2-methyl-2-((2,2,6,6-tetramethylpiperidin-1-yl)oxy)propanenitrile | 71983-04-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 2-methyl-2-((2,2,6,6-tetramethylpiperidin-1-yl)oxy)propanenitrile
• 英文别名: 2-methyl-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)propionitrile；CP-TEMPO；2-methyl-2-((2,2,6,6-tetramethyl-1-piperidinyl)oxy)propanenitrile；2-methyl-2-[(2,2,6,6-tetramethyl-1-piperidinyl)oxy]propanenitrile；2-methyl-2-(2,2,6,6-tetramethylpiperidin-1-yl)oxypropanenitrile
• CAS: 71983-04-5
• 化学式: C₁₃H₂₄N₂O
• 分子量: 224.346
• InChiKey: IZMUYZWVFCIQJQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2,2,6,6-四甲基哌啶氧化物 、 偶氮二异丁腈 在 2-异氰基二苯甲酮 作用下， 以 甲苯 为溶剂， 生成 2-methyl-2-((2,2,6,6-tetramethylpiperidin-1-yl)oxy)propanenitrile
  参考文献：
  名称：

  无金属和添加剂条件下异氰化物与 AIBN 自由基介导级联环化合成 2,4-二氰基烷基化苯并恶嗪

  摘要：

  描述了芳基异氰化物与 AIBN 自由基级联环化的通用且新颖的方法。该策略可以在不含金属和添加剂的条件下以中等至良好的产率直接获得各种 2,4-二氰基烷基化苯并恶嗪。该反应可适用于克级并耐受不同的官能团。 2,4-二氰基烷基化苯并恶嗪衍生物具有大斯托克斯位移和分子内电荷转移特性。

  DOI：

  10.1021/acs.joc.3c02809

文献信息

• Copper-catalyzed cyanoisopropylation of beta-keto esters using azos: synthesis of beta-dicarbonyls bearing an alfa-tertiary nitrile moiety
  作者：Yanni Li、Ruirong Yang、Xiaohui Zhao、Yongchao Yao、Siping Yang、Qiong Wu、Deqiang Liang

  DOI：10.1080/00397911.2019.1574350

  日期：2019.3.4

  copper-catalyzed α-cyanoisopropylation reaction of β-keto esters using azo compounds as cyanoalkylating agents is presented, providing an easy access to β-dicarbonyls containing an α-tertiary nitrile moiety with adjacent tertiary and quaternary carbon centers. It is remarkable because a tremendous steric conflict is involved during reaction. Such nitriles were otherwise unavailable, and the reaction features simple

  摘要 提出了使用偶氮化合物作为氰基烷基化剂的 β-酮酯的铜催化 α-氰基异丙基化反应，提供了一种容易获得 β-二羰基化合物的方法，该反应包含具有相邻叔和季碳中心的 α-叔腈部分。这是值得注意的，因为在反应过程中涉及到巨大的空间冲突。这种腈是无法获得的，而且反应条件简单且相对温和，官能团耐受性好。图形概要
• Process for the synthesis for alkoxy amines and their use in controlled radical polymerization
  申请人：——

  公开号：US20040002606A1

  公开（公告）日：2004-01-01

  A one-pot process for the preparation of alkoxyamines conforming to formulae (I) or (II), preferably (I) 1 is disclosed. The process entails (1) reacting of an oxidizing agent (A) with a sterically hindered secondary amine of the general formula (III), 2 in a water-containing medium to form a reaction product and an aqueous phase, (2) removing of the aqueous phase, and (3) (adding to the reaction product a free-radical initiator (B) under conditions that promote the decomposition of the initiator to generate free radicals. Also disclosed is a process for polymerizing monomers, the process using the alkoxyamine prepared by the inventive process.

