1,7-(Me2S)2B12H10 | 158963-32-7

• 英文名称: 1,7-(Me2S)2B12H10
• 英文别名: 1,7-(SMe2)2B12H10；1,7-(Me2S)B12H10
• CAS: 158963-32-7
• 化学式: C₄H₂₂B₁₂S₂
• 分子量: 264.083
• InChiKey: GBDAGEUGHDSZOO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  1,7-(Me2S)2B12H10 以 neat (no solvent) 为溶剂， 以0%的产率得到1,12-(SMe2)2B12H10
  参考文献：
  名称：

  One-Step Preparation of Dimethyl Sulfide Substituted Icosahedral Boranes:  The Crystal and Molecular Structures of 1,7-(SMe₂)₂B₁₂H₁₀, 1,12-(SMe₂)₂B₁₂H₁₀, and [SMe₃][B₁₂H₁₁(SMe₂)]·MeCN

  摘要：

  1,7-(SMe(2))(2)B12H10, 1,12-(SMe(2))(2)B12H10, and [SMe(3)][B12H11(SMe(2))] were prepared and isolated from the self-condensation reaction of BH3 . SMe(2) in the absence of a solvent. At 150 degrees C the reaction yields, primarily, two isomers: 1,7-(SMe(2))(2)B12H10, the major component, and 1,12-(SMe(2))(2)B12H10 the minor component, that are separated by thin layer chromatography. Single-crystal X-ray structure determinations were performed for both isomers, confirming the structures inferred from H-1, B-11, and B-11{H-1}-B-11{H-1} (COSY) NMR spectra. Crystal data for 1,7-(SMe(2))(2)B12H10: trigonal P3(2)21, a = 12.901(10) Angstrom, b = 12.901(10) Angstrom, c = 23.73(2) Angstrom, gamma = 120 degrees, Z = 9. Crystal data for 1,12-(SMe(2))(2)B12H10: orthorhombic Pbca, a = 10.101(2) Angstrom, b = 11.220(2) Angstrom, c = 13.464(2) Angstrom, Z = 4. At 60 degrees C, the self-condensation of BH3 . SMe(2) is very slow, but yields [SMe(3)][B12H11(SMe(2))] as the major product. Multinuclear and 2-dimensional NMR spectra are in full accord with the structure determined by X-ray methods. Crystal data for [SMe(3)][B12H11(SMe(2))]. MeCN: monoclinic P2(1), a = 8.904(10) Angstrom, b = 9.08(2) Angstrom, c = 12.39(3)Angstrom, beta = 93.820, Z = 2.

  DOI：

  10.1021/ic960433w
• 作为产物：
  描述：

  dimethyl sulfide borane 以 not given 为溶剂， 生成 1,7-(Me2S)2B12H10
  参考文献：
  名称：

  Unusual Cationic Tris(Dimethylsulfide)-Substituted closo-Boranes: Preparation and Characterization of [1,7,9-(Me₂S)₃-B₁₂H₉] BF₄ and [1,2,10-(Me₂S)₃-B₁₀H₇] BF₄

  摘要：

  Rational syntheses of trisubstituted sulfur-bearing closoboranes are presented. In the development of these syntheses unusual cationic closo-boranes [1,7,9-(Me2S)(3)-B12H9] (3) and [1,2,10-(Me2S)(3)-B10H7](+) (4) have been identified. These were initially recognized to be intermediates in the formation of the neutral trisubstituted species 1,7-(Me2S)(2)-9-(MeS)-B12H9 (1) and 1,10-(Me2S)(2)-2-(MeS)-B10H7 (2), respectively. Stable tetrafluoroborate salts were prepared and isolated, and their structures are presented. They are believed to represent the first structural determinations of cationic borane clusters of any type.

