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  • 21
    Electronic Resource
    Electronic Resource
    Gas phase thermolysis of N-(tert-butylthio)allylamine and N-(tert-butylthio)diethylamine (1994)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 7 (1994), S. 585-590 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The title sulphenamides were pyrolysed in a stirred-flow reactor at temperatures of 310-410°C, pressures of 8-15 Torr and residence times of 0·4-2 s using toluene as the carrier gas. N-(tert-Butylthio)allylamine formed 73 ± 4% isobutene, 23 ± 3% propene and N-allylthiohydroxylamine. The first-order rate coefficients for the formation of isobutene and propene, respectively, followed the Arrhenius equations kC4(s-1) = 1012·52 ± 0·36 exp(-163 ± 5 kJ mol-1 RT) and kC3(s-1) = 1010·99 ± 0·29 exp(-151 ± 4 kJ mol-1 RT) N-(tert-Butylthio)diethylamine gave 97 ± 1% isobutene, 1·9 ± 0·4% isobutane and N,N-diethylthiohydroxylamine. The first-order rate coefficients for isobutene elimination followed the Arrhenius equation k(s-1) = 1013·45 ± 0·24 exp(-164 ± 3 kJ mol-1 RT). The formation of the products is interpreted in terms of an elimination reaction with a unimolecular, four-centered, cyclic transition state. The reactivity of these sulphenamides was found to be much higher than that of previously studied alkyl or aryl tert-butyl sulphides and disulphides.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610071102
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  • 22
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of N-substituted diallyl- and allylpropargylamines (1997)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 10 (1997), S. 49-54 
    Details
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ---Various diallyl- and allylpropargylamines were pyrolyzed in a stirred-flow reactor at temperatures in the range of 330-500°C, pressures of 8-16 Torr and residence times of 0·4-2·4 s using toluene as carrier gas. The reaction products were propene, allene and aldimines. The allene to propene ratio changed considerably with the third substituent on the N atom. At conversions in the range 13-55%, the consumption of the amines showed first-order kinetics. The following Arrhenius parameters [A (s-1) and Ea (kJ mol-1)] were obtained from the rate coefficients: diallyl-tert-butylamine, log  A = 10·32 ± 0·12, Ea = 139 ± 2; diallylneopentylamine, log A = 12·87 ± 0·26, Ea = 168 ± 3; allylpropargyl-tert-butylamine, log A = 10·23 ± 0·18, Ea = 126 ± 2; allylpropargyltosylamine, log A = 13·05 ± 0.36, Ea = 197 ± 5; and allylpropargylphenylamine, log A = 12·10 ± 0·35, Ea = 162 ± 4. Polar, six-center cyclic transition states are suggested for the elimination of propene and allene, via non-concerted bond breaking-bond forming mechanisms. © 1997 John Wiley & Sons, Ltd.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 23
    Electronic Resource
    Electronic Resource
    Stereochemistry of organic sulphur compounds: 12For Part 11, see Ref. 1. - Configurational assignment of 2-methylsulphinyl-1-phenylethanol and some O-derivatives (1983)
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 21 (1983), S. 643-648 
    Details
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational analysis of the diastereomeric 2-methylsulphinyl-1-phenylethanol and its O-methyl and O-acetyl derivatives has been performed by 1H NMR spectroscopy. The study of the influence of dilution and solvent polarity changes on the coupling constants has permitted the configurational assignment of each diastereoisomer. The role played by hydrogen bonding in the hydroxysulphoxides has also been studied by IR spectroscopy.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/omr.1270211010
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  • 24
    Electronic Resource
    Electronic Resource
    Enantiomerenreine Palladacyclen aus β-KetosulfoxidenDiese Arbeit wurde durch das CICYT (PB 93-0257 und SAF 93-1122, HB-059) unterstützt. I. L.-S. dankt der Dirección General de Investigación Cientifica y Tecnica (DGlCYT) für finanzielle Unterstützung. (1995)
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 107 (1995), S. 1452-1454 
    Details
    ISSN: 0044-8249
    Keywords: Komplexe mit Schwefelliganden ; ortho-Metallierung ; Palladiumverbindungen ; Sulfoxide ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ange.19951071214
