-459 
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    Materials and Corrosion/Werkstoffe und Korrosion 1 (1950), S. 460-461 
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    Materials and Corrosion/Werkstoffe und Korrosion 1 (1950), S. 461-461 
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    Materials and Corrosion/Werkstoffe und Korrosion 1 (1950), S. 461-463 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 441-444 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Description / Table of Contents: Variation of corrosions by wetting agents. II. The influence of non-ionogen wetting agentsSurface-active substance are able to change the corroding effect of tap water on unalloyed steel in a favourable manner, as far as pitting is avoided and only removing tuberculation takes place. Non-ionogen wetting agents are more effective hereby than anion-active ones. A higher decreasing of the surface tension of the water by addition of over 4%0 of the wetting agent raises the efficacy. The chemical constitution of the used surface-active substances, however, seems to be of essential importance.
    Notes: Oberflächenaktive Stoffe können die korrodierende Wirkung von Leitungswasser auf unlegiertem Stahl insofern günstig verändern, als Lochkorrosion vermieden wird und nur noch abtragende Narbenkorrosion auftritt. Nichtionogene Netzmittel sind dabei wirksamer als anionaktive. Eine stärkere Erniedrigung der Oberflächenspannung des Wasser durch Zusatz von je 4%0 des Netzmittels erhöht die Wirkung. Die chemische Konstitution der verwendeten oberflächenaktiven Körper scheint jedoch von wesentlicher Bedeutung zu sein.
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 465-468 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 461-464 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Description / Table of Contents: Influence of the state of surface on the endurance bending strengthResults of endurance fatigue tests taken from literature are comparable,  -  as well known  - , only in a limited degree. One of the reasons for this disadvantageous limiting in the evaluation is to be found in the differences in the treatment of the surface of the bar. The known performance on the influence of surface qualities and treatment on the fatigue limit gives the highest value for polished surfaces of bar.In contrast hereto lately performed endurance bending tests with non-alloyed steels and brilliant-finish polished bars showed a rotating beam fatigue limit which was 57-18% lower than that on usually smoothed or polished samples. The careful treatment of those bar surfaces was practised by polishing in that manner as in preparing a “metallographic polished specimen”. About one hour of polishing resulted a high-mirror finished surface of bar, free of scratches and grooves. The microhardness of the bar surface has been lowered hereby, e. g. at Armco-iron, from 200 to 130 kg/mm2.For better comparability of results in endurance bending strength stated by different testing offices, the method of treatment of test pieces ought to be indicated.
    Notes: Versuchsergebnisse von Umlaufbiegeversuchen aus dem Schrifttum sind, wie bekannt, nur begrenzt vergleichbar. Einer der Gründe für diese nachteilige Einschränkung bei der Auswertung liegt in Verschiedenartigkeiten bei der Bearbeitung der Staboberfläche. Die bekannte Darstellung über den Einfluß der Oberflächenbeschaffenheit und Bearbeitung auf die Dauerfestigkeit gibt für polierte Staboberflächen den höchsten Wert an.Bei neuerdings durchgeführten Umlaufbiegevrsuchen mit unlegierten Werkstoffen und hochfein polierten Proben war im Gegensatz dazu die Wechselbiegefestigkeit 5-18% niedriger als bei üblich geschliffenen oder polierten Stäben. Die sorgfältige Bearbeitung der Staboberfläche erfolgte hier durch Polieren wie bei der Herstellung eines „metallographischen Schliffes“. Etwa eine Stunde Polierzeit ergab eine spiegelblanke Staboberfläche, frei von Kratzern und Riefen. Die Mikrohärte der Staboberfläche ist dadurch z. B. bei Armco-Eisen von 200 auf 130 kg/mm2 erniedrigt worden.Der Zustand der Bearbeitung von Umlaufbiegeproben sollte zur Verbesserung der Vergleichbarkeit von Ergebnissen der Wechselbiegefestigkeit von verschiedenen Prüfstellen gekennzeichnet sein.
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 478-478 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materials and Corrosion/Werkstoffe und Korrosion 4 (1953) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materials and Corrosion/Werkstoffe und Korrosion 4 (1953), S. I 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materials and Corrosion/Werkstoffe und Korrosion 4 (1953), S. 95-101 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Description / Table of Contents: Metals and TissueThe behaviour of metals when embedded in human tissue and their decomposition by body fluids is examined from the standpoint of the surgen. There is a great demand for metals capable of withstanding corrosion which are at the same time, suitable for use in the human body as supports for injured parts as substitutes for damaged joints. The present shortage of suitable material for this purpose is emphasised by words and pictures. Substitutes for metals (Plexiglas, Paladon etc.,) are touched upon, although these substance are not yet fully capable of taking the place of metals. Tantalum, which has been greatly praised abord, is worthy of serious attention. It is kindly to human tissue, easily formed and worked, is not attacked by body fluids, but, unfortunately, is still extremely expensive in Germany. This metals is now being used experimentally in one or two of the Medical School of German universities.
    Notes: Das Schicksal von Metallen im menschlichen Gewebe, seine Auseinandersetzung mit den Körpersäften wird von Standpunkt des Chirurgen aus beleuchtet. Es besteht ein großer Bedarf seitens der Medizin an korrosionsbeständigen Metallen, die in den Körper entweder als Stütze verlorengegangener Stabilität oder als Ersatz für zerstörte Gelenke gebraucht werden. Die heute noch bestehenden Mängel des Materials werden in Bild und Wort besonders in den Vordergrund gestellt. Es wird auf Ersatzstoffe für Metalle eingegangen (Plexiglas, paladon), die aber auch noch nicht in vollen Maße an die Stelle des Metalls treten können. Unsere Aufmerksamkeit verdient Tantal, das im Ausland sehr gelobt wird. Es ist sehr gewebsfreundlich, gut formbar, wird nicht von Körpersäften angegriffen, ist aber in Deutschland sehr teuer. Dieses Metall wird zur Zeit in einigen deutschen Universitätskliniken ausprobiert.
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    Materials and Corrosion/Werkstoffe und Korrosion 4 (1953), S. 117-119 
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    Materials and Corrosion/Werkstoffe und Korrosion 4 (1953), S. 120-120 
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    Materials and Corrosion/Werkstoffe und Korrosion 2 (1951), S. 480-480 
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    Materials and Corrosion/Werkstoffe und Korrosion 4 (1953) 
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