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  • Organic Chemistry  (3,492)
  • Physics
  • 1985-1989  (3,972)
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Year
  • 101
    Electronic Resource
    Electronic Resource
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010214
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  • 102
    Electronic Resource
    Electronic Resource
    Stereochemical influences upon the opioid ligand activities of 4-alkyl-4-arylpiperidine derivatives (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 202-208 
    Details
    ISSN: 0899-0042
    Keywords: opioid ligand ; 4-arylpiperidines ; conformation, NMR ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and stereochemistry (configuration and preferred solute conformation) of some 4-alkyl (methyl, n-propyl, isobutyl)-4-(3-hydrxyphenyl)-1-methylpiperidines and corresponding 3-methyl diastereoisomeric pairs are reported, together with their in vivo and in vitro activities as opioid ligands. All potent agonists exhibit a preference for axial 4-aryl chair conformations when protonated, and stereochemical analogies with rigid opioids of the benzomorphan class are discussed. Antagonist properties are found in compounds with preference for equatorial 4-aryl chairs, notably the cis 3,4-dimethyl derivative.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010305
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  • 103
    Electronic Resource
    Electronic Resource
    Species differences in the chirality of the carbonyl reduction of [14C] fenofibrate in laboratory animals and humans (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 197-201 
    Details
    ISSN: 0899-0042
    Keywords: fenofibrate ; chiral reduction ; species differences ; prochiral to chiral transformation ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The prochiral carbonyl group of fenofibrate (isopropyl 2-[4-(4-chlorobenzoyl)phenoxy]-2-methyl propionate) is reduced during its metabolism giving rise to a chiral secondary alcohol, “reduced fenofibric acid.” Chiral and diastereomeric HPLC methods have been developed for the determination of its enantiomeric composition and these have been applied to the measurement of the “reduced fenofibric acid” enantiomers in urine of rats, guinea pigs, dogs, and human volunteers given [14C]fenofibrate. In the three animal species, the reduction is markedly enantioselective for the (-)-isomer, the enantiomeric ratios (-/ +) being 95:5. This was not due to differences in the excretion of the enantiomers, since when racemic “reduced fenofibric acid” was given to rats it was recovered in the urine with the same enantiomeric composition as the dose form. In humans the ratio was 52:48 showing the lack of stereoselectivity of reduction in this species.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010304
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  • 104
    Electronic Resource
    Electronic Resource
    Optical resolution of β-lactams by chiral HPLC on tris(phenylcarbamate)s of cellulose and amylose (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 216-222 
    Details
    ISSN: 0899-0042
    Keywords: 4-acetoxy-2-azetidinone ; antibiotics ; carbapenem ; chiral stationary phases ; cellulose tris(phenylcarbamate) ; amylose tris(3,5-dimethylphenylcarbamate) ; CD spectra ; absolute configuration ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Separation and optical resolution of 6 diastereomers and 25 racemates of β-lactams were examined by HPLC on chiral stationary phases composed of six cellulose and one amylose tris(phenylcarbamate) derivatives. Most β-lactams were optically resolved at least by one of the derivatives. The absolute configuration of β-lactams was estimated by CD spectroscopy.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010307
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  • 105
    Electronic Resource
    Electronic Resource
    Direct high-performance liquid chromatographic separation of penbutolol enantiomers on a cellulose tris-3,5-dimethylphenyl carbamate chiral stationary phase (1989)
    New York, NY [u.a.] : Wiley-Blackwell
    Chirality 1 (1989), S. 301-304 
    Details
    ISSN: 0899-0042
    Keywords: β-adrenergic blocker ; chiral resolution ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Penbutolol is a β-adrenoceptor blocking agent, and it contains the clinically relevant (-)-S-enantiomer. It was reported that the (+)-R-enantiomer of penbutolol is pharmacologically 50 times less active than the (-)-S-isomer in β-sympatholysis and without intrinsic sympathomimetic activity and refractory period in the heart muscle. Furthermore, the (+)-R-enantiomer does possess mutagenic activity.A high-performance liquid chromatographic (HPLC) method is described for direct identification, stereochemical separation, and quantitation of (+)-R-enantiomer in the clinically used (-)-S-isomer. The method involves the use of cellulose tris-3,5-dimethylphenyl carbamate chiral stationary phase coated on silica gel (OD-Chiralcel column). The capacity factors (k′) for the first eluted enantiomer and stereochemical separation factor (α) obtained were 1.32 and 1.98, respectively. The maximum stereochemical resolution factor (R) was 5.05. The method could be applied for optical purity determination of (-)-(S)-penbutolol in pharmaceutical formulation to detect for the presence of the undesirable (+)-R-enantiomer.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chir.530010409
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  • 106
    Electronic Resource
    Electronic Resource
    Hydrogen-bonding. Part 4. An analysis of solute hydrogen-bond basicity, in terms of complexation constants (log K), using F1 and F2 factors, the principal components of different kinds of basicityPart 3. M. H. Abraham, P. P. Duce, D. V. Prior, R. A. Schulz, J. J. Morris and P. J. Taylor, J. Chem. Soc. Faraday Trans. 1, 84, 865 (1988). (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 243-254 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The principal components factors F1 and F2 in the equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log K = {\rm BDP}_0 + S_1 F_1 + S_2 F_2 $$\end{document} have been used to obtain S1 and S2 values for sets of hydrogen-bond bases against 32 reference acid/solvent systems. The constants S1 and S2 define an angle θ = tan-1 S2/S1 that is a measure of the electrostatic:covalent bonding ratio in the hydrogen-bond complex. It is shown that θ can vary from 53 (4-fluorophenol in CH2Cl2)to 86 degrees (Ph2NH in CCl4) depending on the reference acid and solvent. This variation in θ can lead to family dependent behaviour in plots of log K for bases against a given reference acid system vs log K for bases against another reference acid system, and precludes the construction of any general scale of hydrogen-bond basicity using log K values. Amongst a quite wide range of reference acid/solvent systems θ varies only from 64 to 73 degrees, and for bases against these reference systems a ‘reasonably general’ scale could be set up. Such a scale could be extended to bases against reference acid/solvent systems outside the 64-73 degree range provided that certain classes of base (e.g. pyridines, alkylamines) were excluded from the additional reference acid/solvent systems.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020307
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  • 107
    Electronic Resource
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    Application of Marcus theory to photochemical proton transfer reactions. II. Modifications based on intersecting state models (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 300-322 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various modifications of the Marcus equation have been applied to the problem of photochemical proton transfer, using available data on general acid-catalyzed photohydration reactions. These include incorporation of asymmetry and tightness parameters, as well as distance variation as a function of exoor endothermicity. The intersecting state model of Formosinho has also been successfully applied to these reactions. The overall conclusion from all of these approaches is that the reactions are characterized by somewhat asymmetric and ‘loose’ transition states, with a small but significant degree of charge development on the in-flight proton at the transition state. Estimates of the intrinsic barriers and work terms place these in the 5-7 kcal and 2-3 kcal ranges respectively. A simple valence bond configuration mixing model leads to similar qualitative conclusions about the nature of the transition states in these reactions.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020403
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  • 108
    Electronic Resource
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    A theoretical and experimental investigation of acid catalyzed rearrangements of small [n]cyclophanes (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 331-348 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The difference in reactivity of small [n]cyclophanes towards CF3CO2H is discussed in terms of charge densities, strain energies and proton affinities. These data are calculated with MNDO and MINDO/3 for para-, meta- and ortho-cyclophanes and for their ipso-protonation products; an attempt is made to transform gas phase ΔHf0 values into liquid phase ΔH0f values. Experimental evidence is presented that the acid catalyzed rearrangement of [5]paracyclophane to its ortho-isomer proceeds via two consecutive 1,2-carbon shifts without deprotonation; intermediate adducts were identified by NMR-spectroscopy. Thus, a gradual shift in reaction pattern in the series [4]-, [5]- and [6]paracyclophane is observed experimentally, in line with the calculational results.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020405
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  • 109
    Electronic Resource
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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.610020501
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  • 110
    Electronic Resource
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    Free-radical reactions of cyclic ethers and sulfides with bromotrichloromethane (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 367-376 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relative rates of hydrogen atom abstraction from a series of twelve saturated cyclic ethers and sulfides were determined at 70°C. The abstracting radical could be generated from bromotrichloromethane both photolytically or by the thermal decomposition of AIBN. The reaction rates did not show a dependence upon method of radical generation. Reaction occurred only at the position adjacent to the heteroatom. The reactivity of the cyclic ethers was in the order C4H8O 〉 C6H12O 〉 C3H6O 〉 C5H10O. This trend would indicate appreciable influence by ring strain, however, the slightly greater reactivity of tetrahydrofuran relative to oxepane suggests a contribution by stereoelectronic factors as well. The reactivity of the cyclic sulfides, which reacted faster than the corresponding ethers, was in the order C4H8S 〉 C5H10S 〉 C6H12S. This would imply little influence of ring strain. The major structural effect would be that of variable electron donating ability of the sulfur atom. The rate of reaction of thietane was also determined. It was found to preferentially undergo SH2 attack at the sulfur atom followed by ring opening rather than hydrogen abstraction. The reactivities of both series of compounds were decreased by the inductive effect of a second heteroatom beta to the reaciton site.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020502
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  • 111
    Electronic Resource
