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  • Organic Chemistry  (487)
  • Wiley-Blackwell  (487)
  • 1995-1999  (72)
  • 1990-1994  (206)
  • 1980-1984  (169)
  • 1945-1949  (40)
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 332 (1990), S. 367-374 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations on Regioselectivity of Wittig-Horner and Reformatsky-Reactions on Selected 3,17-Dioxo SteroidsThe Reformatsky synthesis and the Wittig-Horner olefination of 3,17-dioxo steroids like androsta-1,4-diene-3,17-dione (ADD) 1 and androst-4-ene-3,17-dione (AD) 2 is described. There are differences in the regioselective introduction of identical substructures with these two methods resulting from different nucleophilicity and stereoelectronical relations of these two reagents. In Reformatsky synthesis the oxo group in 3-position predominantly reacts, whereas in the Wittig-Horner olefination (in the case of 1) the reaction occurs mainly in the 17-position.The structures of all new compounds has been confirmed by spectroscopical data.
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  • 2
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pure pencillin N α-sulfoxide (1) and penicillin N β-sulfoxide (2) were obtained by HPLC and tested as substrates for deacetoxycephalosporin C synthetase (DXCS). Neither one of the sulfoxides was utilized under conditions of conversion of penicillin N (8) to deacetoxycephalosporin C (9). The cephalosporin C α and β-sulfoxides (3 and 4, resp.) were also prepared. Relative stabilities of the sulfoxides 3 and 4 are discussed by interpretation of the 13C-NMR spectra.
    Additional Material: 9 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 10 (1998), S. 262-272 
    ISSN: 0899-0042
    Keywords: airway ; beta2-agonist ; racemic ; eutomer ; distomer ; hyperreactivity ; bronchospasm ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Airways of asthma patients can become hyperresponsive to airway spasmogens following regular use of isoprenaline or β2-selective sympathomimetics. Hyperreactivity that results from acute exposure of animals to these drugs is pre-empted by vagal section (a procedure which does not influence spasmolytic efficacy of sympathomimetics), is not diminished by antagonism of β2-adrenoceptors and is not associated with loss of responsivity of β2-adrenoceptors in the airways. Since activation, modulation, or blockade of β2-adrenoceptors does not determine this form of hyperreactivity, the possibility that distomers may induce hyperreactivity must be considered. Ocular and vascular responses to distomers of sympathomimetics have long been recognised and, more recently, comparable observations have been made for the airways. Thus, reactivity of guinea-pig airways to spasmogens was increased following exposure to S-isoprenaline, S-salbutamol, or S-terbutaline and exposure to S-isoprenaline or S-salbutamol can intensify symptoms in asthmatics. Regular exposure to the racemate, especially during or following an allergic reaction, predisposes to expression of hyperreactivity, which is nullified, acutely, by the eutomer. These observations imply that biological effects of sympathomimetic distomers may contribute to morbidity and mortality in asthma patients. Chirality 10:262-272, 1998. © 1998 Wiley-Liss, Inc.
    Additional Material: 3 Ill.
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  • 4
    ISSN: 0899-0042
    Keywords: gastroprokinetic ; serotonin receptors ; 5-HT3 receptors ; guinea pig ileum ; single-crystal X-ray ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rac-ML-1035 (MDL 201,035: 4-amino-5-chloro-2-[2-(methylsulfinyl)ethoxy] -  N-[2-(diethylamino)ethyl] benzamide hydrochloride) is a racemic gastroprokinetic with serotonergic (5-hydroxytryptamine, 5-HT) activity and a novel chiral sulfoxide substituent. Chromatographic and chemical methods have been developed to resolve the enantiomers of rac-ML-1035, and the absolute configuration of the (R)-enantiomer has been determined. We also report pharmacological characterization of rac-ML-1035 and its respective isomers. Radioligand binding to rat cortical membranes revealed that (R)-ML-1035 (MDL 201,226) and (S)-ML-1035 (MDL 201,227) had equivalent activity at the 5-HT3 receptor. However, in isolated tissue studies including field-stimulated guinea pig ileum, field-stimulated rat fundic strip, and nonstimulated guinea pig ileum, (S)-ML-1035 was equally potent yet had greater maximal activity than (R)-ML-1035 in eliciting or facilitating cholinergic contractions. Thus, enantiomers of rac-ML-1035 can be resolved, and the relative configuration of these isomers influences their pharmacological activity. © 1992 Wiley-Liss, Inc.
    Additional Material: 6 Ill.
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  • 5
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been established that the product of the reaction of N-pentafluorophenylcarbonimidoyl dichloride (1) with dibenzylamine, viz. N2-pentafluorophenyl-N1,N1-dibenzylchloroformamidine (4a) is a Z-isomer, whereas according to the concept of stereoelectronic control one might have expected a product with E-configuration. The heat of formation and the geometry of Z- and E isomer of N2-pentafluorophenyl-N1,N1-diethylchloroformamidine (4b) (the latter is a product of the reaction of 1 with diethylamine) were calculated with the semi-empirical MNDO method. The calculated geometry of (Z)-4b was found to be in a good agreement with the experimentally determined structure of 4a. The formation of (Z)-4b is more preferable energetically than that of (E)-4b; the calculated difference in the heats of formation is 2·8 kcal mol-1. Thermodynamic control of the reaction stereochemistry is proposed.
