4-tert-butylbenzonitrile oxide

• 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: 4-tert-butylbenzonitrile oxide
• 英文别名: 4-t-Butylbenzonitrile oxide
• 化学式: C₁₁H₁₃NO
• 分子量: 175.23
• InChiKey: BXMFMDZORWIRIQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  30.7
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-tert-butylbenzonitrile oxide 、 6^A-deoxy-6^A-propynamido-β-cyclodextrin 在 苯甲腈 N-氧化物 作用下， 以 甲醇 为溶剂， 生成 N-(6^A-deoxy-β-cyclodextrin-6^A-yl)-4-(aminocarbonyl)-3-(4-tert-butylphenyl)isoxazole
  参考文献：
  名称：

  通过偶极亲和物与环糊精的瞬时连接，逆转区域选择性并提高一氧化氮环化速率。

  摘要：

  腈氧化物与单取代的亲脂性物质如丙酰胺的反应通常按比例提供80％或更多的3，5-二取代的环加合物。相比之下，6（A）-脱氧-6（A）-丙酰胺基-β-环糊精与4-叔丁基苄腈氧化物和4-苯基苄腈氧化物的反应可提供> 90％的溶液和约85％的相应3,4-二取代异恶唑分别。除了逆转区域选择性外，环糊精还增加了这些环加成的速率。对于环糊精优选的环加合物的生产，加速的程度高达三个数量级以上，但是甚至给出给出较不优选的区域异构体的反应速率也增加了。使用6（A）-脱氧-6（A）-丙酰胺基-β-环糊精，由于酰胺键不容易裂解，因此不容易将环加合物与环糊精分离。相比之下，4-叔丁基苄腈氧化物与丙烯酸，甲基丙烯酸和巴豆酸的环加成反应的区域选择性也通过形成相应的环糊精酯而改变，分别为500，> 10和> 100。环加成的速率也增加了多达475倍，在这些情况下，环加成的产物很容易通过酯水解从环糊精中释放出来。将这些过程

  DOI：

  10.1002/chem.200600627

文献信息

• β-Cyclodextrin as a Scaffold for Supramolecular Chemistry, To Reverse the Regioselectivity of Nitrile Oxide Cycloadditions
  作者：Adam G. Meyer、Christopher J. Easton、Stephen F. Lincoln、Gregory W. Simpson

  DOI：10.1021/jo9817321

  日期：1998.11.1

  beta-Cyclodextrin has been used as a molecular scaffold, whereby tethering dipolarophiles to the cyclodextrin and then allowing preassociation of the modified cyclodextrins with aromatic nitrile oxides, as host-guest complexes, controls the relative orientations of the dipoles and the dipolarophiles in their cycloadditions. In this manner it has been possible to reverse the usual regioselectivity of cycloadditions of nitrile oxides, as illustrated by reactions with a terminal alkene, a terminal alkyne, and a 1,2-disubstituted alkene. For example, iii aqueous solution, 4-tert-butylbenzonitrile oxide reacted with 6(A)-deoxy-6(A)-propynamido-beta-cyclodextrin to give the corresponding 4- and 5-substituted isoxazoles, in a 15:1 ratio. With DMF as the solvent, to reduce the extent of host-guest complexation, the product ratio was 1:1.5. The role of complexation in these reactions is also demonstrated by contrasting these results with that of the reaction of the nitrile oxide with methyl propynoate, which afforded only the 5-substituted cycloaddition product. Molecular recognition by the cyclodextrin scaffolds was demonstrated through treatment of 4-tert-butylbenzonitrile oxide with an equimolar mixture of 6(A)-deoxy-6(A)-prapynamido-beta-cyclodextrin and methyl propynoate, in aqueous solution, which gave only the cycloadducts from reaction of the cyclodextrin dipolarophile.