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    Group transfers 4. Arylselenide aniondiaryl diselenide exchange (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 410-416 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Barriers for group transfers between nucleophiles have been postulated to be lowered when the transferring group can carry a considerable negative charge. Furthermore, anions readily subject to one electron oxidation appear to lead to lower barriers than do those of high oxidation potential. These suggestions are pursued here on the identity reaction ArSe- + ArSeSeAr → ArSeSeAr + ArSe-. Indeed the reaction is very fast, as shown by the appearance of only a single peak in the 77Se-NMR in an acetonitrile solution containing both ArSeNa and ArSeSeAr. The rate constant can be only very roughly estimated at low temperatures and dilute solutions, and is likely diffusion controlled for Ar = phenyl and p-methoxyphenyl. A stable intermediate (ArSe)3-, analogous to Br3-, is indicated, but quantitative stability could not be determined, from either the NMR or the UV spectra. Some properties of 77Se-NMR are discussed.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020506
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  • 112
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    Lack of protonation of benzene and toluene by trifluoromethanesulfonic acid and its significance for evaluating superacid strengths (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 425-427 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Distribution between pentane and trifluoromethanesulfonic acid (TFMSA) and carbon-13 NMR measurements showed that benzene and toluene are not protonated to any significant extent in TFMSA. This finding contradicts previous reports, and validates the ranking of superacids based on the extent of benzene protonation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020508
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  • 113
    Electronic Resource
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    Bifunctionally catalyzed 1,3-proton transfer of a propene by a sec-amidine studied by deuterium isotope effects. A stepwise two-proton transfer mechanism (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 429-447 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A two-hydron transfer mechanism involving hydron transfers from carbon to nitrogen and from nitrogen to carbon was studied. The rearrangement of 1,3,3-triphenylpropene (1) into 1,1,3-triphenylpropene (2) catalyzed by 2,10-diazabicyclo[4.4.0]dec-1-ene (3) in benzene at 25·00°C was studied by 2H-labeling experiments and kinetic 2H-isotope effects. The synthesis and purification of [6,10-2H2]-2,10-diazabicyclo[4.4.0]dec-1-ene ([6,10-2H2]-3), [3-2H]-1,3,3-triphenylpropene ([3-2H]-1), [3-2H]-1,1,3-triphenylpropene ([3-2H]-2) and [3,3-2H2]-1,1,3-triphenylpropene ([3,3-2H2]-2) together with their precursors are reported. Partial reaction of [3-2H]-1 with [6,10-1H2]-3 gave 42% conversion into product 2, which was shown by 1H NMR to be composed of 88% [3-1H]-2 and 12% [3-2H]-2. Partial reaction of [3-1H]-1 with [6,10-2H2]-3 gave 43% of 2, composed of 73% [3-1H]-2 and 27% [3-2H]-2.These results clearly show that a substantial fraction of the reaction takes place in a bifunctional manner but isotope exchange and/or monofunctionally catalyzed reactions interfere. The following kinetic deuterium isotope effects on the rearrangement 1 → 2 were measured: kHH/kDH = 6·56; kHH/kHD = 1·19; kHH/kDD = 7·08; kHD/kDD = 5·94; and kDH/kDD = 1·08.On the basis of these results, a concerted two-hydron transfer mechanism is excluded. Instead, a stepwise mechanism is favored, in which at first the 3-hydron of 1 is abstracted by 3 yielding an ion pair(s), the carbanion of which in a separate step is then hydronated to yield the product 2.The abstraction of the 3-hydron from 1 might be hydrogen bond assisted. The two hydron transfer transition states are together rate limiting, although they limit the rate to different extents. A detailed mechanistic analysis is presented together with the results of an investigation of the nature of the catalyst. The dimerization constant for 3 was determined by 1H NMR to be 1·67 l mol-1 at 25·0°C. Isotopomer composition was measured by 1H NMR and GLC was used for the separation of the substrate and products. Computer-assisted capillary GLC was used for the kinetics.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020602
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  • 114
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    Cross-interaction constants as a measure of the transition state structure (part V).For Part IV, see ref. 3. The transistion state structure for reactions of phenacyl benzenesulphonates with benzylamines in methanol (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 484-490 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Kinetics of reactions of phenacyl benzenesulphonates with benzylamines were investigated in methanol at 45·0 °C and the cross-interaction constants λXY, λYZ and βXZ were determined in order to elucidate the transition-state structure. The unusually small magnitude of λXY can only be accounted for by the resonance ‘shunt’ effect of the α-CO group of the phenacyl system. Large |λYZ| values indicate a small degree of bond breaking whereas relatively large |βXZ| values compared with those for the dissociative SN2 reaction indicate a relatively tight transition state for the reactions. Further, the similar magnitudes of βXZ values compared with those of the corresponding aniline nucleophile series suggest a similar transition-state structure for the two armatic amine nucleophile series.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020607
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  • 115
    Electronic Resource
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    Amines as leaving groups in nucleophilic aromatic substitution reactions. II.For Part 1, see Reference 1. Hydrolysis of N-(2,4,6-trinitrophenyl)amines (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 507-518 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydrolysis reactions of N-(2,4,6-trinitrophenyl)piperidine (2) and N-(2,4,6-trinitrophenyl)-morpholine (3) were studied. Two kinetic processes well separated in time are observed in both reactions. The fastest process, which is reversible, leads to the formation of a species of λmax 260 and 410 nm and is attributed to the formation of a σ complex of stoichiometry 1 : 2 due to the addition of a second HO- to the σ complex of 1 : 1 stoichiometry. The slowest process leads quantitatively to picrate ion. The equilibrium constants for the formation of the σ complexes of 1:1 and 1:2 stoichiometries and the rate of formation and decomposition of the latter complex were determined. The kinetic data for the slow process lead to the conclusion that the picrate ion is formed from the attack of HO- on the two σ complexes, confirming previous findings. There are some differences in the calculated rates for 2 and 3 which may be an indication that the elimination of the amine is partially rate determining.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020703
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  • 116
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    Decarboxylation of 6-nitrobenzisoxazole-3-carboxylate ion in cationic micelles: Effect of head group size (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 553-558 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of decarboxylation of 6-nitrobenzisoxazole-3-carboxylate ion increases sharply with increasing head group size in a series of cetyltrialkylammonium bromides (C16H33NR3Br: R = Me, CTABr; R = Et, CTEABr; R = n - Pr, CTPABr; R = n - Bu, CTBABr) with rate enhancements of 102 (CTABr) and 2·8 × 103 (CTBABr). Micellized tetradecylquinuclidinium bromide and hexadecyl-N-methylmorpholinium bromide are slightly better catalysts than CTABr, as is 1,3-bis(N-cetyl-N,N-dimethylamino)propane dibromide, but p-octyloxybenzyltrialkylammonium bromides (alkyl = Me, n - Bu) are less effective than the corresponding CTA+ surfactants. These differences in catalytic efficiency depend on the head group structure and the extent to which the cationic head groups become less accessible to water rather than the overall micellar structure.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020707
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  • 117
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    Thermodynamic and spectroscopic properties of 2-pyrrolidinones. 3.For Part 2, see P. Ruostesuo and P. Pirilä-Honkanen, submitted for publication, J. Sol. Chem. NMR spectroscopic studies on 2-pyrrolidinone in different solvents (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 565-572 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1H, 13C, 15N and 17O NMR chemical shifts, 1JNH and 1JCH coupling constants and line widths (Δν1/2) of the 14N and 17O resonance lines were determined for 2-pyrrolidinone neat and for several 2-pyrrolidinone-solvent systems. The 17O NMR chemical shift of 2-pyrrolidinone was clearly most sensitive to the solvent effects, but changes with the solvent were also observable in the 13C (C=O) and 15N NMR chemical shifts, the 1JNH coupling constants and especially the line widths of the 14N and 17O resonance lines. In general, the results reflected a hydrogen bonding effect between the oxygen atom of 2-pyrrolidinone and the proton-donating solvents and a weak molecular interaction of the NH proton of 2-pyrrolidinone with the proton-accepting solvents. The results are compared with the NMR data for the corresponding binary mixtures of 1-ethyl-2-pyrrolidinone.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610020709
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  • 118
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    Anionic nucleophile-cation radical combination reactions. The super-electrophilic properties of cation radicals in solution (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 580-584 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate constants were determined for the combination reactions of a series of cation radicals derived from substituted anthracenes with acetate, p-nitrobenzoate, trifluoroacetate, nitrate and perchlorate ions. Rate constants, depending on the identities of the cation radicals and the nucleophiles, ranging from about 200 to 2 × 1010 1 mol-1 s-1 were observed in acetonitrile at 293 K. The key steps in the reaction are (1) reversible complex formation between the anion and the cation radical followed by (2) irreversible bond formation \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\rm{Ar}^{ + \cdot } + \rm{X}^ - \rightleftharpoons {{\rm{Ar}^{ + \cdot } } \mathord{\left/ {\vphantom {{\rm{Ar}^{ + \cdot } } {\rm{X}^ - }}} \right. \kern-\nulldelimiterspace} {\rm{X}^ - }}} &&&&& {(1)} \\ {{{\rm{Ar}^{ + \cdot } } \mathord{\left/ {\vphantom {{\rm{Ar}^{ + \cdot } } {\rm{X}^ - }}} \right. \kern-\nulldelimiterspace} {\rm{X}^ - }} \to \rm{Ar}^ \cdot - \rm{X}} &&&&& {(2)} \\ \end{array} $$\end{document}.The preliminary results show that cation radical-anionic nucleophile reactions can be very facile. The cation radicals of 9-nitro- and 9-cyanoanthracene are particularly reactive, giving rise to rate constants close to the diffusion-controlled limit with all anionic nucleophile studied and even react moderately rapidly with perchlorate ion. The reaction with perchlorate ion can be compared to the behavior of stable carbenium ions that coexist with the anion in solution and in crystalline salts.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610020711
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  • 119
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    Analysis of solvent effect on SN2 reactions by different theoretical models (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 611-622 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solvent effect on two SN2 reactions was evaluated by discrete, continuum and discrete-continuum models. The potential energy profiles were found to change dramatically on introduction of the solvent effect. The double-well shape which characterizes the F- + CH3F → FCH3 + F- reaction in the gas phase becomes unimodal when the solvent is introduced, in good agreement with experimental data. The solvation parameters are found to intervene in the reaction coordinate. Recent Monte Carlo and molecular dynamics calculations are discussed.
