2-diphenylbismuthanyl-2-methylpropionitrile

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-diphenylbismuthanyl-2-methylpropionitrile
• 英文别名: Me2C(CN)BiPh2；2-methyl-2-(diphenylbismuthanyl)-propionitrile
• 化学式: C₁₆H₁₆BiN
• 分子量: 431.29
• InChiKey: OUXQQVDGPKBZOZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-diphenylbismuthanyl-2-methylpropionitrile 在 苯硫酚 作用下， 反应 5.0h， 生成 异丁腈
  参考文献：
  名称：

  Arylthiols as Highly Chemoselective and Environmentally Benign Radical Reducing Agents

  摘要：

  Arylthiols serve as excellent environmentally benign reducing agents for organotellurium, organostibine, and organobismuthine compounds under radical conditions. Both small molecules and macromolecules possessing these heteroatorn groups are reduced under moderate thermal conditions to give near quantitative yields in most cases. The reduction shows high chemoselectivity with respect to the heteroatorn compounds the reactivity decreases in the order alkylbismuthines, alkylstibines, and alkyltellurides, while simple alkyl iodides could not be reduced. Alkyltellurides are selectively reduced in the presence of alkyl iodides even when an excess amount of arylthiol is used. Furthermore, alkylstibines are also selectively reduced in the presence of alkyltellurides. Moreover, the reduction conditions are compatible with the presence of a variety of polar functional groups in the substrates, products, and solvents, which are not tolerant under ionic and metal-catalyzed conditions. Carbon-carbon bond formation is possible with use of the carbon-centered radicals that are generated. The results clearly reveal the synthetic utility of arylthiols in organic synthesis.

  DOI：

  10.1021/jo801200b
• 作为产物：
  描述：

  1-cyano-1-methyl-ethyl 、 diphenyl(2,6-dimesitylphenylthio)bismuthine 在 偶氮二异丁腈 作用下， 生成 2-diphenylbismuthanyl-2-methylpropionitrile
  参考文献：
  名称：

  Development of an Arylthiobismuthine Cocatalyst in Organobismuthine-Mediated Living Radical Polymerization: Applications for Synthesis of Ultrahigh Molecular Weight Polystyrenes and Polyacrylates

  摘要：

  Diphenyl(2,6-dimesitylphenylthio)bismuthine (1a) serves as an excellent cocatalyst in organo-bismuthine-mediated living radical polymerization (BIRP). Both low and high molecular weight polystyrenes and poly(butyl acrylate)s (PBAs) with controlled molecular weights and low polydispersity indexes (PDIs) were synthesized by the addition of a catalytic amount of 1 a to an organobismuthine chain-transfer agent, methyl 2-dimethylbismuthanyl-2-methylpropionate (3). The number-average molecular weight (M,,) of the resulting polymers increases linearly with the monomer/3 ratio. Structurally well-defined polystyrenes with M-n's in the range from 1.0 x 10(4) to 2.0 x 10(5) and PDIs of 1.07-1.15 as well as PBAs with M-n's in the range from 1.2 x 10(4) to 2.8 x 10(6) and PDIs of 1.06-1.43 were successfully prepared under mild thermal conditions. Control experiments suggested that 1 a reversibly reacts with the polymer-end radical to generate an organobismuthine dormant species and 2,6-dimesitylphenylthiyl radical (2a). This reaction avoids the occurrence of chain termination reactions involving the polymer-end radicals and avoids undesired loss of the bismuthanyl polymer end group. The bulky 2,6-dimesitylphenyl group attached to the sulfur atom may prevent the addition of thiyl radicals to the vinyl monomers to generate new polymer chains.

  DOI：

  10.1021/ja8092899

文献信息

• Generation of Carbanions through Stibine–Metal and Bismuthine–Metal Exchange Reactions and Its Applications to Precision Synthesis of ω‐End‐Functionalized Polymers
  作者：Eiichi Kayahara、Hiroto Yamada、Shigeru Yamago

  DOI：10.1002/chem.201100265

  日期：2011.5.2

  by the end‐group transformation of living polymers that bear these heteroatom species at the ω‐polymer end, prepared by using organostibine and bismuthine‐mediated living radical polymerizations. Various polymers that bear polar functional groups and acidic hydrogen—for example, poly(methyl methacrylate), poly(butyl acrylate), poly(N‐isopropyl acrylamide), and poly(2‐hydroxyethyl methacrylate)—could

