The syntheses of pyrazino-containing sultines and their application in Diels-Alder reactions with electron-poor olefins and [60]fullerene

Jing Horng Liu, An Tai Wu, Ming Hwei Huang, Chein Wei Wu, Wen Sheng Chung

Research output: Contribution to journalArticle

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Abstract

The Diels-Alder reactions of heterocyclic o-quinodimethanes, generated in situ from 6,7-disubstituted quinoxalino[2,3-d]-[1,2λ4]oxathiine 2-oxides (6a-c), 2,3-disubstituted-8,9-dihydro-6H-8λ4-[1,2]oxathiino[4,5- g]quinoxalin-8-one (7a-c) (sultines), and pyrazinosultine (22), with electron-poor olefins and [60]fullerene are described. The heterocyclic-fused sultines 7a-c and 22 are readily prepared from the corresponding dibromides 9a-c and 24 with the commercially available Rongalite (sodium formaldehyde sulfoxylate). When heated in the presence of electron-poor dienophiles and [60]fullerene, all of the sultines underwent extrusion of SO2, and the resulting heterocyclic o-quinodimethanes (3a-d, 4a-c, and 25) were intercepted as the 1:1 adducts in good to excellent yields. The temperature- dependent 1H NMR spectra of fullerene derivatives 31-38 show a dynamic process for the methylene protons. The activation free energies (ΔG(c)(+)) determined for the boat-to-boat inversion of these pyrazino-containing C60 compounds (31-34 and 38) are found to be in the range of 14.1-14.8 kcal/mol, but they are in the range of 15.2 to > 17.1 kcal/mol for adducts 35-37. The activation free energies (ΔG(c)(+)) are significantly affected by (1) the orientations and (2) the substituents of the quinoxaline rings and (3) the extended benzannulation in the arenes of C60 adducts (see Table 2), which implies that both electronic interactions and steric effects between the aromatic addends and C60 are important. Tautomerization of methylquinoxaline to its enamine is invoked as a rationalization for the lowering of ΔG(c)(+) in some of the fulleroadducts.

Original languageEnglish
Pages (from-to)3395-3403
Number of pages9
JournalJournal of Organic Chemistry
Volume65
Issue number11
DOIs
Publication statusPublished - 2000 Jun 2

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Alkenes
Quinoxalines
Boats
Oxathiins
Free energy
Electrons
Chemical activation
Fullerenes
Oxides
Formaldehyde
Extrusion
Protons
Sodium
Nuclear magnetic resonance
Derivatives
fullerene C60
Temperature

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Liu, Jing Horng ; Wu, An Tai ; Huang, Ming Hwei ; Wu, Chein Wei ; Chung, Wen Sheng. / The syntheses of pyrazino-containing sultines and their application in Diels-Alder reactions with electron-poor olefins and [60]fullerene. In: Journal of Organic Chemistry. 2000 ; Vol. 65, No. 11. pp. 3395-3403.
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abstract = "The Diels-Alder reactions of heterocyclic o-quinodimethanes, generated in situ from 6,7-disubstituted quinoxalino[2,3-d]-[1,2λ4]oxathiine 2-oxides (6a-c), 2,3-disubstituted-8,9-dihydro-6H-8λ4-[1,2]oxathiino[4,5- g]quinoxalin-8-one (7a-c) (sultines), and pyrazinosultine (22), with electron-poor olefins and [60]fullerene are described. The heterocyclic-fused sultines 7a-c and 22 are readily prepared from the corresponding dibromides 9a-c and 24 with the commercially available Rongalite (sodium formaldehyde sulfoxylate). When heated in the presence of electron-poor dienophiles and [60]fullerene, all of the sultines underwent extrusion of SO2, and the resulting heterocyclic o-quinodimethanes (3a-d, 4a-c, and 25) were intercepted as the 1:1 adducts in good to excellent yields. The temperature- dependent 1H NMR spectra of fullerene derivatives 31-38 show a dynamic process for the methylene protons. The activation free energies (ΔG(c)(+)) determined for the boat-to-boat inversion of these pyrazino-containing C60 compounds (31-34 and 38) are found to be in the range of 14.1-14.8 kcal/mol, but they are in the range of 15.2 to > 17.1 kcal/mol for adducts 35-37. The activation free energies (ΔG(c)(+)) are significantly affected by (1) the orientations and (2) the substituents of the quinoxaline rings and (3) the extended benzannulation in the arenes of C60 adducts (see Table 2), which implies that both electronic interactions and steric effects between the aromatic addends and C60 are important. Tautomerization of methylquinoxaline to its enamine is invoked as a rationalization for the lowering of ΔG(c)(+) in some of the fulleroadducts.",
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The syntheses of pyrazino-containing sultines and their application in Diels-Alder reactions with electron-poor olefins and [60]fullerene. / Liu, Jing Horng; Wu, An Tai; Huang, Ming Hwei; Wu, Chein Wei; Chung, Wen Sheng.

