o-Brom-N-methylformanilid | 344746-77-6

• 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: o-Brom-N-methylformanilid
• 英文别名: 2-bromo-N-methylformanilide；N-(2-bromophenyl)-N-methylformamide
• CAS: 344746-77-6
• 化学式: C₈H₈BrNO
• 分子量: 214.062
• InChiKey: AEIZNPNGJLTOCM-UHFFFAOYSA-N

物化性质

• 沸点：
  297.7±23.0 °C(Predicted)
• 密度：
  1.518±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  o-Brom-N-methylformanilid 在 lithium aluminium tetrahydride 、 potassium tert-butylate 、 palladium dichloride 作用下， 以 乙醚 为溶剂， 生成 N-methyl-2-phosphanylaniline
  参考文献：
  名称：

  Synthesis of 1H-1,3-benzazaphospholes: substituent influence and mechanistical aspects

  摘要：

  Various substituted carboxylic acid 2-chloro- and 2-bromoanilides 1a-j react with triethylphosphite in the presence of anhydrous NiCl2 or NiBr2 to give o-acylamido-benzenephosphonic acid esters 2a-g and 2j. Yields depend strongly on the substituents. 2-Fluoro-4,6-dibromoacetanilide 1g reacts only at 6-position, indicating an o-directed process. Based on substituent effects, we infer a mechanism via Ni(0) intermediates that insert into the carbon-halogen bond. The N-tertiary 2-bromoformanilide 4 does not undergo phosphonylation to 5 in the presence of the Ni-catalyst but reacts in the presence of Pd-catalysts. The subsequent reduction of the N-secondary o-acylamido-benzenephosphonic acid esters 2 with excess LiAlH4 is coupled with an intramolecular cyclisation to the 1H-1,3-benzazaphospholes 6 whereas the N-tertiary derivative 5 does not undergo cyclisation upon reduction. NMR data and the crystal structure of 6d are reported. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)01019-5
• 作为产物：
  描述：

  2-溴-N,N-二甲基苯胺 在 carbon nitride 、 四甲基胍 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以24 %的产率得到o-Brom-N-methylformanilid
  参考文献：
  名称：

  石墨氮化碳作为光催化剂用于苯胺的直接甲酰化

  摘要：

  本文描述了一种新的无金属光催化方法，用于在温和的操作条件下将N,N-二官能化苯胺直接转化为甲酰胺衍生物（产率高达 89%）。在此反应中，石墨氮化碳 (g-CN) 是一种坚固且完全可回收的可见光光催化剂，可以轻松回收并重复使用多达五次，而收率不会出现任何显着下降。

  DOI：

  10.1002/chem.202301718

文献信息

• Anomalous Substituent Effects in the Bischler−Napieralski Reaction of 2-Aryl Aromatic Formamides
  作者：Tsutomu Ishikawa、Kazunari Shimooka、Tomoko Narioka、Shigeru Noguchi、Tatsuru Saito、Akiko Ishikawa、Emi Yamazaki、Takashi Harayama、Hiroko Seki、Kentaro Yamaguchi

  DOI：10.1021/jo0012849

  日期：2000.12.1

  1-naphthylformamides (or formanilides) possessing a 2,4,5-trioxygenated phenyl substituent at the 2-position with POCl(3) caused an unprecedented carbon insertion reaction into a benzene ring, producing 7-5 ring (azaazulene) systems as valence isomers of isoquinoline skeletons. Precise examination of this abnormal Bischler-Napieralski reaction (BNR) using various substrates led to the following scope and limitations:

  用POCl（3）处理在2-位具有2,4,5-三加氧苯基取代基的某些1-萘甲酰胺（或甲萘胺）引起前所未有的碳插入苯环的插入反应，产生7-5环（氮杂氮）系统是异喹啉骨架的价异构体。使用各种底物对该异常Bischler-Napieralski反应（BNR）进行精确检查会导致以下范围和局限性：（i）当2-烷氧基-4、5-亚甲基二氧苯基-或4,5构成7-5环系统-二烷氧基-2-羟苯基取代的甲酰胺用作起始底物；（ii）在前一种情况下，将甲酰基碳插入到2-苯基的C（1）-C（6）键中，并且正常的异喹啉环化与异常的碳插入反应竞争；（iii）在2'-位上存在羟基，因为在后者的情况下引起排他的碳插入，其中定量地形成替代的C（1）-C（2）插入产物；（iv）电子上等同于4，5-二烷氧基-2-羟基衍生物的3，6-二甲氧基-2-羟基苯基取代的甲酰苯胺产生吲哚-吡喃酮作为异常的BNR产物。使用PM-3方法的理论方法表
• Heinicke, J.; Nietzschmann, E.; Tzschach, A., Journal fur praktische Chemie (Leipzig 1954), 1983, vol. 325, # 3, p. 511 - 516
  作者：Heinicke, J.、Nietzschmann, E.、Tzschach, A.

  DOI：——

  日期：——
• HEINICKE, J.;NIETZSCHMANN, E.;TZSCHACH, A., J. PRAKT. CHEM., 1983, 325, N 3, 511-516
  作者：HEINICKE, J.、NIETZSCHMANN, E.、TZSCHACH, A.

  DOI：——

  日期：——
• Synthesis of 1H-1,3-benzazaphospholes: substituent influence and mechanistical aspects
  作者：Joachim Heinicke、Nidhi Gupta、Anushka Surana、Normen Peulecke、Brigitte Witt、Kinga Steinhauser、Raj K Bansal、Peter G Jones

  DOI：10.1016/s0040-4020(01)01019-5

  日期：2001.12

  Various substituted carboxylic acid 2-chloro- and 2-bromoanilides 1a-j react with triethylphosphite in the presence of anhydrous NiCl2 or NiBr2 to give o-acylamido-benzenephosphonic acid esters 2a-g and 2j. Yields depend strongly on the substituents. 2-Fluoro-4,6-dibromoacetanilide 1g reacts only at 6-position, indicating an o-directed process. Based on substituent effects, we infer a mechanism via Ni(0) intermediates that insert into the carbon-halogen bond. The N-tertiary 2-bromoformanilide 4 does not undergo phosphonylation to 5 in the presence of the Ni-catalyst but reacts in the presence of Pd-catalysts. The subsequent reduction of the N-secondary o-acylamido-benzenephosphonic acid esters 2 with excess LiAlH4 is coupled with an intramolecular cyclisation to the 1H-1,3-benzazaphospholes 6 whereas the N-tertiary derivative 5 does not undergo cyclisation upon reduction. NMR data and the crystal structure of 6d are reported. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Graphitic Carbon Nitride as Photocatalyst for the Direct Formylation of Anilines
  作者：Giuseppe Sportelli、Gaia Grando、Manuela Bevilacqua、Giacomo Filippini、Michele Melchionna、Paolo Fornasiero

  DOI：10.1002/chem.202301718

  日期：2023.10.2

  A new metal-free photocatalytic approach for the direct conversion of N,N-difunctionalized anilines into formamides derivatives (up to 89 % yield) under mild operative conditions is described herein. In this reaction, graphitic carbon nitride (g-CN) acts as a robust and fully recyclable visible-light photocatalyst that was easily recovered and reused up to five times without any significant drop in

  本文描述了一种新的无金属光催化方法，用于在温和的操作条件下将N,N-二官能化苯胺直接转化为甲酰胺衍生物（产率高达 89%）。在此反应中，石墨氮化碳 (g-CN) 是一种坚固且完全可回收的可见光光催化剂，可以轻松回收并重复使用多达五次，而收率不会出现任何显着下降。