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  • 1
    Electronic Resource
    Electronic Resource
    Gas-Phase Kinetics of the Pyrolysis of Some 3,3-Dimethyl-1-(trimethylsilyl)-cyclopropenes  -  Unexpected Product Distribution in the Cyclopropene Rearrangement (1994)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 127 (1994), S. 237-245 
    Details
    ISSN: 0009-2940
    Keywords: Cyclopropenes, 3,3-dimethyl-1-trimethylsilyl-substituted ; Cyclopropene, isomerisation ; Gas-phase kinetics ; Ring opening ; Diradical intermediates ; Cyclopropylidene intermediates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase pyrolyses of 1,3,3-trimethyl-2-(trimethylsilyl)-cyclopropene (9), 3,3-dimethyl-1,2-bis(trimethylsilyl)cyclopropeneTextReactantlog (A/s-1)Ea/kj mol-1(kcal mol-1)913.41 ± 0.22192.1 ± 2.5(45.9 ± 0.6)1013.54 ± 0.19184.4 ± 2.1(44.1 ± 0.5)1112.17 ± 0.38124.6 ± 3.1(29.8 ± 0.7)(10), and 3,3-dimethyl-1-(methylthio)-2-(trimethylsilyl)cyclopropene (11) have been studied, and the pressure-independent Arrhenius parameters listed in the table were obtained. All three rearrangements are homogeneous, first-order and unimolecular reactions. Rather surprisingly all reactions give the corresponding isomeric allenes as the main products. Amongst possible mechanisms discussed, 10 is proposed to react via a cyclopropylidene intermediate, whilst the results for 9 and 11 throw light on the relative importance of the diradical- and vinylcarbene-type intermediates produced by cyclopropene ring opening.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19941270134
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  • 2
    Electronic Resource
    Electronic Resource
    Thermolyse von Ansaran, Ansaren und Cuban (1983)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1415-1421 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermolysis of Ansarane, Ansarene and CubaneThe thermolysis and kinetics of decomposition of cubane 4 and of ring enlarged cubanes, the ansaranes 1 - 3, are described. The relief of strain which will be observed breaking specific bonds has been estimated by the aid of force-field calculations thereby disclosing probable reaction pathways. The gas phase pyrolysis of cubane 4 yields vibrationally excited cyclooctatetraene 5 which fragmentates to benzene and acetylene. The gas kinetics of cyclooctatetraene 5 is reported on as well.
    Notes: Die Thermolyse und Zerfallskinetik ringerweiterter Cubane, der Ansarane 1 - 3, sowie des Cubans 4 selbst, werden beschrieben. Mit Hilfe von Kraftfeldrechnungen wird die Spannungserleichterung beim Bruch bestimmter Bindungen abgeschätzt, und wahrscheinliche Thermolysewege werden aufgezeigt. Das bei der Gasphasenthermolyse von Cuban 4 gebildete schwingungsangeregte Cyclooctatetraen 5 fragmentiert zu Benzol und Acetylen. Über die Gasphasenkinetik von Cyclooctatetraen wird ebenfalls berichtet.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19831160417
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  • 3
    Electronic Resource
    Electronic Resource
    An experimental approach to the C8H10 hypersurface. Kinetic and thermochemical investigations on a formally forbidden ground-state [2σ + 2π] cycloaddition (1987)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 120 (1987), S. 177-186 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die C8H10-Kohlenwasserstoffe 1, 3, 4 und 6 wurden im statischen System thermolysiert, und die Arrhenius-Parameter wurden gemessen. Die Bildungswärmen wurden kalorimetrisch bestimmt. Aus diesen Daten läßt sich eine experimentelle Energiehyperfläche konstruieren, die folgende Merkmale aufweist: 1) Die Grundzustandsenergie von endo-1 ist um 8 kcal mol-1 höher als die von exo-4. 2) Der wichtigste Reaktionsweg ausgehend von endo-1 ist die formal verbotene [2σ + 2π]-Cycloaddition zu 3, deren Mechanismus diskutiert wird. 3) Obwohl die Aktivierungsenergien der Wege 4→6 und 4→3 gleich sind, verläft die Reaktion zu 6 aufgrund des größeren A-Faktors rascher. 4) Der Tetracyclus 3 thermolysiert gemäß dem Prinzip der mikroskopischen Reversibilität über exo-4 zu dem Dien 6.
