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  • Organic Chemistry  (5,568)
  • 2010-2014
  • 1985-1989  (3,492)
  • 1950-1954  (2,076)
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  • 1
    Electronic Resource
    Electronic Resource
    A novel oxygen induced reduction of α, β-unsaturated carbonyl compounds by benzeneselenol (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 115-117 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel oxygen induced reduction of α,β-unsaturated carbonyl compounds is discovered. The reduction of the carbon-carbon double bond of α,β-unsaturated carbonyl compounds by benzeneselenol was caused by an introduction of molecular oxygen into the reaction system. This reduction is likely to proceed via a radical chain pathway involving an SH2 type reaction between a phenylseleno radical and a 1,2-adduct of benzeneselenol to the carbonyl group of the α,β-unsaturated carbonyl compound to give an allylic radical which absracts a hydrogen atom from benzeneselenol to form the reduction product.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010207
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  • 2
    Electronic Resource
    Electronic Resource
    ESR studies of photochemical reaction of 2-methyl-3-acetylquinoxaline N,N′-dioxide(MAQO) (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 191-195 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photochemical reaction of MAQO with various aromatic amines were studied by ESR. The results show that nitroxide radicals are stable productrs of the photooxidation of both diphenylamines and phenylamines. The photolyzed phenothiazine does not yield nitroxide as the final product, instead it gives the neutral radical as the stable final product.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010403
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  • 3
    Electronic Resource
    Electronic Resource
    Relative rates of bromination and chlorination of 4-substituted cyclopentenes in methanol, ethanol and acetic acid (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 26-34 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A set of 4-monosubstituted cyclopentenes, , were synthesized and their relative rates (kX/kH) for bromination and chlorination were determined in methanol, ethanol and acetic acid at 25 °C by competitive method. log(kX/kH) for most of the substituents can be correlated by means of Taft's equation, log(kX/kH) = ρI σI + C. In methanol ρI, Br2 = -2·91, ρI, Cl2 = -0·49, in ethanol ρI, Br2 = -3·07, ρI, Cl2 = -0·70 and in acetic acid ρI, Br2 = -1·64, ρI, Cl2 = -0·65. The presence of C(〈0) is due to a constant steric effect. The deviation of X = H is ascribed to the absence of the steric effect and that of X = CO2Me and CO2Et is accounted for in terms of anchimeric assistance. For chlorination no anchimeric assistance was observed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020104
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  • 4
    Electronic Resource
    Electronic Resource
    The cation radical vinylcyclobutane rearrangement (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 57-88 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cation radical vinylcyclobutane (VCB) rearrangement is found to be a reaction of substantial scope, synthetic utility, and exceptional kinetic facility. In conjuction with cation radical cyclobutanation, it constitutes an effective method for net (indirect) Diels-Alder addition to electron rich dienophiles. Reactions can be carried out with either aminium salt or photosensitized electron transfer (PET) initiation and are powerfully facilitated by ionizable substituents such as p-anisyl, phenylthio, and phenoxy at the 2-position of the vinylcyclobutane. The intramolecularity of the reaction is clearly established and in four discrete systems preferred sr (suprafacial/retention) stereochemistry is observed. A theoretical basis for sr stereochemistry in the cation radical VCB rearrangement is advanced. The transition state for the reaction is considered to be similar to that for the direct cation radical Diels-Alder cycloaddition, another cation radical pericyclic reaction which converges on the same product. This model of the VCB rearrangement transition state is used to rationalize the strong rate-retarding effect of a Z-methyl substituent attached to the vinyl group and of a methyl substituent at the 4-position of the vinylcyclobutane ring cis to the vinyl substituent.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020108
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  • 5
    Electronic Resource
    Electronic Resource
    Syntheses, spectroscopic characterization and electronic structure of cyclopropenylidene ligated platinum complexes (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 333-349 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New series of platinum complexes of cyclopropenylidenes of the types of PtX2(CP)2 and trans-PtX(PBu3)2(CP) have been synthesized, where CP is di-t-butylcyclopropenylidene (BCP) or bis(diisopropylamino)cyclopropenylidene (ACP). The 13C-NMR chemical shifts, and 13C-195Pt coupling constants (1JPtC) for the complexes are discussed in comparison with those values derived from closely related series of compounds, trans-PtCl(PR3)2L; L — —CH3, —C6H5 and —C≡CBu-t. An excellent linear relationship through the origin was obtained between 1JPtC and the formal ‘s’ % character of the carbon directly bonded to Pt for the series trans-PtCl(PR3)2L in which the Pt—C bond is regarded as a pure σ-linkage, whereas 1JPtC deviates largely from this relationship when pπ—dπ bonding interaction possibly exists in the Pt—C bond. The NMR data suggest the strong nmr trans-influence of the cyclopropenylidenes and that in the Pt—CP bond the σ-interaction is appreciable but the π-interaction is negligible.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010604
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  • 6
    Electronic Resource
    Electronic Resource
    The ‘dimer mechanism’ in aromatic nucleophilic substitution by amines in aprotic solvents (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 1-14 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanism of aromatic nucleophilic substitutions by amines in protic solvents is well established; on the contrary the mechanism/s of the reactions in aprotic solvents is/are still subject of controversy. The present paper describes several systems for which fourth-order kinetics (third-order in amine) were observed. A mechanism is proposed to account for this as well as other observation such as: overall negative energies of activation, quadratic dependence of kA with non-nucleophilic tertiary bases, spectacular effects of hydrogen-bond donor (HBD) and hydrogen-bond acceptor (HBA) catalysts, etc. Other alternative mechanisms are also discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020102
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  • 7
    Electronic Resource
    Electronic Resource
    Cross interaction constants as a measure of the transition state structure (part III). Mechanism of reactions between 1-phenylethyl benzenesulfonates with N,N-dimethylanilines (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 35-42 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics and mechanisms of the reactions between 1-phenylethyl benzenesulfonates (1-PEB) with N,N-dimethylanilines are investigated in methanol at 35·0°C. Reactivity and selectivity trends were found to be similar to those for the reactions of 1-PEB with anilines, but the magnitudes of cross interaction constants, ρXZ, between substituents X in the nucleophile and Z in the leaving group were substantially smaller indicating no hydrogen-bond bypass bridge formation in the transition state. However, the magnitude of ρXZ suggested a direct electrostatic interaction between the reaction centers in the nucleophile and leaving group in the frontside nucleophilic attack with a loose transition state structure.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020105
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  • 8
    Electronic Resource
    Electronic Resource
    Reassignment of the fundamental vibrations of azetidine from ab initio calculations (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 183-186 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The harmonic vibrational frequencies were calculated analytically at the 6-31** level for azetidine using the GAUSSIAN 82 program. The results strongly indicate the presence of several errors in a recent assignment of the fundamentals of azetidine based on a normal coordinate analysis and a revised assignment is suggested. It is concluded that reliable vibrational data for azetidine in the gas phase are needed in order to resolve the remaining ambiguities in the interpretation of the spectra.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020210
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  • 9
    Electronic Resource
    Electronic Resource
    Masthead (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020201
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  • 10
    Electronic Resource
    Electronic Resource
    Multifunctional catalysis for transamination reaction of α-amino acids with glyoxylic acid in synthetic bilayer memberane (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 110-116 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The transamination reaction of α-amino acids with glyoxylic acid as catalyzed by copper(II) ions was investigated kinetically in an aqueous medium at pH 5·0 and 30·0°C. L-Phenylalanine transferred its amino group to glyoxylic acid most readily among seven different amino acids used here in the single-walled bilayer vesicle formed with N,N-dihexadecyl-Nα-[6-(trimethylammonio)hexanoyl]-L-histidinamide bromide (N+C5His2C16). Such rate enhancement was found to originate from the cooperative trifunctional catalysis: a coordination effect exercised by copper(II) ions, a general acid-base catalysis by the imidazolyl group of the lipid, and a hydrophobic field effect provided by the bilayer vesicle. Lack of any of the three functions failed to give out significant rate enhancement. As regards correlation between the reactivity and the nature of α-amino acids, the copper(II)-catalyzed transamination was progressively enhanced as hydrophobicity of the α-amino acid was increased in the N+C5His2C16 vesicle.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020204
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  • 11
    Electronic Resource
    Electronic Resource
    Masthead (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010301
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  • 12
    Electronic Resource
    Electronic Resource
    Photocyclization of N-Alkyl-N-(3-aryl-3-butenyl) ureas. Hydrogen transfer via charge transfer exciplexes in alkene photochemistry (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 123-131 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photolysis of N-alkyl-N-(3-aryl-3-butenyl) ureas (1) in acetonitrile gave cyclization products, 3-aryl-3-methyl-pyrrolidines, in good yields, whereas irradiation of 1 in methanol afforded methanol adducts as well as the cyclization products. Both the reactions are singlet reactions, and the cyclization is presumed to proceed via 1,6-hydrogen transfer from exciplexes with charge transfer character.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010302
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  • 13
    Electronic Resource
    Electronic Resource
    The Effect of hydrophobic-lipophilic interactions on chemical reactivity. 12. Mechanistic investigations of NaCMA-catalyzed hydrolysis of esters (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 143-151 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependence of the catalytic efficiencies of sodium carboxymethylamylose (NaCMA) for the hydrolysis of N-lauryl-3-acetoxypyridinium iodide (1) and p-nitrophenyl dodecanoate (3) on its degree of substitution (D. S. = 0·00, 0·12, 0·18, 0·24, 0·29 and 0·35) and on the pH values of the solutions (pH = 7·32, 7·80, 8·10 and 9·30) have been studied. At fixed D. S. values, the observed hydrolysis rates of 1 and 3 increase with increasing concentrations of NaCMA and follow saturation kinetics. At fixed concentration of NaCMA, the rates increase with decreasing D. S. values until they reach maxima at D. S. = 0·00. Furthermore, at any D. S. value the catalytic efficiency increases with increasing pH values of the solutions. All these results indicate that the hydroxyl groups are actually the principal catalyzing groups.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010304
