One-pot synthesis of Biginelli and Hantzsch products catalyzed by non-toxic ionic liquid (BMImSac) and structural determination of two products
One-pot synthesis of Biginelli and Hantzsch products catalyzed by non-toxic ionic liquid (BMImSac) and structural determination of two products
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DOI：
10.1016/j.molcata.2006.05.028
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发表时间：
2006-10
影响因子：
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通讯作者：
Ming Li;Weisi Guo;L. Wen;Yafeng Li;Huabin Yang
中科院分区：
文献类型：
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作者：
Ming Li;Weisi Guo;L. Wen;Yafeng Li;Huabin Yang
本文以醛、β-二羰基化合物和尿素为原料，以无毒室温离子液体1-正丁基-3-甲基咪唑糖化钠（BMImSac）为催化剂，在一锅内合成了1,4-二氢吡啶酮（Hantzsch产物）和3,4-二氢嘧啶酮（Biginelli产物）。离子液体（BMImSac）是一种环境友好型离子液体。为了提高反应的收率和选择性，研究了反应物摩尔比和溶剂摩尔比对反应的影响。有趣的是，通过增加乙酰乙酸乙酯的量或用水作为溶剂，会产生一种意想不到的副产品，即不同于Biginelli产品的Hantzsch产品。所有Biginelli和Hantzsch产物同时纯化，并通过IR、1H NMR和13c NMR进行了表征，其中一个Biginelli产物（4h）和一个Hantzsch产物（5b）通过x射线单晶衍射进行了结构鉴定。4 h的晶体数据:三斜晶系的系统,p - 1空间群,a = 7.515 (3), b = 9.011 (4) a, c = 11.218(5),α= 106.288(6)°,β= 104.644(6)°,γ= 100.234(6)°,Z = 2, V = 679.7 (5) A3, Dc = 1.36克/立方厘米,R1 = 0.0603。5b：单斜晶系，P2(1)/c空间群，a=9.765(3)Å， b=7.391(2)Å， c=24.795(7)Å， β=93.669(5)°，Z=4， V=1785.7(9)Å3, Dc=1.292g/cm3, R1=0.0440。
In this paper, both 1,4-dihydropyridinones (Hantzsch products) and 3,4-dihydropyrimidinones (Biginelli products) are synthesized in one-pot of aldehydes, β-dicarbonyl compounds and urea, catalyzing by non-toxic room temperature ionic liquid 1-n-butyl-3-methylimidazolium saccharinate (BMImSac). The ionic liquid (BMImSac) is environmentally benign associated with ionic liquid with F−. In order to improve the yield and selectivity, the effects of the mole proportion of reactants and solvents are investigated. Interestingly, by increasing the amount of ethyl acetoacetate or utilizing water as solvent, an unexpected by-product, Hantzsch product which is distinct from Biginelli product, is generated. All Biginelli and Hantzsch products are simultaneously purified and characterized by IR,1H NMR and13C NMR, of which one Biginelli product (4h) and one Hantzsch product (5b) are structurally determinated by X-ray single crystal diffraction. The crystal data for 4h: triclinic system, P-1 space group, a=7.515(3)Å, b=9.011(4)Å, c=11.218(5)Å, α=106.288(6)°, β=104.644(6)°, γ=100.234(6)°, Z=2, V=679.7(5)Å3, Dc=1.36g/cm3, R1=0.0603. The crystal data for 5b: monoclinic system, P2(1)/c space group, a=9.765(3)Å, b=7.391(2)Å, c=24.795(7)Å, β=93.669(5)°, Z=4, V=1785.7(9)Å3, Dc=1.292g/cm3, R1=0.0440.