Mechanismus der protonkatalysierten gasphasendehydratisierung von furfurylalkohol

H. Thies; R. Wolfschütz; G. Frenking; J. Schmidt; H. Schwarz

doi:10.1016/0040-4020(82)80141-5

Mechanismus der protonkatalysierten gasphasendehydratisierung von furfurylalkohol

H. Thies, R. Wolfschütz, G. Frenking, J. Schmidt, H. Schwarz

Technical University of Berlin

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12 Scopus citations

Abstract

The gas phase proton catalysed water elimination of tetrahydrofurfuryl alcohol (1) gives exclusively the ring-enlarged oxonium-ion 12. There is no experimental indication for the generation of 11 via a [1.2]-hydrogen migration. From the analysis of appropriately ¹³C-labelled precursors in combination with collisional activation mass spectrometry the mechanism for the ring-enlargement has been derived, clearly indicating that the oxygen/carbon bond is cleaved. A comparison of the experimental results with computational investigation (ab initio molecular orbital calculations at the 4-31G level) suggests that free tetrahydrofurfuryl cation 7 is not generated in the gas phase solvolysis. The elimination of H₂O from the protonated molecule of 1 is a process characterised by anchimeric assistance of the ether oxygen 15.

Original language	German
Pages (from-to)	1647-1656
Number of pages	10
Journal	Tetrahedron
Volume	38
Issue number	11
DOIs	https://doi.org/10.1016/0040-4020(82)80141-5
State	Published - 1982
Externally published	Yes

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title = "Mechanismus der protonkatalysierten gasphasendehydratisierung von furfurylalkohol",

abstract = "The gas phase proton catalysed water elimination of tetrahydrofurfuryl alcohol (1) gives exclusively the ring-enlarged oxonium-ion 12. There is no experimental indication for the generation of 11 via a [1.2]-hydrogen migration. From the analysis of appropriately 13C-labelled precursors in combination with collisional activation mass spectrometry the mechanism for the ring-enlargement has been derived, clearly indicating that the oxygen/carbon bond is cleaved. A comparison of the experimental results with computational investigation (ab initio molecular orbital calculations at the 4-31G level) suggests that free tetrahydrofurfuryl cation 7 is not generated in the gas phase solvolysis. The elimination of H2O from the protonated molecule of 1 is a process characterised by anchimeric assistance of the ether oxygen 15.",

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T1 - Mechanismus der protonkatalysierten gasphasendehydratisierung von furfurylalkohol

AU - Thies, H.

AU - Wolfschütz, R.

AU - Frenking, G.

AU - Schmidt, J.

AU - Schwarz, H.

PY - 1982

Y1 - 1982

N2 - The gas phase proton catalysed water elimination of tetrahydrofurfuryl alcohol (1) gives exclusively the ring-enlarged oxonium-ion 12. There is no experimental indication for the generation of 11 via a [1.2]-hydrogen migration. From the analysis of appropriately 13C-labelled precursors in combination with collisional activation mass spectrometry the mechanism for the ring-enlargement has been derived, clearly indicating that the oxygen/carbon bond is cleaved. A comparison of the experimental results with computational investigation (ab initio molecular orbital calculations at the 4-31G level) suggests that free tetrahydrofurfuryl cation 7 is not generated in the gas phase solvolysis. The elimination of H2O from the protonated molecule of 1 is a process characterised by anchimeric assistance of the ether oxygen 15.

AB - The gas phase proton catalysed water elimination of tetrahydrofurfuryl alcohol (1) gives exclusively the ring-enlarged oxonium-ion 12. There is no experimental indication for the generation of 11 via a [1.2]-hydrogen migration. From the analysis of appropriately 13C-labelled precursors in combination with collisional activation mass spectrometry the mechanism for the ring-enlargement has been derived, clearly indicating that the oxygen/carbon bond is cleaved. A comparison of the experimental results with computational investigation (ab initio molecular orbital calculations at the 4-31G level) suggests that free tetrahydrofurfuryl cation 7 is not generated in the gas phase solvolysis. The elimination of H2O from the protonated molecule of 1 is a process characterised by anchimeric assistance of the ether oxygen 15.

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DO - 10.1016/0040-4020(82)80141-5

M3 - 文章

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SN - 0040-4020

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JO - Tetrahedron

JF - Tetrahedron

IS - 11

ER -

Mechanismus der protonkatalysierten gasphasendehydratisierung von furfurylalkohol

Abstract

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