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  • 14
    Electronic Resource
    Electronic Resource
    Masthead (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010401
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  • 15
    Electronic Resource
    Electronic Resource
    Participation of beta carbon-silicon bonds in the development of positive charge in five-membered rings (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 169-178 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of positive charge β to silicon in a saturated five-membered ring has been studied in the cis- and trans-2-(trimethylsilyl)cyclopentyl trifluoroacetates. The cis substrate solvolyzes in 97% trifluoroethanol at 25° C about 5 times faster than the analogous six-membered ring, after correction for differences in ring strain. The trans substrate solvolyzes about 360 times more slowly than the analogous six-membered ring. These changes are in agreement with a hyperconjugative mechanism for interaction between the silyl group and the developing positive charge. The expected cosine-squared dependence of hyperconjugation on the Si—C—C—X dihedral angle suggests that the cis dihedral angle is reduced somewhat from the 60° in the six-membered ring, and the trans dihedral angle is reduced substantially from the 180° in the six-membered ring.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010307
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  • 16
    Electronic Resource
    Electronic Resource
    Acidities of radical cations derived from arylacetonitriles (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 209-223 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The equilibrium acidities of phenylacetonitrile, and 20 of its m- and p-substituted derivatives have been measured in Me2SO solution. Their pKa′s plot linearly with those of the corresponding anilines. Combination of the pKa′s of these acids with their oxidation potentials, Eox(HA), and those of their conjugate bases, Eox(A-), provide an estimate of the acidities of the corresponding radical cations. The pKHA+ values for ArCH2CN+., where Ar is Ph, 1- and 2-naphthyl, and 9-anthryl, are -32, -18·5, -17·5, and -11, respectively, compared to 21·9, 20·85, 20·65, and 19·8 for the corresponding ArCH2CN acids. Acidities of PhCH(Me)CN+., Ph2CHCN+., 9-CN-FlH+., and 9-CN-XnH+. are -33, -35, -25, and -27, respectively, compared to 23·0, 17·5, 8·3, and 13·6 for the corresponding acids from which they were derived. The homolytic bond dissociation energies (BDEs) for the benzylic C—H bonds in these arylacetonitriles, estimated by combining pKHA with Eox(A-), fall in the range of 69 kcal/mol for 9-CN-XnH to 82 kcal/mol for PhCH2CN. For GC6H4CH2CN+. radical cations the acidities are decreased, relative to G=H, when G is an electron donor substituent and increased when G is an acceptor. The BDEs of the benzylic C—H bonds in GC6H4CH2CN are weakened by up to 4 kcal/mol by para donors and strengthened by up to 1·2 kcal/mol by m- or p-acceptors. The significance of these changes in BDEs with regard to the use of σ. scales and the ΔAOP method for estimating substituent effects on radical stabilities is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010405
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  • 17
    Electronic Resource
    Electronic Resource
    Oxygen-atom transfer chemistry of α-AZO hydroperoxides: Effect of competitive intramolecular hydrogen bonding and α-methyl substitution (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 259-265 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1-(Phenylazo)-1-(2-pyridyl)ethyl hydroperoxide, 1, 1-(phenylazo)-1-(2-furyl)ethyl hydroperoxide, 2, phenylazo(2-furyl)methyl hydroperoxide, 3, 1-(phenylazo)-1-(4-anisyl)ethyl hydroperoxide, 4, were synthesized in moderate yield by autoxidation of the phenylhydrazones in benzene. The ionic oxidation of benzyl methyl sulfide in benzene by 1-4 yielded the sulfoxide and the metastable α-azo hydroxides in essentially quantitative yield. The reaction was of the first order in α-azo hydroperoxide and sulfide, respectively. The relative reactivity series found was: 1(1.0) 〈4(1.4) 〈 phenylazo(4-anisyl)methyl hydroperoxide 5 (2·9) 〈2 (3·8) 〈 3 (9·6). α-Methyl substitution was found to slow the rate of oxygen-atom trasfer by a factor of 2 to 2.5. The low relative reactivity of 1 was opposite that expected based on electronic effects. Competitive intramolecular hydrogen bonding of the hydroperoxy proton to the pyridyl nitrogen in 1 accounted for the observed result.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010503
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  • 18
    Electronic Resource
    Electronic Resource
    Extrusions of dibromocarbene under neutral conditions (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 281-285 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal and photochemical decompositions of 5 have been studied. Both reactions lead to CBr2 transfer in good to high yields. With the 2-pentenes as substrates, CBr2 transfer is stereospecific in the classical singlet carbene manner.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010506
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  • 19
    Electronic Resource
    Electronic Resource
    Homocub-1(9)-ene trapped (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 305-308 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Decomposition of the tosylhydrazone salts formed from cubyl carboxaldehyde and homocubanone, potential precursors of cubylcarbene (5) and homocubanylidene (6), leads in each case to products derived from 6. It is suggested that homocub-1(9)-ene (7) is the active ingredient in the formation of 6 from both precursors. The hydrazones formed from N-aziridylamines are useful photochemical sources of 6, and presumably other carbenes. Flash vacuum pyrolysis of the tosyl hydrazone salts and hydrazones at 600°C leads to indene.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010509
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  • 20
    Electronic Resource
    Electronic Resource
    Novel reactions of sterically protected fused 1,2,3-selenadiazole. A new aspect of reactivity of organoselenium intermediates (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 317-332 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light- and heat-induced decompositions and reactions with nucleophiles of 6,6,8,8-tetramethyl-2-selena-3,4-diaza-7-oxabicyclo[3.3.0]octa- 1(5),3-diene have been studied. In contrast with the conversion to the cyclopentyne derivative (9), selenium containing intermediates (6a, 6b, and 7) were efficiently trapped using several reagents to give various kinds of organoselenium compounds. Of particular note is the isolation of a stable selenirane derivative (16) obtained by the cycloaddition of the photochemically generated selenirene intermediate (7) with furan. The character and reactivity of the intermediates are also discussed.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010603
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  • 21
    Electronic Resource
    Electronic Resource
    The solvatochromic equation and insight into chemical reactivity (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 359-362 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reaction rates for solvolysis of a mustard analogue are accurately correlated by the solvatochromic equation without inclusion of a nucleophilicity term, and thus the equation is shown to reveal mechanistically significant information.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010606
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  • 22
    Electronic Resource
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    Kinetics and mechanism of the acid-catalyzed hydration of dihydro-1,4-dioxin (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 43-50 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cyclic vinyl ether dihydro-1,4-dioxin is converted to its cyclic hemiacetal hydration product, 2-hydroxy-1,4-dioxane, in aqueous solution by an acid-catalyzed reaction for which kH+ = 1·80 × 10-5 M-1 S-1 at 25°C. This reactivity and the solvent isotope effect kH+/kD+ = 2·2 show that the reaction occurs by rate-determining proton transfer from catalyst to substrate and not by a pre-equilibrium mechanism as recently proposed.2
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020106
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  • 23
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    Theoretical studies of the singlet and triplet potential energy surfaces of cyclobutanediyl (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 161-176 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclobutanediyl (2) has been studied in both its singlet and triplet states by ab initio electronic structure theory. The triplet, which is the ground state of the molecule, exists in both C2h and C2v forms which interconvert via a Cs transition state. For the singlet, only a C2h form is found. It passes, via a Cs transition state, onto the C2v surface on which bicyclobutane (3) is the only minimum. The ring-flipping (inversion) process in 3 includes the singlet biradical as an intermediate, and involves a novel, non-least motion path similar to one previously proposed by Gassman. Semiclassical periodic orbit theory indicates that the various minima on both the singlet and triplet surfaces can interconvert via quantum mechanical tunneling.
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    Twisted internal charge transfer emission in B,B-bis(mesityl) pyrroloboranes (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 89-92 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Spectral characteristics of several simple substituted B,B-bis(mesityl)pyrroloboranes are reported which support a theoretical treatment by Bonacic-Koutecky and Michl (J. Am. Chem. Soc. 107, 1765 (1985)) describing the excited states of simple aminoboranes as an example of twisted internal charge transfer. In the aminoboranes the pyrrolo moiety functions as the electron donor group and the empty p-orbital of the boron atom as the acceptor.
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    Masthead (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    URL: http://dx.doi.org/10.1002/poc.610010501
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    Concerning the weakness of intramolecular general acid catalysis in the hydrolysis of vinyl ethers. o-carboxy-α-methoxy-β,β-dimethylstyrene (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 247-257 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of hydrolysis of the aromatic vinyl ether o-carboxy-α-methoxy-β,β-dimethylstyrene was found to be accelerated 25-fold by ionization of its carboxylic acid group, but the effective molarity which may be calculated if all of this rate acceleration is ascribed to intramolecular general acid catalysis is only EM = 1 · 1 m. This is similar to the small effective molarities found before for intramolecular catalysis by carboxylic acid groups of aliphatic vinyl ethers, which shows that, unlike the situation in other intramolecular reactions, e.g. ketone enolization, the extra rigidity of aromatic over aliphatic systems does not improve the efficiency of intramolecular catalysis in vinyl ether hydrolysis.It is suggested that this behaviour is the result of reduced conjugation between the vinyl ether group and the aromatic ring in the transition state of the vinyl ether hydrolysis reaction, which retards the rate and offsets any improvement effected by increased rigidity of the aromatic system.
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    Synthesis of optically active 2,2′-diselenocyanato-1,1′-binaphthyl and its molecular structure. Hypervalent nature of divalent selenium atom in crystal state (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 179-184 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2,2′-Diselenocyanato-1,1′-binaphthyl(1), the first selenium-containing binaphthyl derivative, has been synthesized in optically active form the corresponding diamine by diazotization followed by the reaction with potassium selenocyanate. Its molecular structure is determined by X-ray diffraction method. It is revealed that selenium atoms have hypervalent penta-coordination in the crystal.
