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  • Inorganic Chemistry  (95)
  • ACM25/26; ACM25/26_Northwest_2; DATE/TIME; DEPTH, water; MOOR; Mooring; Temperature, water; Temperature recorder, Brancker; WOCE; World Ocean Circulation Experiment  (16)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 3935-3942 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Vibrational Spectra of Dimeric (Isopropylidenamino)dimethylborane, -alane, and -gallaneN-Chloro-2-propanimine (1) reacts with trimethylboron, -aluminium, and -gallium to form the dimeric imino compounds [Me2C=N—MMe2]2 (M=B, Al, Ga) (2-4), which, according to the vibrational spectra, occur as M2N2 four-rings of the point group D2h. Also, the vibrational spectrum of 1 is reported.
    Notes: N-Chlor-2-propanimin (1) reagiert mit den Trimethylverbindungen von Bor, Aluminium und Gallium unter Bildung der dimeren (Isopropylidenamino)dimethyl-Derivate [Me2C=N—MMe2]2 (M=B, Al, Ga) (2-4), die nach den Schwingungsspektren zentrosymmetrische M2N2- Vierringe (Symmetrie D2h) bilden. Das Schwingungsspektrum von 1 wird ebenfalls mitgeteilt.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 486-501 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Bile Pigments, VI: Total Synthesis of (+)(4R,16R)- and (-)(4R,16S)-[18-Vinyl]mesourobilin IXα Dimethyl EstersRacem. methyl 5′-tert-butoxycarbonyl-[4-vinyl]isoneobilirubinate (7a) has been synthesized by oxidation of the 5(2H)-dipyrrylmethanone-selenide 5m with hydrogen peroxide and subsequent thermal decomposition of the formed selenoxide. The corresponding 5′-formyl derivative 7b was condensed with the known (+)(R)-5′-carboxyneobilirubinic acid (6a) yielding, after esterification with diazomethane, the two diastereomeric (+)(4R,16R)- and (-)(4R,16S)-[18-vinyl]mesourobilin IXα dimethyl esters (8a and 8b, respectively) which were for the first time fully characterized on the basis of their CD, ORD, 1H-NMR, UV/VIS, and mass spectra. In the course of this work 4-methyl-3-vinyl-3-pyrrolin-2-one (3) was prepared in 20% yield from 2b.
    Notes: Racem. 5′-tert-Butoxycarbonyl-[4-vinyl]isoneobilirubinsäure-methylester (7a) wurde durch Oxidation des 5(2H)-Dipyrrylmethanon-selenids 5m zum Selenoxid und dessen thermische Zersetzung synthetisiert. Durch Kondensation des entsprechenden 5′-Formyl-Derivats 7b mit der bekannten (+)(R)-5′-Carboxy-neobilirubinsäure (6a) und darauffolgende Veresterung des Reaktionsproduktes wurden die zwei diastereomeren (+)(4R,16R)- und (-)(4R,16S)-[18-Vinyl]mesourobilin IXα-dimethylester (8a bzw. 8b) zum ersten Mal dargestellt und anhand ihrer CD-, ORD-, 1H-NMR-, UV/VIS- und Massenspektren charakterisiert. Weiterhin wurde das schwer zugängliche 4-Methyl-3-vinyl-3-pyrrolin-2-on (3) aus der bekannten 2-Oxo-3-pyrrolin-3-propionsäure 2b in 20 proz. Ausbeute dargestellt.
    Additional Material: 4 Ill.
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  • 3
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Antitumor Active cis-Platinum(II) Complexes with α-Amino Acid Esters and Peptide Esters. X-Ray Structure of cis-Dichlorobis(glycylglycine ethyl ester)platinum(II)A series of cis-platinum(II) complexes X2PtL2 (1-4) (X = halide, 2X = oxalate, malonate; L = α-amino acid ester, peptide ester) has been obtained from Pt42- and L. The dipeptide ester complexes are also accessible via peptide synthesis at the complex from Cl2Pt(NH2CHRCO2H)2 and α-amino acid esters using carbodiimide as coupling agent and the platinum atom as amino protecting group. The complexes Cl2PtL2 with α-amino acid ester ligands have also been prepared from the bis(chelate) compounds cis-Pt(NH2CHRCO2)2 and alcohol in the presence of HCl. The complexes have been characterized by their spectroscopic data, cis-Cl2Pt(GlyGlyOEt)2 (2a) by an X-ray analysis.
