2-Br-4,5-(OCH2O)C6H2C(H)=NCH2CH2NMe2 | 1306773-28-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 2-Br-4,5-(OCH2O)C6H2C(H)=NCH2CH2NMe2
• 英文别名: 2-[(6-bromo-1,3-benzodioxol-5-yl)methylideneamino]-N,N-dimethylethanamine
• CAS: 1306773-28-3
• 化学式: C₁₂H₁₅BrN₂O₂
• 分子量: 299.167
• InChiKey: FYSKWNIFSUNYJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-Br-4,5-(OCH2O)C6H2C(H)=NCH2CH2NMe2 以 水 、 丙酮 、 甲苯 为溶剂， 生成 Pd(2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N)(Cl)
  参考文献：
  名称：

  Mononuclear and tetranuclear palladacycles with terdentate [C,N,N] and [C,N,O] Schiff base ligands. C–H versus C–Br activation reactions

  摘要：

  Reaction of the Schiff base ligands 2-Br-4,5-(OCH2O)C6H2C(H)=NCH2CH2NMe2 (a) and 4,5-(OCH2CH2)-C6H3C(H)=NCH2CH2NMe2 (b) with Pd(OAc)(2) or K-2[PdCl4] leads to the mononuclear cyclometallated compounds [Pd{2-Br-4,5-(OCH2O) C6HC(H)=NCH2CH2NMe2-C6,N,N}(OCOMe)] (1a) and [Pd{4,5-(OCH2-CH2) C6H2C(H)=NCH2CH2NMe2-C6,N,N}(Cl)] (1b), derived from C-H activation at the C6 carbon. Treatment of a with Pd-2(dba)(3) gave [Pd{4-5-(OCH2O) C6H2C(H)=NCH2CH2NMe2-C2,N,N}(Br)] (2a), via C-Br activation.The metathesis reaction of 1a with aqueous sodium chloride gave [Pd{2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N}(Cl)] (3a), with exchange of the acetate group by a chloride ligand. Treatment of the cyclometallated monomers 1a-3a with PPh3 in a 1:1 molar ratio yielded the mononuclear complexes [Pd{2-Br-4,5-(OCH2O) C6HC(H)=NCH2CH2NMe2-C6,N}(L)(PPh3)] (L: OAc, 4a; Cl, 5a) and [Pd{4-5-(OCH2O)C6H2C(H)=NCH2CH2NMe2-C2,N}(Br)(PPh3)] (6a), with Pd-NMe2 bond cleavage. However, treatment of a solution of 3a or 2a with silver trifluoromethanesulfonate, followed by reaction with PPh3 in acetone yielded the cyclometallated complexes [Pd{2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N}(PPh3)][CF3SO3] (7a) and [Pd{4-5-(OCH2O)C6H2C(H)=NCH2CH2NMe2-C2,N,N}(PPh3)][CF3SO3] (8a), respectively, where the Pd-NMe2 bond was retained.The reaction of the ligands 2-Br-4,5-(OCH2O)C6H2C(H)=N(2'-OH-5'-(BuC6H3)-Bu-t) (c) and 4,5-(OCH2CH2)-C6H3C(H)=N(2'-OH-5'-(BuC6H3)-Bu-t) (d) with Pd(OAc) 2 gave the tetranuclear complexes [Pd{2-Br-4, 5-(OCH2O)C6HC(H)=N(2'-O-5'-(BuC6H3)-Bu-t)-C6,N,O}](4) (1c) and [Pd{4,5-(OCH2CH2)C6H2C(H)=N(2'-O-5'-(BuC6H3)-Bu-t)-C6,N,O}](4) (1d), respectively. Treatment of 1c with PPh3 in 1:4 molar ratio, gave the mononuclear species [Pd{2-Br-4,5-(OCH2O)C6HC(H)=N(2'-(O)-5'-(BuC6H3)-Bu-t)-C6,N,O}(PPh3)] (2c) with opening of the polynuclear structure after P-O-bridging bond cleavage. The structure of compounds 2a, 1c and 1d has been determined by X-ray diffraction analysis. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.01.027
• 作为产物：
  描述：

  6-溴-3,4-亚甲基二氧苯甲醛 、 N,N-二甲基乙二胺 以 甲醇 为溶剂， 以100%的产率得到2-Br-4,5-(OCH2O)C6H2C(H)=NCH2CH2NMe2
  参考文献：
  名称：

  Synthesis of Methoxy-, Methylenedioxy-, Hydroxy-, and Halo-Substituted Benzophenanthridinone Derivatives as DNA Topoisomerase IB (TOP1) and Tyrosyl-DNA Phosphodiesterase 1 (TDP1) Inhibitors and Their Biological Activity for Drug-Resistant Cancer

