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  • 1
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of aryl tert-butyl disulphides (1991)
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 4 (1991), S. 579-585 
    Details
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pyrolysis kinetics of RC6H4SS—t—C4H9 (R=H, p-NO2, p-Cl, p-F) were determined at 390-450°C and 7-15 Torr in a stirred-flow reactor using toluene as carrier gas. The reaction products were 95% isobutene, 5% isobutane and the corresponding RC6H4SSH disulphanes. The first-order rate constants, k (s-1), based on isobutene production, followed the Arrhenius equations: phenyl tert-butyl disulphide, k = 1013.49±0.31 exp (- 182 ± 4 kJ mol-1)(RT)-1; pnitrophenyl tert-butyl disulphide, k = 1013.46 ± 0.32 [exp(- 185 ± 5 kJ mol-1)(RT)-1]; p-chlorophenyl tert-butyl disulphide, k = 1014.44 ± 0.66 [exp(- 196 ± 9 kJ mol-1)(RT)-1; p-fluorophenyl tert-butyl disulphide, k = 1010.80 ± 0.16 exp(- 144.5 ± 2 kJ mol -1)(RT)-1]; The observed reactivities, within the above temperature range, follow the order p—F 〉 H 〉 p—Cl 〉 p—NO2. A four-centre, cuadrupolar cyclic transition state mechanism is proposed for the formation of the isobutene and aryldisulphane products. The optimized ground-state molecular geometries of the reactants were calculated by using the MINDO/3 procedure.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/poc.610040909
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  • 2
    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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  • 3
    Electronic Resource
    Electronic Resource
    Gas phase thermolysis of benzyl t-butyl sulfide, phenyl t-butyl sulfide, and phenyl t-butyl ether (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 193-206 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis kinetics of the title compounds has been studied in a stirred-flow reactor over the temperature range 440-530°C and pressures between 5 and 14 torr. Benzyl t-butyl sulfide and phenyl t-butyl ether formed isobutene as product in over 98% yield, together with the corresponding benzyl thiol and phenol. The benzyl thiol decomposes to a large extent into hydrogen sulfide and bibenzyl. In the pyrolysis of phenyl t-butyl sulfide, the hydrocarbon products consisted of 80 ±5% isobutene plus 20% isobutane, while the sulfur containing products were thiophenol and diphenyl disulfide. Order one kinetics was observed for the consumption of the reactants. The first order rate coefficients, based on isobutene production, followed the Arrhenius equations: Benzyl t-butyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$k(s^{ - 1}) = 10^{13.82 \pm 0.41} \exp ( - 214 \pm 6{\rm kJ/mol }RT)$$\end{document} Phenyl t-butyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$k(s^{ - 1}) = 10^{12.03 \pm 0.39} \exp ( - 188 \pm 6{\rm kJ/mol }RT)$$\end{document} Phenyl t-butyl ether: \documentclass{article}\pagestyle{empty}\begin{document}$$k(s^{ - 1}) = 10^{14.30 \pm 0.21} \exp ( - 211 \pm 3{\rm kJ/mol }RT)$$\end{document}For benzyl t-butyl sulfide and phenyl t-butyl ether, the results suggest a unimolecular mechanism involving polar four center cyclic transition states. For phenyl t-butyl sulfide, the t-butyl-sulfur single bond fission mechanism is a parallel, less important process than the complex fission one.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550210305
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  • 4
    Electronic Resource
    Electronic Resource
    Substituent effects in the gas-phase thermolysis of aryl tert-butyl ethers and sulfides (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 1127-1136 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolyses of p-nitrophenyl t-butyl ether, p-methoxyphenyl t-butyl ether, p-aminophenyl t-butyl ether, p-nitrophenyl t-butyl sulfide, and propargyl t-butyl sulfide have been studied in a stirred-flow reactor over the temperature range 430-530°C and pressures in the range 7-14 torr, using toluene as carrier gas. The reactions yielded between 90 and 99% isobutene plus the corresponding phenol, thiophenol, or thiol as products. The first order rate coefficients for reactant consumption, based on isobutene production, followed the Arrhenius equationsp-nitrophenyl t-butyl ether\documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{12.79 \pm 0.24} {\rm exp}(- 179 \pm 3{\rm kJ/mol}RT) $$\end{document} p-methoxyphenyl t-butyl ether \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{14.50 \pm 0.30} {\rm exp}(- 210 \pm 4{\rm kJ/mol}RT) $$\end{document} p-aminophenyl t-butyl ether: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{14.59 \pm 0.28} {\rm exp}(- 208 \pm 4{\rm kJ/mol}RT) $$\end{document} p-nitrophenyl t-butyl sulfide \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{12.12 \pm 0.27} {\rm exp}(- 185 \pm 4{\rm kJ/mol}RT) $$\end{document} propargyl t--butyl sulfide: \documentclass{article}\pagestyle{empty}\begin{document}$$ k({\rm s}^{ - 1}) = 10^{13.79 \pm 0.24} {\rm exp}(- 204 \pm 3{\rm kJ/mol}RT) $$\end{document}The results support a unimolecular elimination of the isobutene involving polar, four-center cyclic transition states.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550221103
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  • 5
    Electronic Resource
    Electronic Resource
    Erratum (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 593-594 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260513
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  • 6
    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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  • 7
    Electronic Resource
    Electronic Resource
    Gas-phase thermolysis of allyl propargyl amine, allyl cyanomethyl propargyl amine, allyl propargyl 2-thiapropyl amine, and allyl methanesulfonyl propargyl amine (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 487-496 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title amines have been pyrolyzed in a stirred-flow reactor, at temperatures of 360-500°C, pressures of 7-16 torr, and residence times of 0.5-2.9 s, using toluene as carrier gas. The reaction products were allene, propene, and the corresponding imines. The ratio allene:propene varied in the range 6.7-1.6. The amines with CH2CN and SO2CH3 substituents also formed HCN and SO2. These appear to arise from complex free radical decomposition of the imine product. The first-order rate coefficients for the production of allene plus propene followed the Arrhenius equations: Allyl propargl amine: \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left({{\rm s}^{- 1}} \right) = 10^{10.07 \pm 0.31} \exp \left({- 133 \pm 4{\rm kj/mol\,}RT} \right) $$\end{document} Allyl cyanomethyl propargyl amine: \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left({{\rm s}^{- 1}} \right) = 10^{10.73 \pm 0.30} \exp \left({- 146 \pm 4{\rm kj/mol\,}RT} \right) $$\end{document} Allyl propargyl 2-thiapropyl amine: \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left({{\rm s}^{- 1}} \right) = 10^{12.55 \pm 0.38} \exp \left({- 166 \pm 5{\rm kj/mol\,}RT} \right) $$\end{document} Allyl methanesulfonyl propargyl amine: \documentclass{article}\pagestyle{empty}\begin{document}$$ k\left({{\rm s}^{- 1}} \right) = 10^{12.56 \pm 0.34} \exp \left({- 184 \pm 5{\rm kj/mol\,}RT} \right) $$\end{document} Nonconcerted mechanisms, involving polar six center cyclic transition states, are suggested for the elimination of allene and propene. © 1994 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260409
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  • 8
    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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  • 9
    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.
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  • 10
    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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