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    Ab initio Mo calculations on the rearrangements of 7-oxa-2-bicyclo[2.2.1]heptyl cations. The facile migration of acyl group in wagner-meerwein rearrangements (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 287-298 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: Ab initio STO-3G and 6-31G minimized geometries of 5-oxo- (9), 6-oxo-7-oxabicyclo[2.2.1]hept-2-yl cation (12) and 7-oxabicyclo[2.2.1]hept-2-yl cation (15) were obtained. The energy barriers for their Wagner-Meerwein rearrangements to the more stable 5-oxo- (11), 6-oxo-3-oxabicyclo[2.2.1]hept-2-yl (13) and 3-oxabicyclo[2.2.1]hept-2-yl (17) cations, respectively, have been evaluated and compared with those calculated for the rearrangement of the 5-oxo (18) and 6-oxobicyclo[2.2.1]hept-2-yl cations (20). In agreement with experimental data, the ‘true migratory aptitude’ of an acyl group is higher than that of β-oxoalkyl group in competitive Wagner-Meerwein rearrangments that are ‘energetically unbiased’. The ease of the acyl group 1,2-shift toward an electron-deficient center is related to the electron-donating ability of the carbonyl group due to favorable n(CO) ↔ σ σ ↔ p(C+) hyperconjugative interaction.
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    Free radical chain reactions of ate complexes. Electron transfer processes 42 (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 299-303 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Iodide ion promotes the free radical reaction of isopropylmercury idide with bromotrichloromethane to yield isopropyl bromide with rate enhancement in the order of 104. The reaction involves electron transfer from i-PrHgI2- to the trichloromethyl radical in a long kinetic chain process. Iodide ion also promotes the free radical chain conjugate addition of tert-butylmercury chloride to α,β-unsaturated ketones, esters, phosphonate esters and sulfones. Competitive reactivity studies indicate that lithium di-tert-butylcuprates or tri-tert-butylzincates react with 2-cycloalkenones by a mechanism involving attack by tert-butyl radicals. No evidence for radical attack is observed for the corresponding n-butyl ate complexes of copper or zinc.
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    A preliminary quantum-chemical study of the mechanisms for the reactions of perchlorofluoroethanes with nucleophiles initiated by chlorophilic attacks (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 103-109 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: A preliminary theoretical study of the mechanisms for the reactions of the perchlorofluoroethanes CF2ClCCl3 (1), CF2ClCCl2F (2) and CF3CCl3 (3), with nucleophiles has been carried out by the MNDO method, following the experimentally suggested process shown in Scheme 1. The unlikely chlorophilic attack in the first step of Scheme 1 has been shown to be feasible for 1, 2 and 3 by analysis of the MO interactions. The second step has been found to be affected by the anionic hyperconjugation which stabilizes the anions CF2ClCCl2- (4), CF2ClCClF- (5) and CF3CCl2- (6) and would make reactions (2) (the second step) unfeasible in gas phase, but in solution reaction (2) may still easily occur for 4 and 5.
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    Studies on organophosphorus compounds XXXII. A molecular mechanics study of the hydrolytic reaction of alkylphosphonates and alkylphosphonyl chlorides (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 146-160 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The alkaline hydrolysis of several alkylphosphonates and alkylphosphonyl chlorides has been investigated by molecular mechanics calculations (MM2, 1985 version). The difference of the steric energies (ΔE) between tetracoordinate substrate and pentacoordinate transition state of phosphorus compounds represents the activation energy (ΔE≠) in hydrolysis. The change of ΔE for various alkyl groups relative to methyl group (ΔΔER) is suggested as a measure of the steric effect of substituents. Thus the correlation analysis involving log k and ΔΔER of the branched alkyl group gives good results and it is reasonable to anticipate that analogous treatment using ΔΔER for the straight chain alkyl group is not satisfactory owing to the minor contribution of steric effect of the latter. However, the multiple regression analysis of log k with ΔΔER and Taft's σ* provides very good results. As shown by us, for the hydrolytic reactions studied, the proposed ΔΔER is much better than Taft's Es and Charton's ν, the commonly used well-known steric parameters in the chemistry of carbon compounds.
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    Mechanism of the Grignard reaction (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 205-213 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanism of the Grignard reactions of aromatic ketones in THF was studied by spectroscopic and kinetic methods. The stable radical intermediates generated in the initial electron transfer from Grignard reagent to ketones are in a state of aggregated dimer of corresponding ion-radical pairs; in which two ketone anion radicals are bridged by a dimer di-cation of Grignard reagent. Subsequent alkyl radical transfer from dimeric Grignard reagent cation moiety to ketone anion radical aggregated each other are promoted by a participation of another neutral Grignard reagent. Proposed mechanism by present authors is able to explain well addition products/reduction products ratios in the Grignard reactions.
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    Non-hierarchical classification of organic solvents using characteristic vector analysis of physical and empirical solvent parameters (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 232-242 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Characteristic vector analysis of a set of six physical and empirical parameters of 103 commonly used organic solvents (bp, ∊r, μ, nD, ETN, and δ) gives four vectors describing 95% of the total data variability. Non-hierarchical cluster analysis, applied to our results, leads to ten separate classes of organic solvents.
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    Effect of cosolvent additives on relative rates of photooxidation on semiconductor surfaces (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 103-114 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The effect of solvent additives on the course of TiO2 photocatalyzed oxygenation of α-methylstyrene has been studied. While the addition of small amounts of nonhalogenated alcohols to TiO2 powders suspended in acetonitrile was found to decrease the rate of photooxygenation, added halogenated alcohols increase the rate of reaction. In addition, the solvent additives affect the observed product distribution.
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    Oxygen induced reduction: Reaction of benzeneselenol with aromatic aldehydes in the presence of oxygen (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 119-121 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reduction of aromatic aldehydes by benzeneselenol is found to be promoted by molecular oxygen to give corresponding alcohols in good yields. No reduction took place without oxygen.A free radical process involving SH2 reaction at the selenium atom is proposed where the phenylseleno radical attacks the selenium atom of selenohemiacetal, the adduct of benzeneselenol to aldehyde, to give the ketyl radical which then abstracts hydrogen from benzeneselenol. The intermediacy of selenohemiacetal is supported by a quantitative reduction of α-methoxybenzyl phenyl selenide, which is used as a model compound of the intermediate.
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    The effect of hydrophobic-lipophilic interactions on chemical reactivity. 11. The dependence of the wrapping-up capability of sodium carboxymethylamylose on its degree of substitution (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 133-141 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependency of the wrapping-up capability of sodium carboxymethylamylose (NaCMA) on its degree of substitution (D. S. = 0·00, 0·12, 0·18, 0·24, 0·29, 0·35 and 0·41) have been studied, using two guest species, iodine and cetyl-trimethylammonium bromide (CTAB). The λmax values of NaCMA-iodine helical inclusion complexes decrease with increasing D. S. values and the amounts of encapsulated iodine by NaCMA as measured by amperometric titrations also decrease with increasing D. S. values. With CTAB as the substrate, the largest number of binding sites, n, and the dissociation constants Kd have been determined by the method of surface tension versus the CTAB concentration plots. The results show that n decreases while Kd increases with increasing D. S. values. All these observations point to the fact that the wrapping-up capability of NaCMA decreases with increasing degrees of substitution. The results are discussed in terms of host-guest and host-solvent hydrophobic-lipophilic interactions as well as intramolecular hydrogen-bonding.
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    Reaction branching as a mechanistic alternative to tunneling in explaining anomalous temperature-dependencies of kinetic isotope effects (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 161-167 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature-dependence of the kinetic isotope effects for branched reactions proceeding via a common intermediate has been simulated by calculations. It is shown that, under certain conditions, anomalously small isotope effects on the Arrhenius preexponential factors, as well as unusually large observed isotope effects, may originate from the branching.
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    Non-planar structures of the pentafluoroallyl and 1,1-difluoroallyl anions (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 153-160 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structures of the allyl anion (1) and two fluoro-substituted derivatives, perfluoro (2) and 1,1-difluoro (3) have been calculated by ab inito molecular orbital theory. Geometries were gradient optimized, and force fields and an MP-2 correlation correction were determined at stationary points. The calculations were done with a double zeta basis set augmented by d functions on carbon (DZ + Dc). Final self-consistent field (SCF) and MP-2 energy calculations were done with the DZ + Dc basis set augmented by diffuse functions. The ground state of 1 is the planar allyl anion (C2v). The rotation barrier in 1 is 21·1 kcal/mol at the MP-2 level. The cyclopropyl carbanion is 27·0 kcal/mol higher in energy at the MP-2 level. The perfluoroallyl anion is not planar, and the rotated structure is 25·7 kcal/mol more stable than the C2v structure at the MP-2 level. The lowest energy structure on the potential energy surface for 2 is the perfluorocyclopropyl carbanion which is 27·8 kcal/mol more stable than the C2v structure at the MP-2 level. The 1,1-difluoroallyl anion is also not planar. Here the most stable structure on the potential energy surface is the rotated allyl anion which is 8·3 kcal/mol more stable than the all-planar allyl anion structure.
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    Nonplanar phenyl ring and inverse order of solvolytic reactivity for tertiary benzylic substrates (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 241-245 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The rates of solvolysis of l-aryl-l-phenyl-2,2-dimethylpropyl(1) p-nitrobenzoates and of aryldiphenylmethyl-p-nitrobenzoates (2) were measured in 80% acetone. An inverse order of reactivity, kp-CF3/km- CF3 〉 l was observed for 1 but not for 2. The X-ray crystallogoraphic study of the parent compounds, l,l-diphenyl-2,2-dimethylpropyl-p-nitrobenzoate (1b) and triphenylemethyl benzoate (3b), and of 2-phenyl-2-propyl-p-nitrobenzoate (4) indicated that in the highly congested system 1 both phenyl rings were nonplanar, whereas the phenyl rings in 3 and 4 were essentially planar.
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    NMR studies on the restricted rotation of 1-[2-(1-phenyl) propyl]-2,5-dimethylpyrrole derivatives (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 185-190 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: From the 1H-NMR spectra of the various pyrrole compounds, 1-substituted 2,5-dimethylpyrroles having two substituent groups on the carbon adjacent to the nitrogen atom were found to be very much hindered compounds. 1-[(1-Substituted)-2-phenylethyl]-2,5-dimethylpyrroles showed the restricted rotation, and the phenyl group of the most stable conformer was in close proximity to the pyrrole group due to dipole interaction. These NMR observations were supported by force field conformational analysis.