  摘要：

  DOI：

  10.1021/acs.jmedchem.1c00318

文献信息

• Mononuclear and tetranuclear palladacycles with terdentate [C,N,N] and [C,N,O] Schiff base ligands. C–H versus C–Br activation reactions
  作者：Leticia Naya、Digna Vázquez-García、Margarita López-Torres、Alberto Fernández、Antonio Rodríguez、Nina Gómez-Blanco、José M. Vila、Jesús J. Fernández

  DOI：10.1016/j.ica.2011.01.027

  日期：2011.5

  Reaction of the Schiff base ligands 2-Br-4,5-(OCH2O)C6H2C(H)=NCH2CH2NMe2 (a) and 4,5-(OCH2CH2)-C6H3C(H)=NCH2CH2NMe2 (b) with Pd(OAc)(2) or K-2[PdCl4] leads to the mononuclear cyclometallated compounds [Pd2-Br-4,5-(OCH2O) C6HC(H)=NCH2CH2NMe2-C6,N,N}(OCOMe)] (1a) and [Pd4,5-(OCH2-CH2) C6H2C(H)=NCH2CH2NMe2-C6,N,N}(Cl)] (1b), derived from C-H activation at the C6 carbon. Treatment of a with Pd-2(dba)(3) gave [Pd4-5-(OCH2O) C6H2C(H)=NCH2CH2NMe2-C2,N,N}(Br)] (2a), via C-Br activation.The metathesis reaction of 1a with aqueous sodium chloride gave [Pd2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N}(Cl)] (3a), with exchange of the acetate group by a chloride ligand. Treatment of the cyclometallated monomers 1a-3a with PPh3 in a 1:1 molar ratio yielded the mononuclear complexes [Pd2-Br-4,5-(OCH2O) C6HC(H)=NCH2CH2NMe2-C6,N}(L)(PPh3)] (L: OAc, 4a; Cl, 5a) and [Pd4-5-(OCH2O)C6H2C(H)=NCH2CH2NMe2-C2,N}(Br)(PPh3)] (6a), with Pd-NMe2 bond cleavage. However, treatment of a solution of 3a or 2a with silver trifluoromethanesulfonate, followed by reaction with PPh3 in acetone yielded the cyclometallated complexes [Pd2-Br-4,5-(OCH2O)C6HC(H)=NCH2CH2NMe2-C6,N,N}(PPh3)][CF3SO3] (7a) and [Pd4-5-(OCH2O)C6H2C(H)=NCH2CH2NMe2-C2,N,N}(PPh3)][CF3SO3] (8a), respectively, where the Pd-NMe2 bond was retained.The reaction of the ligands 2-Br-4,5-(OCH2O)C6H2C(H)=N(2'-OH-5'-(BuC6H3)-Bu-t) (c) and 4,5-(OCH2CH2)-C6H3C(H)=N(2'-OH-5'-(BuC6H3)-Bu-t) (d) with Pd(OAc) 2 gave the tetranuclear complexes [Pd2-Br-4, 5-(OCH2O)C6HC(H)=N(2'-O-5'-(BuC6H3)-Bu-t)-C6,N,O}](4) (1c) and [Pd4,5-(OCH2CH2)C6H2C(H)=N(2'-O-5'-(BuC6H3)-Bu-t)-C6,N,O}](4) (1d), respectively. Treatment of 1c with PPh3 in 1:4 molar ratio, gave the mononuclear species [Pd2-Br-4,5-(OCH2O)C6HC(H)=N(2'-(O)-5'-(BuC6H3)-Bu-t)-C6,N,O}(PPh3)] (2c) with opening of the polynuclear structure after P-O-bridging bond cleavage. The structure of compounds 2a, 1c and 1d has been determined by X-ray diffraction analysis. (C) 2011 Elsevier B.V. All rights reserved.
• Synthesis of Methoxy-, Methylenedioxy-, Hydroxy-, and Halo-Substituted Benzophenanthridinone Derivatives as DNA Topoisomerase IB (TOP1) and Tyrosyl-DNA Phosphodiesterase 1 (TDP1) Inhibitors and Their Biological Activity for Drug-Resistant Cancer
  作者：De-Xuan Hu、Wen-Lin Tang、Yu Zhang、Hao Yang、Wenjie Wang、Keli Agama、Yves Pommier、Lin-Kun An

  DOI：10.1021/acs.jmedchem.1c00318

  日期：2021.6.10