3-nitrobenzaldehyde O-methyl oxime | 33499-33-1

• 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: 3-nitrobenzaldehyde O-methyl oxime
• 英文别名: 3-nitrobenzaldoxime O-methyl ether；3-nitrobenzaldehyde O-methyloxime；m-Nitrobenzaldoxim-O-methylether；N-methoxy-1-(3-nitrophenyl)methanimine
• CAS: 33499-33-1
• 化学式: C₈H₈N₂O₃
• 分子量: 180.163
• InChiKey: UQGUNWSOIBZIJT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  67.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-nitrobenzaldehyde O-methyl oxime 在 N-溴代丁二酰亚胺(NBS) 、 聚合甲醛 、 Ag^(1-)*C₂F₃O₂^(1-) 、 palladium diacetate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 水 、 1,2-二氯乙烷 为溶剂， 反应 24.25h， 生成 2-溴-5-硝基苯甲醛
  参考文献：
  名称：

  Selectiveortho-Bromination of Substituted Benzaldoximes Using Pd-Catalyzed C–H Activation: Application to the Synthesis of Substituted 2-Bromobenzaldehydes

  摘要：

  Substituted 2-bromobenzaldehydes were synthesized from benzaldehydes using a three-step sequence involving a selective palladium-catalyzed ortho-bromination as the key step. O-Methyloxime serves as a directing group in this reaction. A rapid deprotection of substituted 2-bromobenzaldoximes afforded substituted 2-bromobenzaldehydes with good overall yields.

  DOI：

  10.1021/jo200853j
• 作为产物：
  描述：

  benzaldehyde O-methyloxime 在 十二羰基三钌 、 PIFA 、 氧气 、 silver nitrate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 30.0h， 以46%的产率得到3-nitrobenzaldehyde O-methyl oxime
  参考文献：
  名称：

  具有可移动助剂的芳烃的单体八面体钌（II）络合物的meta -C–H硝化

  摘要：

  据报道，一种可移动的肟辅助的芳烃间位-CH硝化硝化反应。机理研究和DFT计算表明，新的单体八面体钌（II）络合物负责亚选择性硝化。作为共氧化剂的双氧对于实现高转化率和高收率至关重要。此外，通过临床CNS药物地西p和氟伏沙明的后期修饰进一步展示了本反应方案的实用性。

  DOI：

  10.1021/acs.orglett.7b01297

文献信息

• Oxidative Conversion of Aldoximes into Carboxylic Acid Esters
  作者：Said、Skarzewski、Mlochowski

  DOI：10.1080/00397919208021316

  日期：1992.7

  Aromatic and aliphatic aldoximes or their O-methyl ethers can be efficiently converted into the corresponding carboxylic acid esters by treatment with an alcoholic solution of 30% hydrogen peroxide in the Presence of catalytic amounts of 2-nitrobenzeneseleninic acid. Primary alcohols give excellent to good yields, secondary ones - good to moderate, but with tertiary alcohols no esterification is obserwed.
• Selective<i>ortho</i>-Bromination of Substituted Benzaldoximes Using Pd-Catalyzed C–H Activation: Application to the Synthesis of Substituted 2-Bromobenzaldehydes
  作者：Emmanuelle Dubost、Christine Fossey、Thomas Cailly、Sylvain Rault、Frederic Fabis

  DOI：10.1021/jo200853j

  日期：2011.8.5

  Substituted 2-bromobenzaldehydes were synthesized from benzaldehydes using a three-step sequence involving a selective palladium-catalyzed ortho-bromination as the key step. O-Methyloxime serves as a directing group in this reaction. A rapid deprotection of substituted 2-bromobenzaldoximes afforded substituted 2-bromobenzaldehydes with good overall yields.
• Monomeric Octahedral Ruthenium(II) Complex Enabled <i>meta</i>-C–H Nitration of Arenes with Removable Auxiliaries
  作者：Zhoulong Fan、Jie Li、Heng Lu、Dong-Yu Wang、Chao Wang、Masanobu Uchiyama、Ao Zhang

  DOI：10.1021/acs.orglett.7b01297

  日期：2017.6.16

  A removable oxime-assisted meta-C–H nitration of arenes is reported. Mechanistic investigations and DFT calculations reveal a new monomeric octahedral ruthenium(II) complex is responsible for the meta-selective nitration. Dioxygen as a cooxidant is crucial for achieving high conversion and good yields. Moreover, the utility of the present reaction protocol is further showcased by the late-stage modification

  据报道，一种可移动的肟辅助的芳烃间位-CH硝化硝化反应。机理研究和DFT计算表明，新的单体八面体钌（II）络合物负责亚选择性硝化。作为共氧化剂的双氧对于实现高转化率和高收率至关重要。此外，通过临床CNS药物地西p和氟伏沙明的后期修饰进一步展示了本反应方案的实用性。