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  • Analytical Chemistry and Spectroscopy  (7)
  • Life and Medical Sciences  (2)
  • 1-phosphabicyclo[4.3.0]nonanes  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 6 (1974), S. 568-573 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The geometric factor G [G = (3 cos2 θ -1) r-3] of selected protons relative to a centre of co-ordination [Eu(dpm)3] is determined using Dreiding models of different conformers of 1,3-aza- and 1,3-oxaphospholanes. The centre of co-ordination is supposed to be joined to the oxygen of the carbonyl group or to the nitrogen and oxygen in the hetero-ring, respectively. The graphs of the geometric factors against the paramagnetic shifts of the relevant protons are straight lines only for the preferred conformers on the basis of a correct centre of co-ordination.As a measure for the paramagnetic shift of a proton the slope of the graph of chemical shift against the concentration of Eu(dpm)3 (in mol %) is chosen. By variation of the relative configuration at C-5 in the models and calculation of the geometric factor, it is possible to determine the different diastereomers, which are distinguished by the relative position of the substituent at phosphorus and C-5.
    Notes: An Dreiding-Modellen der verschiedenen Konformere von 1,3-Aza- und 1,3-Oxaphospholanen werden die Geometriefaktoren G [G = (cos2θ - 1)r-3] einzelner Protonen bezüglich eines Koordinationszentrums [Eu(dpm)3] bestimmt. Das Koordinationszentrum wird entweder an dem Sauerstoff der Carbonylgruppe oder an dem Stickstoff oder Sauerstoff im Heteroring gebunden angenommen. Die graphische Darstellung der Geometriefaktoren gegen die paramagnetischen Verschiebungen der betreffenden Protonen ergibt nur für die bevorzugten Konformere bei Zugrundelegung der richtigen Koordinationszentren Geraden. Als Maßzahl für die paramagnetische Verschiebung eines Protons wird die Steigung der Geraden gewählt, die sich beim graphischen Auftragen der chemischen Verschiebung gegen den Gehalt an Eu(dpm)3 (in Mol-%) ergibt. Durch Variation der relativen Konfiguration am C-Atom 5 an den Modellen und Berechnung der Geometriefaktoren ist es möglich, die unterschiedlichen Diastereomere zuzuordnen, die sich bezüglich der Substituentenstellung am Phosphor und am C-Atom 5 unterscheiden.
    Additional Material: 2 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 5 (1973), S. 401-402 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1H and 31P—NMR parameters are reported for dimethyl-aminomethylene phosphoranes (1 to 4). The reaction of \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{\left\{ {\left({{\rm CH}_{\rm 3} } \right)_2 {\rm N}} \right\}_3 {\rm P - CH}_{\rm 2} {\rm - CH}_{\rm 3} } \right]{\rm Br} $\end{document}with NaNH2 gives 4.
    Notes: Es Werden die 1H- und 31P—NMR-Spektren der Dimethylamino methylen-phosphorane mitgeteilt und ein einfaches Herstellungsverfahren für 4 beschricben.
    Additional Material: 2 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 7 (1975), S. 470-474 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The diastereomers of 16 1,3-oxa-, 1,3-aza- and 1,3- thiaphospholanes were assigned by means of the coupling constants 2J(P—C—H) and 3J(P—C—CH3) and the linewidths of the 31P signals and 1H chemical shifts of CH3 groups. It is shown that the change in the 31P chemical shifts allows the estimation of the relative configuration in these compounds.
    Notes: Die Diastereomeren von 16 1,3 Oxa-, 1,3-Aza-und 1,3-Thiophospholanen wurden mit Hilfe der Kopplungs-konstanten 2J(P—C—H) und 3J(P—C—CH3), der Signalbreite der 31P-Signale und der 1H-chemischen Verschiebungen der CH3-Gruppen zugeordnet. Es wird gezeigt, daß auch die 31P-chemischen Verschiebungen eine Bestimmung der relativen Konfiguration dieser Verbindungen gestatten.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 7 (1975), S. 478-484 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1H NMR chemical shifts of 18 methyl substituted cyclohexane-1,2-dicarboxylic anhydrides were determined. In compounds with asymmetric substitution vicinal coupling constants were measured. In the series of trans-anhydrides it can be deduced from the NMR data, that the 6-membered ring has a chair-like conformation. Additionally, in the series of the cis-anhydrides a twisted chair conformation is favoured for the most part.
