N-(tert-Butyl)-2-methylpropylidenamin-N-oxid | 85664-55-7

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: N-(tert-Butyl)-2-methylpropylidenamin-N-oxid
• 英文别名: N-tert-butyl-α-isopropylnitrone；N-tert-butyl-alpha-isopropylnitrone；N-tert-butyl-2-methylpropan-1-imine oxide
• CAS: 85664-55-7
• 化学式: C₈H₁₇NO
• 分子量: 143.229
• InChiKey: IJUWLQKHCVLFIY-UHFFFAOYSA-N

物化性质

• 沸点：
  55-58 °C(Press: 0.9 Torr)
• 密度：
  0.842±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 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-(tert-Butyl)-2-methylpropylidenamin-N-oxid 在 ammonium hydroxide 、 (-)-chloro((1R,2R)-4,4',6,6'-tetra-tert-butyl-2,2'-[cyclohexane-1,2-diylbis(nitrilomethylidyne)]diphenolato)manganese(III) 、 二叔丁基过氧化物 、 四丁基氟化铵 、 copper(II) acetate monohydrate 、 caesium carbonate 、 magnesium 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 、 乙醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 73.17h， 生成 4-(1-tert-butyl-(2-methyl-1-(3'-ethynylphenylpropyl)aminooxy)ethyl)benzyl 4-azidobenzoate
  参考文献：
  名称：

  环烷氧基胺引发剂通过叠氮化物/炔烃“点击”化学键合，可进行扩环乙烯基聚合，从而提供大环聚合物

  摘要：

  用于氮氧化物介导的受控自由基聚合（NMP）的环状引发剂是通过扩环乙烯基聚合机理制备大环聚合物的有力工具。为此，我们制备了一种霍克型NMP引发剂，其中包括叠氮化物和末端炔烃作为无环前体，随后通过分子内叠氮化物/炔烃“点击”反应进行束缚，产生最终的环状NMP引发剂。证明了苯乙烯与环状引发剂的聚合反应，并通过凝胶渗透色谱（GPC）和基质辅助激光解吸/电离飞行时间质谱（MALDI-TOF MS）对所得的聚合物进行了表征。这些结果证明，苯乙烯的扩环聚合与自由基环交换反应一起发生，自由基的环交换反应源于固有的氮氧化物的交换，从而生成具有较高扩环的大环聚苯乙烯。©2010 Wiley Periodicals，Inc. J Polym Sci A部分：Polym Chem 48：3402–3416，2010

  DOI：

  10.1002/pola.24126
• 作为产物：
  描述：

  2-甲基-2-硝基丙烷 、 异丁醛 在 氯化铵 、 锌 作用下， 以 乙醚 、 水 为溶剂， 以74%的产率得到N-(tert-Butyl)-2-methylpropylidenamin-N-oxid
  参考文献：
  名称：

  聚烯烃-聚乙烯嵌段共聚物的串联活性插入和可控自由基聚合

  摘要：

  活性烯烃聚合的串联聚合和通过大螯合物的光引发引入自由基陷阱（MILRad 官能化）提供的受控自由基聚合使大分子引发剂可以产生一系列包含烯烃、丙烯酸、苯乙烯和乙烯基嵌段链段的二嵌段和三嵌段。

  DOI：

  10.1002/anie.202112742

文献信息

• Advanced supramolecular initiator for nitroxide-mediated polymerizations containing both metal-ion coordination and hydrogen-bonding sites
  作者：Ulrich Mansfeld、Martin D. Hager、Richard Hoogenboom、Christina Ott、Andreas Winter、Ulrich S. Schubert

  DOI：10.1039/b902636c

  日期：——

  The synthesis of a new difunctional nitroxide initiator combining two orthogonal supramolecular entities is reported; controlled radical polymerization of styrene using this initiator is demonstrated to generate well-defined heterotelechelic polymers in a one-step procedure.