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    Electron spin resonance study on radicals stabilized by the σ-π captodative effect1 (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 197-207 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: ESR spectra of l-cyano-2-(trimethylsilyl)ethyl and related radicals were recorded. Temperature dependent ESR spectra of these radicals revealed that electron-releasing trimethylsilylmethyl and electron-withdrawing cyano groups synergetically functioned to stabilize the radical centers due to σ-π captodative effects.
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    Acidities of benzyl phenyl sulfones and of the corresponding radical cations. Homolytic bond dissociation energies (BDEs) of α—C—H bonds in benzyl phenylsulfones (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 225-239 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: The excellent linearity (R2 = 0·997) of a plot of pKa values for 17 m- and p-substituted benzyl phenyl sulfones, GC6H4CH2SO2Ph, vs. those for the corresponding arylacetonitrile, GC6H4CH2CN, demonstrates that substituent solvation and substituent solvation assisted resonance (SSAR) effects for p-CN, p-COPh, and p-SPh are nearly identical in these two substrates. The PhSO2 group in PhCH2SO2Ph increases the BDE of the α-C—H bond by 2 kcal/mol, relative to toluene. The α-C—H bonds in GC6H4CH2SO2Ph sulfones are stabilized by 1-2 kcal/mol by acceptor G′s (m-CN, p-CN, m-CF3, p-CF3), but weakened by 1 and 5 kcal/mol, respectively, by donors (p-OMe and p-NMe2). The GC6H4CH2SO2Ph+. radical cation with G = H has a pKHA+. = -25. Its acidity is increased when G is an acceptor by as much as 9 to 10 kcal/mol (G = 3-CN, 3-CF3, 4-CF3, 4-NO2), but is decreased when G is a donor by as much as 33 kcal/mol (G = NMe2). When G = 4-SPh the radical cation is stabilized, relative to G = H, by a larger amount (25 kcal/mol) than when G = 4-OMe (18 kcal/mol). Structural changes along the series PhCH2SO2Ph, 2-naphthyl-CH2SO2Ph, 9-anthryl CH2SO2Ph cause negligible changes in the acidities of these acids, but sizable decreases in the acidities of the corresponding radical cations. Introduction of a phenylsulfonyl group into the methyl group of 9-methylanthracene or the 9-position of fluorene or xanthene increase the BDEs by 3, 2, and 7 kcal/mol, respectively. These effects of PhSO2 groups are compared and contrasted with those of CN groups.
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    The lone-pair orbitals of triaziridine (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 267-273 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The PE spectra of four stable bicyclic triaziridines with trifluoromethyl, methyl, phenyl, spirocyclopentane and spirocyclohexane substituents are measured. From a comparison of these experimental data with MNDO calculations the energies and the interactions of the nitrogen lone-pair orbitals were obtained. The trifluoromethyl group may be reliably simulated by a fluorine atom. The ionization potentials are unexpectedly high and so are the cyclovoltammetric anodic potentials. The MNDO valence electron densities are in agreement with the comparatively small differences in the chemical shifts of the differently substituted nitrogens of the triaziridine rings.
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    2,3:5,6-bis(ethylenedithio)- and bis(trimethylenedithio)-N,N′- dicyanoquinonediimines as new electron acceptors (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 275-280 
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    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to examine the substituent effect of ethylenedithio and trimethylenedithio groups on electron acceptors, the two title compounds were prepared in one step from the corresponding quinones. These species behave as weak π-electron acceptors owing to the electronic and sterical effects of the fused groups. Only the bis(ethylenedithio) derivative formed a charge-transfer complex with tetrathiotetracene, which showed a moderate electric conductivity of 2·0 × 10-2 S cm-1. In addition, both species oxidized copper, sodium, and potassium iodides to give the corresponding deeply colored metal salts, most of which were semiconductive. The naphtho analogs were similarly studied, but hardly served as electron acceptors.
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    Masthead (1988)
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    Journal of Physical Organic Chemistry 1 (1988) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610010601
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    Photoinduced potentiometric response of poly(vinyl chloride)/spirobenzopyran/crown ether composite memberanes modified with urease (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 309-315 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photoresponse of the poly(vinyl chloride) membranes, which contain spirobenzopyran and crown ether, covered with a urease layer was studied in the presence and absence of urea. In the absence of urea, UV light irradiation induced more than 160 mV of membrane potential change, whereas the photoresponse decreased with an increase in the concentration of urea in the solution. The effects of such operating variables as crown loading and pH and ionic strength in the aqueous phase on the potentiometric response were also elucidated in the presence of urea. The results were explicated using the fact that the local concentration on NH4+ and H+ ions changed as a result of the urease-catalyzed decomposition reaction of urea.
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    Masthead (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020101
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    Complex formation between 1,3,5-trinitrobenzene and 1,8-diazabicyclo-[5,4,0]-undec-7-ene (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 351-357 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The title reaction is an instance of a simple nucleophilic attack of neutral nitrogen on aromatic sp2 carbon. The kinetic data (obtained in dimethyl sulphoxide) are compared to the results reported by the literature for the same reaction of aliphatic amines. Some possible interactions (substrate/nucleophile, substrate/salt) preceding the attack of the nucleophile are discussed.
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    Ion pairs in solvolysis reactions. Kinetic deuterium isotope effects for deprotonation of carbocation intermediates in aqueous solvent (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 15-25 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvolysis of 2-X-2-phenylpropane (1-X) in 25 vol% acetonitrile in water at 25°C produces 2-hydroxy-2-phenylpropane (1-OH) and 2-phenylpropene (3). The carbocationic intermediate discriminates between different nucleophiles; azide anion, acetate anion, and methanol are more efficient nucleophiles than water, kN3/kH2O = 42 kOAc/kH2O = 3, and kMeOH/kH2O = 2·9 (ratio of second-order rate constants). The fraction of the elimination product 3 increases with increasing basicity of the leaving group X as well as by addition of general bases. The Brønsted parameter for this catalysis is small, β = 0·13, with substituted acetate anions. The kinetic deuterium isotope effect for the dehydronation of the intermediate has been measured (assuming the reaction from intermediate to alcohol is insensitive to isotopic substitution) employing the hexadeuterated substrate d6-1-X as k3H/k3d6 = 3·5 ± 0·2 for the chloride 1-Cl with acetate anion, and, without added base, 3·1 ± 0·2 for the acetate 1-OAc, and 3·1 ± 0·2 for the p-nitrobnzoate 1-PNB, respectively, and ∼5 for the protonated methyl ether 1-OMeH+. The variation in isotope effect with change in leaving group is discussed in terms of elimination from contact ion pairs and ‘free’ carbocation. The overall kinetic isotope effect for the solvolysis was found to be kobsH/kobsd6 = 1·31 (1-OMeH+), 1·38 (1-OAc), 1·40 (1-PNB), and 5·7 (1-OH2+). These isotope effects consist of the isotope effect k12H/k12d6 for the formation of the substitution product 1-OH and k13H/k13d6 for production of the olefin 3. It is concluded that the latter isotope effect is enlarged owing to a branched mechanism in which the deprotonation of the carbocationic intermediate competes with formation of the substitution product. As large an isotope effect as k13H/k13d6 ∼6·5 has been measured for 1-OMeH+.
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    Implications of chirality and geometric isomerism in some psychoactive drugs and their metabolites (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 99-120 
    Details
    ISSN: 0899-0042
    Keywords: asymmetry ; enantiomers ; geometric isomers ; (+)- (-)-isomers ; D- and L-isomers ; R- and S-isomers ; Z- and E-isomers ; drug metabolism ; stereoselectivity and stereospecificity in drug action ; stereoselectivity and stereospecificity in drug metabolism ; psychotropic drugs ; stimulants ; antidepressants ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Many drugs contain a chiral centre, or such a centre is introduced during metabolism of the drug in man and in animals. If a single chiral centre is present, the drug will normally exist as a mixture of two enantiomers, of which one may have quite different pharmacologic and/or toxic effects than the other. Chiral drugs that are used in psychiatry, and some other pharmacologically related drugs are identified, and the implications of the presence of one or two chiral centres in these drugs are discussed. Differences in pharmacologic properties of drug and metabolite enantiomers are identified and discussed. Also reviewed are the properties of some drugs used in psychiatry that both are chiral and display geometric isomerism.
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    Pharmacokinetic data of propranolol enantiomers in a comparative human study with (S)- and (R,S)-propranolol (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 10-13 
    Details
    ISSN: 0899-0042
    Keywords: (S)-, (R,S)-propranolol ; pharmacokinetic ; human study ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pharmacokinetics of (S)-propranolol were compared after the oral administration of a 40 mg dose of the pure enantiomer and an 80 mg dose of a racemic mixture of (R,S)-propranolol. The results of this study indicate that the bioavailability of (S)-propranolol, as expressed by the mean area uner the concentration-time curve (AUC) and maximum serum concentration, is lower after 40mg of the optically pure drug than after the racemic drug.
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    Masthead (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989) 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010301
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    Stereochemistry of tissue distribution of racemic propranolol in the dog (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 192-196 
    Details
    ISSN: 0899-0042
    Keywords: propranolol enantiomers ; enantiomers ; propranolol ; β-receptor-blocking drugs ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Only limited information is available on the stereochemistry of the in vivo distribution of β-receptor-blocking drugs. In this study we determined the levels of the propranolol enantiomers in plasma, cerebrospinal fluid (CSF) and central nervous system (CNS), and peripheral tissues in the dog following an intravenous dose of a deuterium-labeled pseudoracemate. The appearance of the propranolol enantiomers in the CSF was rapid and nonstereoselective, with maximum concentrations reached at 15 min after dosing. The levels of the enantiomers in both CSF and plasma then declined in a parallel biphasic fashion, with a terminal t1/2 of about 125 min. Except for an early high CSF/plasma concentration ratio of 0.35, the CSF propranolol levels corresponded to the unbound concentration in plasma, CSF/plasma 0.20. All areas of the brain showed a similar uptake of propranolol, with a tissue concentration exceeding that in plasma about 10-fold during the terminal phase of elimination. The uptake of propranolol by peripheral tissues varied widely, ranging from a 50-fold accumulation by the lungs compared to plasma to no accumulation by adipose tissue. However, as for the CSF, there was no evidence of stereoselective uptake of propranolol by any CNS or peripheral tissue except for the liver. A significantly higher level of (+)- vs. (-)-propranolol in liver tissue presumably was a reflection of stereoselective hepatic metabolism of (-)-propranolol by this tissue. The slight stereoselectivity in plasma binding of propranolol known to exist in the dog had no significant influence on tissue or CSF distribution.