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  • 25
    Electronic Resource
    Electronic Resource
    Gas phase thermolysis of allyl cyanomethyl amine, diallyl cyanomethyl amine, diethyl cyanomethyl amine, and diethyl propargyl amine (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 99-108 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title amines were pyrolyzed in a stirred-flow reactor at 380-510°C, pressures of 8-15 torr and residence times of 0.3-2.4 s, using toluene as carrier gas. The substrates with an allyl group yielded propene and iminonitriles as reaction products. HCN is formed by decomposition of the iminonitriles. The first-order rate coefficients for propene formation fit the Arrhenius equations Allyl cyanomethyl amine:\documentclass{article} \pagestyle{empty} \begin{document} $$ k({\rm s}^{ - {\rm 1}}) = 10^{13.29 \pm 0.35} {\rm exp(} - {\rm 189} \pm 5{\rm kJ/mol }RT{\rm)} $$ \end{document}Diallyl cyanomethyl amine:\documentclass{article} \pagestyle{empty} \begin{document} $$ k({\rm s}^{ - {\rm 1}}) = 10^{13.00 \pm 0.20} {\rm exp(} - {\rm 183} \pm 3{\rm kJ/mol }RT{\rm)} $$ \end{document} Diethyl cyanomethyl amine gave a 20:1 gas mixture of ehylene and ethane, plus HCN. The liquid product fraction contained mainly N-ethyl methanaldimine. The first-order rate coefficients for ethylene formation followed the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - {\rm 1}}) = 10^{15.30 \pm 0.24} {\rm exp(} - {\rm 226} \pm 3{\rm kJ/mol }RT{\rm)} $$\end{document} Diethyl propargyl amine decomposed cleanly into allene and N-ethyl ethanaldimine. The first-order rate coefficients for allene formation fit the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - {\rm 1}}) = 10^{12.84 \pm 0.30} {\rm exp(} - {\rm 168} \pm 4{\rm kJ/mol }RT{\rm)} $$\end{document} The results suggest that the above allyl and propargyl amines decompose unimolecularly by mechanisms involving six-center cyclic transition states. For diethyl cyanomethyl amine, a nonchain free radical mechanism is proposed. © 1995 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270203
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  • 26
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of t-butylsulfenamides: N, N-dimethyl t-butylsulfenamide, 2,6-dimethylpiperidinyl t-butylsulfenamide, and N-t-butyl t-butylsulfenamide (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 353-359 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amide derivatives of t-butylsulfenic acid mentioned in the title have been thermolyzed in a stirred-flow reactor at temperatures of 273-390°C and pressures of 7-15 torr, using toluene as carrier gas, at residence times of 0.4-2 s. Isobutene formed in 95-99% yields, through order one reactions, following the Arrhenius equations: N, N-dimethyl t-butylsulfenamide: $$k(s^{-1})=10^{14.45\pm 0.46}\exp(-175\pm 5 {\rm kJ/mol}\,{\bf RT})$$ 2,6-dimethylpiperidyl t-butylsulfenamide: $$k(s^{-1})=10^{14.38\pm 0.26}\exp(-161\pm 3 {\rm kJ/mol}\,{\bf RT})$$ N-t-butyl t-butylsulfenamide: $$k(s^{-1})=10^{14.75\pm 0.37}\exp(-184\pm 7 {\rm kJ/mol}\,{\bf RT})$$These thermolyses are considered to take place through unimolecular, four-center cyclic transition-state reaction mechanisms, giving rise to isobutene plus the corresponding S-unsubstituted thiohydroxylamines. The latter decompose outside the reactor at temperatures above -78°C forming free sulfur and dimethylamine, 2,6-dimethylpiperidine, and t-butylamine, respectively. © 1996 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.4
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  • 27
    Electronic Resource
    Electronic Resource
