Department of Bioorganic Chemistry, Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
Laboratory of Experimental Anticancer Therapy, Department of Experimental Oncology, Ludwik Hirszfeld Institute of Immunology and Experimental Therapy Polish Academy of Sciences, Rudolfa Weigla 12, 53-114 Wrocław, Poland.
Molecules. 2020 Mar 20;25(6):1424. doi: 10.3390/molecules25061424.
A three-component reaction between diamines (diaminobenzenes, diaminocyclohexanes, and piperazines), triethyl orthoformate, and diethyl phosphite was studied in some detail. In the case of 1,3- and 1,4-diamines and piperazines, products of the substitution of two amino moieties-the corresponding tetraphosphonic acids-were obtained. In the cases of 1,2-diaminobenzene, 1,2-diaminocyclohexanes and 1,2-diaminocyclohexenes, only one amino group reacted. This is most likely the result of the formation of hydrogen bonding between the phosphonate oxygen and a hydrogen of the adjacent amino group, which caused a decrease in the reactivity of the amino group. Most of the obtained compounds inhibited the proliferation of RAW 264.7 macrophages, PC-3 human prostate cancer cells, and MCF-7 human breast cancer cells, with 1, trans-7, and 16 showing broad nonspecific activity, which makes these compounds especially interesting in the context of anti-osteolytic treatment and the blocking of interactions and mutual activation of osteoclasts and tumor metastatic cells. These compounds exhibit similar activity to zoledronic acid and higher activity than incadronic acid, which were used as controls. However, studies of sheep with induced osteoporosis carried out with compound trans-7 did not support this assumption.
我们详细研究了二胺(二氨基苯、二氨基环己烷和哌嗪)、原甲酸三乙酯和亚磷酸二乙酯之间的三组分反应。在 1,3-和 1,4-二胺及哌嗪的情况下,得到了两个氨基取代产物——相应的四膦酸。在 1,2-二氨基苯、1,2-二氨基环己烷和 1,2-二氨基环己烯的情况下,只有一个氨基发生反应。这很可能是由于膦酸酯氧和相邻氨基的氢之间形成氢键,导致氨基的反应性降低。所得到的大部分化合物都抑制了 RAW 264.7 巨噬细胞、PC-3 人前列腺癌细胞和 MCF-7 人乳腺癌细胞的增殖,其中 1,trans-7 和 16 表现出广泛的非特异性活性,这使得这些化合物在抗溶骨性治疗和阻断破骨细胞和肿瘤转移细胞的相互作用和相互激活方面特别有趣。这些化合物的活性与唑来膦酸相似,比用作对照的伊班膦酸的活性更高。然而,用化合物 trans-7 对诱导骨质疏松的绵羊进行的研究并不支持这一假设。