Hydroamination reactions of dialkyl esters of 2-buthenedioic acids with polyetheramines under catalytic and non-catalytic conditions

Emília Tálas, Gábor P. Szíjjártó, A. Tompos

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The addition reaction of maleate esters and Jeffamine polyetheramines under mild conditions was fairly rapid in the initial period, then it became extremely slow. In the case of the Jeffamine D-230-dibutyl maleate reactant pair, 0.70 conversion was already achieved after 2 h reaction time, but after 1 day, this value was only 0.83. Product inhibition was excluded. Infrared spectroscopic measurements indicated that an amine catalyzed fast isomerization of the maleates to fumarates can be responsible for the unusual slowdown. While heterogeneous catalysts (Cu-, Zn- and Ni-oxides supported by H-beta zeolite, sulfated zirconia, Al2O3, SiO2) had no effect on the reaction rate, the presence of organocatalysts (3,5-dimethylpyrazole, imidazole, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,1′,3,3′-tetramethylthiourea, etc.) enhanced the activity in the low conversion regime. Azole containing reaction mixtures showed about 10 % larger conversion than the catalyst-free one. However, at high conversions (≥0.95), which could be reached after a week the advantage of the catalyst decreased significantly. The effect of organocatalyst can be explained by the inhibition of the maleate-fumarate isomerization.

Original languageEnglish
JournalReaction Kinetics, Mechanisms and Catalysis
DOIs
Publication statusAccepted/In press - Mar 17 2015

Fingerprint

maleates
esters
Esters
Fumarates
Isomerization
Maleates
acids
Catalysts
Acids
Quinuclidines
catalysts
isomerization
Zeolites
Azoles
Addition reactions
azoles
Zirconia
Oxides
Reaction rates
Amines

Keywords

  • Dibutyl maleate
  • Diethyl maleate
  • Jeffamine D-230
  • Jeffamine D-400
  • Maleate-fumarate isomerization
  • Organocatalysts

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

@article{12f09f5bbfeb49b380aa8e69513255be,
title = "Hydroamination reactions of dialkyl esters of 2-buthenedioic acids with polyetheramines under catalytic and non-catalytic conditions",
abstract = "The addition reaction of maleate esters and Jeffamine polyetheramines under mild conditions was fairly rapid in the initial period, then it became extremely slow. In the case of the Jeffamine D-230-dibutyl maleate reactant pair, 0.70 conversion was already achieved after 2 h reaction time, but after 1 day, this value was only 0.83. Product inhibition was excluded. Infrared spectroscopic measurements indicated that an amine catalyzed fast isomerization of the maleates to fumarates can be responsible for the unusual slowdown. While heterogeneous catalysts (Cu-, Zn- and Ni-oxides supported by H-beta zeolite, sulfated zirconia, Al2O3, SiO2) had no effect on the reaction rate, the presence of organocatalysts (3,5-dimethylpyrazole, imidazole, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,1′,3,3′-tetramethylthiourea, etc.) enhanced the activity in the low conversion regime. Azole containing reaction mixtures showed about 10 {\%} larger conversion than the catalyst-free one. However, at high conversions (≥0.95), which could be reached after a week the advantage of the catalyst decreased significantly. The effect of organocatalyst can be explained by the inhibition of the maleate-fumarate isomerization.",
keywords = "Dibutyl maleate, Diethyl maleate, Jeffamine D-230, Jeffamine D-400, Maleate-fumarate isomerization, Organocatalysts",
author = "Em{\'i}lia T{\'a}las and Sz{\'i}jj{\'a}rt{\'o}, {G{\'a}bor P.} and A. Tompos",
year = "2015",
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TY - JOUR

T1 - Hydroamination reactions of dialkyl esters of 2-buthenedioic acids with polyetheramines under catalytic and non-catalytic conditions

AU - Tálas, Emília

AU - Szíjjártó, Gábor P.

AU - Tompos, A.

PY - 2015/3/17

Y1 - 2015/3/17

N2 - The addition reaction of maleate esters and Jeffamine polyetheramines under mild conditions was fairly rapid in the initial period, then it became extremely slow. In the case of the Jeffamine D-230-dibutyl maleate reactant pair, 0.70 conversion was already achieved after 2 h reaction time, but after 1 day, this value was only 0.83. Product inhibition was excluded. Infrared spectroscopic measurements indicated that an amine catalyzed fast isomerization of the maleates to fumarates can be responsible for the unusual slowdown. While heterogeneous catalysts (Cu-, Zn- and Ni-oxides supported by H-beta zeolite, sulfated zirconia, Al2O3, SiO2) had no effect on the reaction rate, the presence of organocatalysts (3,5-dimethylpyrazole, imidazole, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,1′,3,3′-tetramethylthiourea, etc.) enhanced the activity in the low conversion regime. Azole containing reaction mixtures showed about 10 % larger conversion than the catalyst-free one. However, at high conversions (≥0.95), which could be reached after a week the advantage of the catalyst decreased significantly. The effect of organocatalyst can be explained by the inhibition of the maleate-fumarate isomerization.

AB - The addition reaction of maleate esters and Jeffamine polyetheramines under mild conditions was fairly rapid in the initial period, then it became extremely slow. In the case of the Jeffamine D-230-dibutyl maleate reactant pair, 0.70 conversion was already achieved after 2 h reaction time, but after 1 day, this value was only 0.83. Product inhibition was excluded. Infrared spectroscopic measurements indicated that an amine catalyzed fast isomerization of the maleates to fumarates can be responsible for the unusual slowdown. While heterogeneous catalysts (Cu-, Zn- and Ni-oxides supported by H-beta zeolite, sulfated zirconia, Al2O3, SiO2) had no effect on the reaction rate, the presence of organocatalysts (3,5-dimethylpyrazole, imidazole, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,1′,3,3′-tetramethylthiourea, etc.) enhanced the activity in the low conversion regime. Azole containing reaction mixtures showed about 10 % larger conversion than the catalyst-free one. However, at high conversions (≥0.95), which could be reached after a week the advantage of the catalyst decreased significantly. The effect of organocatalyst can be explained by the inhibition of the maleate-fumarate isomerization.

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KW - Maleate-fumarate isomerization

KW - Organocatalysts

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