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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 623 (1959), S. 9-16 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diisobutyl-aluminiumhydrid und Aluminiumtriisobutyl verhalten sich aromatischen und α.β-ungesättigten Aldehyden sowie Chloral und ω-Trichlor-acetophenon gegenüber wie Mischungen von Aluminiumhydrid und Isobutylen: Je Aluminiumatom werden 3 Moleküle der Carbonylverbindung reduziert. Dialkyl-aluminiumhydride mit normalen Resten reagieren den gleichen Stoffen gegenüber fast stets (Ausnahme: Chloral) nur mit ihrer A1 - H-Gruppe. Ketone, Carbonsäureester, Nitrile und Schiffsche Basen reagieren in allen Fällen nur mit der einen Al - H-Bindung der Dialkyl-aluminiumhydride. Aluminiumtriisobutyl verhält sich den gleichen Stoffen gegenüber wie eine Mischung von Isobutylen und Diisobutyl-aluminiumhydrid. Alle diese Reaktionen sind denen des LiAlH4 analog.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclohepten-(1)-yl-, Cycloocten-(1)-yl- und Cyclononen-(1)-yl-äthylamin (1, X = NH2, n = 5-7) ergeben bei der Desaminierung mit salpetriger Säure unter Beteiligung der Doppel-bindung neben anderen Produkten die Cyclopropan-spiroalkohole 2 (Y = OH) und die Cyclobutanole 3 (Y = OH). Das Verhältnis von 2 zu 3 wird vom pH-Wert der Reaktionslösung bei der Desaminierung bestimmt. Cycloalken-(1)-yl-äthyltosylate (1, X = OSO2C6H4CH3-p) solvolysieren in Aceton/Wasser (20 : 80) bevorzugt zu den Cyclopropan-spiroalkoholen 2 (Y = OH). Der Mechanismus der Isomerisierung wird anhand der genauen Produktanalysen dieser Reaktionen sowie der Produkte diskutiert, die bei Solvolysen von Cyclopropanspiro- 2 und kondensierten Cyclobutan-Derivaten 3 erhalten werden. Die Nachbargruppen-Wirkung der Doppelbindung wird mit Hilfe kinetischer Methoden am Cyclohexen-(1)-yl-äthyltosylat untersucht. Die Aktivierungsenthalpien und -entropien bei der Solvolyse des Cyclohexen-(1)-yl-äthyltosylates in 30-, 50- und 70 proz. Aceton unterscheiden sich nur wenig. Dagegen ergibt das gesättigte Vergleichssystem in 30 proz. Aceton eine stärker negative Entropie. Der Vergleich der Solvolyse-Geschwindigkeiten sowie der Aktivierungs-parameter läßt den Schluß zu, daß die Nachbargruppen-Wirkung der Doppelbindung primär eine Verschiebung zu einer SN 1-Reaktion hin bewirkt. Dies wird durch systematische Messungen der Hydrolyse-Geschwindigkeiten in Lösungsmitteln verschiedener Ionisierungsstärke bestätigt (Tab. 5). Die Solvolyse-Konstanten von bicyclischen Cyclopropylmethyl- und Cyclobutyl-p-nitrobenzoaten zeigen die erwartete nichtklassische Stabilisierung der entsprechenden Carbonium-Ionen an.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 722 (1969), S. 234-236 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Automatic Acidimetric Procedure for Measuring Rates of SolvolysisA method for the continuous determination of reaction rates by means of an automatic titrator is described (figure 1). The scope of the technique as well as its precision and accuracy are discussed (figure 2).
    Notes: Zur kontinuierlichen Reaktionsgeschwindigkeitsbestimmung dient ein pH-Stat (Abb. 1). Die Anwendungsbreite des Verfahrens sowie Reproduzierbarkeit und Fehler werden dargestellt (Abb. 2).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1975 (1975), S. 1690-1699 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mode of Formation and Solvolyses of Tertiary 2-Bicyclo[2.2.l]heptyl EstersPreparation and solvolyses of the tertiary chlorides obtained by hydrogen chloride addition to 2-methylenenorbornane, camphene, and α- and β-fenchene are discussed. Neither these reactions nor reinvestigated reactions with fenchyl chlorides yielded any tertiary endo chlorides. The solvolysis results with p-nitrobenzoates of β-fenchene hydrates and other tertiary alcohols can be rationalized by intramolecular steric interactions without invoking charge delocalized intermediates.
