Hydroamination reactions of dialkyl esters of 2-buthenedioic acids with polyetheramines under catalytic and non-catalytic conditions
Hydroamination reactions of dialkyl esters of 2-buthenedioic acids with polyetheramines under catalytic and non-catalytic conditions
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2-丁烯二酸二烷基酯与聚醚胺在催化和非催化条件下的氢胺化反应
DOI：
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发表时间：
2015
期刊：
影响因子：
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通讯作者：
A. Tompos
中科院分区：
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作者：
E. Tálas;Gábor P. Szíjjártó;A. Tompos
在温和条件下，马来酸酯与Jeffamine聚醚胺的加成反应在初始阶段相当迅速，然后变得非常缓慢。在Jeffamine D-230-马来酸二甲酯反应物对的情况下，在2小时反应时间后已经达到0.70转化率，但在1天后，该值仅为0.83。排除产物抑制。红外光谱测量表明，胺催化的马来酸酯到马来酸酯的快速异构化可以负责不寻常的减速。非均相催化剂（H-β沸石负载的Cu-、Zn-和Ni-氧化物、硫酸化氧化锆、Al 2 O3、SiO2）对反应速率没有影响，有机催化剂（3，5-二甲基吡唑、咪唑、奎宁环、1，4-二氮杂双环[2.2.2]辛烷、1，1 ′，3，3 ′-四甲基硫脲等）的存在对反应速率有影响。提高了低转化率范围内的活性。含唑的反应混合物显示出比不含催化剂的反应混合物高约10%的转化率。然而，在高转化率（≥0.95）下，其可在一周后达到，催化剂的优势显著降低。有机催化剂的作用可以通过抑制马来酸-富马酸异构化来解释。
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.