    Gas phase thermolysis of aryl t-butyl amines (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 631-638 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-t-butylaniline, N-t-butyl-p-anisidine, and N-t-butyl-p-nitroaniline have been pyrolyzed in a stirred-flow reactor at 510-620°C, 8-15 torr total pressure, and 0.5-1.5 s contact time, using toluene as carrier gas. An order one kinetics was observed for the consumption of the amines. The reactions yielded 95 ± 2% isobutene plus the corresponding anilines as reaction products. The rate coefficients followed the Arrhenius equations N-t-butylaniline \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 10^{14.19 \pm 0.32} \exp (- 234 \pm 5\,{\rm kJ/mol}\, RT) $$\end{document} N-t-butyl-p-anisidine \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 10^{13.05 \pm 0.23} \exp (- 208 \pm 4\,{\rm kJ/mol}\, RT) $$\end{document} N-t-butyl-p-nitroaniline \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 10^{13.73 \pm 0.28} \exp (- 235 \pm 6\,{\rm kJ/mol}\, RT) $$\end{document}The results are consistent with an unimolecular elimination of isobutene involving polar four-center cyclic transition states. © John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550240703
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  • 28
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of N-cyanomethyl-N-ethyl aniline, N-cyanomethyl-N-ethyl-p-anisidine, and N-cyanomethyl-N-ethyl-p-nitroaniline (1998)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 451-456 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-cyanomethyl-N-ethyl aniline (CEAN) and N-cyanomethyl-N-ethyl-p-anisidine (CEPA) have been thermolyzed in a stirred-flow reactor, in the range of 510-560 °C, pressures of 7-11 torr and residence times of 0.5-0.9 s, using toluene as carrier gas. N-cyanomethyl-N-ethyl-p-nitroaniline (ECNA) was thermolyzed at 640°C and 13% conversion. Ethylene and HCN formed in 43% yield each as products from all three starting materials. Phenyl methanaldimine and p-anisidyl methanaldimine were also products of CEAN and CEPA, respectively. The consumption of CEAN and CEPA showed first-order kinetics for a three-fold increase of reactant inflow and initial conversions of up to 40 percent. The following Arrhenius equations were obtained from the rate coefficients for the production of ethylene: CEAN: k=1015.10±0.74 exp(-238±11 kJ/mol·RT); CEPA: k=1015.61±0.29 exp(-246±4 kJ/mol·RT). The results are explained by means of radical, nonchain thermolysis mechanisms. The thermochemistry of relevant reaction steps has been estimated from thermochemical parameters calculated by using the semiempirical AM1 method. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 451-456, 1998
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 29
    Electronic Resource
    Electronic Resource
    Semiempirical study of compounds with intramolecular O—H…O hydrogen bonds. II. Further verification of a modified MNDO method (1994)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 15 (1994), S. 183-189 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: In the forerunner of this article, we described a MNDO modification designed for studies of compounds with intramolecular O—H…O hydrogen bonds. Here, we report the further verification of the modification by means of its application to 14 compounds not considered in its development. Comparison of the calculated structural parameters and proton transfer characteristics with available experimental or ab initio results, and with those obtained using MNDO, AM1, MNDO/H, MNDO/M, and PM3, supports the validity of the new modification for prediction of hydrogen bond characteristics. © 1994 by John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540150208
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  • 30
    Electronic Resource
    Electronic Resource
    Semiempirical study of compounds with O-H—O intramolecular hydrogen bond (1992)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 13 (1992), S. 860-866 
    Details
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Application of MNDO, AM1, PM3, MNDO/H, and MNDO/M methods to a set of compounds with intramolecular hydrogen bonds suggested that none of these methods accurately modeled the characteristics of the hydrogen bonds. Since the MNDO/H and MNDO/M methods work well for intermolecular hydrogen bonds, we followed their example and modified MNDO for intramolecular hydrogen bonds by altering the empirical core-core repulsion energy function for all pairs of atoms involved in intramolecular O-H—O bonds. The resulting modified method models the behavior of these bonds quite well, especially as regards their geometry and the barrier to proton transfer. © 1992 by John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jcc.540130710
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