C-(2-methylphenyl)-N-tert-butylnitrone | 135485-37-9

• 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: C-(2-methylphenyl)-N-tert-butylnitrone
• 英文别名: (Z)-N-tert-butyl-1-(o-tolyl)methanimine oxide；N-tert-butyl-1-(2-methylphenyl)methanimine oxide
• CAS: 135485-37-9
• 化学式: C₁₂H₁₇NO
• 分子量: 191.273
• InChiKey: WVTAFDBGFFSTGP-LCYFTJDESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  28.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N-二乙基甲酰胺 、 C-(2-methylphenyl)-N-tert-butylnitrone 在 lithium diisopropyl amide 作用下， 以 甲苯 为溶剂， 反应 0.33h， 以88%的产率得到2-(tert-butyl(hydroxy)amino)-N,N-diethyl-2-(o-tolyl)-acetamide
  参考文献：
  名称：

  氨基甲酸酯中的氨基甲酸酯阴离子

  摘要：

  氨基甲酰基阴离子的衍生自除Ñ，Ñ二取代的甲酰胺和LDA到ñ -叔丁基硝酮进行说明。用多种甲酰胺和硝酮证明了该反应，并提供了直接通往α-（N-羟基）氨基酰胺的途径。在叔胺上使用叔亮氨酸衍生的手性助剂可提供具有良好非对映选择性的产物。证明了通过叔丁基脱保护或N-脱氧使产物衍生化。

  DOI：

  10.1021/jo500848a
• 作为产物：
  描述：

  2-甲基-2-硝基丙烷 、 2-甲基苯甲醛 在 溶剂黄146 、 锌 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以66%的产率得到C-(2-methylphenyl)-N-tert-butylnitrone
  参考文献：
  名称：

  Synthesis and characterization of phenyl-substituted C-phenyl-N-tert-butylnitrones and some of their radical adducts

  摘要：

  Synthesis of C-phenyl-N-tert-butylnitrone (PBN) and several of its analogues with substituents in the 2-, 3-, or 4-position on the phenyl ring is described. While a one-pot reduction/condensation method proved suitable for most compounds, it was necessary to prepare some examples by direct condensation or through oxidation of the appropriate imine. The H-1 NMR data for the 3-X- and 4-X-PBN's can be correlated with the Hammett equation. For the 3-X series DELTA-delta for the alpha-proton correlates best with sigma(+) and has a correlation coefficient of 0.90. For the 4-X series a dual substituent parameter equation using sigma(R)0 gives the best correlation with r = 0.99. The hyperfine splitting constants (hfsc's) of the HO. and HOO. adducts of several substituted PBN's are also included and their correlation with the Hammett equation is discussed.

  DOI：

  10.1021/jo00035a020

文献信息

• Palladium-catalyzed C–H Alkenylation of <i>C</i>-Aryl Nitrones
  作者：Megumi Hasegawa、Arisa Nomoto、Takuya Suga、Takahiro Soeta、Yutaka Ukaji

  DOI：10.1246/cl.160821

  日期：2017.1.5

  Palladium-catalyzed C–H alkenylation of C-aryl N-t-butyl nitrones with ethyl acrylate produced ortho-alkenylated benzamide derivatives via isomerization of the nitrone moiety. The use of 1,1,1,3,3,3-hexafluoro-2-propanol/acetic acid as a solvent resulted in effective C–H alkenylation, while competitive 1,3-dipolar cycloaddition was completely suppressed.

  钯催化的 C-芳基 N-叔丁基硝酮与丙烯酸乙酯的 C-H 烯基化通过硝酮部分的异构化产生邻烯基化的苯甲酰胺衍生物。使用 1,1,1,3,3,3-六氟-2-丙醇/乙酸作为溶剂导致有效的 C-H 烯基化，同时完全抑制了竞争性 1,3-偶极环加成。
• Iridium(III)-Catalyzed C–H Amidation of Nitrones with Dioxazolones
  作者：Xia Mi、Weisheng Feng、Chao Pi、Xiuling Cui

  DOI：10.1021/acs.joc.9b00300

  日期：2019.5.3

  efficiently achieved through Ir(III)-catalyzed direct C–H amidation of nitrones with good to excellent yields and tolerance of broad functional groups. This reaction smoothly proceeded at room temperature in the absence of acid or base in a short reaction time. Carbon dioxide was generated as the sole byproduct, thus providing an environmentally benign amidation process. The title products could be efficiently

  通过Ir（III）催化的硝基甲烷的直接C–H酰胺化反应，可以高效地获得各种酰胺化的硝酮，并具有良好至优异的收率和宽泛的官能团耐受性。该反应在短时间内在室温下在不存在酸或碱的条件下平稳地进行。产生二氧化碳作为唯一的副产物，因此提供了对环境无害的酰胺化过程。标题产物可以有效地转化为取代的苯并异恶唑啉。
• Abe, Yukino; Seno, Shin-ya; Sakakibara, Kazuhisa, Journal of the Chemical Society. Perkin transactions II, 1991, # 6, p. 897 - 903
  作者：Abe, Yukino、Seno, Shin-ya、Sakakibara, Kazuhisa、Hirota, Minoru

  DOI：——

  日期：——
• Carbamoyl Anion Addition to Nitrones
  作者：Jonathan T. Reeves、Chris Lorenc、Kaddy Camara、Zhibin Li、Heewon Lee、Carl A. Busacca、Chris H. Senanayake

  DOI：10.1021/jo500848a

  日期：2014.6.20

  The addition of carbamoyl anions derived from N,N-disubstituted formamides and LDA to N-tert-butyl nitrones is described. The reaction was demonstrated with a variety of formamides and nitrones and provided a direct route to α-(N-hydroxy)amino amides. The use of a tert-leucinol derived chiral auxiliary on the nitrone provided products in good diastereoselectivity. Derivatization of the products by

  氨基甲酰基阴离子的衍生自除Ñ，Ñ二取代的甲酰胺和LDA到ñ -叔丁基硝酮进行说明。用多种甲酰胺和硝酮证明了该反应，并提供了直接通往α-（N-羟基）氨基酰胺的途径。在叔胺上使用叔亮氨酸衍生的手性助剂可提供具有良好非对映选择性的产物。证明了通过叔丁基脱保护或N-脱氧使产物衍生化。
• Synthesis and characterization of phenyl-substituted C-phenyl-N-tert-butylnitrones and some of their radical adducts
  作者：Randall D. Hinton、Edward G. Janzen

  DOI：10.1021/jo00035a020

  日期：1992.4

  Synthesis of C-phenyl-N-tert-butylnitrone (PBN) and several of its analogues with substituents in the 2-, 3-, or 4-position on the phenyl ring is described. While a one-pot reduction/condensation method proved suitable for most compounds, it was necessary to prepare some examples by direct condensation or through oxidation of the appropriate imine. The H-1 NMR data for the 3-X- and 4-X-PBN's can be correlated with the Hammett equation. For the 3-X series DELTA-delta for the alpha-proton correlates best with sigma(+) and has a correlation coefficient of 0.90. For the 4-X series a dual substituent parameter equation using sigma(R)0 gives the best correlation with r = 0.99. The hyperfine splitting constants (hfsc's) of the HO. and HOO. adducts of several substituted PBN's are also included and their correlation with the Hammett equation is discussed.