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    Separation and quantitation of (R)- and (S)-atenolol in human plasma and urine using an α1-AGP column (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 209-215 
    Details
    ISSN: 0899-0042
    Keywords: enantiomeric separation ; bioanalysis ; α1-acid glycoprotein column ; disposition (R)- and (S)-atenolol ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for the determination of (R)- and (S)-atenolol in human plasma and urine is described. The enantiomers of atenolol are extracted into dichloromethane containing 3% heptafluorobutanol followed by acetylation with acetic anhydride at 60°C for 2 h. The acetylated enantiomers were separated on a chiral α1-AGP column. Quantitation was performed using fluorescence detection. A phosphate buffer pH 7.1 (0.01 M phosphate) containing 0.25% (v/v) acetonitrile was used as mobile phase. The described procedure allows the detection of less than 6 ng of each enantiomer in 1 ml plasma. The relative standard deviation is 4.4% at 30 ng/ml of each enantiomer in plasma. The plasma concentration of (R)- and (S)- atenolol did not differ significantly in two subjects who received a single tablet of racemic atenolol. The R/S ratio of atenolol in urine was ∼ 1.
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    First announcement and call for papers (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 246-248 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/chir.530010312
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    Improved performance of the second generation α1-AGP columns: Applications to the routine assay of plasma levels of alfuzosin hydrochloride (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 243-245 
    Details
    ISSN: 0899-0042
    Keywords: stereochemistry ; enantiomers ; direct separation ; alfuzosin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Described is a direct enantioselective separation of the enantiomers of alfuzosin hydrochloride on the second generation α1-AGP column which offers improved efficiency, shorter analysis, and improved stability with respect to the first generation columns. The method has been applied to the analysis of drug substance in rat plasma. This highly efficient extraction method and the use of fluorimetric detection result in selective and sensitive determination of the enantiomers. The analytical validation parameters demonstrate the applicability of this method to pharmacokinetic and metabolic studies.
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    URL: http://dx.doi.org/10.1002/chir.530010311
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    Polarimetric detection in high-performance liquid chromatography (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 251-264 
    Details
    ISSN: 0899-0042
    Keywords: optical activity ; optical rotation ; chiroptical detection ; enantiomeric purity ; chiral separation ; enantioselective reactions ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiroptical detection for HPLC is particularly useful as a selective detection method for chiral molecules, and in enantiomeric purity determination with partial chiral separation or without chiral separation. The recent development of laser-based polarimeters with microdegree sensitivity has increased the applicability of optical rotation detection in HPLC. The detection limit of these instruments is submicrogram on-column for many chiral compounds in analytical HPLC. A variety of applications of the selective detection of optically active molecules are reviewed. The use of polarimetric detection with partial chiral separation is considered, both as an aid to method development and for enantiomeric purity determination. Finally applications to enantiomeric purity determination without chiral separation are reviewed, with the dual use of nonchirally selective and chiroptical detectors to determine the total amount and optical purity of the analyte. Determinations of chiral purity for samples of high enantiomeric excess are described, which with laser-based instrumentation may give accuracies of better than ± 1% with sample loadings of 50 μg on an achiral column. Applications to the study of enantioselective reactions are also considered, with determination of enantiomeric excess in near-racemates to better than ± 0.1%.
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    The role of configuration and conformation in the binding of 2,3-benzodiazepines to human serum albumin (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 271-275 
    Details
    ISSN: 0899-0042
    Keywords: HSA-affinity chromatography ; interconverting conformers ; conformational selectivity ; conformational diastereomers ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,3-Benzodiazepines containing a centre of asymmetry at C-5 possess both central and helical chiralities, and the solution of their racemates contains four molecular species. The binding of these compounds to human serum albumin (HSA) was studied by affinity chromatography. The binding strength depended both on the steric orientation of the 5-ethyl substituent and on the conformation of the diazepine ring. Conformation P (defined by the positive sign of C-1-N-2-N-3-C-4 torsion angle) is favoured, while the quasiaxial orientation -of the 5-ethyl substituent is not favoured by the albumin molecule.
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    Stereoisomeric flavour compounds XXXV: Chiral aroma compounds of sherry I. Optically pure stereoisomers of solerone and solerole (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 293-300 
    Details
    ISSN: 0899-0042
    Keywords: optical isomers ; chirality and odour ; chiral flavour compound resolution ; enantiomer separation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantioseparation of the sherry aroma components 5-oxo-4-hydroxyhexanoic acid γ-lactone (solerone) and 4,5-dihydroxyhexanoic acid γ-lactone (solerole) is achieved, using Chiraspher (Merck) as the chiral HPLC phase and the optical purity ascertained directly by HRGC with heptakis(3-O-acetyl-2,6-di-O-pentyl)-β-cyclodextrin (Lipodex D) as the chiral stationary phase. The absolute configurations of 4,5-dihydroxyhexanoic acid γ-lactones are assigned by 1H-NMR spectral data of diastereomeric α-methoxy-α-trifluoromethylphenylacetic acid (MTPA) esters, according to Mosher's model. Sensory qualities of the isomers are given.
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    The determination of (-)-(S)- and (+)-(R)- ifosfamide in plasma using enantioselective gas chromatography: A validated assay for pharmacokinetic and clinical studies (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 235-238 
    Details
    ISSN: 0899-0042
    Keywords: ifosfamide enantiomers, GC chiral stationary phase, pharmacokinetic studies, clinical validation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An enantioselective gas chromatographic method has been developed and validated for the determination of the plasma concentration of the enantiomers of the anticancer drug ifosfamide (IFF). In this approach, the IFF enantiomers are separated from the plasma matrix by solid phase extraction, chromatographically resolved by gas chromatography on a chiral stationary phase, and detected by mass selective detection using selective ion monitoring. The assay has been validated for routine clinical and pharmacokinetic use and has a limit of detection in plasma of 250 ng/ml of each isomer.
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    Optical enrichment of dansyl-rac-amino acids by formation of crystalline inclusion complexes with cyclodextrins (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 137-141 
    Details
    ISSN: 0899-0042
    Keywords: resolution by crystallization ; racemic mixture ; dansyl-D-leucine ; dansyl-L-leucine ; dansyl-D-norleucine ; dansyl-L-norleucine ; dansyl-D-phenylalanine ; dansyl-L-phenylalanine ; β-cyclodextrin ; γ-cyclodextrin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical enrichment from racemic dansyl-leucine, dansyl-norleucine, and dansyl-phenylalanine with both β- and γ-cyclodextrins in water is reported. Initial crystallization yielded the dansyl-L-leucine isomer complexed in excess with β-cyclodextrin with an optical purity of 62-78% depending on experimental conditions. The optical purities obtained for L-norleucine and L-phenylalanine were 71 and 64%, respectively. The optical purity can be increased with continued recrystallization. The dansyl-D-leucine isomer was obtained in the mother liquor with an optical purity of 54-93% depending on experimental conditions. The optical purities obtained for D-norleucine and D-phenylalanine were 72 and 58%. The optical purity of the isomer depended on the molar ratio of host:guest and the pH value of the solution. Optimum enrichment of both enantiomers was achieved with host:guest ratios of 2 : 1 and 3 : 1. Although maximum crystalline yield of the dansyl-leucine/CD inclusion complex was obtained at a pH of 3.5, optical purity of both enantiomers was less than that obtained at other pHs. The influence of the molar ratio of host:guest and the pH value of the solution are discussed. This method is suitable for large-scale enantiomeric separations.
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    Direct separation of albendazole sulfoxide enantiomers by liquid chromatography on a chiral column deriving from (S)-N-(3,5-dinitrobenzoyl)tyrosine: application to enantiomeric assays on plasma samples (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 142-153 
    Details
    ISSN: 0899-0042
    Keywords: enantiomeric separations ; chiral stationary phase ; Pirkle-type phases ; HPLC ; anthelmintics ; benzimidazole sulfoxides ; albendazole ; fenbendazole ; oxfendazole ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The direct enantiomeric resolution of albendazole sulfoxide (SOABZ), an anthelmintic drug belonging to the benzimidazole class, is reported on a chiral stationary phase (CSP) synthesized by covalent binding of (S)-N-(3,5-dinitrobenzoyl)tyrosine-O-(2-propen-1-yl) methyl ester on a γ-mercaptopropylsilanized silica gel. A comparison with the resolution achieved on commercially available Pirkle-type CSPs obtained from N-(3,5-dinitrobenzoyl) derivatives of (R)-phenyglycine or (S)-phenylalanine is described. Some structurally related chiral sulfoxides including oxfendazole (SOFBZ) are also studied. Optimization of the mobile phase nature and composition is investigated showing that a hexane-dioxane-ethanol ternary mixture affords an almost baseline resolution (Rs = 1.25); however, in this case, albendazole sulfone (SO2ABZ) is eluted between the two sulfoxide enantiomers; accordingly, a hexane-ethanol mobile phase would be preferred for biological samples containing both metabolites. The influence of temperature on the resolution is depicted with a hexane-ethanol mobile phase. Finally, application to the enantiomeric assays of SOABZ in plasmatic extracts of rat, sheep, bovin, and man after oral administration of albendazole (sulfoxidized to SOABZ and SO2ABZ) is reported. Some distortions in the enantiomeric ratios are evidenced depending on the species.
