Z. Naturforsch. 2013,
68b, 804 – 810
doi:10.5560/ZNB.2013-3098
Synthesis and Characterization of 3-Chloropropyl-substituted o-Carboranes: Crystal Structures of 1,2-(1,3-Propanediyl)-o-carborane, 1-(3-Chloropropyl)-o-carborane and 1,2-Bis(3-chloropropyl)-o-carborane
Deqian
Bian,
Yong
Nie,
Jinling
Miao,
Zhenwei
Zhang, and
Ping
Lu
School of Chemistry and Chemical Engineering, Shandong Provincial Key Laboratory of Fluorine Chemistry and Chemical Materials, University of Jinan, 106 Jiwei Road, 250022 Jinan, P. R. China
Received March 10, 2013 / published online July 19, 2013
Dedicated to Professor Walter Siebert
The reactions of the lithio-o-carborane Li2C2B10H10 with ClCH2CH2CH2Br were studied under various conditions. While the main product is the known exo-polyhedrally cyclized 1,2-(1,3-propanediyl)-o-carborane (2), the expected 3-chloropropyl-substituted carborane products 1-(ClCH2CH2CH2)C2B10H11 (3) and 1,2-(ClCH2CH2CH2)2C2B10H10 (4) can be obtained in a total yield of 22 %. In the presence of CuCl, the same reaction proceeded rather slowly and gave compound 3 and bis(o-carborane) (5) in small yields, with the recovery of the starting o-C2B10H12. Compounds 2–4 were characterized by means of IR and NMR spectroscopy and mass spectrometry, as well as by single-crystal X-ray diffraction.
Key words: o-Carborane, Chloropropyl, Functionalization, Synthesis, Crystal Structure