An effort to generalize the thermal isomerization of 6,6-dimethylbicyclo[3.1.1]heptanes and 6,6-dimethylbicyclo[3.1.1]heptenes: Comparative pyrolysis of pinane, α-pinene, and β-pinene

Stolle, Achim; Ondruschka, Bernd

doi:10.1016/j.jaap.2008.12.002

Cited by 16 publications

(24 citation statements)

References 45 publications

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“…The reaction mechanism for the thermal isomerization of pinane-and pinene-type compounds has been extensively discussed in literature and it is generally agreed upon that the fragmentation of the four-membered ring is the initial step in the thermal isomerization of bicyclic monoterpenes consisting of a bicyclo[3.1.1]heptane system [26][27][28][29][30][31][32][33][34][35][36]. Two types of cyclobutane rupture mechanisms were proposed to explain the formation of the different primary acyclic and monocyclic pyrolysis products: a concerted mechanism of the cyclobutane fragmentation containing a 4--electron anti-aromatic transition state and a stepwise mechanism with biradical intermediates.…”

Section: Introductionmentioning

confidence: 99%

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Kinetic study of the thermal rearrangement of cis- and trans-2-pinanol

Vandewiele

Reyniers

Marin

2011

Journal of Analytical and Applied Pyrolysis

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Section: Introductionmentioning

confidence: 99%

“…Stolle et al investigated the mechanism and kinetics of the gasphase isomerization of monoterpenes [26,31] and showed that there are mechanistic analogies in the isomerization of pinaneand pinene-type structures. Moreover, the authors were able to model reactivity differences between cis-pinane and trans-pinane.…”

Section: Introductionmentioning

confidence: 99%

Kinetic study of the thermal rearrangement of cis- and trans-2-pinanol

Vandewiele

Reyniers

Marin

2011

Journal of Analytical and Applied Pyrolysis

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“…Bicyclo[3.1.1]hept-2-ene (1), named "norpinene," was first established in 1972, [1] well after the C 10 H 16 terpene hydrocarbon α-pinene had been and still is studied intensively. [2][3][4][5][6] In 1974, Dietrich and Musso followed two C 7 H 9 D bicyclo[3.1.1]hept-2-enes demonstrating a degenerate thermal isomerization (Scheme 1). [7] Starting with 3-d-1, thermal energy results in evolution toward a 50:50 1-d-1:d-3-1 pair of the two compounds.…”

Section: Introductionmentioning

confidence: 99%

Degenerate thermal isomerizations of bicyclo[3.1.1]hept‐2‐ene: strategy and analysis

Baldwin

Hudson

2014

J of Physical Organic Chem

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Bicyclo[3.1.1]hept‐2‐ene was first prepared and well identified in 1972. In 1974, the degenerate thermal isomerization involving 1‐d‐ and 3‐d‐bicyclo[3.1.1]hept‐2‐ene was approached successfully, as one of the two deuterium‐labeled structures was selected, heated, and equilibrated. There has been no further study of this degenerate isomerization. Here, a detailed outline of reaction trajectories for d2‐labeled bicyclo[3.1.1]hept‐2‐enes is given that will establish the four independent kinetic parameters needed for 20 linking paths between six d2‐species. The use of racemates, eliminating chiral separations and dissections, provides degenerate isomerization paths providing this method with general utility. Copyright © 2014 John Wiley & Sons, Ltd.

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“…has reported that (3 Z )‐ocimene ( 3 ) is mainly obtained from the thermal isomerization reaction of α‐pinene ( 1 ). Moreover, a fast isomerization of ocimene ( 3 ) to allo‐ocimene ( 4 ) at a relatively high temperature has been proposed by various authors . In this paper, the thermal isomerization reaction of α‐pinene is discussed once more from a mechanistic and kinetic point of view.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, a fast isomerization of ocimene (3) to allo-ocimene (4) at a relatively high temperature has been proposed by various authors. [11][12][13] In this paper, the thermal isomerization reaction of a-pinene is discussed once more from a mechanistic and kinetic point of view.…”

Section: Introductionmentioning

confidence: 99%

A comparative study on the gas‐phase and liquid‐phase thermal isomerization reaction of α‐pinene

Gong

Zhao

et al. 2012

J of Physical Organic Chem

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In this paper, a method of preparation of ocimene is investigated, which is obtained from isomerization reaction of α‐pinene. Two kinds of experimental apparatus are established for the investigation of the thermal isomerization reaction of α‐pinene. The behavior of thermal isomerization reaction of α‐pinene is respectively discussed in the gas phase and in the liquid phase. Under gas phase conditions, the conversion of α‐pinene is 80% and the selectivity of ocimene is 30%–33%. Under liquid phase conditions, the conversion of α‐pinene is 60% and the selectivity of ocimene is 50%–54%. According to the kinetic‐molecular theory of ideal gases, two kinds of reaction models are proposed to visualize the reaction process. In addition, the mechanism and kinetics of thermal isomerization reaction of α‐pinene are respectively discussed. The conclusion is that the gas phase reaction temperature is calculated to be 390–450 °C and the liquid phase reaction temperature is calculated to be 450–550 °C. From a bond dissociation energy point of view, results support the hypothesis that the reaction involves biradical intermediates. Copyright © 2012 John Wiley & Sons, Ltd.

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An effort to generalize the thermal isomerization of 6,6-dimethylbicyclo[3.1.1]heptanes and 6,6-dimethylbicyclo[3.1.1]heptenes: Comparative pyrolysis of pinane, α-pinene, and β-pinene

Cited by 16 publications

References 45 publications

Kinetic study of the thermal rearrangement of cis- and trans-2-pinanol

Kinetic study of the thermal rearrangement of cis- and trans-2-pinanol

Degenerate thermal isomerizations of bicyclo[3.1.1]hept‐2‐ene: strategy and analysis

A comparative study on the gas‐phase and liquid‐phase thermal isomerization reaction of α‐pinene

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