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    Comparative kinetic study of solvent effects in the reactions of 1,2-dinitrobenzene with butylamine and piperidine (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 631-645 
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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 kinetics of the aromatic nucleophilic substitution (SNAr) reactions of 1,2-dinitrobenzene (1,2-DNB) with butylamine (BA) and piperidine (PIP) were investigated as a function of the amine concentration and temperature, in chloroform, ethyl acetate, tetrahydrofuran (THF), acetonitrile (ACN), dimethylformamide (DMF), dimethyl sulphoxide (DMSO). benzene, toluene, chlorobenzene and diisopropyl ether.In the set of solvents consisting of ethyl acetate, THF, ACN, DMF and DMSO, neither reaction is catalysed (kA = k1). The sequence and range of reactivity for BA and PIP are similar in these solvents. These results indicate that reactions in which nitro in the leaving group behave differently from SNAr reactions with other leaving groups, such as halogens or alkoxy groups, since an intramolecular hydrogen bond may be expected between the leaving nitro group and the ammonium H of the nucleophiles. The correlations of the rate coefficients obtained with Taft and Kamlet's solvatochromic method support these conclusions.On the other hand, these reactions show mild acceleration with relatively non-polar solvents such as the aromatics and diisopropyl ether. The donor properties of these solvents and experiments with solvent mixtures suggest the formation of electron donor-acceptor complexes between them and 1,2-DNB. Hence the preferential solvation of 1,2-DNB by the donor solvent accounts for the mechanism observed.
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    Selective 1,2-addition of organocerium(III) reagents to α,β-unsaturated carbonyl compounds (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 93-102 
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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: Organocerium(III) reagents reacted with α,β-unsaturated carbonyl compounds to give 1, 2-addition products (allylic alcohols) in good to high yields. The reaction was studied from a mechanistic point of view by the use of (E)- and (Z)-1-(4′-methoxyphenyl)-3-phenyl-2-propen-1-ones and 4,4-ethylenedioxy-2,6-dimethyl-2,5-cyclohexadienone as the probe compounds. A polar pathway was suggested for the reaction with the former enones. On the other hand, the operability of single electron transfer processes was demonstrated in the reaction with the latter probe compound.
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    Formation of 1:1 adducts between bis(1,2-diaryl-1,2-ethylenedithiolato)metal(0) (metal = NI, PD, and PT) and quadricyclane and their photodissociation (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 131-145 
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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: Bis(1,2-diaryl-1,2-ethylenedithiolato)metal(0) complexes (1; metal = Ni, Pd, and Pt) react with quadricyclane (Q) to give selectively 1:1 adducts which are identical with the adducts between 1 and norbornadiene (NBD). In the adducts, two sulfur atoms of the different dithiolato ligands are added to one of the double bonds of NBD. The reactions of 1 with Q are 103-104 times faster than those with NBD. The more electropositive dithiolatometal complexes react faster with Q and NBD. The adducts are dissociated to the free dithiolatometal complexes and NBD by UV-irradiation (254-436 nm). Upon irradiation with 254 nm light, the photodissociation occurs before the decomposition of the dithiolatometal complexes.
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    Gas phase reactivities of isomeric ions: Methylenediphenylcyclopropane and diphenylmethylenecyclopropane (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 117-130 
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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: Gas phase ion/molecule reactions have been used to probe the structure of ions obtained by electron impact upon 1-(diphenylmethylene)cyclopropane and 2,2-diphenyl-1-methylenecyclopropane. The resulting ions of molecular composition C16H14 (m/z 206+) were reacted with charge transfer reagents (6·9 〈 IP 〈 8·8eV), giving evidence for the presence of isomeric ions with different reactivities. The less reactive ion is identified as a trimethylenemethane species (TMM+) in which one cyclopropane bond is broken; the more reactive ions are assigned as vertical ions in which the cyclopropane ring is unaffected. The vertical ions have recombination energies of 8·44 ± 0·05eV, whereas TMM+ has one of 7·41±0·05eV. The TMM+ fraction is not constant; it increases with increasing IP of the reagent. This is attributed to a reagent-catalyzed isomerization of the vertical ion to TMM+. In addition, the reagent ions are observed to undergo a unique reaction with the neutral methylenecyclopropane derivatives: electron transfer and ring opening to yield TMM+. These findings limit the application of the customary equilibrium measurements as a method to determine the substrate IP.
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    General base catalysis of photo-smiles rearrangement of 1-(4-nitrophenoxy)-2-anilinoethane in aqueous solution. Identity of the proton-donating intermediate (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 177-182 
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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: 4-O2NC6H4OCH2CH2NHPh undergoes clean base-catalyzed Smiles photorearrangement to 4-O2NC6H4N(Ph)CH2CH2OH in dimethyl sulfoxide-water (25:75). A linear plot of φ-1 vs [OH-]-1 indicated that the limiting quantum yield at high [OH-] is 0·12 and that uncatalyzed photorearrangement does not occur. Rate constants for the deprotonation step were determined for a variety of bases having conjugate acid pKa values in the range 5-10. When plotted according to the Brønsted Catalysis Law, these data gave a non-linear plot approaching slopes of zero and unity above and below a pKa of 6-7. This indicates that the proton-donating intermediate in this photo-Smiles rearrangement is the zwitterion diradical (pKa ≈ 7) rather than the Meisenheimer complex (pKa ≈ 2).
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    Theoretical study of pyrazole elimination of N-alkyl pyrazoles (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 225-231 
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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 gas-phase pyrazole elimination of N-alkyl pyrazoles has been studied using MNDO semi-empirical molecular orbital (MO) theory with complete geometry optimization of all stationary points. We found that the activation energies (Ea) of the concerted processes are around 80 kcal/mol, 25 Kcal/mol higher than experimental values. But the differences in Ea between compounds with different substituents are in good agreement with the experimental ones.
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    Photostimulated reactions of neopentyl halides with nucleophiles by the SRN1 mechanism (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 255-262 
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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 photostimulated reaction of neopentyl halides with different nucleophiles by the SRN1 mechanism of nucleophilic substitution has been studied. Neopentyl halides do not react with carbon nucleophiles, diethylphosphite, diphenylphosphonite and azide ions, but they react with arsenide and selenide ions. The photostimulated reaction of neopentyl bromide with diphenylarsenide ions gave only the straightforward substitution product neopentyldiphenylarsine. On the other hand, the photostimulated reaction of bromobenzene with dineopentyl arsenide ions gave three arsines: dineopentylphenylarsine, neopentyldiphenylarsine and triphenylarsine. Neopentyl chloride reacts under irradiation with diphenylphosphide ions giving good yields of the substitution product.
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    Masthead (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
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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.610020401
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    Theoretical studies on the hydrolysis of urea in acid solution (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 281-299 
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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: Mechanisms of the hydrolysis of urea have been investigated using the MNDO and AMI methods. All geometries were fully optimized and the transition states were characterized by calculating force constants. The results showed that: (i) The unimolecular decomposition process via the direct intramolecular proton transfer is preferred to both the A1 and the bimolecular nucleophilic attack by water, in agreement with the experimental results of Shaw et al. in the low acidity medium. (ii) The diprotonated form of urea exists as an equilibrium species, which undergoes the A2 type hydrolysis more favorably than the monoprotonated form, as Moodie et al. found in the intermediate acidity medium. (iii) The A2 hydrolysis of the monoprotonated form is very similar to those of acetamide and methyl carbamate. (iv) As the number of the solvate water molecules increases, the activation barrier for the A2 process of the monoprotonated form increases while that for the unimolecular decomposition of the free base form decreases, indicating a possibility of the barrier height reversal in the bulk solvent in favor of the latter process, thus accommodating all the experimentally found trends in the urea hydrolysis. The A1 mechanisms involving six-membered ring type intermediates can be ruled out as untenable since no such equilibrium species was obtained by both the MNDO and AM1 calculations.
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    Lack of manifestation of an anomeric effect in 2-diphenylphosphinoyl-1, 3-dioxane and 2-diphenylphosphinoyl-1, 3-oxathiane1Dedicated to Prof. Xorge A. Domínguez, Tecnológico de Monterrey, on the occasion of his 60th birthday. (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 349-358 
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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 spectroscopic evidence for the predominance of the equatorial conformers in the title compounds was confirmed by the study of derivatives containing counterpoise substituents, and by chemical equilibration of anancomeric models. ΔG27o°C [P(O)Ph2] ≳ 3·2 kcal/mol was determined in the dioxane, and ΔG55o°C [P(O)Ph2] = 1·42 ± 0·12 kcal/mol in the oxathiane. It follows then that the strong anomeric interaction observed previously in S—C—P segments does not show up in the six-membered heterocycles 2 and 7, which contain O—C—P moieties. This may be due to an inherent inability of oxygen to act as an electron donor to the axial P(O)Ph2 substituent, or to a dominant repulsive steric interaction in the axial conformers.
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    Oxygen-17 NMR study on substituted α, α, α-trifluoroacetophenonesPart VI of Nuclear Magnetic Resonance Studies. For Part V, see. K.-T. Liu, Tetrahedron Lett. 1207-1208 (1977). (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 363-366 
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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: An excellent linear correlation of oxygen-17 substituent chemical shifts (SCS) for twelve α, α, α-trifluoroacetophenones with single σ+ constants, δ = 24·6σ+ + 556·3 (correlation coefficient 0·998) has been observed. However, from this plot, an SCS of 34·3 ppm for 1,1,1-trifluoroacetone will give a corresponding σ+ (γ+) value of 1·44 for a methyl group, which is not in agreement with 0·63-0·79 obtained from solvolytic rate data.
