Phenyl vs. carbomethoxy group effect on selectivity during hydrogenation and exchange of α,β-unsaturated esters over modified and unmodified deuterated Raney nickel

Gerard V. Smith, Ruozhi Song, Joseph M. Delich, M. Bartók

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2 Citations (Scopus)

Abstract

A series of variously substituted α,β-unsaturated methyl esters were hydrogenated with deuterium (deuteriumated) over deuterated Raney nickel, modified deuterated Raney nickel, and Pd/C. The deuterated Raney nickel catalysts were prepared by leaching Ni-Al alloy with NaOD in D2O. Each gram of deuterated Raney nickel can furnish approximately 45 to 50 m2L of D2 (STP), which is readily exchanged even from traces of atmospheric water. Deuterium distributions are similar for deuteriumations using either D2 or N2 gas overlaying reaction mixtures of deuterated Raney nickel and substrate in dioxane. However, N2produced less deuterium in the products because of atmospheric water contamination. L-glutamic acid modification of deuterated Raney nickel also produces less deuterium in the products, but deuterium distributions remain unchanged. Raney nickel does not catalyze simple 1,2-cis (syn) addition of deuterium across C=C double bonds but distributes deuterium among carbons contiguous to the double bonds. The distributions are influenced by structure and substituents; however, the results are adequately explained by the half-hydrogenated state mechanism.

Original languageEnglish
Pages (from-to)67-74
Number of pages8
JournalStudies in Surface Science and Catalysis
Volume78
Issue numberC
DOIs
Publication statusPublished - 1993

Fingerprint

Deuterium
Nickel
Hydrogenation
hydrogenation
esters
deuterium
Ion exchange
Esters
selectivity
nickel
glutamic acid
Water
leaching
products
water
Leaching
Glutamic Acid
contamination
Contamination
Carbon

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Catalysis
  • Physical and Theoretical Chemistry
  • Materials Chemistry
  • Surfaces, Coatings and Films

Cite this

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title = "Phenyl vs. carbomethoxy group effect on selectivity during hydrogenation and exchange of α,β-unsaturated esters over modified and unmodified deuterated Raney nickel",
abstract = "A series of variously substituted α,β-unsaturated methyl esters were hydrogenated with deuterium (deuteriumated) over deuterated Raney nickel, modified deuterated Raney nickel, and Pd/C. The deuterated Raney nickel catalysts were prepared by leaching Ni-Al alloy with NaOD in D2O. Each gram of deuterated Raney nickel can furnish approximately 45 to 50 m2L of D2 (STP), which is readily exchanged even from traces of atmospheric water. Deuterium distributions are similar for deuteriumations using either D2 or N2 gas overlaying reaction mixtures of deuterated Raney nickel and substrate in dioxane. However, N2produced less deuterium in the products because of atmospheric water contamination. L-glutamic acid modification of deuterated Raney nickel also produces less deuterium in the products, but deuterium distributions remain unchanged. Raney nickel does not catalyze simple 1,2-cis (syn) addition of deuterium across C=C double bonds but distributes deuterium among carbons contiguous to the double bonds. The distributions are influenced by structure and substituents; however, the results are adequately explained by the half-hydrogenated state mechanism.",
author = "Smith, {Gerard V.} and Ruozhi Song and Delich, {Joseph M.} and M. Bart{\'o}k",
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T1 - Phenyl vs. carbomethoxy group effect on selectivity during hydrogenation and exchange of α,β-unsaturated esters over modified and unmodified deuterated Raney nickel

AU - Smith, Gerard V.

AU - Song, Ruozhi

AU - Delich, Joseph M.

AU - Bartók, M.

PY - 1993

Y1 - 1993

N2 - A series of variously substituted α,β-unsaturated methyl esters were hydrogenated with deuterium (deuteriumated) over deuterated Raney nickel, modified deuterated Raney nickel, and Pd/C. The deuterated Raney nickel catalysts were prepared by leaching Ni-Al alloy with NaOD in D2O. Each gram of deuterated Raney nickel can furnish approximately 45 to 50 m2L of D2 (STP), which is readily exchanged even from traces of atmospheric water. Deuterium distributions are similar for deuteriumations using either D2 or N2 gas overlaying reaction mixtures of deuterated Raney nickel and substrate in dioxane. However, N2produced less deuterium in the products because of atmospheric water contamination. L-glutamic acid modification of deuterated Raney nickel also produces less deuterium in the products, but deuterium distributions remain unchanged. Raney nickel does not catalyze simple 1,2-cis (syn) addition of deuterium across C=C double bonds but distributes deuterium among carbons contiguous to the double bonds. The distributions are influenced by structure and substituents; however, the results are adequately explained by the half-hydrogenated state mechanism.

AB - A series of variously substituted α,β-unsaturated methyl esters were hydrogenated with deuterium (deuteriumated) over deuterated Raney nickel, modified deuterated Raney nickel, and Pd/C. The deuterated Raney nickel catalysts were prepared by leaching Ni-Al alloy with NaOD in D2O. Each gram of deuterated Raney nickel can furnish approximately 45 to 50 m2L of D2 (STP), which is readily exchanged even from traces of atmospheric water. Deuterium distributions are similar for deuteriumations using either D2 or N2 gas overlaying reaction mixtures of deuterated Raney nickel and substrate in dioxane. However, N2produced less deuterium in the products because of atmospheric water contamination. L-glutamic acid modification of deuterated Raney nickel also produces less deuterium in the products, but deuterium distributions remain unchanged. Raney nickel does not catalyze simple 1,2-cis (syn) addition of deuterium across C=C double bonds but distributes deuterium among carbons contiguous to the double bonds. The distributions are influenced by structure and substituents; however, the results are adequately explained by the half-hydrogenated state mechanism.

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