    Notes: The C8H10 hydrocarbons 1, 3, 4, and 6 have been thermolyzed in a static system and the Arrhenius parameters have been obtained. Calorimetric measurements have been carried out to determine the heats of formation. From these data an experimental energy hypersurface is constructed which shows the following remarkable features: 1) The ground-state energy of endo-1 is higher than that of exo-4 by 8 kcal mol-1. 2) The predominant reaction pathway of endo-1 is the formally forbidden [2σ + 2π] cycloaddition to 3, the mechanism of which is discussed. 3) Although the activation energies of the routes 4→6 and 4→3 are the same, the reaction yielding 6 is faster due to a sizeably higher A factor. 4) The tetracycle 3 chooses the microscopic reverse pathway, i.e. its thermolysis proceeds via exo-4 to give the diene 6.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19871200209
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  • 4
    Electronic Resource
    Electronic Resource
    Gas-Phase Kinetics of the Thermal 1-Alkoxy-1-vinylcyclopropane to 1-Alkoxy-1-cyclopentene Rearrangement (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 939-945 
    Details
    ISSN: 0009-2940
    Keywords: 1-Vinylcyclopropane ; 1-methoxy- ; 1-ethoxy- ; Vinylcyclopropane ; isomerization ; Gas-phase kinetics ; Ring expansion of 1-alkoxy-1-vinylcyclopropanes ; Diradical intermediates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title studies have been carried out with both 1-vinyl-1-cyclopropyl methyl ether (1-OMe) and 1-vinyl-1-cyclopropyl ethyl ether (1-OEt) in the temperature ranges 274.6-324.5 and 273.6 - 323.0°C, respectively. Both reactions predominantly give the vinylcyclopropane-cyclopentene (VCP-CP) rearrangement products 1-cyclopenten-1-yl methyl ether (2-OMe) and 1-cyclopenten-1-yl ethyl ether (2-OEt). Additionally, 2-OEt eliminates ethene (3) in a consecutive reaction at a lower reaction rate compared with the VCP-CP rearrangement. The rearrangements obey first-order kinetics and have been shown to be homogeneous, pressure-independent reactions with the following Arrhenius equations:\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {1 - {\rm OMe:}} {{\rm lg}\left({k/s^{-1}} \right) = \left({13.89 \pm 0.23} \right) - \left({191.30 \pm 2.55{\rm kJ mol}^{-1}} \right)/RT\ln 10} \\\end{array} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {1 - {\rm OMt:}} {{\rm lg}\left({k/s^{-1}} \right) = \left({13.77 \pm 0.01} \right) - \left({188.80 \pm 1.85{\rm kJ mol}^{-1}} \right)/RT\ln 10} \\\end{array} $$\end{document}The Arrhenius parameters represent reliable values for general 1-vinyl-1-cyclopropyl alkyl ether→1-cyclopenten-1-yl-alkyl ether (1-OR→2-OR) rearrangements within a large temperature interval in the gas phase. The results support a mechanism proceeding via a diradical. The stabilizing effect of methoxy substitution is discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240439
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  • 5
    Electronic Resource
    Electronic Resource
    Thermal Rearrangements, XX[1] The Kinetics of Thermal Isomerisation of 4-Methyl-1,2,5-hexatriene in the Gas Phase (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 711-721 
