Comprehensive kinetic and mechanistic considerations for the gas-phase behaviour of pinane-type compounds

被引：24

作者：

Stolle, Achim ^{[1
]}

Ondruschka, Bernd

Bonrath, Werner

机构：

[1] Univ Jena, Inst Tech Chem & Environm Chem, D-07743 Jena, Germany

[2] DSM Nutr Prod, R&D Chem Proc Technol, CH-4002 Basel, Switzerland

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 2007卷 / 14期

关键词：

terpenoids; pyrolysis; reaction mechanisms; rearrangement; radical reactions; kinetic modelling;

D O I：

10.1002/ejoc.200601098

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The thermal behaviour of selected pinane-type compounds, alpha-pinene (1), beta-pinene (2), pinane (3) and nopinone (4), has been investigated. The conversion of the bicyclic starting materials to their acyclic and monocyclic isomers as well as the consecutive reactions of the acyclic main isomerisation products are discussed. The conversion of 1-4 in a reaction network is presented and the experimental evidence for the formation of pyrolysis products by a biradical pathway is discussed. In addition to these results a kinetic model describing the isomerisation of the bicyclic compounds to their acyclic and monocyclic isomers is presented. A good correlation between kinetic simulations and experimental data is revealed. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).

引用

页码：2310 / 2317

页数：8

共 25 条

[1] PYROLYSIS OF PINANES .8. PYROLYSIS OF SOME PINANONES [J].

COXON, JM ;

GARLAND, RP ;

HARTSHOR.MP .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1972, 25 (11) :2409-&

[2]

ELOERS B, 1996, ULLMANNS ENCY IND A, V27, P267

[3] The kinetics, stereochemistry, and deuterium isotope effects in the α-pinene pyrolysis.: Evidence for incursion of multiple conformations of a diradical [J].

Gajewski, JJ ;

Kuchuk, I ;

Hawkins, C ;

Stine, R .

TETRAHEDRON, 2002, 58 (34) :6943-6950

[4] Evidence for concert in the thermal unimolecular vinylcyclopropane to cyclopentene sigmatropic 1,3-shift [J].

Gajewski, JJ ;

Olson, LP ;

Willcott, MR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (02) :299-306

[5]

HAWKINS JE, 1954, J PHYS CHEM-US, V57, P902

[6] THE RATES OF THE THERMAL ISOMERIZATION OF ALPHA-PINENE AND BETA-PINENE IN THE LIQUID PHASE [J].

HUNT, HG ;

HAWKINS, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1950, 72 (12) :5618-5620

[7] REACTIONS OF DIOLEFINS AT HIGH TEMPERATURES .2. THE CYCLIZATION OF 1,6-OCTADIENE AND 7-METHYL-1,6-OCTADIENE [J].

HUNTSMAN, WD ;

SOLOMON, VC ;

EROS, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1958, 80 (20) :5455-5458

[8] Kinetics of 2-pinanol isomerization to linalool on the monolith carbon-containing catalyst [J].

Il'ina, II ;

Simakova, IL ;

Semikolenov, VA .

KINETICS AND CATALYSIS, 2001, 42 (05) :686-692

[9]

Joshi PL, 2000, J CHEM RES, P38

[10] Gas-phase OH oxidation of monoterpenes: Gaseous and particulate products [J].

Larsen, BR ;

Di Bella, D ;

Glasius, M ;

Winterhalter, R ;

Jensen, NR ;

Hjorth, J .

JOURNAL OF ATMOSPHERIC CHEMISTRY, 2001, 38 (03) :231-276

← 1 2 3 →