  从合成和机理的角度研究了通过杂原子-金属交换反应从有机stibines和有机bismuthines生成碳负离子。交换反应在用各种有机金属试剂（如烷基锂，四烷基锌酸盐和烷基卤化镁）处理后自发进行，以定量提供相应的碳负离子。由于这些杂原子化合物的高反应性，即使在可能与有机金属物质发生反应的各种极性官能团的存在下，交换反应也仅发生。这种方法的优势体现在通过使用有机锑和铋介导的活性自由基聚合制备的，在ω-聚合物末端带有杂原子的活性聚合物的端基转化。N-异丙基丙烯酰胺）和聚（甲基丙烯酸2-羟乙酯）可用于交换反应，随后用亲电试剂捕集，可得到具有可控分子量，分子量分布和端基官能团的相应聚合物。竞争实验表明，有机stibines和organobismuthines是对有机金属试剂反应性最高的杂原子化合物，它们的高反应性是交换反应中高化学选择性的原因。
• Organic Bismuth Compound, Method for Producing Same, Living Radical Polymerization Initiator, Method for Producing Polymer Using Same, and Polymer
  申请人：Yamago Shigeru

  公开号：US20070265404A1

  公开（公告）日：2007-11-15

  An organobismuth compound represented by the formula (1) wherein R 1 and R 2 are C 1 -C 8 alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R 3 and R 4 are each a hydrogen atom or C 1 -C 8 alkyl, and R 5 is aryl, substituted aryl, an aromatic heterocyclic group, acyl, amido, oxycarbonyl or cyano.

  一种有机铋化合物，其化学式为(1)，其中R1和R2为C1-C8烷基、芳基、取代芳基或芳香族杂环基，R3和R4分别为氢原子或C1-C8烷基，R5为芳基、取代芳基、芳香族杂环基、酰基、酰胺基、氧羰基或氰基。
• Organic bismuth compound, method for producing same, living radical polymerization initiator, method for producing polymer using same, and polymer
  申请人：Otsuka Chemical Co., Ltd.

  公开号：US07847043B2

  公开（公告）日：2010-12-07

  An organobismuth compound represented by the formula (1) wherein R1 and R2 are C1-C8 alkyl, aryl, substituted aryl or an aromatic heterocyclic group, R3 and R4 are each a hydrogen atom or C1-C8 alkyl, and R5 is aryl, substituted aryl, an aromatic heterocyclic group, acyl, amido, oxycarbonyl or cyano.

  一种有机铋化合物，其化学式为（1），其中R1和R2为C1-C8烷基，芳基，取代芳基或芳香族杂环基，R3和R4分别为氢原子或C1-C8烷基，R5为芳基，取代芳基，芳香族杂环基，酰基，酰胺基，氧羰基或氰基。
• ORGANIC BISMUTH COMPOUND, METHOD FOR PRODUCING SAME, LIVING RADICAL POLYMERIZATION INITIATOR, METHOD FOR PRODUCING POLYMER USING SAME, AND POLYMER
  申请人：Otsuka Chemical Co., Ltd.

  公开号：EP1829883B1

  公开（公告）日：2011-08-17
• Arylthiols as Highly Chemoselective and Environmentally Benign Radical Reducing Agents
  作者：Shigeru Yamago、Atsushi Matsumoto

  DOI：10.1021/jo801200b

  日期：2008.9.19

  Arylthiols serve as excellent environmentally benign reducing agents for organotellurium, organostibine, and organobismuthine compounds under radical conditions. Both small molecules and macromolecules possessing these heteroatorn groups are reduced under moderate thermal conditions to give near quantitative yields in most cases. The reduction shows high chemoselectivity with respect to the heteroatorn compounds the reactivity decreases in the order alkylbismuthines, alkylstibines, and alkyltellurides, while simple alkyl iodides could not be reduced. Alkyltellurides are selectively reduced in the presence of alkyl iodides even when an excess amount of arylthiol is used. Furthermore, alkylstibines are also selectively reduced in the presence of alkyltellurides. Moreover, the reduction conditions are compatible with the presence of a variety of polar functional groups in the substrates, products, and solvents, which are not tolerant under ionic and metal-catalyzed conditions. Carbon-carbon bond formation is possible with use of the carbon-centered radicals that are generated. The results clearly reveal the synthetic utility of arylthiols in organic synthesis.