    Details
    ISSN: 0009-2940
    Keywords: 1,2,5-Hexatriene, 4-methyl-, thermal isomerisation ; Kinetic measurements ; Thermal isomerisations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Methyl-1,2,5-hexatriene (13) has been prepared and subjected to gas-phase pyrolysis. Above 220°C, 13 rearranges reversibly to both trans-5-hepten-1-yne (14) and its cis-isomer 15. Formation of 14 is faster than that of 15. These isomerisations are accompanied by a slower irreversible rearrangement to 1-methyl-4-methylene-1-cyclopentene (16) and 1-methyl-3-methylene-1-cyclopentene (17). Rate constants and Arrhenius parameters have been obtained for all these reactions which were shown to be homogeneous and unimolecular. For the processes 13 ⇄ 14 and 13 ⇄ 15 the data are consistent with [3,3] Cope-type sigmatropic rearrangements. For the process 13 → 16 + 17, a rate-determining formation of the 1-methyl-3-methylenecyclopentane-2,5-diyl diradical is proposed. The rearrangements form a consistent pattern with other known examples. - The equilibrium data are shown to be in good agreement with thermodynamic estimates based on Group Additivity. The additivity scheme of Benson required extension to provide values for two new group contributions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250326
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  • 6
    Electronic Resource
    Electronic Resource
    Gas phase kinetics of pyrolysis of 1-methyl-1-cyclopropene (1985)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 3579-3587 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Die Gasphasenkinetik der Pyrolyse von 1-Methyl-1-cyclopropenDie Pyrolyse von 1-Methyl-1-cyclopropen wurde im Temperaturbereich von 210 - 250°C untersucht. Als Isomerisierungsprodukte wurden 2-Butin (91 - 94%), 1,3-Butadien (5 - 8%) und 1,2-Butadien (1 - 2%) nachgewiesen; andere Produkte entstehen bei vollständiger Materialbilanz (±5% Abweichung vom berechneten Wert) nicht. Die Reaktion verläuft nach einem Zeitgesetz 1. Ordnung, wobei die isomeren Produkte in parallelen Reaktionswegen gebildet werden. Die Umlagerungen erfolgen unimolekular und homogen, obwohl in gepackten Reaktionsgefäßen eine gewisse Oberflächenabhängigkeit beobachtet wurde. Charakteristisches „fall-off“-Verhalten tritt in Gegenwart von SF6 unterhalb von 20 Torr, in Gegenwart von N2 unterhalb von 100 Torr ein. Die Gesamtreaktion läßt sich innerhalb des Hochdruckbereichs durch die folgende Arrhenius-Gleichung beschreiben: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log ({\rm k/s}^{{\rm - 1}}) = (12.91 \pm 0.15) - (160 \pm 1.5{\rm kJ\, mol}^{{\rm - 1}})/RT\ln 10 $$\end{document} Auf ähnliche Weise wurden die Arrhenius-Gleichungen der konkurrierenden Reaktionswege ermittelt. Die Resultate werden im Rahmen der Theorie des Übergangszustands diskutiert und stellen eine beträchtliche Verbesserung früherer Untersuchungen dar. Es wird vorgeschlagen, daß alle Produkte durch 1,2-Wasserstoffwanderungen aus einem diradikalischen Intermediat entstehen; die Wanderungstendenz der verschiedenen Wasserstoffatome wird diskutiert. Überraschenderweise desaktiviert ein 1-Methylsubstituent die Isomerisierungsneigung des Cyclopropensystems.
