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

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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.

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Acknowledgments

The authors thank to Dr. Benedek Vakulya for providing organocatalyst (thiourea-CN) and Dr. Magdolna Mihályi for providing H-beta zeolite as a gift. The help in the infrared analysis by Prof. Enikő Földes is greatly acknowledged. The ESI–MS measurement by Dr. Ágnes Gömöry (Core Technologies Centre, RCNS, HAS) and the NMR measurements by Dr. Orsolya Egyed (Core Technologies Centre, RCNS, HAS) are also greatly acknowledged.

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Authors and Affiliations

  1. Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok körútja 2, Budapest, 1117, Hungary

    Emília Tálas, Gábor P. Szíjjártó & András Tompos

  2. P.O.Box 286, Budapest, 1519, Hungary

    András Tompos

Authors
  1. Emília Tálas
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  2. Gábor P. Szíjjártó
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  3. András Tompos
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Correspondence to András Tompos.

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Tálas, E., Szíjjártó, G.P. & Tompos, A. Hydroamination reactions of dialkyl esters of 2-buthenedioic acids with polyetheramines under catalytic and non-catalytic conditions. Reac Kinet Mech Cat 115, 431–447 (2015). https://doi.org/10.1007/s11144-015-0851-2

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