  披露了一种用于制备符合公式(I)或(II)，最好是(I)的烷氧基胺的一锅法工艺。该工艺包括：(1)使氧化剂(A)与具有空间位阻的二级胺反应，该二级胺的通用公式为(III)，在水含介质中形成反应产物和水相，(2)移除水相，以及(3)在促进分解引发剂以产生自由基的条件下，向反应产物中添加自由基引发剂(B)。还披露了一种用于聚合单体的工艺，该工艺使用由发明工艺制备的烷氧基胺。
• Systematic Study on Alkyl Iodide Initiators in Living Radical Polymerization with Organic Catalysts
  作者：Lin Lei、Miho Tanishima、Atsushi Goto、Hironori Kaji、Yu Yamaguchi、Hiroto Komatsu、Takuya Jitsukawa、Michihiko Miyamoto

  DOI：10.1021/ma501569j

  日期：2014.10.14

  Several low-molar-mass alkyl iodides were studied as initiating dormant species in living radical polymerization with organic catalysts. Primary, secondary, and tertiary alkyl iodides with different stabilizing groups (ester, phenyl, and cyano groups) were systematically studied for the rational design of initiating alkyl iodides. The activation rate constants of these alkyl iodides were experimentally

  研究了几种低摩尔质量的烷基碘，它们是在有机催化剂的活性自由基聚合中引发休眠的物质。为了合理设计引发烷基碘，系统地研究了具有不同稳定基团（酯，苯基和氰基）的伯，仲和叔烷基碘。通过实验确定这些烷基碘的活化速率常数，以进行定量比较。这些烷基碘用于甲基丙烯酸甲酯和丙烯酸丁酯的聚合反应中，以检查它们在这些聚合反应中的引发能力。使用具有官能团的烷基碘来制备远螯聚合物。还研究了具有多个起始位点的烷基碘。
• General and Efficient α-Oxygenation of Carbonyl Compounds by TEMPO Induced by Single-Electron-Transfer Oxidation of Their Enolates
  作者：Emanuela Dinca、Philip Hartmann、Jakub Smrček、Ina Dix、Peter G. Jones、Ullrich Jahn

  DOI：10.1002/ejoc.201200736

  日期：2012.8

  for the synthesis of protected α-oxygenated carbonyl compounds is reported. It is based on the single-electron-transfer oxidation of easily generated enolates to the corresponding α-carbonyl radicals. Coupling with the stable free radical TEMPO provides α-(piperidinyloxy) ketones, esters, amides, acids or nitriles in moderate-to-excellent yields. Enolate aggregates influence the outcome of the oxygenation

  报道了一种普遍适用的合成受保护的 α-氧化羰基化合物的方法。它基于将容易生成的烯醇化物单电子转移氧化为相应的 α-羰基自由基。与稳定的自由基 TEMPO 结合以中等至优异的产率提供 α-(哌啶基氧基) 酮、酯、酰胺、酸或腈。烯醇化物聚集体显着影响氧化反应的结果。对竞争反应进行了分析，并提出了将其最小化的条件。产物的化学选择性还原导致 N-O 键裂解为 α-羟基羰基化合物或羰基官能团还原为单保护的 1,2-二醇或 O-保护的氨基醇。
• Copper-Catalyzed Oxidative Coupling of AIBN and Ketone-Derived Enoxysilanes to γ-Ketonitriles
  作者：Xuexia Zhang、Hanmin Huang

  DOI：10.1021/acs.orglett.8b02154

  日期：2018.8.17

  A new and efficient oxidative coupling reaction between enoxysilane and alkylnitrile radicals derived from readily available AIBN and its analogues has been developed by using redox-active metal as a catalyst in which the redox-active copper is used for enhancing the electrophilicity of a free radical via coordination and bringing the radical and nucleophilic enol ether closer to facilitate the single-electron

  通过使用氧化还原活性金属作为催化剂开发了一种新的，有效的环氧乙烷与衍生自易得的AIBN及其类似物的烷基腈自由基之间的氧化偶联反应，其中氧化还原活性铜用于增强自由基的亲电子性配位，使自由基和亲核烯醇醚更接近以促进单电子转移。本催化方案以良好的产率至优异的产率和良好的官能团耐受性提供了多种γ-乙腈。