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    Joining hands (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 1-1 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010102
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    Determination of terbutaline enantiomers in biological samples using liquid chromatography with coupled columns (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 20-26 
    Details
    ISSN: 0899-0042
    Keywords: terutaline ; enantiomers ; determination ; liquid ; chromatography ; coupled columns ; cyclodextrin ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The purpose of this work was to develop and validate a method for the separation and determination of the enantiomers of terbutaline in plasma and intestinal juice. Terbutaline was extracted from plasma and intestinal juice by liquid-solid extraction on small C18 cartridges. The extract was then analyzed by coupled column liquid chromatography with amperometric detecton. For ciral separation a β-cyclodextrin phase was used.The within-day variation (Cv) on spiked plasma samples was in the rane 0.8-6.4% at 3.8-33.8 nmol/liter for the (-)-enantiomer, and 2.6-23.0% at 1.3-11.3 nmol/liter for the (+)-enantiomer. The between-day variation on spiked plasma samples was 5.5% at 10.7 nmol/liter and 13.6% at 4.3 nmol/liter for the (-)- and (+)-enantiomers, respectively. The within-day variation for inestinal juice was i the range 0.7-1.5% at 5.6-30.0 μmol/liter for the (+)-enantiomer.
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    A general criterion for molecular recognition: Implications for chiral interactions (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 69-79 
    Details
    ISSN: 0899-0042
    Keywords: chiral recognition ; three-point model ; distance matrix ; molecular graph ; molecular complexes ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general criterion is formulated for molecular recognition. The criterion for recognition is the ineqality of the distance matrices of complexes of different compounds with a resolving agent under ambient experimental conditions. It is shown how this criterion provides for an objective, cell-defined, and simple explanation for recognition of chiral compounds. This approach may be used to explain models (e.g., three-point of attachment1) and relationships for chiral recognition. It is also shown how one-, two-, or three-point mechanisms are equivalent in this formalism and could result in chiral recognition. Examples are used to illustrate how the so called one- or two-point mechanisms may be operative in many experimental findings. Symmetry rreqirements of resolving agents may also be derived from considerations of distance matrices. Finally, the reciprocal relationship of chiral resolving agents is easily derived from the present method of analysis.
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    Masthead (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989) 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010201
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    Letter to the editor (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 97-97 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010202
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    Preparation of chiral statonary phase from an α-amino phosphonate (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 57-62 
    Details
    ISSN: 0899-0042
    Keywords: chiral stationary phase ; α-amino phosphonate ; chromatographic separation of enantiomers ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A chiral statonary phase (CSP) derived from an N-(3,5-dinitrobenzoyl)-α-aminobenzylphosphonate has been prepared and evaluated for its utility in the direct separation of enantiomers. This CSP, 2, is structurally related to earlier N-(3,5-dinitrobenzoyl)-α-acids acid-derived phases (e.g., CSP 1), but the mode of attachment to the support is different. In scope; CSP 2 is qualitaively similar to CSP 1. However, it differs quantitatively from CSP 1, showing either greater or lesser selectivity for different pairs of enantiomers.
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    Evaluation of π-acid chiral stationary phases deriving from tyrosine and related amino acids for the chromatographic resolution of racemates: Specific requirements for enantiorecognition ability (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 45-56 
    Details
    ISSN: 0899-0042
    Keywords: enantiomeric separations ; chiral stationary phases ; tyrosine chiral selector ; γ-mercaptopropyl silica gel ; HPLC ; SubFC ; preparative LC ; chiral recognition mechanisms ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chromatographic applications of three novel chiral stationary phases (CSPs) deriving from (S)-(N)-(3,5-dinitrobenzoyl)tyrosine are reported, under liquid chromatographic (LC) and subscritical fluid chromatographic (SubFC) conditions. Two grafting modes of the chiral moiety have been experimented starting either from γ-mercaptopropyl-silanized (type 1) or γ-aminopropyl-silanized (type 2) silica gels. For type 2 CSPs an evaluation of the stability of the amide linkage was achieved by means of SubFC; the relative contriution of ionic and covalent bindings to the ciral recognitio aility was then outlined. The chromatographic properties of these CSPs were compared with those of the corresponding CSPs deriving from phenylglycine, p-hydroxyphenylglycine, and phenylalanine for the resolution of some tertiary phosphine oxide, naphthoyl amide, and α-methylene γ-lactam enantiomers. Some simple requirements regarding the solute and CSP structures for chiral recognition ability can be inferred from these results. In addition, the resolutio of π-acid α-N-(3,5-dinitrobenzoyl)amino esters was investigated on these π-acid CSPs. An example of preparative scale chromatography is also presented.
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    Enantioselective inclusion complexation of 2,3,4,6-tetra-O-acetyl-D-glycopyranose as a chiral host with (+)-(r)-phenylethylamine: x-ray characterization of the complex (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 80-85 
    Details
    ISSN: 0899-0042
    Keywords: crystal structure ; inclusion ; chiral host ; complexation ; glucopyranose ; cellulose triacetate ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: X-ray analysis of the crystalline product obtained by reaction of 2,3,4,6-Tetra-O-acetyl-D-glycopyranose with phenylethylamine revealed the formation of a real one-to-one inclusion complex. This complexaion is highly stereoselective, because only the (+)-R-enantiomeric form of the amine is included. Analogies to the mode of complexation of cellulose triaceate with chiral molecules in „inclusion chromatography“ are discussed.
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    URL: http://dx.doi.org/10.1002/chir.530010114
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    Stereocontrolled synthesis of peptide bond isosteres (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 89-91 
    Details
    ISSN: 0899-0042
    Keywords: asmmetric induction ; bacterial cell wall ; D-Ala-D-Ala ; dipeptide ; peptidoglycan ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute stereochemical control is employed in the synthesis of isosteres for dipeptide subunits 1; see Fig. (1) in which the amide linkage has been replaced by a trans carbon-caron double bond. The synthesis affords access to the four stereoisomers of 1 in which R and R' = CH3, including the isostere of D-alanine-d-alanine (D-ala-D-Ala), 2.
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    Investigation on the enantiomeric impurity of epinephrine hydrochloride injections (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 92-93 
    Details
    ISSN: 0899-0042
    Keywords: ciral resolution ; high-performance liquid chromatography ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Epinephrine enantiomers were derived into diastereoisomers with the chiral reagent 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylisothiocyanate. The resolutions was carried out on a C18 column. The RS between (-)-R- and (+)-S-isomers was 2.3. The retention time could be changed by adding a proper amount of acetonirile into the mobile phase. The results showed that (+)-S-isomer in the epinephrine hydrochloride injections increased during the period of storage.
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    The development of concepts of chiral discrimination (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 183-191 
    Details
    ISSN: 0899-0042
    Keywords: enantiomorphism ; dissymmetry ; chirality ; enantioselectivity ; diastereoselectivity ; steric complementarity ; asymmetric induction ; three-point contact ; circularly polarized radiation ; circular dichroism ; parity nonconservation ; electroweak interaction ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pasteur's conjecture (1860) that biomolecular homochirality arose from a chiral natural force as yet inaccessible in the laboratory was supplanted by Fischer's (1894) “key and lock” hypothesis of stereoselection in enantiomer to diastereomer conversions, whether in the laboratory or in living organisms. Elaborations of the “key and lock” hypothesis by Haldane (1930) and Pauling (1948) have been illustrated and supported with modification by X-ray diffraction crystal structures of enzyme-substrate complexes over the past quarter century.Two types of mechanism for the product diastereoselectivity in the reactions of an enantiomer with an achiral reagent, early proposed, have recent support: one proposes a quasidiastereomeric structure for the enantiomer attacked in the ground state, the other for the corresponding transition state of the reaction. Approaches to the differential biological activity of two enantiomers postulate either the complete binding of each isomer to a chiral receptor site, resulting in diastereomeric complexes with inequivalent bioactivities, or the differential binding of the two isomers to a set of three sites, with which only one isomer is sterically congruent.Biochemical homochirality, based on the chiral stereoselectivity of both biosynthetic and metabolic reactions, derives from the evolutionary pressure for a progressive enhancement of the kinetic efficiency and economy of those reactions. Recently Pasteur has been vindicated in part, and the problem of the original prebiotic enantiomeric excess left outstanding by Fischer has been solved. The unification of the electromagnetic with the weak interaction provided a universal chiral natural force, the electroweak interaction, which favours the chiral series selected during the course of biochemical evolution, both the D-sugars and the L-amino acids.
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    Masthead (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989) 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010401
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    St. Mary's discussion forum: “Racemates and enantiomers: Scientific and regulatory aspects” (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 249-250 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010402
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    Chiral stationary phase high-performance liquid chromatographic resolution and absolute configuration of enantiomeric benzo[a]pyrene diol-epoxides and tetrols (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 276-283 
    Details
    ISSN: 0899-0042
    Keywords: benzo[a]pyrene diol-epoxides ; benzo[a]pyrene tetrols ; high-performance liquid chromatography ; chiral stationary phase ; optical isomers ; resolution of enantiomers ; absolute configuration ; circular dichroism spectra ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Enantiomers of diastereomeric benzo[a]pyrene (BP) diol-epoxides, r-7,t-8-dihydroxy-t-9,10-epoxy-7,8,9,10-tetrahydro-BP (BP 7,8-diol-anti-9,10-epoxide), r----7,t-8-dihydroxy-c-9,10-epoxy-7,8,9,10-tetrahydro-BP (BP 7,8-diol-syn-9,10-epoxide), r-9,t-10-dihydroxy-t-7,8-epoxy-7,8,9,10-tetrahydro-BP (BP 9,10-diol-antiy7,8-epoxide), and several 7,8,9,10-tetrahydroxy-7,8,9,10-tetrahydrobenzo[a]pyrenes (BP tetrols) were resolved by high-performance liquid chromatography (HPLC) using columns packed with either (R)-N-(3,5-dinitrobenzoyl)phenylglycine[(R)-DNBPG] or (S)-N-(3,5-dinitrobenzoyl)leucine [(S)-DNBL], which is either ionically or covalently bonded to γ-aminopropylsilanized silica. Resolution of enantiomers was confirmed by ultraviolet-visible absorption and circular dichroism spectral analyses. Resolved enantiomers of BP diol-epoxides were each hydrolyzed in acidic solution to a pair of diastereomeric tetrols which were separated by reversed-phase HPLC. Absolute stereochemistries of enantiomeric diol-epoxides were deduced by the absolute configuration of their hydrolysis products.