  DOI：

  10.1021/ic2023709

文献信息

• S-Alkylation and S-Amination of Methyl Thioethers − Derivatives of <i>closo</i>-[B₁₂H₁₂]^2-. Synthesis of a Boronated Phosphonate, <i>gem</i>-Bisphosphonates, and Dodecaborane-<i>ortho</i>-carborane Oligomers
  作者：Roman G. Kultyshev、Jianping Liu、Shengming Liu、Werner Tjarks、Albert H. Soloway、Sheldon G. Shore

  DOI：10.1021/ja0123857

  日期：2002.3.1

  which establishes between, on the one hand, one of the former species and, on the other hand, 1,2(7,12)-(Me(2)S)(2)B(12)H(10) (2-4) and [1,2(7,12)-(MeS)(2)B(12)H(10)](2-) (9-11). A boronated phosphonate 1-(MeS(CH(2))(4)P(O)(OEt)(2))-7-(Me(2)S)B(12)H(10) (14g) and a gem-bisphosphonate 1-(MeS(CH(2))(3)CH[P(O)(OEt)(2)](2))-7-(Me(2)S)B(12)H(10) (14h) were prepared from thioether 7 and the corresponding

  通过甲基硫醚 [MeSB(12)H(11)](2-) (5)、[1-(MeS)-2(7,12)-(Me(2) )S)B(12)H(10)](-) (6-8) 和 [1,2(7,12)-(MeS)(2)B(12)H(10)](2- ) (9-11) 在乙腈中使用烷基卤化物和甲苯磺酸盐。由于这些甲基硫醚可以很容易地以富含 B-10 的形式大规模制备，并且由于它们的化学多功能性，它们是潜在非常有吸引力的硼实体，用于设计和合成用于癌症硼中子捕获疗法的疗法。发现 6-8 的烷基化可能因平衡而变得复杂，该平衡一方面是前一种物质，另一方面是 1,2(7,12)-(Me(2) S)(2)B(12)H(10) (2-4) 和 [1,2(7,12)-(MeS)(2)B(12)H(10)](2-) (9 -11）。硼化膦酸酯 1-(MeS(CH(2))(4)P(O)(OEt)(2))-7-(Me(2)S)B(12)H(10)
• Synthesis of Mono- and Dihalogenated Derivatives of (Me₂S)₂B₁₂H₁₀ and Palladium-Catalyzed Boron−Carbon Cross-Coupling Reactions of the Iodides with Grignard Reagents
  作者：Roman G. Kultyshev、Shengming Liu、Hoitung T. Leung、Jianping Liu、Sheldon G. Shore

  DOI：10.1021/ic020600u

  日期：2003.5.1

  7-(Me(2)S)(2)B(12)H(9) and 9,10-X(2)-1,7-(Me(2)S)(2)B(12)H(8) (X = Cl, Br, I), have been synthesized from reactions of 1,7-(Me(2)S)(2)B(12)H(10) with various halogenating reagents. In addition, reactions of 1,7-(Me(2)S)(2)B(12)H(10) with 2,4-(NO(2))(2)C(6)H(3)SCl and PhSeBr resulted in 9-(2',4'-(NO(2))(2)C(6)H(3)S)-1,7-(Me(2)S)(2)B(12)H(9) and 9,10-(PhSe)(2)-1,7-(Me(2)S)(2)B(12)H(8), respectively.

  两个系列的化合物9-X-1,7-（Me（2）S）（2）B（12）H（9）和9,10-X（2）-1,7-（Me（2） S）（2）B（12）H（8）（X = Cl，Br，I）是由1,7-（Me（2）S）（2）B（12）H（10）的反应合成的）与各种卤化试剂。此外，1,7-（Me（2）S）（2）B（12）H（10）与2,4-（NO（2））（2）C（6）H（3）SCl的反应和PhSeBr生成9-（2'，4'-（NO（2））（2）C（6）H（3）S）-1,7-（Me（2）S）（2）B（12 ）H（9）和9,10-（PhSe）（2）-1,7-（Me（2）S）（2）B（12）H（8）。X射线对二溴，一碘和芳基硫醚衍生物的研究表明，在1,7-（Me（2）S）（2）B（12）H（10）中的亲电子取代发生在位置9和10，如就间碳氢化合物1,7-C（2）B（10）H（12）而言。由1,12-（Me（2）S）（2）B（12）H（10）卤化物2-X-1
• Synthesis and Characterization of Sulfide, Sulfide−Sulfonium, and Bissulfide Derivatives of [B₁₂H₁₂]^2-. Additivity of Me₂S and MeS^- Substituent Effects in ¹¹B NMR Spectra of Disubstituted Icosahedral Boron Clusters
  作者：Roman G. Kultyshev、Jianping Liu、Edward A. Meyers、Sheldon G. Shore