    Notes: The title study has been carried out in the temperature range 210 - 250°C. The isomerisation products are 2-butyne (91 - 94%), 1,3-butadiene (5 - 8%), and 1,2-butadiene (1 - 2%). No other products were detected and material recovery was complete within experimental error (±5%). The reaction obeyed first-order kinetics, with the products formed by parallel pathways, and appeared to be both unimolecular and homogeneous although some surface sensitivity was detected in packed vessels. Studies of pressure dependence showed characteristic rate constant „fall-off“ below 20 Torr (SF6) and 100 Torr (N2). Within at least 2% of the high pressure limit, the following Arrhenius equation for overall decomposition was found: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log ({\rm k/s}^{{\rm - 1}}) = (12.91 \pm 0.15) - (160 \pm 1.5{\rm kJ\, mol}^{{\rm - 1}})/RT\ln 10 $$\end{document}Arrhenius equations were similarly found for the individual pathways. The figures are discussed in the light of Transition State Theory and represent a significant improvement over a previous study. It is argued that all products arise via 1,2-H shifts in a diradical-like intermediate and the propensities for different H shifts are discussed. A 1-methyl substituent, rather surprisingly, deactivates cyclopropene in its isomerisation reactions.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19851180914
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  • 7
    Electronic Resource
    Electronic Resource
    Thermal Behaviour of C8H8 Hydrocarbons Gas-Phase Thermolysis of Cuneane, a New Example of a High-Strain Energy Release Process (1988)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 121 (1988), S. 369-372 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Das Thermolyseverhalten von C5H8-Kohlenwasserstoffen.  -  Gasphasen-Thermolyse von Cuncan, ein neues Beispiel für die Freisetzung hoher SpannungsenergieDie Kinetik der Gasphasenthermolyse von Cunean2) (1) wurde im Temperaturbereich von 180-220°C untersucht. Es handelt sich um eine Reaktion erster Ordnung, die zu zwei C8H8-Isomeren führt, zu Semibullvalen (2) und Cyclooctatetraen (3). Die Geschwindigkeitskonstante ist abhängig von der Temperatur entsprechend der Arrhenius-Gleichung log(k/s-1) = (13.82 ± 0.09) - (37.7 ± 0.2 kcal mol-1)/RT In10. Die Arrheniusparameter stimmen mit einem biradikalischen Mechanismus überein, der zur Bildung von Semibullvalen (2) führt. Die Produktverteilung ist druckabhängig. Dies deutet darauf hin, daß das zuerst gebildete Semibullvalen (2) hoch schwingungsangeregt (ca. 74 kcal mol-1) ist und zu Cyclooctatetraen (3) weiterreagiert.
    Notes: The kinetics of thermal decomposition of cuneane2) (1) in the gas phase have been investigated in the temperature range 180-220°C. The reaction is a clean first-order homogeneous process leading to the formation of two C8H8 isomers, viz., semibullvalene3) (2) and cyclooctatetraene (3). The rate constant varies with temperature according to the Arrhenius equation log(k/S-1) = (13.82 ± 0.09) - (37.7 ± 0.2 kcal mol-1)/RT In10. The Arrhenius parameters are consistent with a biradical mechanism leading to the formation of semibullvalene (2). The product proportions are pressure-dependent which strongly suggests that semibullvalene (2) is initially formed with high vibrational energy content (ca. 74 kcal mol-1) and can react further to give cyclooctatetraene (3).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19881210225
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  • 8
    Electronic Resource
    Electronic Resource
    Thermal Rearrangements, XIX. The Kinetics of the Thermal Isomerization of 1-Ethynyl-2,2,3,3-tetramethylcyclopropane (1989)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 377-382 
    Details
    ISSN: 0009-2940
    Keywords: Cyclopropane, 1-ethynyl-2,2,3,3-tetramethyl- ; Isomerization, thermal ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermische Umlagerungen, XIX. - Kinetik der thermischen Isomerisierung von 1-Ethinyl-2,2,3,3-tetramethylcyclopropanDie Darstellung und Gasphasenpyrolyse von 1-Ethinyl-2,2,3,3-tetramethylcyclopropan (9) werden beschrieben. Oberhalb 200°C lagert sich der Kohlenwasserstoff in 4,4,5-Trimethyl-1,2,5-hexatrien (10) und 5,6-Dimethyl-5-hepten-1-in (11) um. Während sich das Allen durch eine 1,5-Wasserstoffwanderung direkt aus 9 bildet, handelt es sich bei dem Alkin um ein Sekundärprodukt, das aus 10 durch eine [3,3]-sigmatrope Umlagerung entsteht. Die Aktivierungsparameter (Ea, lg A) dieser beiden Prozesse wurden im Temperaturbereich von 210-250°C ermittelt. Die erhaltenen Zahlenwerte werden diskutiert und mit denjenigen anderer konzertierter Reaktionen von Alkinen und Alkenen verglichen.
