1-cyano-1-methyl-ethyl | 3225-31-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-cyano-1-methyl-ethyl
• 英文别名: 2-Cyanopropyl radical；α-dehydro-isobutyronitrile；α-Dehydro-isobutyronitril；2-Cyano-2-propyl radical
• CAS: 3225-31-8
• 化学式: C₄H₆N
• 分子量: 68.0983
• InChiKey: PPGAFAOTXHZHCA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  2-cyano-2-nitrosopropane 以 N,N-二甲基甲酰胺 为溶剂， 生成 1-cyano-1-methyl-ethyl
  参考文献：
  名称：

  一氧化氮的C-亚硝基供体

  摘要：

  一氧化氮（NO）的生物活性的完整理解因其各种物种的不同反应谱以及通常使用的NO祖细胞通常复杂的分解行为而变得复杂。在这里，我们报道适当取代的C-亚硝基化合物仅通过一级均相C-N键断裂而充当中性一氧化氮的供体，从而在25°C的DMSO中释放高达88％的一氧化氮。该反应产生碳自由基，一氧化氮的产率取决于自由基陷阱的可用性。C-亚硝基化合物是具有生物活性的中性NO的来源，在兔主动脉环测定中显示出强大的NO生物活性。

  DOI：

  10.1021/jo802517t

文献信息

• Liquid xenon as a solvent for e.s.r. studies
  作者：Malcolm D. Cook、Brian P. Roberts

  DOI：10.1039/c39830000264

  日期：——

  Liquid xenon is a useful inert solvent for e.s.r. studies of reactive free radicals; the g-factors of many types of radical are not the same in xenon as in normal solvents.

  液态氙是用于研究反应性自由基的有用的惰性溶剂。氙中许多类型自由基的g因子与普通溶剂中的g因子不同。
• Radical adducts of dibenzofulvenes and 9-methylenanthrone - an esr study
  作者：Angelo Alberti、Gian Franco Pedulli、Rino Leardin、Antonio Tundo、Giuseppe Zanardi

  DOI：10.1016/0040-4020(86)80018-7

  日期：1986.1

  R3M. radicals (M=C, Si, Ge, Sn, P, O, S) to give the corresponding paramagnetic adducts. In the case of 9-methylenanthrone radical addition occurred selectively at the exocyclic carbon-carbon double bond even with Group IV B organometallic radicals for which attack at the carbonyl oxygen would give rise to thermodynamically more stable adducts. When irradiating solutions of 9-methylenanthrone a photoinduced

  使标题化合物与一系列R 3 M.基团（M = C，Si，Ge，Sn，P，O，S）反应，得到相应的顺磁性加合物。在9-亚甲基蒽酮基团的情况下，即使在IV B族有机金属基团上，环碳-碳双键选择性地发生加成，其对羰基氧的攻击将产生热力学上更稳定的加合物。辐射9-甲基蒽酮溶液时，发生了光致自反应，导致形成了二聚体。根据测得的ESR光谱参数，讨论了加合物的结构，以及R n M基团对β-质子超细分裂常数的影响。
• FTIR and computational studies of gas-phase hydrogen atom abstraction kinetics by t-butoxy radical
  作者：Shuping Li、Wai Yip Fan

  DOI：10.1016/j.cplett.2006.06.100

  日期：2006.8

  for the hydrogen atom abstraction reactions of several substrates including halogenated organic compounds and amines by t-butoxy radical generated from the uv photolysis of t-butyl nitrite in the gas phase. Arrhenius parameters for selected reactions have been measured in the temperature range 299–318 K. Transition states and activation barriers for such reactions have been computed with the help of

  通过使用傅立叶变换红外（FTIR）吸收光谱法，已确定了包括卤代有机化合物和氢氧烷在内的几种底物的氢原子提取反应的速率系数在10 -16至10 -14  cm 3 分子-1  s -1范围内。通过叔丁氧基自由基在气相中亚硝酸叔丁酯的紫外光解而生成胺。在299–318 K的温度范围内测量了所选反应的Arrhenius参数。借助Gaussian 03软件计算了此类反应的过渡态和激活势垒，发现与实验值非常吻合。
• Rearrangements and cyclizations in vinyl radicals. Unusual example of 1,4-radical translocation
  作者：Pier Carlo Montevecchi、Maria Luisa Navacchia

  DOI：10.1016/0040-4039(96)01405-0

  日期：1996.9

  Vinyl radical 5 undergoes 5-exo cyclization onto the CC double bond in competition with the 5-exo cyclization onto the aryl ring. In addition, radical 5 exhibits an unusual 1,4-radical translocation/β-fragmentation process. In contrast, radical 4 exclusively undergoes 5-exo cyclization onto the benzene ring. This latter reaction leads to spiro radical intermediates which can either give the 1,4-aryl

  乙烯基基团5与CC的双键进行5- exo环化反应，并与芳基环上的5- exo环化反应竞争。另外，基团5表现出不寻常的1，4-自由基易位/β-片段化过程。相比之下，自由基4仅在苯环上进行5- exo环化。这后一种反应导致螺自由基中间体，其可以得到1,4-芳移植产品，或可通过2-氰基捕集异-丙基的基团。
• 4-Nitrosopyridine 1-oxide and its derivatives: a new range of spin-traps
  作者：J. Kenneth Brown、Philip J. Coldrick、Eric J. Forbes

  DOI：10.1039/c39820000770

  日期：——

  4-Nitrosopyridine 1-oxide and its derivatives have been shown to be highly efficient water-soluble spin-traps for C- and O-centred radicals giving rise to persistent nitroxides.

  已经证明4-亚硝基吡啶-1-氧化物及其衍生物是高效的水溶性自旋捕集器，用于产生C-和O-中心自由基，产生持久的一氧化氮。