  DOI：10.1021/ic000198o

  日期：2000.7.24

  monosubstituted anions 1 and 2. Some evidence is found for small partial double bond character of the B-SMe bonds in anions. [MePPh3]+ salts of [MeSB12H11]2- (2) and [1-(MeS)-7-(Me2S)B12H10]- (M1-) are structurally characterized by single-crystal X-ray diffraction analysis. Crystal data: [MePPh3]2[MeSB12H11], P2(1) (No. 4), a = 9.243(1) A, b = 18.272(1) A, c = 12.548(1) A, beta = 103.17(1) degrees, Z =

  （Me2S）2B12H10（O，M和P）的1,2-，1,7-和1,12-异构体在回流时与DMF中的邻苯二甲酰亚胺钾或CH3CN / EtOH中的EtSNa反应生成相应的[ （MeS）（Me2S）B12H10]-（O1-，M1-，P1-）。如果使用了过量的亲核试剂，[Me2SB12H11]-（1）和O，M，P可以转化为二价阴离子[MeSB12H11] 2-（2）和[（MeS）2B12H10] 2-（O2-，M2-， P2-）。推荐使用EtSNa，因为与邻苯二甲酰亚胺钾法相比，它有助于分离产物。当在-40摄氏度下在液态氨中用过量的碱金属（Na，K）处理1或O，M，P时，几乎立即即刻获得硫化物2或双硫化物二价阴离子O2-，M2-，P2- 。尽管亲核取代法和碱金属还原法均可用于合成二价阴离子2，O2-，M2-和P2-，只有前一种方法适合于合成硫化物-ulf阴离子O1-，M1-，P1-。对1，O，M，P和衍生自它们的阴离子的11B
• Reduction of Inner Sulfonium Salts, Thioethers, and Sulfones Derived from <i>closo-</i>[B₁₂H₁₂]²^- by Lithium in Methylamine:  A New Route to Mercaptododecaborates
  作者：Roman G. Kultyshev、Shengming Liu、Sheldon G. Shore

  DOI：10.1021/ic0011011

  日期：2000.12.1

  methylamine at -15 degrees C to yield [HSB12H11]2- (1) after workup. Such behavior toward this reducing system is similar to that of alkyl aryl sulfides. The sulfone [MeSO2B12H11]2- (12) also yields 1 as a major boron product upon reduction, while alkyl aryl sulfones produce the corresponding arenes under the same conditions. Similarly, isomers of (Me2S)2B12H10 (4-6) are reduced by lithium in methylamine

  阴离子[Me2SB12H11]-（2）和[MeSB12H11] 2-（3）可以在-15℃下通过甲胺中过量的锂还原，以在处理后产生[HSB12H11] 2-（1）。针对该还原系统的这种行为类似于烷基芳基硫化物的行为。砜[MeSO2B12H11] 2-（12）还原后还生成1作为主要的硼产物，而烷基芳基砜在相同条件下产生相应的芳烃。同样，（Me2S）2B12H10（4-6）的异构体在甲胺中被锂还原，生成二硫醇[（HS）2B12H10] 2-（7-9）。以80-90％的收率获得1和7-9的四丁基铵盐，并通过多核NMR和质谱进行表征，后三种化合物首次被分离和表征。还原反应提供了二硫醇7-9的途径，用于生物学评估和用于合成。从而，通过两步还原烷基化方法，可以容易地将图2和图4-6的化合物转化为[R2SB12H11]-和（R2S）2B12H10。通过单晶X射线衍射分析对通过苄基氯对4的还原产物进行烷基化而获得的1
• Isolation, Characterization, and Molecular Structure of 1,2-(Me₂S)₂B₁₂H₁₀
  作者：Roman G. Kultyshev、Jianping Liu、Edward A. Meyers、Sheldon G. Shore

  DOI：10.1021/ic990808o

  日期：1999.10.1

  The pyrolysis of BH3. SMe2 at 130 degrees C and 1000 psi yields isomers of (Me2S)(2)B12H10. The previously unreported 1,2 isomer has been isolated and characterized by single-crystal X-ray analysis and multinuclear NMR spectroscopy. Its physical and spectral characteristics are compared to those of the earlier reported 1,7 and 1,12 isomers of (Me2S)(2)B12H10.