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    Photochemistry of matrix-isolated norbornadiene (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 383-388 
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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: Norbornadiene, isolated in argon, xenon and nitrogen matrices at 20 K, was irradiated with UV light. Characterized by UV-VIS-IR absorption spectroscopy the photoproduct, representing a single species, was assigned to quadricyclane. This result is compared with the literature data on photochemistry of norbornadiene in the gas and liquid phase. The role of the rigid matrix environment on selectivity of the photochemical reaction is discussed.
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    Masthead (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
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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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    Binding of pyridoxal-5′-phosphate and pyridoxamine-5′-phosphate: Electrochemical characterization (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 448-454 
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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 interaction between pyridoxal-5′-phosphate (PLP) and pyridoxamine-5′-phosphate (PMP) was studied by d.c. and differential pulse polarography. Two reduction waves (or two peaks) were observed. The first wave corresponds to the reduction of the adduct and the second to the reduction of free PLP. The behaviour was similar in analogous Schiff bases. The effects of pH, PMP concentration and the capillary characteristics were studied. The apparent formation constant as a function of the pH was calculated. Thermodynamic parameters were estimated at pH 7 and 0 · 1 M ionic strength. The polarographic and kinetic results show that the overall electrode process appears to be irreversible in a basic medium.
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    Dipole moments and electron distribution of acyl chlorides and acyl bromides (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 476-483 
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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: Dipole moments of para-substituted benzoyl chlorides and bromides, partly measured in benzene and partly recalculated from elderly literature, were analysed in terms of bond moments and additional contributions expressing the conjugation. Although the gross moments are similar, their decomposition yields different pictures for acyl chlorides and bromides. Only in the latter can significant electron transfer from the halogen be observed. On the other hand, conjugation with the benzene nucleus is strong in both aromatic acyl chlorides and bromides, but stronger in chlorides. There is agreement with the evidence from some other physical quantities but not from all.
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    Aromatic substitution by free benzyl cations from the nuclear decay of multi-tritiated toluene. Competitive benzylation of benzene and toluene in the gas phase and in solution (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 467-475 
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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: Benzyl cations, free of counter ions, have been generated from the nuclear decay of tritium atoms contained exclusively in the side-chain of multi-labelled toluene and allowed to react in competition experiments with benzene and toluene. The aromatic substitution was studied in both the gaseous and liquid phase, employing pure aromatics or aromatics dissolved in n-hexane, carbon tetrachloride and nitromethane as the reaction medium. In the gaseous systems, at 20 Torr total pressure, High meta substitution of toluene indicates extensive isomerization of the excited intermediates, while the increase of the kT/kB value in the Presence of NH3 suggests that selective transalkylation competes with proton transfer to ammonia from the benzyl cation adducts with benzene, but not with toluene. High positional and low substrate selectivities were measured in solution, the decrease in kT/kB (from 2·8 to 1·7) in the different solvents being accompanied by an increase in the o/2p ratio. Competition experiments between benzene and methanol indicate that the reaction is not diffusion controlled. The influence of the reaction medium on the substrate selectivity is explained by postulating the formation of a cation-solvent adduct, where the solvent molecule undergoes displacement by the substrate. Positional selectivity would be controlled in a subsequent step.
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    Micellar catalysis of organic reactions. 24.For Part 23, see T. J. Broxton, J. R. Christie and R. P.-T. Chung, J. Org. Chem. 53, 3081 (1988). Comparison of SNAr reactions in hydroxy-functionalized micelles and in the presence of cyclodextrins (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 519-530 
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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 basic hydrolysis of 2,4-dinitrochlorobenzene (DNCB) and 2,4-dinitrofluorobenzene (DNFB) was studied in the presence of β-cyclodextrin (CDOH) and in the presence of hydroxy-functionalized micelles containing either a primary hydroxy group [hexadecyl-2-hydroxyethyldimethylammonium bromide (CHEDAB)] or a secondary hydroxy group [headecyl-2-hydroxypropyldimethylammonium bromide (CHPDAB) and 2-hydroxyhexadecyltrimethylammonium bromide (2-OHCTAB)].In all systems a biphasic reaction was observed. The first phase consisted of a competition between the additive (either micelle or cyclodextrin) and hydroxide ion for the aromatic substrate, and the second phase consisted of the hydrolysis of the trapped aryl micellar or cyclodextryl ether.The percentage of trapping of the aromatic substrate by the cyclodextrin was similar to that found for reactions in the hydroxy-functionalized micelles (CHPDAB and 2-OHCTAB) which contained secondary hydroxy groups. The relative rates of reaction for DNFB and for DNCB, i.e. F/Cl rate ratios, in the presence of CDOH were similar to those obtained in the presence of 2-OHCTAB but less than that obtained in the presence of CHEDAB. These results support the assumption that in CDOH the secondary hydroxy groups of C-2 or C-3 are involved in covalent bond formation with the aromatic substrate rather than the primary hydroxy group of C-6. All the reactions studied proceed much more slowly in the presence of CDOH than in the presence of the hydroxy-functionalized micelles. This may reflect a catalytic effect of the positively charged surface present in the micelles but not in the cyclodextrin.
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    Hydrogen-bonding 8.Part 7; M. H. Abraham, P. L. Grellier, D. V. Prior, P. P. Duce, J. J. Morris and P. J. Taylor. J. Chem Soc., Perkin Trans. 2, (in press). Possible equivalence of solute and solvent scales of hydrogen-bond basicity of non-associated compounds (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 540-552 
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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: Using the solvatochromic indicator method, a scale of solvent hydrogen-bond basicity, β1 (General), has been set up using a series of double regression equations, \documentclass{article}\pagestyle{empty}\begin{document}$$ \nu = \nu _0 + s\pi _1^* + b\beta _1 $$\end{document} for 11 aniline-type indicators. A similar solvent scale, β1 (Special), has been constructed by the homomorphic comparison method using only results by Laurence et al. on the indicators 4-nitroaniline and 4-nitro-N,N-dimethylaniline. Results are available from our previous work on a general solute scale, β2H, and we have also obtained a special solute scale, β2 (pKHB) from available log K values for hydrogen-bond complexation of bases with 4-fluorophenol in CCl4. However, the two solute β2 scales are virtually identical.It is shown that there is a general connection between β1(General) and β2H, with r = 0·9775 and s.d. = 0·05 for 32 compounds, and between β1(Special) and β2H, with r = 0·9776 and s.d. = 0·06 for the same 32 compounds. The latter correlation over 60 compounds yields r = 0·9684 and s.d. = 0·07. However, there are so many compounds in these regressions for which the differences in the solvent and solute β values are larger than the total expected error of 0·07 units that the use of β1 to predict β2 or vice versa is a very hazardous procedure. About 70 new β1 values obtained by the double regression method are also reported.
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    Molecular mechanics (MM2) calculations on siloxanesThis paper is taken from Ref. 1. (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 573-579 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The MM2 force field has been extended so that calculations may be carried out on siloxanes. The parameters chosen give a good fit to available experimental data.
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    Energy-minimum structure of the hydrocarbon portion of [45] (1,2,3,4,5)ferrocenophane (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 602-610 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Notes: In order to assist in the interpretation of the D5h molecular structure of [45] (1,2,3,4,5)ferrocenophane (1) obtained from x-ray crystallographic analysis, a hypothetical hydrocarbon C30H40 (2) was derived from 1 by removing the iron atom and subjected to geometry optimization by molecular mechanics. A stable D5 conformer was found for 2, which has a g+ g- g+ helical bridge conformation and a ring-ring distance almost identical with that in 1 and ferrocene itself. Optimization of a perhydrogenated hydrocarbon model gave a highly strained C1 structure.
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    The double photodissociation of a geminal dichloride: Evidence for the stepwise formation of a diaryl carbene (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 623-630 
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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: Photolysis of dichlorodiphenylmethane in glassy 2-methyltetrahydrofuran at 77 K results in the formation of diphenylcarbene and the diphenylchloromethyl radical, which were detected by their fluorescence emission and excitation spectra. The relative yields of the carbene and biradical are shown to vary dramatically as a function of photolysis time. The photolability of the diphenylchloromethyl radical is also demonstrated. These results were interpreted in terms of a two-step mechanism, in which the diphenylchloromethyl radical is an intermediate in the formation of diphenylcarbene.
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    Self-catalysis and molecular complexes in aromatic nucleophilic substitution reactions: Reaction between 1,3,5-trinitrobenzene and 1,8-diazabicyclo [5.4.0] undec-7-ene in toluene (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 653-659 
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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 formation of a σ-like complex by reaction between 1,3,5-trinitrobenzene and 1,8-diazabicyclo [5.4.0]-undec-7-ene was investigated in toluene at various temperatures. The kinetic data showed autocatalytic behaviour. Inspection of the reaction mixtures at zero reaction time indicated the presence of an equilibrium preceding the attack of the nucleophile, affording a molecular complex (substrate-nucleophile) which is responsible for the observed kinetic features. The present and the previous data led to the conclusion that the catalytic behaviours usually observed in SNAr reactions (in apolar solvents with amines as nucleophiles) are better explained by the presence of substrate-catalyst interactions than by catalysis on departure of the proton and leaving group from the zwitterionic intermediate.
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    Masthead (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
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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.610020701
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    Reflections on the π-complex theory of benzidine rearrangementsDedicated, with respect, for the 70th birthday of Professor Michael Dewar, who, on scribbled, lunch-time table napkins at the 1961 American Chemical Society meeting in Chicago tried but (fortunately) failed to convince me of the validity of his π-complex theory. I wish I had kept the napkins. (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 491-506 
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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 ups and downs, and reasons therein, of the π-complex theory of the mechanism of the benzidine rearrangements, and the possible role of π-complexes in a newer understanding of the rearrangements, are described.