    Notes: Die chemischen Verschiebungen der 1H-NMR-Spektren von 18 methylsubstituierten Cyclohexandicarbonsäure-(1,2)-anhydriden wurden bestimmt. Von den unsymmetrisch sub-stituierten Verbindungen wurden die vicinalen Kopplungskonstanten ermittelt. Bei den trans-Anhydriden lässtsich aus den NMR-Daten ableiten, dass der Sechsring in einer sesselähnlichen Form vorliegt. Auch bei den cis-Anhydriden sind in den meisten Fällen Konformationen mit verdrillter Sesselanordnung des Cyclohexans bevorzugt.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 5 (1973), S. 119-124 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The chemical shifts of methyl protons of 51 methyl and tert-butyl substituted cyclohexanes were determined. The resonance range of axial methyls extends from δ = 0,63 to 0,98 ppm and equatorial groups from δ = 0,81 to 1,02 ppm. the chemical shifts of axial methyl groups are more greatly influenced by neighbouring groups than those of equatorial methyls. The shift effects of alkyl groups on the chemical shifts of methylprotons and ring protons were compared.
    Notes: Die chemischen Verschiebungen der Alkylprotonen von 51 methyl- und tert-butyl-substituierten Cyclohexanen wurden bestimmt. Der Resonanzbereich axialer Methyl-gruppen erstreckt sich von δ = 0,63 bis 0,98 ppm, der von äquatorialen von δ = 0,81 bis 1,02 ppm. Die chemischen Verschiebungen axialer Methylgruppen werden durch Nachbargruppen stärker beeinflusst als die der äquatorialen Methylgruppen. Die Shifteffekte von Alkylgruppen auf Methylprotonen werden mit denen auf Ringprotonen verglichen.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 5 (1973), S. 179-186 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemical shifts and coupling constants of methyl substituted 4-cyclohexene-1,2-dicarboxylic anhydrides were determined. The NMR data demonstrate the boat conformation of the cis-anhydrides. The orientation of the cis-anhydride ring relative to the cyclohexene boat depends on the constitution and configuration of the compounds, and can be deduced from coupling constants and δ-values of the H1- and H2-protons. Methyl groups in the neighbourhood of these protons shift the resonance frequencies dependent upon molecular conformation.
    Notes: Es wurden die chemischen Verschiebungen und Kopplungskonstanten von methylsubstituierten Cyclohexen-(4)-dicarbonsäure-(1,2)-anhydriden bestimmt. Die NMR-Daten beweisen die Bootkonformation der cis-Anhydride. Die Orientierung des cis-Anhydridringes relativ zum Cyclohexenboot wird durch die Konstitution und Konfiguration der Verbindungen bestimmt und kann von den Kopplungskonstanten und den δ-Werten der H1- und H2-Protonen abgeleitet werden. Methylgruppen in Nachbarschaft zu diesen Protonen verschieben die Resonanzfrequenzen in Abhängigkeit von der konformativen Anordnung.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 21 (1983), S. 315-318 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The analysis of the 1H NMR spectra of 2,8-dithia-1,5-diphosphabicyclo[3.3.0]octane, 2,8-dithia-1-phospha-5-azabicyclo[3.3.0]octane and 2,8-dithia-1-arsa-5-phosphabicyclo[3.3.0]octane is supported by means of 2D- J-resolved NMR measurements. The spectra suggest a preferred conformer with strong puckering of the fused five membered rings.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, N.Y. : Wiley-Blackwell
    Journal of Cellular Biochemistry 23 (1983), S. 203-209 
    ISSN: 0730-2312