    Notes: Eine Reihe von cis-Platin(II)-Komplexen X2PtL2(1-4) (X = Halogenid, 2X = Oxalat, Malonat; L = α-Aminosäureester, Peptidester) wird aus PtX42- und L erhalten. Entsprechende Komplexe mit Dipeptidester-Liganden sind auch durch Peptidsynthese am Komplex aus Cl2Pt-(NH2CHRCO2H)2 und α-Aminosäureestern mit Carbodiimid als Kupplungskomponente und Platin als Aminoschutzgruppe zugänglich. Die Verbindungen Cl2PtL2 mit α-Aminosäureester-Liganden lassen sich auch aus den Bis(chelat)-Komplexen cis-Pt(NH2CHRCO2)2 und Alkohol in Gegenwart von HCl gewinnen. Die cis-Struktur der Verbindungen wurde spektroskopisch, die von Cl2Pt(GlyGlyOEt)2 (2a) durch Röntgenstrukturanalyse nachgewiesen.
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  • 4
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chiral Dicarbonyl(η5-cyclopentadienyl) Complexes of Molybdenum and Tungsten with Anions of α-Amino AcidsA series of chiral complexes (η5-C5H5)M(CO)2(L-L′) (M = Mo, W; L-L′ = Gly-O, Sar-O, Me2Gly-O, L-Ala-O, 2-Me-L-Ala-O, L-Val-O, L-Ser-O, L-Thr-O, L-His-O, L-Phe-O, Bzl-L-Phe-O, L-Pro-O, S-Me-L-Cys-O, L-Lys-O, L-Glu-O, L-Cys-O, L-Pen-O) (1a-t, 2a, b, 3, 4) has been prepared and spectroscopically characterized. The diastereomers can be distinguished by their 1H and 13C NMR spectra. They are configurationally stable in solution. The sarcosinato complex 1b can be resolved into the diastereomeric pairs of enantiomers. In alkaline medium a rapid equilibrium of the diastereomers (1:1) is obtained due to isomerization at the coordinated N-atom. The structure of the DL-serinato complex 1i has been determined by X-ray analysis. The unit cell contains two pairs of enantiomers (RMoRC and SMoSC).
    Notes: Eine Reihe von chiralen Komplexen (η5-C5H5)M(CO)2)(L-L′) (M = Mo, W; L-L′ = Gly-O, Sar-O, Me2Gly-O, L-Ala-O, 2-Me-L-Ala-O, L-Val-O, L-Ser-O, L-Thr-O, L-His-O, L-Phe-O, Bzi-L-Phe-O, L-Pro-O, S-Me-L-Cys-O, L-Lys-O, L-Glu-O, L-Cys-O, L-Pen-O) (1a-t, 2a, b, 3, 4) wurde dargestellt und spektroskopisch charakterisiert. Die Diastereomeren lassen sich durch ihre 1H- und 13C-NMR-Spektren unterscheiden. Sie sind in Lösung konfigurationsstabil. Der Sarkosinato-Komplex 1b läßt sich in die diastereomeren Enantiomerenpaare trennen. In alkalischem Medium stellt sich infolge Isomerisierung am koordinierten N-Atom das Diastereomerengleichgewicht 1:1 ein. Die Struktur des DL-Serinato-Komplexes 1i wurde röntgenographisch bestimmt. Die Elementarzelle enthält zwei Enantiomerenpaare (RMoRC und SMoSC).
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1729-1743 
    ISSN: 0009-2940
    Keywords: Antibiotics, aminoglycoside ; Sannamine building blocks ; Aminoglycosides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminoglycosid-Antibiotika - Enantiomerenreine Sannamin-BausteineAusgehend vom prochiralen Dianhydrodesoxy-epi-inosit 9 wurde eine leistungsfähige Synthese für enantiomerenreine rac-Sannamine (1, Salze, Derivate) und rac-Des-O-methylsannamin (18, Salz) ausgearbeitet. Essentielle Schritte sind zwei regiospezifische, praktisch quantitative Epoxidöffnungen: Intramolekular in den Diepoxyurethanen 11 und intermolekular in den Epoxyurethanen rac-13. Mit (R)-1-Phenylethylamin als potentieller primärer Aminogruppe im zweiten Schritt gelingt die Diastereomerentrennung (16, 16′) ohne signifikante Verluste. Es werden direkt enantiomerenreine (Des-O-methyl)Sannamin-Derivate gewonnen, in welchen alle Substituenten bis auf die zu glycosidierende OH-Gruppe geschützt sind. Versuche zur asymmetrischen Durchführung der Synthese brachten nur bescheidene ee(de)-Werte.
