Tailoring the cooperative acid-base effects in silica-supported amine catalysts: Applications in the continuous gas-phase self-condensation of n-butanal

Sankaranarayanapillai Shylesh, David Hanna, Joseph Gomes, Siddarth Krishna, Christian G. Canlas, Martin Head-Gordon, Alexis T. Bell*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

33 Scopus citations

Abstract

A highly efficient solid-base organocatalyst for the gas-phase aldol self-condensation of n-butanal to 2-ethylhexenal was developed by grafting site-isolated amines on tailored silica surfaces. The catalytic activity depends largely on the nature of amine species, the surface concentration of amine and silanol groups, and the spatial separation between the silanol and amine groups. In situ FTIR measurements demonstrated that the formation of nucleophilic enamines leads to the enhanced catalytic activity of secondary amine catalysts, whereas the formation of imines (stable up to 473 K) leads to the low activity observed for silica-supported primary amines. Blocking the silanol groups on the silica support by silylation or cofeeding water into the reaction stream drastically decreased the reaction rates, demonstrating that weaker acidic silanol groups participate cooperatively with the amine groups to catalyze the condensation reaction. This work demonstrates that the spatial separation of the weakly acidic silanols and amines can be tuned by the controlled dehydration of the supporting silica and by varying the linker length of the amine organosilane precursor used to graft the amine to the support surface. A mechanism for aldol condensation was proposed and then analyzed by DFT calculations. DFT analysis of the reaction pathway suggested that the rate-limiting step in aldol condensation is carbon-carbon bond formation, which is consistent with the observed kinetics. The calculated apparent activation barrier agrees reasonably with that measured experimentally. Secondary amines come first: A solid-base organocatalyst achieved by grafting amines onto silica surfaces is applied to the gas-phase aldol self-condensation of n-butanal to 2-ethylhexenal. Silica-supported secondary amine catalysts demonstrate a much higher catalytic activity than the primary amine analogues, owing to the respective formation of enamines as shown by in situ FTIR analysis. The reaction pathway is analyzed by DFT calculations.

Original languageEnglish (US)
Pages (from-to)1283-1290
Number of pages8
JournalChemCatChem
Volume6
Issue number5
DOIs
StatePublished - 2014
Externally publishedYes

Keywords

  • acidity
  • aldol reaction
  • amines
  • organocatalysis
  • silica

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Catalysis

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