One of the most helpful strategies for the synthesis of the title compounds is that of multicomponent reactions (MCRs). In MCRs three or more reactants form products such that all or most of the initial atoms are present in the final product. This has clear benefits in terms of cost, efficiency and environmental stewardship. There are some literature methods for the synthesis of ortho-aminocarbonitrile derivatives, and these include using such reagents as N-butylpyridinium tetrafluoroborate [BPy]BF4, 5 ammonium acetate, imidazole, ethanediamine, b-1-imidazol-2,3,4,6-tetraacetyl-D-glucopyranosyl bromide ([Bmim-G]þ[Br]-),9 ortho-benzenedisulfonimide (OBS) or triethylammonium acetate (TEAA), and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) 11 as catalysts. Although all of the above synthetic methods have advantages, they also suffer from some limitations such as long reaction times, low yields, and extensive work-up. We would now like to report our method for the synthesis of ortho-aminocarbonitrile derivatives by condensation of aldehydes (1 equiv.) and malononitrile (2 equiv.) with cyclohexanone (1 equiv) utilizing the nanostructured diphosphate Na2CaP2O7 12–18 as catalyst (Scheme 1). This was done in continuation of our previous studies. In order to obtain the best conditions for our reaction, we optimized the parameters as listed in Table 1. We found that the best conditions for this reaction constituted reflux in ethanol in the presence of 30mol% of nanostructured diphosphate Na2CaP2O7. To illustrate the effect of nanostructured diphosphate Na2CaP2O7 in promoting the formation of the bicyclic ortho-aminocarbonitriles, the model reaction was performed under the optimized reaction conditions but in the absence of catalyst. No significant product formation was observed even after 240min (Entry 7). In order to explore the extent of this reaction, we investigated the use of several aldehydes as substrates. Moreover, the scope and efficiency of the reaction were explored for cyclopentanone (entries 4l-4m). The results are listed in Table 2. The recyclability of the nanocatalyst in the reaction among benzaldehyde, malonontrile and cyclohexanone was evaluated in the presence of 30mol % nanocatalyst. After

中文翻译：

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使用纳米结构的二磷酸盐 Na2CaP2O7 简便有效地合成双环邻氨基甲腈衍生物

合成标题化合物最有用的策略之一是多组分反应 (MCR)。在 MCR 中，三个或更多反应物形成产物，使得所有或大部分初始原子都存在于最终产物中。这在成本、效率和环境管理方面具有明显的好处。有一些合成邻氨基甲腈衍生物的文献方法，其中包括使用四氟硼酸N-丁基吡啶鎓[BPy]BF4、5醋酸铵、咪唑、乙二胺、b-1-咪唑-2,3,4等试剂， 6-四乙酰基-D-吡喃葡萄糖基溴化物 ([Bmim-G]þ[Br]-)、9 邻苯二磺酰亚胺 (OBS) 或三乙基乙酸铵 (TEAA) 和 1-丁基-3-甲基咪唑鎓四氟硼酸盐 ([BMIm][BF4 ]) 11 作为催化剂。以上合成方法虽然各有优势，它们还受到一些限制，例如反应时间长、产率低和需要大量后处理。我们现在想报告我们使用纳米结构的二磷酸盐 Na2CaP2O7 12-18 作为催化剂，通过醛（1 当量）和丙二腈（2 当量）与环己酮（1 当量）缩合合成邻氨基甲腈衍生物的方法（方案1）。这是为了继续我们之前的研究。为了获得我们反应的最佳条件，我们优化了表 1 中列出的参数。我们发现该反应的最佳条件是在 30 mol% 纳米结构二磷酸盐 Na2CaP2O7 存在下在乙醇中回流。为了说明纳米结构的二磷酸盐 Na2CaP2O7 在促进双环邻氨基甲腈形成中的作用，模型反应在优化的反应条件下进行，但没有催化剂。即使在 240 分钟后也没有观察到明显的产物形成（条目 7）。为了探索这种反应的程度，我们研究了几种醛作为底物的使用。此外，还探讨了环戊酮的反应范围和效率（条目 4l-4m）。结果列于表2中。在30mol％纳米催化剂存在下评价纳米催化剂在苯甲醛、丙二腈和环己酮之间的反应中的可回收性。后 研究了环戊酮的反应范围和效率（条目 4l-4m）。结果列于表2中。在30mol％纳米催化剂存在下评价纳米催化剂在苯甲醛、丙二腈和环己酮之间的反应中的可回收性。后 研究了环戊酮的反应范围和效率（条目 4l-4m）。结果列于表2中。在30mol％纳米催化剂存在下评价纳米催化剂在苯甲醛、丙二腈和环己酮之间的反应中的可回收性。后