ethyl (o-methoxybenzoyl)formate oxime | 131934-11-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: ethyl (o-methoxybenzoyl)formate oxime
• 英文别名: Ethyl 2-hydroxyimino-2-(2-methoxyphenyl)acetate
• CAS: 131934-11-7
• 化学式: C₁₁H₁₃NO₄
• 分子量: 223.229
• InChiKey: MJYGHWMIRYBJMJ-UHFFFAOYSA-N

物化性质

• 沸点：
  367.0±44.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  68.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  硝基乙酸乙酯 、 苯甲醚 在 三氟甲磺酸 作用下， 以30%的产率得到2-(羟基亚氨基)-2-(4-甲氧基苯基)乙酸乙酯
  参考文献：
  名称：

  过酸和硫醇-烯反应，可得到具有HDAC抑制活性的psammaplin类似物

  摘要：

  基于超强酸，微波和S-ene化学的原始方法，提出了一种新颖的类似psammaplin结构的合成方法。新化合物被评估为组蛋白脱乙酰基酶抑制剂。结果突出了使用在还原/氧化条件下活化的二硫键前药时的重要考虑因素，必须根据肿瘤细胞类型仔细选择二硫键前药。

  DOI：

  10.1016/j.tet.2014.10.053

文献信息

• Lewis acid promoted electrophilic aromatic substitution reaction of nitrile oxide: Increase of the electrophilicity of carbon atom of nitrile oxide by Lewis acid complexation
  作者：Jae Nyoung Kim、Eung K. Ryu

  DOI：10.1016/s0040-4039(00)73637-9

  日期：1993.5

  Nitrile oxides complexed with Lewis acid have their increased electrophilic character at the carbon atom and could be used as hydroxynitrilium ion equivalents toward aromatic compounds.

  与路易斯酸络合的腈氧化物在碳原子上具有增强的亲电子特性，可以用作芳族化合物的羟基腈离子当量。
• Friedel-Crafts-type reactions involving di- and tricationic species. Onium-allyl dications and O,O-diprotonated aci-nitro species bearing a protonated carbonyl group
  作者：Tomohiko Ohwada、Naoko Yamagata、Koichi Shudo

  DOI：10.1021/ja00004a044

  日期：1991.2

  Stable carbocations do not react with nonactivated benzenes. For example, acetophenone does not react with benzene in the presence of trifluoromethanesulfonic acid (TFSA), while trifluoroacetophenone does do so under acidic conditions owing to activation of the electrophilicity of the hydroxycarbenium cation by the trifluoromethyl group. This and other studies suggest that an electron-withdrawing substituent on the cationic center increases the reactivity toward benzenes. In this paper, involvement of multiply positively charged (dicationic and tricationic) species, which have sufficient electrophilicity toward benzene, is demonstrated in the acid-catalyzed reactions of cinnamaldehyde and its derivatives and also in the acid-catalyzed reactions of nitromethanes. The species formed from cinnamaldehyde, cinnamaldimine, cinnamaldoxime, and their derivatives in TFSA or TFSA-SbF5 have an adequate reactivity toward benzene. O-Protonated cinnamaldehyde and its derivatives, N-protonated cinnamaldimine, and N,N-dimethylcinnamaldiminium salt do not react with benzene. Since a strong acid catalyst is required for the reactions, participation of doubly protonated species, onium-allyl dications, is proposed. Ab initio calculations of (1) the donor-acceptor interaction energies of a neutral donor (such as water and ammonia) and a doubly charged allyl dication and (2) proton affinities demonstrated that the ammonium-allyl dication is more stable than the oxonium-allyl dication, in accordance with the experimental observation. Nitronic acids also react with benzene at the ipso position with respect to the nitro group to give the phenylated oximes in the presence of TFSA. The reaction with benzene is not catalyzed by trifluoroacetic acid, which is sufficiently acidic to monoprotonate a nitronic acid to the protonated aci-nitro form. The reaction requires a stronger acid, trifluoromethanesulfonic acid, suggesting intervention of the dication formed by O,O-diprotonation of aci-nitroalkanes rather than the monoprotonated aci-nitroalkane. As a result of further study on the phenylation reactions, we found a facile phenylation reaction of nitromethanes substituted with an electron-withdrawing group, catalyzed by TFSA, to give phenylated alpha-carbonyloximes in high yields. A triply positively charged cation, an O,O-diprotonated aci-nitro species bearing a protonated ethoxycarbonyl group, which can react with nonactivated benzene, is proposed to be an intermediate in this reaction.