Synthesis of the covalent benzene-carbon monoxide cycloadduct, norborna-2,5-dien-7-one: Correlation of kinetic and thermodynamic stabilities in cycloreversion reactions

Synthesis of the covalent benzene-carbon monoxide cycloadduct, norborna-2,5-dien-7-one: Correlation of kinetic and thermodynamic stabilities in cycloreversion reactions

endo-Tricyclo[4.2.1.02,5]non-7-ene-3,4,9-trione (14) is prepared from the 5,5-diethoxy-cyclopcntadiene-diethyl maleate Diels-Alder adduct. Photolysis of the trione in CD2Cl2 solution at 192 K forms norborna-2,5-dien-7-one (2). The latter substance is thermally unstable and decomposes to benzene and...

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Veröffentlicht in:Tetrahedron 1986, Vol.42 (6), p.1561-1570
Hauptverfasser: Birney, David M., Berson, Jerome A.
Format: Artikel
Sprache:eng
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Alicyclic compounds
Alicyclic compounds, terpenoids, prostaglandins, steroids
Chemistry
Exact sciences and technology
Organic chemistry
Preparations and properties
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container_title Tetrahedron
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creator Birney, David M.
Berson, Jerome A.
description endo-Tricyclo[4.2.1.02,5]non-7-ene-3,4,9-trione (14) is prepared from the 5,5-diethoxy-cyclopcntadiene-diethyl maleate Diels-Alder adduct. Photolysis of the trione in CD2Cl2 solution at 192 K forms norborna-2,5-dien-7-one (2). The latter substance is thermally unstable and decomposes to benzene and CO with ΔG‡ =15 kcal mol-1. This appears to be the lowest activation energy for a cycloreversion yet measured. A correlation is found for the kinetic and thermodynamic stabilities in a series of 18 orbital symmetry allowed cycloreversions by plotting ΔG‡ vs ΔHr.
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Photolysis of the trione in CD2Cl2 solution at 192 K forms norborna-2,5-dien-7-one (2). The latter substance is thermally unstable and decomposes to benzene and CO with ΔG‡ =15 kcal mol-1. This appears to be the lowest activation energy for a cycloreversion yet measured. 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subjects Alicyclic compounds
Alicyclic compounds, terpenoids, prostaglandins, steroids
Chemistry
Exact sciences and technology
Organic chemistry
Preparations and properties
title Synthesis of the covalent benzene-carbon monoxide cycloadduct, norborna-2,5-dien-7-one: Correlation of kinetic and thermodynamic stabilities in cycloreversion reactions
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