Simple Synthesis, Halogenation, and Rearrangement of closo-1,6-C2B8H10
Simple Synthesis, Halogenation, and Rearrangement of closo-1,6-C2B8H10
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DOI：
10.1021/om500988z
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发表时间：
2015-01-26
期刊：
影响因子：
2.8
通讯作者：
Ruzicka, Ales
中科院分区：
文献类型：
--
作者：
Bakardjiev, Mario;Stibr, Bohumil;Ruzicka, Ales
室温下，在三乙胺存在下，碘与巢-5，6-C2 B8 H12（1）在二氯甲烷中反应，得到氯-1，6-C2 B8 H10（2）二碳硼烷，产率85%。2的所有亲电卤代反应都只导致B（8）-取代，得到一系列8-X-闭-1，6-C2 B8 H9（8X-2）衍生物（其中X = Cl，Br，I）。2和8X-2在500-600 ℃的热重排分别产生closo-1，10-C2 B8 H10（3）和一系列卤代衍生物2-X-closo-1，10-C2 B8 H9（2X-3）。所有分离的化合物已通过多核（B-11、H-1和C-13）NMR光谱、质谱和元素分析表征，并且8 Br-2的结构通过X-射线衍射研究确定。
Room-temperature reaction between nido-5,6-C2B8H12 (1) and elemental iodine in the presence of triethylamine in CH2Cl2 gave the closo-1,6-C2B8H10 (2) dicarbaborane in 85% yield. All the electrophilic halogenation reactions of 2 led exclusively to B(8)-substitution to get a series of 8-X-closo-1,6-C2B8H9 (8X-2) derivatives (where X = Cl, Br, and I). Thermal rearrangements of 2 and 8X-2 at similar to 500-600 degrees C produced closo-1,10-C2B8H10 (3) and a series of halo derivatives 2-X-closo-1,10-C2B8H9 (2X-3), respectively. All the compounds isolated have been characterized by multinuclear (B-11, H-1, and C-13) NMR spectroscopy, mass spectrometry, and elemental analyses, and the structure of 8Br-2 was established by X-ray diffraction study.