- METHOD FOR PREPARING PARA-CARBORANE USING MICROPOROUS MATERIALS
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The present invention relates to a method of preparing para-carborane using a microporous material, the method is characterized by including: a mixing step for mixing ortho-carborane and a microporous material to prepare a mixture; a heat treatment step for isomerization which converts the ortho-carborane into para-carborane by heat treating the mixture, and thus obtaining a solution or a solid matter which contains the para-carborane; an extraction step for dissolving the solution or the solid matter in an organic solvent to extract an extract containing the para-carborane and the microporous material; and a separation step for separating the para-carborane from the extract.
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Paragraph 0058
(2017/05/06)
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- Thermal isomerizations of monothiolated carboranes (HS)C2B10H11 and the solid-state investigation of 9-(HS)-1,2-C2B10H11 and 9-(HS)-1,7-C2B10H11
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At 300-500 °C, three C-thiolated closo-dicarbadodecaborane isomers 1-(HS)-1,2-C2B10H11 (1-o), 1-(HS)-1,7-C2B10H11 (1-m), and 1-(HS)-1,12-C2B10H11 (1-p), and two B-thiolated isomers 9-(HS)-1,7-C2B10H11 (9-m) and 9-(HS)-1,2-C2B10H11 (9-o) show two types of reaction: first, removal of an SH group from the closo-dicarbadodecaborane skeleton, and second, skeletal isomerizations from ortho to meta to para that lead to new isomers. A previously unreported SH skip from carbon-to-boron is also observed. The effect of the thiol group on the skeletal rearrangement is discussed. The isomerisation products are assigned on the basis of correlation of their computationally obtained dipole moments with their gas-chromatographic retention times. Computational results on molecular energies for the mono-thiolated species show good agreement between the calculated relative stabilities and the incidence and relative quantities of the isomerization products. Two of the starting B-thiolated isomers, 9-o and 9-m, were characterized using single-crystal X-ray diffraction analyses and their crystallographic packings as well as some selected structural parameters are discussed. All starting compounds were characterized using multinuclear NMR spectroscopy.
- Ba?e, Tomá?,Machá?ek, Jan,Hájková, Zuzana,Langecker, Jens,Kennedy, John D.,Carr, Michael J.
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p. 132 - 140
(2015/12/18)
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- Palladium-catalyzed amination of 2-Iodo-para-carborane
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The palladium-catalyzed Buchwald-Hartwig amination of B-iodocarborane by various azoles and amines is described for the first time. The reactions of 2-iodo-p-carborane with indole, imidazole, benzimidazole, or carbazole in the system Pd(dba)2-BINAP-ButONa in dioxane at 100 °C gave 2-p-carboranyl derivatives of these azoles in high yields together with 2-hydroxy-p-carborane as a side product. The reactions of 2-iodo-p-carborane with aromatic amines in the same system gave the amination products in 60-70% yields and also were accompanied by the formation of hydroxy derivatives (up to 30% yields). In a special investigation it was shown that the base Bu tONa was responsible for its formation. The principle possibility of the amination of 2-iodo-p-carborane by morpholine (with 30% yield) as an example of aliphatic amination was shown. The structures of N-(1,12-dicarba-closo- dodecaboran-2-yl)carbazole (1), N-(1, 12-dicarba-closo-dodecaboran-2-yl) benzimidazole (2), N-(1, 12-dicarba-closo-dodecaboran-2-yl)indole (4), and 2-hydroxy-1,12-dicarba-closo-dodecaborane (5) have been established by X-ray diffraction studies.
- Beletskaya, Irina P.,Bregadze, Vladimir I.,Kabytaev, Kuanysh Z.,Zhigareva, Galina G.,Petrovskii, Pavel V.,Glukhov, Ivan V.,Starikova, Zoya A.
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p. 2340 - 2347
(2008/10/09)
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- Direct synthesis of closo-carboranes
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Pentaborane-9 and acetylene can react in a continuous-flow system to produce directly the smaller closo-carboranes 1,5-C2B3H5, 1,6-C2B4H6, and 2,4-C2B5H7 in combined yields approaching 65-70%. Reactions of decaborane-14 with acetylene under the same conditions, excepting a somewhat higher temperature, give predominantly 1,7-C2B10H12 in yields also on the order of 70%. Optimal conditions for both systems include short residence times (~0.5 sec), high temperatures (500-600°, depending on the system), a diluent gas, and a steel wool plug or diffuser. The reactions are highly exothermic, and drastic reduction of yields can occur if the heat is not dissipated, as was evident in a scaled-up unit where very careful diluent control had to be exercised to prevent sudden surges to very high temperatures.
- Ditter,Klusmann,Oakes,Williams, Robert E.
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p. 889 - 892
(2008/10/08)
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