    Additional Material: 1 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 26-30 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Slight structural moiecular variations are known to affect different properties of compounds. In solution, different solute-solvent interactions are known also to alter the properties of numerous compounds. Quantitative structure-activity relationships (QSAR) are used regularly to analyze and predict the variations of different properties of compounds that are caused by structural variations and significant solute-solvent interactions. The relative basicities of n-propylamine, dipro;ylamine and tripropylamine were determined in nine different solvents from potentiometric titrations. QSAR that were developed from these experimental basicity values were used to evaluate the type and significance of the solute-solvent interactions. The important interactions that influence basicity variations for the propylamines studied are dipolarity-polarizability interaction between the solute and the solvent and hydrogen bonds from the propylammonium ions to basic solvents. The role of hydrogen bonds from the propylamines to acidic solvents is minor.
    Additional Material: 2 Tab.
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  • 7
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The title compounds (1 and 3, respectively) were studied by X-ray crystal structure analysis. Both are trigonal, space group R3, with lattice parameters a = 27.718(6), c = 8.161(2) Å, Z = 3 and a = 31.267(7), c = 6.560(2), Z = 18, respectively. The dodecamethyl compound 1 is isomorphous with its parent hexakis(4-benzylphenoxy)benzene (2), a known host. However, ‘collapse’ along the c-axial direction has occurred such that the appreciable clathrate cavity of 2 has been replaced by only a very small residual void for 1. Phenol 3 does not pack in discrete [OH]6 hydrogenbonded hexamers; instead, molecules are assembled in infinite chains, linked by OH…O hydrogen bonds of length 2.735(3) Å, which are propagated along threefold screw axes. A variable-temperature CPMAS NMR study of sidechain aryl group rotation in 1 gives a value ΔG≠ of 14.0 ± 0.7 kcal mol-1 (at 42 °C) for the (crystallographically unique) para -disubstituted ring, a similar 14 kcal mol-1 free energy barrier being found hindering rotation of this ring, and of the outer phenyl ring of 1, at 9°C.
    Additional Material: 5 Ill.
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  • 8
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Dependence of Fluorescence Quantum Yields of Donor Substituted 4′-Diphenylphosphinyl trans-Stilbenes on Temperature and Viscosity in Low Viscous Solvents of Different PolarityThe dependence of fluorescence quantum yields of donor substituted 4′-diphenylphosphinyl trans-stilbenes 1 on temperature was investigated between 15-65°C in toluene and n-propanol. It is concluded that the fluorescence quantum yield dependence on temperature is due to the dependence of nonradiative deactivation on solvent viscosity. The nonradiative deactivation is attributed to the ethylene bond rotation in 1. The rotation around the ethylenic bond and the fluorescence are the two most important deactivation processes detected up to now for the first excited singlet of 1 in liquid solution.
    Additional Material: 1 Ill.
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  • 9
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hammett Relationships between 1H-NMR and 31P-NMR Chemical Shifts, Respectively, and Substituent Constants in ω-Diphenylphosphinyl and ω-Diphenylthiophosphinyl trans-StyrenesA well linear correlation between the chemical shifts of the ethylenic protons HB and the 31P nuclei, respectively, and the Hammett constants σp of substituents R in 4-position for diphenylphosphinyl trans-styrenes 1 and the analogous diphenylthiophosphinyl trans-styrenes 2 has been found. A similar relationship for the proton HA has been observed in the case of 1 only, but the substituent-induced shifts are not so sensitive. Donor substituents R in 1 and 2 effect an increase in the shielding of HB and a deshielding of the P atom being connected with shifts of the i. r. P=O absorption bands in 1 in the direction of lower wavenumbers. A mesomeric interaction between R and P=Y substituents (Y = O, S) is concluded to produce polymethin-like π-electron density distribution.
    Additional Material: 2 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 325 (1983), S. 881-892 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N.M.R. Spectroscopical Investigations on the Conformational Behaviour of Some 2′ - and 3′-Halogen-substituted Pyrimidine NucleosidesA series of 2′- and 3′-halogenated pyrimidine nucleosides has been synthesized and investigated by 1H, 13C and 19F n.m.r. spectroscopy. The 1H and 13C chemical shifts for the positions 2′ and 3′ depend linearly but oppositely on the substituent electronegativities XR.The conformational equilibrium N ⇌ S of the nucleosides in solution is determined. An approximately linear correlation between the prefered gauche-gauche interaction of the exocyclic CH2OH groups and the ribose N conformation has been found.
    Additional Material: 4 Ill.
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