    Notes: Darstellung und Solvolysen der aus 2-Methylennorbornan, Camphen, α- und β-Fenchen erhaltenen tertiären Chloride werden beschrieben. endo-Chloride konnten in keinem Fall nachgewiesen werden, auch nicht bei der Neuuntersuchung früher beschriebener Reaktionen mit Chloriden der Fenchanreihe. Die Solvolyseergebnisse mit den p-Nitrobenzoaten von endo- und exo-β-Fenchenhydrat und anderen epimeren p-Nitrobenzoaten lassen sich ohne Annahme ladungsdelokalisierter Zwischenstufen durch intramolekulare sterische Wechsel- wirkungen verstehen.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 66 (1983), S. 1101-1109 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Peptidic model conjugates carrying a single 2-carboxy-4,6-dinitrophenyl haptenic group, and as carbohydrate moieties D-gluconoyl, β-D-mannopyranosyl, 2-deoxy-β-D-glucopyranos-2-yl, or lactobionoyl residues, including the pseudocarbohydrate residue 1,3,4,5-tetrahydroxycyclohexane-1-carbonyl, were synthesized. Conjugates carrying the lactobionoyl of the bis(2-deoxy-β-D-glucopyranos-2-yl) moiety were anaphylactogenic in the guinea pig, passively sensitized against 2-carboxy-4,6-dinitrophenyl antigen.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Selected oligo-L-lysine carriers and a poly-L-lysine were penicilloylated with benzylpenicillin. The resulting conjugates 2-6 were studied by IR. absorption in the solid state and circular dichroism measurements in solution. The IR. data demonstrate the lack of β-structure formation even in medium-sized peptides where such structures might be expected on the basis of previous studies on differently substituted oligo-L-lysines. Considerable proportions of right-handed α -helical conformation are exhibited by the icosa-L-lysine and poly-L-lysine conjugates 5 and 6 in water and 2,2,2-trifluoroethanol. Difficulties in obtaining fully penicilloylated conjugates are not related to the extent of α-helical conformation in aqueous solution.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 67 (1984), S. 1000-1002 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nα-L-Iysine with a 2-carboxy-4, 6-dinitrophenyl (Dncp) haptenic group on the ε-amino function is a potent anaphylactogen in the guinea pig. We prepared Nε -Dncp- Nα-benzoly-L-Iysinamide and Nε-Dncp-Nα-benzoyl-L-lysyl-1-aminopropane where the carboxyl group of Iysine is blocked. Both compounds were non-elections of anaphylaxis.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This study involves L-lysine oligo peptides, protected at the N-terminus by the Nps and at the ε-amino functions by Boc groups. Two series were prepared from dimer to octamer, one containing the p-[(cholestan-3β-yloxy)carbonyl]benzyl, the other one the benzyl ester group at the C-terminus. Conformational analyses were performed by IR absorption. The occurrence of the intermolecular β-structure in the solid state and in CH2Cl2 solution was demonstrated for the highest oligomers. The relative stabilities of the self-associated species were determined by adding a variety of polar solvents to the CH2Cl2 solutions. The cholestanyl-containing peptides have a lower propensity to self-aggregate than the benzyl-ester analogues. Self-aggregation and decreasing solubility run in parallel. It was also directly shown that soluble urea derivatives may disrupt intermolecular H-bonds in CH2Cl2, a point of practical interest, particularly in solid-phase peptide synthesis.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiomerically pure β-necrodol (1) and its 1-epimer 16 have been synthesized starting from aldehyde 5. The two key steps are an asymmetric conjugate addtion/Mannich reaction tandem (10→12) and a type-II-magnesiumene cyclization/oxidation sequence (14→1 + 16).
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 196-202 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lipstatin (1), a natural product, and tetrahydrolipstatin (2) are pancreatic lipase inhibitors. Non-stereoselective and partially stereoselective syntheses of 2 are used to establish the absolute configuration of tetrahydrolipstatin and lipstatin.
    Type of Medium: Electronic Resource
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