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    Crystal structure and absolute configuration of (+)546-[copy4Cl2]HDBT: An example of torsional isomerism (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 284-292 
    Details
    ISSN: 0899-0042
    Keywords: absolute configuration ; crystal structure ; resolution ; solid-state circular dichroism ; torsional isomerism ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure and absolute configuration of the (-)589-dibenzoylmonohydrogentartrate salt of the cation [Co(pyridine)4Cl2]+ have been determined from a three-dimensional X-ray analysis. Single crystals were grown from dimethylsulfoxide: space group P212121, Z = 4, and cell dimensions a = 21.463(4), b = 23.112(3), and c = 7.490(1) Å. Full-matrix least-squares refinement on F converged at R = 0.075, 196 variables and 2029 observations. The cation has pseudotetragonal coordinate geometry, with axial Cl and equatorial N atoms. The dihedral angles between the pyridine ligands and the equatorial plane are 47(1), 39(1), 50(1), and 45(1)° and torsional isomerism is responsible for the solid-state chiroptical properties of the cation. The preferential crystallization of the P atropisomer of the cation is attributed to a general electrostatic attraction between cation and anion.
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    (-)-(S)-Flunoxaprofen and (-)-(S)-naproxen isocyanate: Two new fluorescent chiral derivatizing agents for an enantiospecific determination of primary and secondary amines (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 223-234 
    Details
    ISSN: 0899-0042
    Keywords: enantiomers ; diastereoisomeric ureas ; high-performance liquid chromatography (HPLC) ; fluorophores ; inversion of optical rotation ; antiarrhythmics ; propranolol ; plasma ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and analytical testing of two new fluorescent chiral derivatizing agents (-)-(S)-flunoxaprofen and (-)-(S)-naproxen isocyanate, is described. In a few simple steps the free carboxylic acids [(S)-flunoxaprofen and (S)-naproxen] are activated with ethyl chloroformate/sodium azide and transformed to the corresponding isocyanates. The crystalline reaction products display high enantiomeric and chemical purity and stability. The direction of the optical rotation of both substances is inverse to that of the corresponding carboxylic acids. At ambient temperature the reagents swiftly react with primary and secondary amines, yielding highly fluorescent ureas. The applicability of the two reagents for the resolution of racemic amines was tested with a number of pharmaceuticals (antiarrhythmics, β-adrenergic antagonists, calcium channel blockers, centrally acting antidepressants). The diastereoisomeric derivatives were efficiently resolved and separated from side-products by means of normal and reversed-phase high-performance liquid chromatography (HPLC). The use and sufficient sensitivity of the two reagents for pharmacokinetic studies were demonstrated with a determination of plasma levels of propranolol enantiomers after oral administration of the racemic drug [80 mg (R,S)-propranolol-HCl] to two volunteers.
    Additional Material: 7 Ill.
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    Direct chromatographic separation of 2-arylpropionic acid enantiomers using tris(3,5-dimethylphenylcarbamate)s of cellulose and amylose as chiral stationary phases (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 239-242 
    Details
    ISSN: 0899-0042
    Keywords: optical resolution ; HPLC ; chromatography ; antiinflammatory drug ; ibuprofen ; ketoprofen ; flurbiprofen ; tiaprofenic acid ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Direct optical resolution of antiinflammatory drugs such as ibuprofen, ketoprofen, flurbiprofen, and tiaprofenic acid were attempted by high-performance liquid chromatography using tris(3,5-dimethylphenylcarbamate)s of cellulose and amylose as chiral stationary phases. Although ibuprofen was not sufficiently resolved, the other three 2-arylpropionic acids were completely resolved by amylose tris(3,5-dimethylphenylcarbamate). Ibuprofen was resolved as anilide derivative.
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    The interaction of the enantiomers of carvedilol with α1- and β1-adrenoceptors (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 265-270 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereoselectivity of carvedilol, a novel β-adrenoceptor antagonist and vasodilator with one asymmetric carbon atom, was examined at α1- and β1-adrenoceptors in vitro and in vivo. (-)-(S)-Carvedilol is a potent, competitive antagonist of the β1-adrenoceptor-mediated positive chronotropic response to isoproterenol in guinea pig atrium, with a dissociation constant (KB) of 0.4 nM. (+)-(R)-Carvedilol was more than 100-fold less potent than the (-)-S-enantiomer as an antagonist of β;1-andrenoceptors, having a KB of approximately 45 nM. Consistent with these findings (-)-(S)-carvedilol (0.1 mg/kg, i.v.) produced a 25-fold rightward shift in the β1-adrenoceptor-mediated positive chronotropic response to isoproterenol in pithed rats, whereas the (+)-R-enantiomer had no β1-adrenoceptor blocking activity in vivo at this dose. In contrast to the marked degree of stereoselectivity observed at βl1-adrenoceptors, both (-)-(S)- and (+)-(R)-carvedilol produced equal antagonism of the α1----adrenoceptor-mediated vasoconstrictor response to norepinephrine in rabbit aorta, with KB values of 14 and 16 nM, respectively. Furthermore, in the pithed rat, the α1-adrenoceptor-mediated pressor dose-response curve to cirazoline was shifted approximately 6-fold to the right by both the (+)-R- and (-)-S-enantiomers of carvedilol at a dose of 1 mg/kg, i.v. In anesthetized spontaneously hypertensive rats, (-)-(S)-carvedilol was 6-fold more potent as an antihypertensive than (+)-(R)-carvedilol. The vasodilator and acute antihypertensive activity of carvedilol results from α1-andrenoceptor blockade produced by both enantiomers, and the concomitant β1-adrenoceptor blockade produced by the (-)-S-enantiomer, which prevents reflex tachycardia that can offset the antihypertensive response, leading to greater overall antihypertensive potency of (-)-(S)-carvedilol relative to the (+)-R-enantiomer. These data also suggest that distinct regions of the carvedilol molecule are responsible for blocking α1- and β1-adrenoceptors, with β1-adrenoceptor blockade resulting from an area of the molecule containing the asymmetric carbon atom, specifically the carbazolyloxy propanolamine moiety, and α1-adrenoceptor blockade resulting from a part of the molecule that does not contain the asymmetric carbon atom, most likely the phenoxyethylamine moiety.
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    First announcement and call for papers (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 309-312 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010410
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    Mechanisms of chiral recognition in xenobiotic metabolism and drug-receptor interactions (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 7-9 
    Details
    ISSN: 0899-0042
    Keywords: substrate enantioselectivity ; product enantioselectivity ; Michaelis-Menten analysis ; intrinsic activity ; potency ; receptor affinity ; efficacy ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010104
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    Pharmacologic implications of α-adrenocreceptor interactive parameters for epinephrine enantiomers in the rat vas deferens (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 14-19 
    Details
    ISSN: 0899-0042
    Keywords: affinity ; efficacy ; dissociation ; constants ; steroselectivity ; entropy ; enthalpy ; receptor ; interaction ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: After alkylation of a fraction of the total α-adrenoreceptors by phenoxybenzamine in rat vas deferens, the dissociation constants of (-)- and (+)-epinephrine in functional studies were 7 × 10-7 M and 2 × 10-5 M, respectively. In the adrenoreceptor-containing tissue fraction, when 3H-labeled WB4101 was used as the interacting ligand, for each enantiomer who affinity sites were found. Only the low-affinity dissociation consant for each isomer correlates with the constant obtained from the functional studies. If the change in Gibb's free energy. ΔG°, is calculated from the low-affinity binding constants, the values -8.1 and -6.2 kcal/mol for (-)- and (+)-isomer, respectively, are obained. The small difference in the value between isomers forms a hydrogen bond with the receptor. The interaction of epinephrine with this receptor appears to be driven largely by the entropy of the drug-receptor interaction with only a small nonsteroselective contribution from the enthalpy of ineraction.
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    The stereochemical resolution of enantiomeric free and derivatized amino acids using and hplc chiral stationary phase based on immobilized α-chymotrypsin: Ciral separation due to solue structure or enzyme activity (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 38-44 
    Details
    ISSN: 0899-0042
    Keywords: column liquid chromatography ; chiral separations ; chymotrypsin on silica ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stereochemical separation of free and derivatized amino acids on active α-chymotrypsin bonded to silica is governed by two mechanisms based on the structure of the solutes or on the enzymatic activity of the enzyme. Te deactivation of the hydrolytically active site of the enzyme demonstrated that a significant portion of the retention on this support is due to hydrophobic interactions at other sites. These sites appear to be stereoselective for the ester derivatives of amino acids but not for the other studied solutes.
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    Moleclar imprinting by noncovalent interactions: Tailor-made chiral stationary phases of high selectivity and sample load capacity (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 63-68 
    Details
    ISSN: 0899-0042
    Keywords: optical resolution ; chromatography ; amino acid derivatives ; molecular recognition ; preparative ciral separation ; macroporous polymers ; mass transfer limitaions ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A moleclar imprinting technique based on electrostatic and hydrogen bonding interactions was used to prepare polymers of high selectvity for the original print molecule (D or L form of an amino acid derivative). In the chromatographic mode ig enantioselectivity was observed, in particular for amino acid amides and basic amino acid esters. As indicated y he broad peaks obtained, the mass transfer, including the kinetics of the binding and dissociation process, was slow and appeared to be slower in systems where a higher number of interactions between the solute and the stationary phase could be expected. In such systems enhanced selectivity was observed. For polymers prepared at a lower temperature the mass transfer was more rapid and a higher selectivity was observed, wich allowed the separations to be performed at room temperature. A more rapid mass transfer and a higher selectivity could also be achieved by increasing the column temperature. Furthermore the polymers showed a high sample load capacity and a high stability, and the can easily be prepared.
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    The absolute configuration of benproperinium dihydrogen phosphate, an antitussive drug (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 86-88 
    Details
    ISSN: 0899-0042
    Keywords: stereochemistry ; stereoselective snthesis ; (S)-2-hydroxypropanoic acid ; chiral synthon ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The (+)- and (-)-enantiomers of benproperinium dihydrogen phosphate, an antitussive drug, have been assigned the R- and S-configurations, respectively, by syntheses of both enantiomers using (S)-2-hydroxypropanoic acid (L-lactic acid) as chiral synthon. The key intermediate, (S)-2-metyl-2-[-2-(phenylmethyl)phenoxy]ethyl p-toluenesulfonate, was subjected to an SN2-type reaction with piperidine furnishing (+)-(R)-benproperinium dihydrogen phosphate. (-)-(S)-Benproperinium dihydrogen phosphate was obtained by submitting the same tosylate to two consecutive SN2-type reactions with Br- and piperidine, respectively, acting as nucleophiles.