    Notes: Starting from the prochiral dianhydrodeoxy-epi-inositol 9 a highly efficient synthesis for rac-sannamines (1, salts, derivatives) and rac-de-O-methylsannamine (18, salt) has been developed. Key steps are two regiospecific, practically quantitative epoxide opening reactions: intramolecularly in the diepoxyurethanes 11 and intermolecularly in the epoxyurethanes rac-13. With (R)-1-phenyl-ethylamine as potential primary amino group in the second step separation of the corresponding diastereomers (16, 16′) is achieved without significant loss of material. By this route enantiomerically pure (de-O-methyl)sannamines become available in which all functionalities are protected except that to be glycosidated. Attempts for an asymmetric realization of this synthesis resulted in only very small ee(de) values.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 1745-1755 
    ISSN: 0009-2940
    Keywords: Antibiotics, aminoglycoside ; Sporamine building blocks ; Aminoglycosides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminoglycosid-Antibiotika - Enantiomerenreine Sporamin-BausteineAusgehend vom 1,2:4,5-Dianhydro-epi-desoxyinosit 2a (letztlich erhältlich aus Benzol) wurde eine leistungsfähige Synthese für rac-Sporamin (rac-3) entwickelt. Zentrale Schritte sind zwei regiospezifische, praktisch quantitative Epoxidöffnungen, intramolekular beim Diepoxyurethan 2b und intermolekular mit Kaliumiodid bei den Epoxyurethanen rac-4, sowie eine gleichermaßen einheitliche Substitution in dem Iodid rac-5d durch Hexa(tetra)alkyl-guanidiniumazid. Die Trennung diastereomerer (-)-Camphansäureester (19/19′) eröffnet einen Zugang zu den reinen Enantiomeren 3/ent-3. Der Syntheseweg erlaubt chemische Modifizierungen und führt zu Sporamin-Äquivalenten, in welchen nur die letzt-endlich zur Glycosidierung vorgesehene OH-Gruppe ungeschützt bleibt.
    Notes: Starting from the 1,2:4,5-dianhydro-epi-deoxyinositol 2a (available ultimately from benzene) and expedient total synthesis of rac-sporamine (rac-3) has been developed. Key steps are two regiospecific and quantitative epoxide openings, effected intramolecularly in the diepoxyurethane 2b and intermolecularly by potassium iodide in the epoxyurethanes rac-4, and the equally uniform substitution in the iodide rac-5d by hexa(tetra)methylguanidinium azide. The separation of diastereomeric esters with (-)-camphanic acid (19/19′) opens the way to the pure enantiomers 3/ent-3. The scheme allows chemical modifications and provides sporamine equivalents in which only the OH group to be ultimately glycosidated remains unprotected.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 1207-1211 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Reaction of Bis(η5-Cyclopentadienyl)(1,2,3-triphenyltriphosphane-1,3-diyl)zirconium(IV), , with Ethyl Diazoacetate (Cp = η5-C5H5)The reaction of bis(η5-cyclopentadienyl) (1,2,3-triphenyltriphosphane-1,3-diyl)zirconium(IV), (1), with ethyl diazoacetate leads to insertion into both Zr—P bonds with formation of (2), which contains the novel 1,2,3-triphenyltriphosphane-1,3-bishydrazonido(2 -) ligand. The 31P-NMR spectrum shows that only the meso isomer of the P3Ph3 fragment is present in solution. The crystal structure analysis shows this, too, as well as the η2-bonding mode of both N,N′ units to the zirconium atom.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 2039-2044 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation, Vibrational Spectrum, and Crystal Structure of Dimeric (Isopropylideneamino) dimethylindiumThe title compound [Me2C=N—InMe2]2 was prepared from N-chloro-2-propanimine and trimethylindium. Its IR and Raman spectra were assigned; together with the 1H-NMR spectrum and the mass spectrum a centrosymmetric molecular structure with a four-membered (InN)2 ring was deduced. This was confirmed by an X-ray structure determination, according to which there exist two dimeric molecules per unit cell in the space group P21/c. The structure was refined with 958 reflexions up to a residual index of R = 0.024.
    Notes: Die Titelverbindung [Me2C=N-InMe2]2 wurde aus N-Chlor-2-propanimin und Trimethylindium synthetisiert. Das IR-und Raman-Spektrum wurde zugeordnet; zusammen mit dem 1H-NMR- und dem Massenspektrum ergibt sich eine zentrosymmetrische Molekülstruktur mit einem (InN)2-Vierring. Dies wird durch die Röntgenstrukturbestimmung bestätigt, nach der eine Struktur mit zwei dimeren Molekülen pro Elementarzelle in der Raumgruppe P21/c vorliegt. Die Struktur wurde bis zu einem Übereinstimmungsindex von R = 0.024 für 958 Reflexe verfeinert.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 1603-1611 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Bile Pigments, X. Synthesis and Photoisomerization of Racemic Phytochromobilin Dimethyl EsterPhytochromobilin dimethyl ester (5) which can be isolated from plant chromoprotein phytochrome, but hitherto in insufficient quantities for the elucidation of its structure, has been prepared by total synthesis and fully characterized. On irradiation of 5, dissolved in benzene, only change of configuration at the ethylidene group takes place yielding the thermodynamic unstable Z-isomer 6. Under the same conditions, phycocyanobilin dimethyl ester can also be photoisomerized to its Z-isomer.