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    Influence of aromatic substituents on the configuration and conformation of calix[4]areneoctols (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 531-539 
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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: Acid-catalysed condensation of resorcinol with aromatic aldehydes results in 2,8,14,20-tetrasubstitued calix[4] areneoctols. Sixteen compounds of this type containing different aromatic substituents were synthesized. The ring closure step, under the conditions of the reaction, is a reversible process. Four configurations are possible for every constitution, viz. cccc, cctt, ccct and ctct, but only cccc and cctt were formed in detectable amounts. In seven cases the thermodynamically more stable cccc isomers (1a-5a, 7a, 8a) and also the kinetically controlled cctt isomers (1b-5b, 7b, 8b) could be isolated. The configurations of the compounds were assigned by temperature-dependent 1H NMR analysis. The conformational motions of the macrocyclic ring permit only the cccc isomers to show coalescence for the signals of the aromatic Hb protons. The coalescence temperature was determined for isomers 1a (ΔG384≠ = 83·5 kJmol-1) and 3a (ΔG369≠ = 83·7 kJ mol-1). For steric reasons the ‘chair-chair’ conformers B and the ‘quasi-boat-chair’ conformers F are favoured. 1H and 13C NMR shifts show that compounds 1a-5a and 1b-5b have a quasi-axial arrangement of the aromatic substituents, whereas 6-9 have a quasi-equatorial arrangement of the substituents.
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    Structure of radical intermediates appearing in the grignard reaction of monoketones (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 21-27 
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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 structure of radical intermediates appearing in the reactions of MeMgBr with aromatic monoketones was investigated by using ESR and visible spectroscopy. Stable radical intermediates in the reacting solutions were assigned to the dimeric radical ion pairs.
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    Circular dichroism of In-Situ trinuclear organotransition metal complexes with optically active ligands (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 33-38 
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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: Several Cotton effects are developed within absorption bands of trinuclear organotransitionmetal complexes in the presence of acids, diols, amines and aminoalcohols even in the case of bulky substituents on nitrogen; with monohydroxy compounds no circular dichroism could be detected.
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    Marcus-grunwald theory and the nitroalkane anomaly (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 29-31 
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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 Disparity reaction proposed in a recent application of Marcus-Grunwald theory to nitroalkane ionization is shown to put the reaction's transition state in an energy-diagram region where electronic rearrangement leads proton transfer, contrary to experimental evidence; it is suggested that addition of solvent reorganization to electronic rearrangement as the second reaction progress variable would remedy this situation.
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    Reaction of triethylsilyl radical with sulfides, a laser flash photolysis study (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 39-46 
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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: Triethylsilyl radical was generated by laser flash photolysis of a 1:1 (v/v) solution of triethylsilane and di-tert-butyl peroxide. The silicon centered radical was reacted with sulfides to give carbon centered radicals by displacement at sulfur. The carbon radicals were readily detected by their transient absorption spectra. The absolute rate of reaction of triethylsilyl radical with 9-fluorenylphenylsulfide, di-n-butylsulfide, di-sec-butyl sulfide, di-tert-butyl sulfide and di-n-butyl disulfide are 2.40 ± 0.12 × 108 M-1S-1, 1.1 × 107±0.89×106M-1S-1, 8.79± 0.73×106M-1S-1, 3.29±0.18×106 M-1S-1, and 3.41±0.09×108 M-1S-1, respectively.
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    The use of IR spectroscopy to monitor the conversion of matrix isolated phenylacetyl chloride to phenylacetyl cation, without decarbonylation to benzyl cation (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 51-56 
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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: IR spectroscopy is presented as a convenient means to monitor the formation of acyl (and alkyl) cations from corresponding acid chlorides, with Lewis acids at low temperature in the solid state. Phenylacetyl chloride is co-deposited (under vacuum at -173°C with antimony pentafluoride on a KBr window), as in the ‘molecular beam’ method of cation generation. The initial IR spectrum of the deposition shows (in addition to starting materials) that a small amount of phenylacetyl cation (2274 cm-1) has been formed. Warming the solid matrix to -123°C Promotes the smooth conversion of acid chloride to acyl cation. Ultraviolet irradiation (through quartz windows) at -123°C to -73°C facilitates this conversion but does not result in the loss of carbon monoxide from the acyl cation to form benzyl cation. When benzyl chloride is used in place of phenylacetyl chloride, there is no noticeable difference between IR spectra taken before and after warming and/or photolysis of the solid deposition.
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    Long range electrical field effects in solvolysis and 13C-NMR shielding of androstanes with halogen, hydroxy and oxo substituents (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 214-224 
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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 solvolysis of 21 different 3- or 17-androstanyl tosylates or chlorides with halogen, hydroxy or oxo substituents in 17- or 3-position shows rate constant variations in hexafluoro isopropanol of up to 6·3 with regular differences for epimeric substituents. Similar variations ae seen over a distance of ∼10 Å in 13C-NMR shifts at C-17-ones of androstan-17-ones with varied halogen substituents in C-3, whereas the shielding observed at other distant carbon atoms excludes significant through bond effects. It is shown how, on the basis of suitable Coulomb-type equations and of force field minimized geometries, both the stability variation of carbocationic transition states and the carbonyl group polarization are predictable by linear electric field effects, using the same parametrization.
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    Alkylating properties of phosphate esters. 3. Reactivity of dialkyl 2-(dimethylamino) ethyl phosphates (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 263-270 
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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: Reactivity of dialkyl 2-(dimethylamino)ethyl phosphates, (RO)2P(O)OCH2CH2NMe2 (R = Me, PhCH2) was studied in aqueous solutions. Depending on the initial substrate's concentration, reaction can involve the unimolecular fragmentation to N,N-dimethylaziridinium dialkylphosphate, or the bimolecular isomerization to the zwitterionic derivative. The latter reaction proceeds via two consecutive SN2 steps and involves the formation of two ionic intermediates which were synthesized independently and allowed to react to give the zwitterionic product. Rate constants for the isomerization of the dimethyl ester (R = Me), as well as rate constant for the reaction between the corresponding intermediates have been determined, and the reactivity of the dimethyl ester has been compared with that of the dibenzyl derivative.
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    Crystal and molecular structures of dimesitylketene and bis(3,5-dibromo-2,4,6-trimethylphenyl)ketene. Intrinsic torsional angles and buttressing effects in 1,1-dimesitylvinyl propellers (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 271-280 
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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: The crystal and molecular structures of dimesitylketene (1) and bis(3,5-dibromo-2,4,6-trimethylphenyl)ketene (2), the first free ketenes to be studied by X-ray diffraction, have been determined. The molecules of 1 and 2 have crystallographic C1 and C2 symmetry, respectively, and exist in a propeller conformation. Molecular mechanics calculations of 1 and 2 using a modification of Allinger's new allene parameters reproduce satisfactorily the structural parameters of the ketenes. The torsional angles of the aryl rings in 1 and 2 are similar (ca. 50°) and are regarded as ‘intrinsic’ values for a 1,1-dimesitylvinyl propeller. From the similarity in aryl torsional angles in 1 and 2 it is concluded that the buttressing effects in 2 (if any) are not markedly manifested in the structural parameters of 2.
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    Laser flash photolysis of a chromium carbene complex: Pentacarbonyl(1,3-dimethyl-4-imidazolin-2-ylidene)chromium(0) (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 323-330 
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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: Photoreactions of Cr(CO)5(Im) (Im = 1,3-dimethyl-4-imidazolin-2-ylidene) have been investigated by laser flash and continuous photolysis. Quantum yields for the disappearance of Cr(CO)5(Im) in benzene under Ar or CO were very low, although transients observed by laser flash photolysis reacted rapidly with CO. This suggests that photodissociation of the carbene ligand is very minor. The laser flash photolysis at 337 nm in benzene (B) gave a transient (λmax = 630 nm), which converted to the second transient (λmax = 455 nm) within ∼100 ns. The kinetic studies of these transients revealed that the first one is a ‘free’ coordinatively unsaturated species (Cr(CO)4(Im)) and the second one carries a solvent molecule as a ligand (Cr(CO)4(Im)(B)). From the comparison of Cr(CO)4(Im) and Cr(CO)5, apparently lower reactivity of Cr(CO)5 was found to be due to the strong coordination of a solvent molecule. The Im ligand neutralizes the deficit of electron density on Cr. A simple synthesis of Cr(CO)5(Im) was also described.
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    A mechanistic study of the selenium-catalysed carbonylation of secondary amines with carbon monoxide (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), 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: The reaction pathway of urea formation by selenium-catalysed carbonylation of secondary amines with carbon monoxide in the presence of oxygen was studied using piperidine as a secondary amine. It was established that selenium reacts with carbon monoxide and piperidine to give carbamoselenoate as an intermediate, which affords biscarbamoyl diselenide by the oxidation with molecular oxygen. Aminolysis of biscarbamoyl diselenide gives the urea derivative, accompanying the regeneration of selenium catalyst.
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    Alkylating properties of phosphate esters. 4. Medium effects on methylation of pyridines by trimethyl phosphate (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 377-382 
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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 rates of N-methylation of pyridine and its ring-substituted derivatives by trimethyl phosphate were measured in D2O and in CDCl3. Relative rates, together with the solvent activity coefficients of substrates for the transfer form chloroform to water, were used for determining the solvent activity coefficients of the activated complexes for this SN2 reaction. The results indicate early activated complexes for all pyridines, with the most nucleophilic substrate showing the most reactant-like activated complex.