In: Journal of Organic Chemistry, Vol. 65, No. 11, 02.06.2000, p. 3395-3403.

Research output: Contribution to journalArticle

TY - JOUR

T1 - The syntheses of pyrazino-containing sultines and their application in Diels-Alder reactions with electron-poor olefins and [60]fullerene

AU - Liu, Jing Horng

AU - Wu, An Tai

AU - Huang, Ming Hwei

AU - Wu, Chein Wei

AU - Chung, Wen Sheng

PY - 2000/6/2

Y1 - 2000/6/2

N2 - The Diels-Alder reactions of heterocyclic o-quinodimethanes, generated in situ from 6,7-disubstituted quinoxalino[2,3-d]-[1,2λ4]oxathiine 2-oxides (6a-c), 2,3-disubstituted-8,9-dihydro-6H-8λ4-[1,2]oxathiino[4,5- g]quinoxalin-8-one (7a-c) (sultines), and pyrazinosultine (22), with electron-poor olefins and [60]fullerene are described. The heterocyclic-fused sultines 7a-c and 22 are readily prepared from the corresponding dibromides 9a-c and 24 with the commercially available Rongalite (sodium formaldehyde sulfoxylate). When heated in the presence of electron-poor dienophiles and [60]fullerene, all of the sultines underwent extrusion of SO2, and the resulting heterocyclic o-quinodimethanes (3a-d, 4a-c, and 25) were intercepted as the 1:1 adducts in good to excellent yields. The temperature- dependent 1H NMR spectra of fullerene derivatives 31-38 show a dynamic process for the methylene protons. The activation free energies (ΔG(c)(+)) determined for the boat-to-boat inversion of these pyrazino-containing C60 compounds (31-34 and 38) are found to be in the range of 14.1-14.8 kcal/mol, but they are in the range of 15.2 to > 17.1 kcal/mol for adducts 35-37. The activation free energies (ΔG(c)(+)) are significantly affected by (1) the orientations and (2) the substituents of the quinoxaline rings and (3) the extended benzannulation in the arenes of C60 adducts (see Table 2), which implies that both electronic interactions and steric effects between the aromatic addends and C60 are important. Tautomerization of methylquinoxaline to its enamine is invoked as a rationalization for the lowering of ΔG(c)(+) in some of the fulleroadducts.

AB - The Diels-Alder reactions of heterocyclic o-quinodimethanes, generated in situ from 6,7-disubstituted quinoxalino[2,3-d]-[1,2λ4]oxathiine 2-oxides (6a-c), 2,3-disubstituted-8,9-dihydro-6H-8λ4-[1,2]oxathiino[4,5- g]quinoxalin-8-one (7a-c) (sultines), and pyrazinosultine (22), with electron-poor olefins and [60]fullerene are described. The heterocyclic-fused sultines 7a-c and 22 are readily prepared from the corresponding dibromides 9a-c and 24 with the commercially available Rongalite (sodium formaldehyde sulfoxylate). When heated in the presence of electron-poor dienophiles and [60]fullerene, all of the sultines underwent extrusion of SO2, and the resulting heterocyclic o-quinodimethanes (3a-d, 4a-c, and 25) were intercepted as the 1:1 adducts in good to excellent yields. The temperature- dependent 1H NMR spectra of fullerene derivatives 31-38 show a dynamic process for the methylene protons. The activation free energies (ΔG(c)(+)) determined for the boat-to-boat inversion of these pyrazino-containing C60 compounds (31-34 and 38) are found to be in the range of 14.1-14.8 kcal/mol, but they are in the range of 15.2 to > 17.1 kcal/mol for adducts 35-37. The activation free energies (ΔG(c)(+)) are significantly affected by (1) the orientations and (2) the substituents of the quinoxaline rings and (3) the extended benzannulation in the arenes of C60 adducts (see Table 2), which implies that both electronic interactions and steric effects between the aromatic addends and C60 are important. Tautomerization of methylquinoxaline to its enamine is invoked as a rationalization for the lowering of ΔG(c)(+) in some of the fulleroadducts.

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