    Notes: Phytochromobilin-dimethylester (5), der aus pflanzlichem Phytochrom bisher nur in für die Aufklärung seiner Konstitution unzureichenden Mengen isoliert werden kann, wurde totalsynthetisch dargestellt und eindeutig charakterisiert. Bei Bestrahlung von 5 in benzolischer Lösung findet lediglich Konfigurationswechsel an der Ethyliden-Gruppe unter Bildung des thermodynamisch labilen Z-konfigurierten Isomeren 6 statt. Unter gleichen Bedingungen läßt sich Phycocyanobilin-dimethylester ebenfalls in sein Z-Isomeres photoisomerisieren.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 580 (1990), S. 18-26 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structures of [ReCl4(PhC≡CPh)]2 · 2 CH2Cl2 and PPh4[ReOCl4]Single crystals of [ReCl4(PhC≡CPh)]2 · 2 CH2Cl2 were obtained by chilling dilute solutions of the solvate [ReCl4(PhC≡CPh)POCl3] in CH2Cl2. PPh4[ReOCl4] was formed by the reaction of the diphenyl acetylene complex [ReCl5(PhC≡CPh)] with PPh4Cl · H2O in CH2Cl2 solution.[ReCl4(PhC≡CPh)]2 · 2 CH2Cl2: space group P21/c, Z = 2, 2244 observed independent reflexions, R = 0.038. Lattice parameters (19°C): a = 987.2 pm; b = 1533.9 pm; c = 1193.8 pm; β = 90.17° The compound forms centrosymmetrical dimeric molecules with ReCl2Re bridges with Re—Cl distances of 241.2 and 267.6 pm. The longer Re—Cl bond is situated in trans-position to the equatorial, side-on coordinated diphenyl acetylene ligand with mean Re—C distances of 200 pm.PPh4[ReOCl4]: space group P4/n, Z = 2, 1487 observed, independent reflexions, R = 0.047. Lattice parameters (19°C): a = b = 1272.0 pm; c = 771.3 pm. The compound crystallizes in the AsPh4[RuNCl4] type; it consists of [ReOCl4]- anions and PPh4+ cations. The anions are tetragonal with C4v symmetry and bond lengths Re—O = 165.4 pm and Re—Cl = 232.6 pm; the bond angle OReCl is 106.7°.
    Notes: Einkristalle von [ReCl4(PhC≡CPh)]2 · 2 CH2Cl2 wurden aus verdünnten Lösungen des Solvats [ReCl4(PhC≡CPh)(POCl3)] in CH2Cl2 durch Abkühlen erhalten. PPh4[ReOCl4] entstand durch Umsetzung des Diphenylacetylenkomplexes [ReCl5(PhC≡CPh)] mit PPh4Cl · H2O in CH2Cl2-Lösung.[ReCl4(PhC≡CPh)]2 · 2 CH2Cl2: Raumgruppe P21/c, Z = 2, 2244 unabhängige beobachtete Reflexe, R = 3,8%. Gitterkonstanten (19°C): a = 987,2; b = 1533,9; c = 1193,8 pm; β = 90,17°. Die Verbindung bildet zentrosymmetrische dimere Moleküle mit ReCl2Re-Brücken mit Re—Cl-Abständen von 241,2 und 267,6 pm. Die lange ReCl-Bindung befindet sich in trans-Position zu dem äquatorial angeordneten, seitlich koordinierenden Diphenylacetylenliganden mit Re—C-Abständen von im Mittel 200 pm.PPh4[ReOCl4]: Raumgruppe P4/n, Z = 2, 1487 unabhängige beobachtete Reflexe, R = 4,7%. Gitterkonstanten (19°C): a = b = 1272,0; c = 771,3 pm. Die Verbindung kristallisiert im AsPh4[RuNCl4]-Typ; sie besteht aus PPh4+- und [ReOCl4]--Ionen. Die Anionen haben C4v-Symmetrie mit Abständen ReO = 165,4 pm und ReCl = 232,6 pm bei einem OReCl-Bindungswinkel von 106,7°.
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