    Notes: 1-Ethynyl-2,2,3,3-tetramethylcyclopropane (9) has been prepared and subjected to gas phase pyrolysis. Above 200°C the hydrocarbon rearranges to 4,4,5-trimethyl-1,2,5-hexatriene (10) and 5,6-dimethyl-5-hepten-1-yne (11). Whereas the allene is produced directly from 9 by a 1,5-hydrogen shift, the alkyne is a secondary product formed from 10 by a [3,3] sigmatropic rearrangement. The activation parameters (Ea, lg A) for both processes have been determined for the 210 to 250°C temperature range. The data are discussed and compared with those for other concerted reactions of alkynes and alkenes.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19891220228
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  • 9
    Electronic Resource
    Electronic Resource
    Gas-Phase Kinetics of Pyrolysis of 3,3-Dimethylcyclopropene and Its 1-Trimethylsilyl Derivative The Effect of Silyl Substitution on Cyclopropene Isomerisation (1989)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 122 (1989), S. 637-642 
    Details
    ISSN: 0009-2940
    Keywords: Cyclopropene, 3,3-dimethyl-1-trimethylsilyl- ; Cyclopropene, isomerisation ; Gas-phase kinetics ; Ring-opening of 3,3-dimethylcyclopropene ; Vinylcarbene intermediates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Gas-Phasen-Kinetik der Pyrolyse von 3,3-Dimethylcyclopropen und seinem 1-Trimethylsilyl-Derivat. - Der Effekt der Silyl-Substitution auf die Cyclopropen-IsomerisierungDie Gasphasen-Pyrolyse von 3,3-Dimethylcyclopropen (1) im Temperaturbereich 185-225°C ergibt 3-Methyl-1-butin (2) (91%) und Isopren (3) (9%). Die Gasphasen-Pyrolyse von 3,3-Dimethyl-1-trimethylsilylcyclopropen (4) führt zu 3-Methyl-1-trimethylsilyl-1-butin (5) (99%) und trans-3-Methyl-1-trimethylsilyl-1,3-butadien (6) (1%). Beide Umlagerungen sind homogene, unimolekulare Reaktionen erster Ordnung mit den folgenden druck-unabhängigen Arrhenius-Parametern.Überraschenderweise desaktiviert die Trimethylsilyl-Gruppe das Cyclopropen in bezug auf seine Isomerisierung. Mögliche Mechanismen werden diskutiert.
    Notes: The gas-phase pyrolysis of 3,3-dimethylcyclopropene (1) in the temperature range of 185-225°C gives 3-methyl-1-butyne (2) (91%) and isoprene (3) (9%). The gas-phase pyrolysis of 3,3-dimethyl-1-trimethylsilylcyclopropene (4) in the temperature range of 195-235°C gives 3-methyl-1-trimethylsilyl-1-butyne (5) (99%) and trans-3-methyl-1-trimethylsilyl-1,3-butadiene (6) (1%). Both rearrangements are homogeneous, first-order, unimolecular reactions with the following pressure-independent Arrhenius parameters.Rather surprisingly, the trimethylsilyl group deactivates cyclopropene with respect to its isomerisation. Possible mechanisms are discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19891220409
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reaction between iodine and trifluorosilane and the bond dissociation energy D(F3Si—H) (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 101-110 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction has been investigated in the temperature range 667-715K. The only reaction products were trifluorosilyl iodide and hydrogen iodide. The rate law \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d\left[{{\rm I}_2} \right]}}{{dt}} = \frac{{k\left[{{\rm I}_2} \right]^{1/2} \left[{{\rm F}_3 {\rm SiH}} \right]}}{{1 + k\prime \left[{{\rm HI}} \right]/\left[{{\rm I}_2} \right]}} $$\end{document} was obeyed over a wide range of iodine and trifluorosilane pressures. This expression is consistent with an iodine atom abstraction mechanism and for the step \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}^ \cdot + {\rm F}_3 {\rm SiH}\mathop {\longrightarrow}\limits^1 {\rm F}_3 {\rm Si}^\cdot + {\rm HI} $$\end{document} log k1(dm3/mol·sec) = (11.54 ± 0.17) - (130.5 ± 2.2 kJ/mol)/RT In 10 has been deduced. From this the bond dissociation energy D(F3Si—H) = (419 ± 5) kJ/mol (100.1 kcal/mol) is obtained. The kinetic andthermochemical implications of this value are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100108
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