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    Experimental determination of carbon vs. oxygen regioselectivity in reactions of gas-phase enolate ions (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 389-409 
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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: A gas-phase experimental investigation of the competition between carbon and oxygen alkylation of a series of cyclic and acyclic enolate ions is described. Perfluoropropylene is shown to react in a characteristic way with oxyanions and carbanions to produce distinctive ionic products. The relative yields of these products formed in reactions with ambident enolate ions provides a measure of their intrinsic carbon vs. oxygen regioselectivity. The results for a series of enolates derived from aldehydes, ketones, esters, amides and related compounds show a wide range of reactivity which is a function of the nature of the central substituent. Most aldehyde and ketone enolates react mainly through oxygen, while enolates with σ-acceptor of π-donor type central substituents react mainly thorugh carbon. Ring-size in cyclic ketone enolates also influences C vs. O regioselectivity, i.e. small-ring enolates react mainly through carbon, while larger ring enolates (C7-C9) react preferentially through oxygen. The enolate reactivity patterns can be generally accounted for by the keto-enol energy differences for the parent carbonyl compounds, although some exceptions are evident. The origins of the highly variable, kinetically determined regioselectivities are discussed.
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    ESCA studies of carbanionic compounds: Butyllithium in heptane solution and dibutylmercury in the gas phase (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 417-424 
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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: Two organometallic reagents, butyllithium in heptane solution and dibutylmercury in the gas phase, have been studied by means of core electron spectroscopy. The property of particular interest was the charge polarization as reflected by the ESCA shifts. In the butyllithium compound the C1s binding energy is shifted to a lower value by 1·8 eV for C-1 (situated closest to the Li+ ion) relative to the heptane solvent carbon. This is due to the anionic character of the C-1. The interpretation of the experiments was supported by comparing the results with ab initio calculations made on geometry-optimized butyllithium, butyl anion and butane.
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    Dynamic isotope dilution kinetic study of the thermal conversions of bicyclo[3.2.0]hept-2-ene to bicyclo[2.2.1]hept-2-ene and to cyclopentadiene and ethene (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 455-466 
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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: Mixtures of bicyclo[3.2.0]hept-2-ene and bicyclo[2.2.1]hept-2-ene, with one isomer labeled with two deuterium atoms, were isomerized in the gas phase at 276 °C. By following the concentration ratios of d0 and d2 versions of bicyclo[2.2.1]hept-2-ene as functions of time one finds that the partitioning of bicyclo[3.2.0]hept-2-ene between the primary products bicyclo[2.2.1]hept-2-ene and cyclopentadiene plus ethene is 2:1. This and earlier stereochemical results permit the calculation of the partitioning of the [3.2.0] olefin between the orbital symmetry allowed [1,3] carbon shift-with-inversion product and several forbidden or non-concerted reaction channels (approximately 1:1) and the stereochemistry of the ethene d2 formed from exo,exo-[6,7-2H2]bicyclo[3.2.0]hept-2-ene directly (1:1 E: Z).
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    Editorial (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. ii 
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    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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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.610010101
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    Nucleophilic substitution at saturated carbon atoms. Mechanisms and mechanistic borderlines: Evidence from studies with neutral leaving groups (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 1-20 
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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: Substrates with neutral leaving groups undergo unimolecular solvolysis in nonpolar solvents. Whereas t-alkyl substrates invariably solvolyze by a unimolecular mechanism, s-alkyl and primary alkyl substrates can undergo both uni and bimolecular reactions, and the bimolecular step can take place on either the substrate itself or on an intimate ion-molecule pair formed in either a pre-equilibrium or in a rate determining step. Study of reactions at borderlines indicates that the individual reaction types remain distinct and do not merge.
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    Switching of reaction pathways due to methylene chain length effects (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 187-204 
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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 products of bifunctional chain molecules with structure X—(CH2)n—Y may critically depend on the chain length n. When the chain length is short (n ≤ 5), reaction products particular to an intramolecular reaction can be dominant, while a process corresponding to an intermolecular reaction between X—CH3 and H3C—Y may take place for higher homologues having large n (≥10). The reaction switching dependent on n is explained in terms of the encounter probability for both end groups (X and Y) with conformations pertinent to product formation. The reaction switching of this sort is discussed on the basis of a reactivity profile recorded as a function of the chain length. Similar reactivity profiles have been observed for thermal Friedel-Crafts cyclization and photo-Smiles rearrangement/photoredox reaction. It is anticipated that the magic methylene chain length of 7 may give rise to an appreciable decrease in reaction yields (e.g. ‘difficulty in medium-sized ring closure’) or an anomalous switching of reaction pathways due to chain length effects.
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    Solute-solvent interactions in chemical and biological systems. IV. Correlations of ΔG, ΔH and TΔS of transfer of aliphatic and aromatic solutes from 2,2,4-trimethylpentane to aqueous solution (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 559-564 
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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: ΔG, ΔH and TΔS of transfer of 25 aliphatic and aromatic solutes from 2,2,4-trimethylpentane to aqueous buffer (pH 7) at 298 K have been examined in terms of intrinsic volumes and the solvatochromic parameters π*, δ, β and α of the pure solutes Correlations of the form \documentclass{article}\pagestyle{empty}\begin{document}$$ XYZ = XYZ_0 + {{mV_{\rm I} } \mathord{\left/ {\vphantom {{mV_{\rm I} } {100}}} \right. \kern-\nulldelimiterspace} {100}} + s\pi ^* + d\delta + d\beta + a\alpha $$\end{document} indicate that the thermodynamic quantities of transfer are unequally affected by solute properties; most notably, for aromatic solutes the cavity term mVI/100 is a principal (unfavorable) factor affecting TΔS, but has little effect on ΔH. Transfer to water is favored by increasing solute π* (dipolarity-polarizability), β (H-bond basicity) and α (H-bond acidity), because water has greater dipolarity, H-bond acidity and H-bond basicity than trimethylpentane. Hydrogen bonding contributes exothermically to ΔH, but unfavorably to TΔS, as would be expected from a loss of transitional entropy. Correlations of ΔG, ΔH and TΔS with solute VI/100, β, α, μ2 and polarizability function [(n2 - 1)/(n2 + 2)] give closely comparable results.
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    Masthead (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
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    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.610020801
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    Cation radical pericyclic reactions: CyclopropanationDedicated to Michael J. S. Dewar in the year of his seventieth birthday. (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 585-601 
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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: Triarylaminium salts smoothly catalyze the cyclopropanation of dienes, styrenes and tetrasubstituted alkenes by ethyl diazoacetate. The reactions are regioselective and, in the case of additions to conjugated dienes, cyclopropane-periselective. A cation radical chain mechanism involving carbene transfer from ethyl diazoacetate to a substrate cation radical is proposed.
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    Calorimetric study of the effect of N-methylation in azoles: Loss of an active centre of solvation (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 646-652 
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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: Using a series of equations connecting experimental and theoretical values, it is possible to discuss the origin of the N-methylation effect in azoles dissolved in water and dimethyl sulphoxide. The existence in the azoles studied of a linear relationship between the gas → solution transfer enthalpies and the charge on the pyrrole hydrogen atom demonstrated the fundamental importance of the loss of an active centre for solvation. For the imidazole-N-methylimidazole pair, the complete thermochemical cycle has been determined, allowing the apparent lack of an effect of N-methylation on the basicity in solution to be discussed.
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    URL: http://dx.doi.org/10.1002/poc.610020807
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    Oxidation of substituted ethanols by sodium N-bromobenzenesulphonamide: A kinetic study (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 660-671 
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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 kinetics of the oxidation of seven substituted ethanols by sodium N-bromobenzenesulphonamide or bromamine-B (BAB) in the presence of HCl was studied at 45 °C. The rate shows a first-order dependence on [BAB]0 and is fractional in [alcohol]0, [H+] and [Cl-]. Ionic strength variations, addition of benzenesulphonamide reaction product and variation of dielectric constant of the medium have no effect on the rate. The solvent isotope effect kH2O′/kD2O′ ≈ 0·97. The rates do not correlate satisfactorily with Taft's substituent constants. Activation parameters ΔH≠, ΔS≠, ΔG≠ and log A were calculated by studying the reaction at different temperatures (308-323 K). It was found that ΔH≠ and ΔS≠ are linearly related and an isokinetic relationship is observed with isokinetic temperature β = 393 K, indicating enthalpy as a controlling factor.
    Additional Material: 3 Ill.
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    Generation of α- oxo selenoaldehydes by treatment of α, α′ -diketo selenides with base (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 59-61 
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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: Treatment of α, α′ -diketo selenides, which recently became readily obtainable, with base affords α-oxo selenoaldehydes and ketones. The seleno-carbonyl compounds thus formed are reactive transient species, but can be trapped by Diels-Alder reaction to give 3,6-dihydro-2H-selenapyran derivatives in moderate to good yields.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/poc.610010110
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    Ethenediylidene-2,2′ -bis(1,3-dithiole) and butatriene-1,4-diylidene-2,2′-bis(1,3-dithiole) (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 47-51 
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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: This paper describes the synthesis and electrochemical behavior of dicationic salts of ethenediylidene-2,2′ -bis(1,3-dithiole) (3) and butatriene-1,4-diylidene-2,2′ -bis(1,3-dithiole) (4). These are expected as donor components for developing organic conducting and superconducting materials, on the grounds of high electron donating ability and of rigid skeletal structure with two and four cumulenic carbons inserted between two 1,3-dithioles. These salts were obtained in good overall yields by several steps starting from (2-morpholino-4,5-dimethyl or -diphenyl)-1,3-dithiolylium salt. From the 1H and 13C NMR, and electronic spectra it is suggested that the π conjugation between two 1,3-dithiolylium ions through an acetylenic bond is less effective than that through an olefinic bond of the corresponding salts of ethanediylidene-2,2′ -bis(1,3-dithiole) (1) and 2-butene-1,4-diylidene-2,2′-bis(1,3-dithiole) (2). The cyclic voltammetric study shows that the corresponding radical cations, and in particular 3 and 4, are less stable even at -40°C, thus providing reasons for our current lack of success in isolation of 3 and 4. From comparison of the first redox potentials of neutral species, it is deduced that the donating ability increases in the order of TTF 〈 1 ⋍ 2 ≲ 3 ≪ 4.