  报告了一种结合了两种正交超分子实体的新型双官能团亚硝基氧化物引发剂的合成过程；使用这种引发剂对苯乙烯进行受控自由基聚合反应的实验结果表明，只需一步即可生成定义明确的杂交链烯聚合物。
• Process for the preparation of a block copolymer
  申请人：Heise Andreas

  公开号：US20060100390A1

  公开（公告）日：2006-05-11

  The invention relates to a process for the preparation of a block copolymer, the process being carried out in the presence of a multifunctional initiator and comprising at least one enzymatically catalyzed homo- or copolymerization reaction and at least one non-enzymatically catalyzed controlled homo- or copolymerization reaction, wherein the non-enzymatically catalyzed controlled homo- or copolymerization reaction is chosen from the group comprising a free radical polymerization reaction, an ionic polymerization reaction, a polycondensation reaction, and a ring opening polymerization (ROP) reaction. The invention also relates to a chiral block copolymer wherein at least one block comprises at least one substituted ε-caprolactone derivative.

  本发明涉及一种制备嵌段共聚物的方法，该方法在多功能引发剂的存在下进行，包括至少一种酶催化的同源或共聚反应和至少一种非酶催化的受控同源或共聚反应，其中非酶催化的受控同源或共聚反应选择自由基聚合反应、离子聚合反应、聚缩合反应和环开聚合（ROP）反应中的一种。本发明还涉及一种手性嵌段共聚物，其中至少一个块包括至少一个取代的ε-己内酯衍生物。
• Oxidation of imines to nitrones by the permanganate ion
  作者：Dorthe Christensen、Karl Anker Joergensen

  DOI：10.1021/jo00262a029

  日期：1989.1
• Aurich, Hans Guenter; Eidel, Joachim; Schmidt, Michael, Chemische Berichte, 1986, vol. 119, # 1, p. 18 - 35
  作者：Aurich, Hans Guenter、Eidel, Joachim、Schmidt, Michael

  DOI：——

  日期：——
• Spectral properties of bichromophoric probes based on pyrene and benzothioxanthene in solution and in polymer matrices
  作者：Jozef Kollár、Štefan Chmela、Pavol Hrdlovič

  DOI：10.1016/j.jphotochem.2013.06.017

  日期：2013.10

  The new initiator for controlled radical polymerization labeled with highly fluorescent chromophores was prepared. Highly fluorescent chromophores, such as pyrene and benzo[k,l]thioxanthene (BTX), were used for fluorescent labeling. The chromophores were combined with nitroxide on 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO), which is one of the best systems for mediating the radical polymerization of olefins. The spectral properties of a labeled initiator were measured in solution and in polymer matrix. In the absorption spectra of the bichromophoric initiator there is a broad band with a maximum in the range 450-485 nm depending on the medium. This band corresponds to the BTX moiety, whereas the band with vibrational structure at 320-345 nm arises from the pyrene structural unit. The emission spectra of the probes, recorded at an excitation of 480 nm in solution and in the polymer matrices exhibit a broad band in the range 490-525 nm and it is red-shifted in polar media. Excitation of the labeled initiator in the region of the maximum absorption of pyrene results exclusively in emission due to BTX which is caused by efficient transfer of the excitation energy from pyrene to the benzothioxanthene chromophore. Quenching of the fluorescence of the donor chromophore pyrene moiety of the labeled initiator was observed in solution and in the polymer matrices, and this process is primarily intra-molecular. The quantum yield of florescence of the labeled initiator is very high in all the studied environments and is between 0.5 and 1 depending on the polarity of medium. Both chromophores exhibit fluorescence, but the lifetimes of the fluorescence are very different. The lifetime is 100-400 ns for pyrene and is 4-8 ns for benzothioxanthene. The intermolecular quenching rate constant of 3.6 x 10(10) dm(3) mol(-1) s(-1) was determined from the Stern-Volmer plot for the quenching of the decay of pyrene with the BTXD model dye. Based on the intermolecular quenching rate of the pyrene-BTXD, the rate of intramolecular energy transfer from pyrene to the BTX chromophore in this bichromophoric initiator was estimated to be greater than 10(11) s(-1). (C) 2013 Elsevier B.V. All rights reserved.