4,5-(OCH2CH2)C6H3C(H)=NCH2CH2NMe2 | 1306773-29-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 香豆素
• 英文名称: 4,5-(OCH2CH2)C6H3C(H)=NCH2CH2NMe2
• 英文别名: 4,5-(OCH2CH2)C6H2C(H)=NCH2CH2NMe2；2-(2,3-dihydro-1-benzofuran-5-ylmethylideneamino)-N,N-dimethylethanamine
• CAS: 1306773-29-4
• 化学式: C₁₃H₁₈N₂O
• 分子量: 218.299
• InChiKey: BYYOVLWBWBAYJC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  24.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  potassium tetrachloropalladate(II) 、 4,5-(OCH2CH2)C6H3C(H)=NCH2CH2NMe2 以 乙醇 、 水 为溶剂， 以29%的产率得到Pd(4,5-(OCH2CH2)C6H2C(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：

  2,3-二氢苯并呋喃-5-甲醛 、 N,N-二甲基乙二胺 以 氯仿 为溶剂， 反应 8.0h， 以89%的产率得到4,5-(OCH2CH2)C6H3C(H)=NCH2CH2NMe2
  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

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.