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    URL: http://dx.doi.org/10.1002/poc.610010108
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    Reaction of sulfur ylides with elemental sulfur and selenium. Aspects and mechanistic considerations (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 53-57 
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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 reaction of sulfur ylides with elemental sulfur or selenium initially affords thio- or seleno-carbonyl compounds, which then react with starting ylides to give episulfides or episelenides from which the heteroatom (sulfur or selenium) is extruded to give olefins as the final product. In the case of carbonyl-stabilized ylides, the resulting thio- or seleno-carbonyl compounds react with starting ylides to afford 1,3-oxathioles or 1,3-oxaselenoles as previously reported. Supporting evidence for the intermediacy of thio(seleno)-carbonyl compounds and episulfides (episelenides) is presented.
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    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.610010201
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    Study on 5, 15-dialkylporphyrins interconversion between two conformers in solution (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 63-73 
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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: Novel structural features of 5, 15-dialkylporphyrins in solution are described. The 1H-NMR spectra of these compounds showed broad signals at room temperature, which split into two sets of signals at lower temperatures. This unusual phenomenon was ascribed to a dynamic interconversion between tow distorted structures. The 5, 15-dialkylporphyrin has a distorted ring due to the steric hindrance between the 5(or 15)-alkyl group and the 3, 7(or 13, 17)-alkyl groups and, depending on the position of the 5, 15-alkyl groups relative to the average ring plane, can exist in two conformations; syn (where the two alkyl groups are on the same side of the ring plane) and anti (on the opposite sides). Preliminary kinetic study of this interconversion using the NMR line shape analyses is also reported.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/poc.610010202
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    Thiophilic reactions of 2,4,6-tri-t-butylphenyllithium with carbon disulfide and thiophosgene (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 75-81 
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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: Highly sterically demanding 2,4,6-tri-t-butylphenyllithium (1) reacts with carbon disulfide to give 1,2-dibutylthio-1,2-bis(2,4,6-tri-t-butylphenylthio) ethene (3), l-butylthio-1-(2,4,6-tri-t-butylphenylthio)pent-l-ene (4), and 2-butylthio-3-(2,4,6-tri-t-butylphenylthio)-1,3-dithiole-2-thione (5) when 1 is prepared by the reaction of 1-bromo-2,4,6-tri-t-butylbenzene with n-butyllithium. When the reaction is carried out using 1 prepared from 2 and t-butyllithium and then quenched with l-iodoethane, 2-ethylthio-3-(2,4,6-tri-butylphenylthio)-1,3-dithiole-2-thione and 1,2-diethylthio-1,2-bis(2,4,6-tri-t-butylphenylthio) ethene are produced. The formation of all these products can be explained in terms of initial thiophilic attack of 1 on the sulfur of carbon disulfide and an intermediate with a dual property of carbanion and carbene (i.e., ArSC(Li)(=S) ⇌ ArSC̈SLi) is suggested. The reaction of 1 with thiophosgene affords 1,2-dichloro-1,2-bis(2,4,6-tri-t-butylphenylthio) ethene, bis(2,4,6-tri-t-butylphenylthio)acetylene, and 1-chloro 2,4,6-tri-t-butylbenzene, the first two of which are explained to be formed by thiophilic attack of 1 with thiophosgene.
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    Intramolecular orientation at the micellar interface: Control of norrish type I and type II reactivity of benzoinalkylethers via conformational effects (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 91-102 
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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 photolysis of benzoinalkylethers 1-5 solubilized in detergents show a significant deviation from the course of reaction in isotropic organic solvents. Remarkable difference in photobehaviour is noticed between the short chain (1-3) and the long chain (4 and 5) benzoinalkylethers in the micellar media. However, the influence of the micellar media on the photobehaviour of alkyldeoxybenzoins 6 and 7 was small. The importance of ‘cage effect’ in controlling the product distribution was evident from its dependence on the micellar size and on the occupancy number. More importantly, a comparative analysis of the photobehaviour of the ketone 1-7 reveals that the micellar interface can be used to control the conformations of organic molecules.
    Additional Material: 1 Ill.
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    Theoretical studies on the acylation reactions of ammonia by ketenes: Determination of reactivity by molecular orbital theory (part 54) (1988)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 83-90 
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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: Theoretical studies on the reactions of ammonia with ketene and dimethylketene using the MNDO method are reported. The single step addition of ammonia to the olefinic bond of ketenes was found to provide a lower energy-barrier path than the two step carbonyl addition mechanism. The barrier height was lower in the reaction of keten compared with that of dimethylketene in support of the faster rate of solution phase reactions of aniline and ketenes. The deformation energies of reactants had an overwhelming influence in determining the activation barriers in all the reactions investigated.
    Additional Material: 4 Ill.
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    Masthead (1989)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989) 
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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.610020301
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    Nucleophilic Heteroaromatic Substitutions. XLII [1] The Reaction of 5-Methyl-4-Phenoxyquinazoline with Piperidine in Isooctane: Further Evidence for Steric Inhibition of Bifunctional Catalysis (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 865-867 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/prac.19853270520
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    Eine einstufige Synthese von Azomethan (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 868-870 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A One-pot Synthesis of Azomethane
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    URL: http://dx.doi.org/10.1002/prac.19853270521
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    Zur Struktur und dem Komplexbildungsverhalten von 7-[1-(Anilino)-1-(aryl)-methyle]-chinolin-8-olen (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 871-877 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Structure of 7-[1-(Anilino)-1-(aryl)-methyl]-quinolin-8-oles and Their Behaviour in Forming of Complexes
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    URL: http://dx.doi.org/10.1002/prac.19853270522
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    Kalinowski, H.-O.; Berger, St.; Braun, S.: 13C-NMR-Spektroskopie. XII, 685S., 142Abb., 200 Tab., Format 15,5 × 23cm. Stuttgart-New York: Georg Thieme Verlag 1984. brosch. 98,-DM (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 878-879 
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    ISSN: 0021-8383
    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/prac.19853270523
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    Masthead (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985) 
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    ISSN: 0021-8383
    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/prac.19853270601
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    Synthesis, electronic spectra and solvatochromic behaviour of 4-arylidene-1-(2,4-dinitrophenyl)-3-methyl-2-Pyrazolin-5-ones (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 923-931 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The u.v.-visible electronic spectra of 4-arylidene-1-(2, 4-dinitrophenyl)-3-methyl-2-pyrazolin-5-ones (1a-f) have been studied. The different bands observed have been assigned to the proper electronic transition. Solvatochromic behaviour of these compounds is investigated by studying their visible spectra in organic solvents of different polarity. The longer wavelength band displayed by the hydroxy derivatives is assigned to an intermolecular CT transition. The H-bonding solvated complexes formed between ethanol or DMF and p-hydroxy substituted derivative are investigated. Transition moment (μCT), ΔG and Kf values of these complexes have been determined.
    Additional Material: 4 Ill.
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    Synthesis of Methyl 7-Bromo-5-heptynoate - a building block for the carboxylic side chain of prostaglandinsProstaglandins and Prostaglandin Intermediates. XVI. 15th communication see [1]. The content of this publication is subject of GDR-patent 200 468 (Chem. Abstr. 99 (1983) 194 443) and GDR-patent 214374 (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 917-922 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl 7-bromo-5-heptynoate (11) was synthesized in 8 steps using the alkylation of 1-(2H-tetrahydropyran-2-yloxy)-2-propyne with 1-bromo-4-chloro-butane as a key reaction step. Furthermore it was shown, that also the unprotected propargyl alcohol (12) can be C-alkylated with high chemoselectivity using 1-bromo-4-chloro-butane. In this way the number of necessary reaction steps could be reduced without decrease in the total yield. Attempts failed to use trimethylsilyl 4-bromo-butanoate or 4-bromo-butyl acetate as alkylating reagent in this synthesis.
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    Zur Rhodium-katalysierten Carbonylierung aromatischer Nitroverbindungen zu Isocyanaten. III. Zur Sauerstoffübertragung bei der Carbonylierung von Nitromesitylen in Gegenwart von Rhodium(I)carbonylchlorid und Molybdänoxychlorid (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 932-936 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rhodium Catalyzed Carbonylation of Aromatic Nitro Compounds to Form Arylisocyanates. III. On Oxygen Transfer in the Carbonylation of Nitromesitylene in the Presence of Rhodium(I)Carbonyl Chloride and Molybdenum OxytrichlorideRh2Cl2(CO4) and MoOCl3 or MoOCl4 catalyze the carbonylation of nitromesitylene to form mesityl isocyanate at 1000C and normal pressure. Experiments with Mo18OCl3 show that the deoxygenation of the nitro group proceeds directly by the CO ligand. The 18O-atom of the cocatalyst is not involved in the oxygen transfer process. Experimental evidence is given for the formation of an oxomolybdenum complex in situ containing the deoxygenated nitromesitylene as a structure unit.
