2,2,6,6-tetramethyl-1-((tetrahydrofuran-2-yl)oxy)piperidine | 197246-28-9

• 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: 2,2,6,6-tetramethyl-1-((tetrahydrofuran-2-yl)oxy)piperidine
• 英文别名: 2,2,6,6-Tetramethyl-1-(oxolan-2-yloxy)piperidine
• CAS: 197246-28-9
• 化学式: C₁₃H₂₅NO₂
• 分子量: 227.347
• InChiKey: VNRZJXBCSTZVOJ-UHFFFAOYSA-N

物化性质

• 沸点：
  278.6±50.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  21.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,2,6,6-tetramethyl-1-((tetrahydrofuran-2-yl)oxy)piperidine 在 1,4-环己二烯 作用下， 生成 tetrahydrofuran-2-yl 、 2,2,6,6-四甲基哌啶氧化物
  参考文献：
  名称：

  Thermal Stability of 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO) and Related N-Alkoxyamines

  摘要：

  The carbon-oxygen bond dissociation enthalpies, BDE(C-O), in several N-alkoxyamine derivatives based on 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) have been determined in the liquid phase by photoacoustic calorimetry. The BDE(C-O) and the BDE(C-H) in the corresponding hydrocarbons follow a linear correlation: BDE(C-O) = 1.04BDE(C-H) - 62.1 kcal mol(-1). When an electronegative element adjacent to the C-O bond is present, as in tetrahydrofuryl, a substantial deviation from the correlation is noticed. Due to the anomeric interaction the (THF) N-alkoxyamine is stabilized by an additional 14 kcal mol(-1). The Arrhenius expression for the homolytic decomposition of methyl-TEMPO in the gas phase obeys k/s(-1) = 10(15.3) exp(-45.3/RT) to yield a BDE(C-O) of 47 +/- 1 kcal mol(-1) at 298 K. Furthermore, a high reactivity of TEMPO toward hydrogen donors, 1,4-cyclohexadiene or 9,10-dihydroanthracene, has been observed. Above 380 K, TEMPO is converted into the hydroxyamine 2,2,6,6-tetramethyl-1-piperidinol (TEMPOH) and the amine 2,2,6,6-tetramethylpiperidine (TEMPH). An acid-catalyzed mechanism for TEMPO deoxygenation is proposed.

  DOI：

  10.1021/ja9837102
• 作为产物：
  描述：

  四氢呋喃 、 2,2,6,6-tetramethyl-piperidine-N-oxyl 在 caesium carbonate 作用下， 以 乙腈 为溶剂， 反应 20.0h， 以65%的产率得到2,2,6,6-tetramethyl-1-((tetrahydrofuran-2-yl)oxy)piperidine
  参考文献：
  名称：

  高亲电性二氧化钛孔作为多功能和高效的光化学自由基源

  摘要：

  纳米半导体（如 TiO2）中的光生空穴构成了强大的亲电中心，能够从众多供体（如醚）或未活化的底物（如甲苯或乙腈）中捕获电子，并构成异常清洁和有效的自由基来源。与典型的自由基前体相比，半导体产生单个自由基（而不是成对自由基），其中前体可以在使用后通过过滤或离心轻松去除，从而使其成为有机化学中的便利工具。该过程可以描述为张力障碍质子耦合电子转移的一个例子。

  DOI：

  10.1021/jacs.8b13422

文献信息

• Photochemical C−H Amination of Ethers and Geminal Difunctionalization Reactions in One Pot
  作者：Daniel Hernández‐Guerra、Anna Hlavačková、Chiranan Pramthaisong、Ilaria Vespoli、Radek Pohl、Tomáš Slanina、Ullrich Jahn

  DOI：10.1002/anie.201905209

  日期：2019.9.2

  (nonaflyl, Nf) azide as the aminating reagent to give N-sulfonyl hemiaminals is reported. This enables unprecedented C(sp3 ) difunctionalization reactions, leading to diverse functionalized amino group containing compounds starting from simple ethers in one pot.