    Keywords: cell cycle ; cytoplasmic plasma membrane surface ; control of cell proliferation ; proadipocyte stem cells ; Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Two proteins which are localized to the cytoplasmic surface of the plasma membrane, p14 and p24, undergo cyclic AMP-dependent phosphorylation in rapidly growing nontransformed murine embryo cells. In this cell system, growth arrest in the G1 phase of the cell cycle induced by growth factor deprivation is associated with the reversible loss in ability to phosphorylate these substrates. By contrast Simian virus 40 and methylcholanthrene transformed cells show both defective G1 growth control and defects in their ability to phosphorylate p14 and p24 under all tested growth conditions. These data suggested a correlation between defects in the physophorylation of p14 and p24 and defects in the ability of transformed cells to G1 growth arrest. The results of the current studies by contrast show that 3T3 T proadipocytcs which have been transformed by the smooth surface tumorigenesis method show different characteristics. They retain the ability to G1 growth arrest in serum-deficient medium. They show cyclic AMP-dependent phosphorylation of p14 and p24 during exponential growth. They do not, however, down regulate p14 and p24 phosphorylation in association with G1 growth arrest. These observations suggest that neoplastic transformation is not necessarily associated with absolute defects in the ability to phosphorylate p14 and p24. Rather, the results of the current study suggest that the inability to modulate the cyclic AMP-dependent phosphorylation of plasma membrane p14 and p24 proteins during the G1 phase of the cell cycle may be more tightly associated with neoplastic transformation.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 600 (1991), S. 195-202 
    ISSN: 0044-2313
    Keywords: Intramolecular hydrophosphorylation ; bicyclic organophosphorus compounds ; 1-phosphabicyclo[4.3.0]nonanes ; conformational analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cis-1-Phosphabicyclo[4.3.0]nonanecis-1-Phosphabicyclo[4.3.0]nonane has been synthesized by free-radical cyclization of 4-phophino-octa-1.7-diene. The bicyclic phosphine is characterized by reactions with CS2, Ni(CO)4, HSO3F, CH3I, H2O2, sulfur, and selenium, respectively. The determination of the relative configuration of the phosphine is done by a qualitative conformational analysis from the 13C n.m.r. data.
    Notes: Durch radikalische Cyclisierung von 4-Phosphino-octa-1,7-dien erhält man cis-1-Phosphabicyclo [4.3.0]nonan, das durch Reaktionen mit CS2, Ni(CO)4, HSO3F, CH3I, H2O2, Schwefel und Selen charakterisiert wird. Die Bestimmung der relativen Konfiguration des Phosphins erfolgt durch eine qualitative Konfigurationsanalyse aus den 13C-NMR-Daten.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Cellular Physiology 121 (1984), S. 357-367 
    ISSN: 0021-9541
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Medicine
    Notes: The plasma membrane of 3T3 cells contains at least two different endogenous cyclic AMP-dependent protein kinase systems. One catalyzes the phosphorylation of endogenous protein substrates, i.e., PP24 and PP14, whereas the other catalyzes the phosphorylation of exogenous substrates. In this paper the topography of these cyclic AMP-dependent phosphorylation systems is described. The results show that the kinases which phosphorylate only exogenous substrates are primarily localized to the outer plasma membrane surface whereas the endogenous cyclic AMP-dependent protein kinase and its two endogenous substrates are localized to the cytoplasmic plasma membrane surface. The data also establish that neither the cytoplasmically orientated kinase nor its substrates has a transmembrane orientation even though factors acting on the outer plasma membrane can affect these proteins. This suggests that functional modulation of the cytoplasmically localized cyclic AMP-dependent phosphorylation system can be mediated by a transmembrane regulatory mechanism. The importance of determining the topography of such plasma membrane phosphorylation systems is emphasized by recent studies which show that neoplastic transformation can be mediated at least in part by protein kinases and/or phosphoproteins which are localized on the cytoplasmic surface of the plasma membrane.
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