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    Determination of relative Autoxidation Rates of Simple Alkylaromatic Hydrocarbons by competitive reactions (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 945-952 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rates of oxidative attack at the C—H bonds in α-position to the aromatic nucleus were determined for 10 simple alkylaromatic hydrocarbons. The results obtained by competitive oxidations of binary mixtures were shown to be consistent. From these results and the regioselectivity data already published, relative reactivities referring to the tertiary C—H bond of cumene were calculated for all C—H bonds of the hydrocarbons studied.As expected, p-alkyl groups increase the reactivity of C—H bonds in α-position to the aromatic nucleus. On the other hand, large alkyl groups, bound to the α-C atoms, decrease the reactivity of the α-C—H bonds.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/prac.19853270612
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    Racematspaltung von 2,3-Diphenylbernsteinsäure (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 1023-1024 
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    ISSN: 0021-8383
    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/prac.19853270622
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    Dynamic N.M.R. studies of hindered rotation on N—C(X) bond fragment XVIIIpart XVII: E. Kleinpeter, S. Behrendt and L. Beyer, Z. anorg. allg. Chem. 495 (1982) 105.. Restricted rotation about the partial C,N-double bond in substituted thioacetamides (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 1025-1027 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270623
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    Use of a Mercury Bubble Electrode for preparative organic electrolysis (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 1028-1032 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270624
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  • 189
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    Nuhn, P.; Hofmann, H.- J.: Molekulare Wirkungsmechanismen von Pharmaka. Eine Einfuhrung in die Molekularpharmakologie. - E. Hofmann, 188 S., 30 Abb., 17 Tab., Berlin: Akademie-Verlag 1985. Wissenschaftliche Taschenbücher (WTB/Biologie) Brosch. 16, - M (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 1036-1036 
    Details
    ISSN: 0021-8383
    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/prac.19853270626
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  • 190
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    Synthese von 2,7,12,17-Tetraoxa-teranaphtho-(1,2-f h f′h′)-dispiro[8.0.8.1]-nonadecan-ein Vertreter des[8.0.8.1] Dispiran-Typs (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 1033-1036 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of 2,7,12,17-Tetraoxa-tetranaphtho-(1,2-fhf′h′)-dispiro[8.0.8.1]-nonadecanes-An Example of [8.0.8.1] DispiranesIn einer früheren Mitteilung[1] wurden Dispiran-Systeme beschrieben, welche Repräsentanten der Klasse [6.0.6.1] waren. Die Synthesen dieser Dispirane erfolgten durch Kondensation des 1,1,2,2-Tetrakis(brommethyl)cyclopropans mit 1,2-Diolen,in die gegenseitige Lage der funktionellen Gruppen jedesmal fixiert und genau bestimmt war. Gegenstand der vorliegenden betrachtungen sind Versuche, eine Synthese des [8.0.8.1]-Dispirans auf ähnlichem Wege, wenn auch unter Verwendung labiler Diphenole auszuarbeiten. Zu diesem Zweck wurden zwei reaktive Diphenole mit extrem verschiedenen Rotationsmöglichketen um die Einfachbindung gewählt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270625
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  • 191
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    Synthese von Heterocyclen durch Cycloaddition. IV. Azomethine als Dienophile (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 1041-1044 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of Heterocyclic Compounds by Cycloaddition Reactions. IV Azomethines as Dienophiles
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270628
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  • 192
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    Radikalabfang. II. Abfang und ESR-spektroskopischer Nachweis von Radikalen CH-acider Pyrazolidin-3,5-dione (1985)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 1037-1040 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spin Trapping. II. Trapping of radicals from CH-acidic Pyrazolidin-3,5-diones and their Detection by ESR-Spectroscopy
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19853270627
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  • 193
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    Masthead (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986) 
    Details
    ISSN: 0021-8383
    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/prac.19863280101
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  • 194
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    Synthesis and reactions of 2-(p-chloroanilino)-5- (D-galacto-1,2,3,4,5-pentahydroxypentyl)-1,3,4-thiadiazole (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 1-6 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidative cyclization of D-galactose (p-chlorophenyl)thiosemicarbazone gave 2-(p-chloroanilino)-5-(D-galacto-1,2,3,4,5-pentahydroxypentyl)-1,3,4-thiadiazole (1), whose acetylation afforded 2-[N-acetyl-N-(p-chlorophenyl)]-amino-5-(D-galacto-1,2,3,4,5-pentacetoxypentyl)- 1,3,4-thiadiazole (3). Its periodate oxidation of the glycol groups gave 2-(p-chloroanilino)-1,3,4-thiadiazole-5-carboxaldehyde (4), which can be transformed into 1,2-[2-(p-chloroanilino)-1,3,4-thiadiazol-5-yl]-1-hydroxy-2-oxoethane. A number of hydrazones of the formyl thiadiazole was prepared and its reduction with sodium borohydride gave 2-(p-chloroanilino)-5-hydroxymethyl-1,3,4-thiadiazole (6), whose acetylation gave a mono-O-acetyl derivative (7). Oxidation of the formyl thiadiazole gave 2-(p-chloroanilino)-1,3,4-thiadiazole (9). The spectral data of the compounds were discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280102
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  • 195
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    Elektrochemische Adamant-1-ylierungen und Tetrahydro-exo-dicyclopentadien-9-ylierungen von Azomethinen (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 7-20 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electrochemical Reductive Alkylation of Azomethines with 1-Bromadamantane and 9-Bromo-tetrahydro-exo-dicyclopentadieneElectrochemically generated radical anions of Schiffbases 1a - 11 react in DMF and in the presence of bridgeheadhalogenides as 1-bromoadamantane and 9-bromo-tetrahydro-exo-dicyclopentadiene to 1-[α-(aryl- or alkylamino)-α-arylmethyl]-adamantanes and the correspondent 9-tetrahydro-exo-dicyclopentadienes. In the course of SET-mechanism originating bridgehead radicals couple with the azomethine-radicalanions at the position of the highest unpaired electron density, which is predominantly the carbon of the C,N-double bond. Only in cases when this density at the N-atom is relatively high, or steric hindrance impedes C-alkylation, N-hydroalkylated products as N,N-disubstituted 1-aminoadamantanes and 9-amino-tetrahydro-exo-dicyclopentadienes are formed. Product distribution, cyclic-voltammetric results and quantumchemical data are discussed in terms of mechanism.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280103
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  • 196
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    NMR-study of the stereochemistry and dynamic behaviour of thioacrylamidesDynamic N. M. R.-Study of Hindered Rotation on NC(X) - Bond Fragment. XIX. (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 120-126 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several model thioacrylamides, Me2N—CH = C(R)—C(S)—NMe2 (R = H, Ph  -  2a, b) and (p)MeO—C6H4—NH—CH=C(R)—C(S)—NMe2 (R = H, Ph  -  3a, b) have been synthesized. The 1H-n.m.r. spectra have been taken for discussing the E/Z-isomerism of the thioacrylamides and the assignment further strengthened by an added LIS-study. The 2-unsubstituted compounds have been found to exist exclusively in preferred configurations/conformations: 2a  -  E(s-cis); 3a  -  Z(s-cis); the 2-phenylsubstituted analogs are of divergent behaviour: in 2b the C(S)—NMe2 moiety is found to be twisted out of the common plane, and 3b prefers the flat s-trans conformations (E(s-trans) ⇌ Z(s-trans)). The compounds show restricted rotations about C1, N- and C3, N-partial double bonds. The corresponding rotational barriers, determined as ΔGc#-values by dynamic n.m.r. spectroscopy, are discussed with respect to (i) the resonance branch at C1, (ii) the influence of substituents, and (iii) the effect of steric hindrance in the thioacrylamide moiety generally.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280115
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  • 197
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    Neue Heterocyclensynthesen mittels Schwefelhalogenverbindungen: Eine neue Synthese von 2,3-Dihydrobenzo-1,4-dioxinen (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 137-141 
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    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Syntheses of Heterocycles by Means of Sulfur-Halogen Compounds: A New Synthesis of 2, 3-Dihydrobenzo-1, 4-dioxins
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280118
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  • 198
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    Anwendung verschiedener chromatographischer Methoden (GC, HPLC und GPC) zur Ermittlung der quantitativen Zusammensetzung verschiedener Anilin-Formaldehyd-Kondensate (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 142-148 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Quantitative Determination of Some Different Condensation Products of Aniline and Formaldehyd by Different Chromatographic Methods
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280119
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  • 199
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    Zur Interpretation relativer Bildungskonstanten von Komplexen mit Lanthanoiden NMR-Verschiebungsreagenzien (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 156-162 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Interpretation of Relative Binding Constants of Complexes with Lanthanide N.M.R. Shift ReagentsThe determination of relative complex binding constants of lanthanide n.m.r. shift reagents (LSR) with organic molecules are based on the assumption that in all cases 1:1 complexes exist. A new interpretation of relative binding constants is given which is applicable also to 1:2 complexes. The new defined constant K* describes the relative tendency of the substrate under consideration to form LSR complexes.Using this method it is shown that Eu(fod)3 and Pr(fod)3 form other complexes than that of the 1 : 1 type.The K* of benzaldehyde-LSR complexes correlate linearly with the Hammett substituent parameters.The occurrence of other than 1:1 associates in the complex formation of para-substituted benzaldehydes with Eu(fod)3 and Pr(fod)3, respectively, could be shown; so we used the new model for these systems. The lg K* of the benzaldehydes in its reaction with the mentioned LSR, as well as with Eu(dpm)3, correlate linearly to the Hammett parameter of the para-substituents.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280203
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  • 200
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    Untersuchungen zur Sensibilisierung von Azofarbstoff-Perhalogenid-Systemen (1986)
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 328 (1986), S. 190-198 
    Details
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Investigations Concerning Sensitization of Silver Free Information Recording Materials with Azo Dyes and Polyhalogen CompoundsRecording materials mentioned in the title are sensitive to the visible region of light. The reason therefore is an energy transfer from the azo dye to the polyhalogen compounds, preferentially CBr4. It's possible to separate the absorption spectra of azo compounds used in this work into two gaussian functions, which relates to n,π*- and π,π*-transitions. Only the excitation of the n,π*-transition causes sensitization. A mechanisms of sensitization is proposed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/prac.19863280207
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