  据报道，使用相对稳定的九氟丁烷磺酰基（nonaflyl，Nf）叠氮化物作为胺化试剂进行醚的温和，无原子经济且无金属的α-CH胺化反应，可得到N-磺酰基半缩醛。这使空前的C（sp3）双官能化反应成为可能，从而导致从一锅中的简单醚开始的各种官能化的含氨基化合物。
• Oxidation of Enolate Anion by Hypervalent Iodine Compounds: Synthesis of α-Tempo Carbonyl Compound, A New Living Radical Polymerization Initiator
  作者：Kwang-Hyun Ahn、Younghun Kim

  DOI：10.1080/00397919908086598

  日期：1999.12.1

  Abstract Oxyfunctionalization of esters, 1, by (diacetoxyiodo)benzene and 2,2,6,6-tetramethylpiperidinyl-l-oxy radical produced α-TEMPO esters, 2, which are an efficient unimolecular initiator for the living radical polymerization.

  摘要 通过（二乙酰氧基碘）苯和 2,2,6,6-四甲基哌啶基-1-氧基自由基对酯 1 进行氧官能化生成 α-TEMPO 酯 2，这是活性自由基聚合的有效单分子引发剂。
• Copper nitrate-catalyzed oxidative coupling of unactivated C(sp³)–H bonds of ethers and alkanes with <i>N</i>-hydroxyphthalimide: synthesis of <i>N</i>-hydroxyimide esters
  作者：Xiaohe Xu、Jian Sun、Yuyan Lin、Jingya Cheng、Pingping Li、Yiyan Yan、Qi Shuai、Yuanyuan Xie

  DOI：10.1039/c7ob02249b

  日期：——

  between N-hydroxyphthalimide (NHPI) and ethers/alkanes has been described. The reaction is accomplished smoothly by using simple and green molecular oxygen as the oxidant, providing an alternative for the efficient synthesis of N-alkoxyphthalimides. In addition, it was found that when tert-butyl ethers were used as substrates, unexpected N-hydroxyimide ester derivatives were obtained in moderate to

  已经描述了N-羟基邻苯二甲酰亚胺（NHPI）与醚/烷烃之间的硝酸铜催化的交叉脱氢偶联反应。通过使用简单的绿色分子氧作为氧化剂，可以顺利完成反应，为有效合成N-烷氧基邻苯二甲酰亚胺提供了一种选择。另外，发现当将叔丁基醚用作底物时，以中等至优异的产率获得了意想不到的N-羟基酰亚胺酯衍生物。为了进一步理解这种不寻常的转化，进行了对照实验并提出了合理的机制。
• Oxidative Radical-Mediated Addition of Ethers to Quinone Imine Ketals: An Access to Hemiaminals
  作者：Satish G. More、Rohit B. Kamble、Gurunath Suryavanshi

  DOI：10.1021/acs.joc.0c02254

  日期：2021.2.5

  synthesis of substituted hemiaminal via addition of ethers to quinone imine ketals (QIKs) has been developed under metal-free conditions. In the presence of tetrabutylammonium chloride and potassium persulfate (K2S2O8), QIKs couple efficiently with cyclic and acyclic ethers to give hemiaminals. This strategy offers an easy access to substituted hemiaminal ethers with high functional group tolerance in good

  通过在无金属条件下开发通过将醚添加到醌亚胺缩酮（QIKs）的高度区域选择性合成取代的烟酰胺的方法。在氯化四丁基铵和过硫酸钾（K 2 S 2 O 8）的存在下，QIK与环状和非环状醚有效偶联，得到缩醛。此策略可轻松获得具有高官能团耐受性且产率高至优异的取代的人类薄荷醚。
• Chelation-promoted Efficient C−H/N−H Cross Dehydrogenative Coupling between Picolinamides and Simple Ethers under Copper Catalysis
  作者：Qiang Yue、Zhen Xiao、Zhengkun Kuang、Zhengding Su、Qian Zhang、Dong Li

  DOI：10.1002/adsc.201701508

  日期：2018.3.20

  A highly efficient copper‐catalyzed C−H/N−H cross dehydrogenative coupling between picolinamides and simple ethers was developed. The reaction was promoted by the chelation assistance of removable picolinyl group and exhibited excellent TON and TOF number. This method was applicable to both N‐aryl and alkyl picolinamides as well as various cyclic and acyclic ethers with good functional group compatibility

  在吡啶甲酰胺和简单醚之间开发了一种高效的铜催化CH / NH交叉脱氢偶联剂。可移动的吡啶基的螯合辅助促进了反应，并显示出优异的TON和TOF值。该方法适用于N-芳基和烷基吡啶甲基酰胺以及具有良好官能团相容性的各种环状和无环醚。它还具有耐空气和潮湿的优点，并且易于操作。