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    Announcements (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 94-95 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010118
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    Stereoselectivity at muscarinic receptor subtypes: observations with the enantiomers of phenglutarimide (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 170-173 
    Details
    ISSN: 0899-0042
    Keywords: phenglutarimide enantiomers ; enantioselectivity ; antiparkinsonian drugs ; M1-selective antagonists ; rabbit vas deferens ; pirenzepine ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The affinity of the enantiomers of phenglutarimide at three muscarinic receptor subtypes was examined in vitro using field-stimulated rabbit vas deferens (M1 receptors) and guinea pig atria (M2α receptors) and ileum (M2β receptors). Extremely high stereoselectivity was observed and higher affinities (up to 6000-fold) were found for the (+)-S-enantiomer. The stereoselectivity ratios were different at the three subtypes, and the stereochemical demands made by the muscarinic receptors were most stringent at M1 receptors. (+)-(S)-Phenglutarimide was found to be a potent M1-selective antagonist (pA2 at M1 = 8.53). Its receptor selectivity profile is qualitatively similar to that of pirenzepine. (-)-(R)-Phenglutarimide showed no comparable discriminatory properties.
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    URL: http://dx.doi.org/10.1002/chir.530010212
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    Masthead (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989) 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010101
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    The FDA perspective on the development of stereoisomers (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 2-6 
    Details
    ISSN: 0899-0042
    Keywords: optical isomers ; stereochemistry ; enantiomers ; Food and Drug Administration ; drug development ; drug regulation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The current regulatory position of the Food and Drug Administration is discussed with regard to the approval of racemates and pure stereoisomers. Circumstances in which stereochemically sensitive analytical methods are necessay to ensure the safety and efficacy of a drug are described. Regulatory guidelines are interpreted for applications for the approval of a pure enantiomer in which the racemate is marketed, for the approval of eitehr a racemate or a pure enantiomer in which neither is marketed, and for clinical investigations to compare the safety and efficacy of a racemate and its enantiomers. Examples of te basis for such regulation are drawn from historical situations (thalidomide, benoxaprofen) as well as currently marketed drugs (arylproionic acids, disopyramide, indacrinone).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010103
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    Liquid chromatographic separation of anomeric forms of saccharides with cyclodextrin bonded phases (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 27-37 
    Details
    ISSN: 0899-0042
    Keywords: mutarotation ; sugars ; carbohydrates ; isomeric ; separation ; temperature effects ; selectvity ; optimization ; hemiacetal ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A brief review of sugar stereochemistry is given. The separation of 84 different pairs of anomers was accomplished on both α- and β-cyclodextrin columns. Five different mobile phases were evaluated. The separation of anomers temperature, flow rate, and so on. The separation of anomers that mutarotate is somewhat more difficult than those that do not. Prior knowledge as to the rate of mutaroation is useful so that the chromatographic conditions can be arranged to minimize any deleterious effects on the separation.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/chir.530010108
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    Stereoselective sulfation of terbutaline by the rat liver cytosol: evaluation of experimental approaches (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 121-126 
    Details
    ISSN: 0899-0042
    Keywords: stereoselective metabolism ; sulfate conjugation ; in vitro sulfation ; sympathomimetic amines ; chiral separation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Little is known about the stereochemistry of sulfation of chiral phenolic drugs. In this study we examined several in vitro approaches to this question, using (+)-, (-)-, or (±)-terbutaline as the substrate and the rat liver cytosol as the phenolsulfotransferase enzyme source. The cosubstrate PAPS was either generated by the cytosol from inorganic sulfate and ATP or added to the cytosol. The intact sulfate conjugates formed were determined by HPLC. Using the PAPS generating system, which is best suited for the production of relatively large quantities of sulfate conjugates, with the individual enantiomers as substrates, (+)-terbutaline was conjugated to a much greater extent than (-)-terbutaline; the (+)/(-)-enantiomer ratio was 7.3 ± 0.3 (mean ± SE). When (±)-terbutaline was the substrate and chiral derivatization was employed to separate the sulfate enantiomers formed, a similar (+)/(-)-enantiomer ratio of 7.9 ± 0.2 was obtained. With PAP35S added to the cytosol, an approach best suited for kinetic studies, the substrate concentration dependence of sulfation could be determined. The Km app for this reaction was identical for (+)- and (-)-terbutaline. However, the Vmax app was 8.1 ± 0.4 times greater for (+)-terbutaline. This study for the first time shows enantioselectivity in sulfation of a chiral phenolic drug. The experimental approaches used should be valuable for human studies of stereoselectiven sulfation of terbutaline and other chiral drugs.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/chir.530010205
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    Resolution of some β-hydroxyphenethylamines as N-(3,5-dinitrobenzoyl) amides on chiral stationary phases derived from cinchona alkaloids (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 161-166 
    Details
    ISSN: 0899-0042
    Keywords: chromatography ; chirality ; chiral recognition ; β-aminoalcohols ; stereochemistry ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three chiral stationary phases, obtained by derivatizing γ-mercaptopropylsilanized silica gel with quinine, quinidine, and cinchonidine, have been employed in the resolution of N-acyl derivatives of β-hydroxyphenethylamines. The use of circular dichroism for detection and NMR analysis of analyte-selector mixtures provides an experimental basis for preliminary assignment of a recognition mechanism.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/chir.530010210
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    Optical resolution of some biologically active compounds by chiral liquid chromatography on BSA-silica (resolvosil) columns (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 154-160 
    Details
    ISSN: 0899-0042
    Keywords: enantiomers ; chiral discrimination ; drugs ; hydrophobic interaction ; biopolymers ; elution order ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical resolution on the analytical scale of a number of racemic pharmaceuticals and some other biologically active compounds has been studied using immobilized bovine serum albumin (BSA) as the stationary phase. For some of the compounds the elution order was determined by the use of optically enriched fractions obtained from a preceding passage of a sample through a preparative column containing microcrystalline triacetylcellulose (MCTA). The reversal in the sign of optical rotation shown in the polarimetric elution profile from the latter, combined with the integrated peak area ratio obtained on resolution on the analytical column, gave directly the order of elution. For one of the benzothiadiazines studied (bendroflumethiazide), increasing the pH of the mobile phase produced opposite effects on the retention of the two enantiomers, leading to a large effect on the separation factor. For many of the compounds studied, high separation factors (α 〉 2) could be achieved.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/chir.530010209
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    Announcements (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 178-179 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010215
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    Pharmacokinetics of the enantiomers of terbutaline after repeated oral dosing with racemic terbutaline (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 174-177 
    Details
    ISSN: 0899-0042
    Keywords: pharmacokinetics ; terbutaline ; enantiomers ; human ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Terbutaline is a β2-agonist and administered as the racemic mixture. The pharmacokinetics of the separate enantiomers differ with respect to degree of absorption and clearance. In the present study, repeated doses of racemic terbutaline were given to six healthy volunteers. Plasma was analyzed for the concentrations of the two enantiomers. The observed plasma concentrations at steady state differed from those predicted from the values observed after single dose administration of the separate enantiomers. The difference between the observed and predicted values can be tentatively explained by a combined influence of (-)-terbutaline on the absorption of (+)-terbutaline and the influence of (+)-terbutaline on the elimination of (-)-terbutaline. The results have implications for the interpretation of effect/concentration studies with terbutaline, but do not affect the doses used in clinical practice.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/chir.530010213
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    Response to letter to the editor (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 98-98 
    Details
    ISSN: 0899-0042
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010203
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    Cytochrome P-450-catalyzed asymmetric epoxidation of simple prochiral and chiral aliphatic alkenes: species dependence and effect of enzyme induction on enantioselective oxirane formation (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 127-136 
    Details
    ISSN: 0899-0042
    Keywords: enantioselective epoxidation ; cytochrome P-450-dependent monooxygenases ; species dependence of microsomal epoxidation ; product enantioselectivity ; substrate enantioselectivity ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantioselectivity of the in vitro conversion of simple prochiral and chiral aliphatic alkenes into oxiranes by liver microsomes of untreated or induced (phenobarbital) rats, of untreated or induced (phenobarbital, benzo[α] pyrene) mice, and of humans was determined by complexation gas chromatography. The enantiomeric excess (ee) of the epoxides extends from 0 (trimethyloxirane) to 50% (ethyloxirane). The configuration (R or S) of the enantiomers formed in excess is consistent for homologous oxiranes but is species dependent and in some cases influenced by enzyme induction. Enantioselectivity differences of aliphatic alkene epoxidation by human liver microsomes of four individuals are negligible.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/chir.530010206
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    A vivid model of chiral recognition (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 167-169 
    Details
    ISSN: 0899-0042
    Keywords: enantioselectivity ; three-point model ; chiral receptors ; chiral separations ; didactic model ; elusion of the three-point model ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hands can be used to demonstrate the three-point model of chiral recognition. The points of attachment are thumb, forefinger, and middle finger. This vivid model has the advantages of simplicity, perspicuity, and availability at any time, although two persons are necessary. It can be shown that two interactions are not sufficient for chiral recognition but that three attractive or two attractive and one repulsive attraction are needed. It can also be used to explain some possibilities of weakening or elusion of the three-point model.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/chir.530010211
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    Methiodide of the GABA antagonist (+)-bicuculline is levorotatory (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 178-179 
    Details
    ISSN: 0899-0042
    Keywords: CD spectra ; optical rotation ; phthalideisoquinoline base and salts ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The appearance of positive charge on the nitrogen moiety of phthalideisoquinoline alkaloids brings about a strong change in the intensities of CD Cotton effects. Hence the optical rotations of enantiomeric salts and their parent base of identical configuration are often of opposite sign. Thus, the name (+)-bicuculline-methiodide for the methiodide salt of (+)-bicuculline is false.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/chir.530010214
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