diethyl 4-methyl-1,3-phenylenebis(oxamate) | 24200-25-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: diethyl 4-methyl-1,3-phenylenebis(oxamate)
• 英文别名: N,N'-(4-methyl-m-phenylene)-bis-oxalamic acid diethyl ester；N,N'-(4-Methyl-m-phenylen)-bis-oxalamidsaeure-diaethylester；(asymm.-m-Toluylen)-bis-oxamidsaeure-diaethylester；N.N'-Diaethoxalyl-asymm.-m-toluylendiamin；Ethyl 2-[3-[(2-ethoxy-2-oxoacetyl)amino]-4-methylanilino]-2-oxoacetate
• CAS: 24200-25-7
• 化学式: C₁₅H₁₈N₂O₆
• 分子量: 322.318
• InChiKey: PZXSZZCHJKJFES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  111
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  diethyl 4-methyl-1,3-phenylenebis(oxamate) 在 氢氧化钾 作用下， 以81.3%的产率得到4-methyl-1,3-phenylenedioxamic acid
  参考文献：
  名称：

  Synthesis and pharmacological activity of phenylenedioxamic and derivatives

  摘要：

  DOI：

  10.1007/bf00776331
• 作为产物：
  描述：

  2,4-二氨基甲苯 在 乙醇 作用下， 生成 diethyl 4-methyl-1,3-phenylenebis(oxamate)
  参考文献：
  名称：

  Schiff,H.; Vanni, Justus Liebigs Annalen der Chemie, 1892, vol. 268, p. 315

  摘要：

  DOI：

文献信息

• Variation of the ground spin state in homo- and hetero-octanuclear copper(ii) and nickel(ii) double-star complexes with a meso-helicate-type metallacryptand core
  作者：Emilio Pardo、Marie-Claire Dul、Rodrigue Lescouëzec、Lise-Marie Chamoreau、Yves Journaux、Jorge Pasán、Catalina Ruiz-Pérez、Miguel Julve、Francesc Lloret、Rafael Ruiz-García、Joan Cano

  DOI：10.1039/b926709c

  日期：——

  Homo- and heterometallic octanuclear complexes of formula Na2[Cu2(mpba)3][Cu(Me5dien)]6}(ClO4)6·12H2O (1), Na2[Cu2(Mempba)3][Cu(Me5dien)]6}(ClO4)6·12H2O (2), Na2[Ni2(mpba)3][Cu(Me5dien)]6}(ClO4)6·12H2O (3), Na2[Ni2(Mempba)3][Cu(Me5dien)]6}(ClO4)6·9H2O (4), [Ni2(mpba)3][Ni(dipn)(H2O)]6}(ClO4)4·12.5H2O (5), and [Ni2(Mempba)3][Ni(dipn)(H2O)]6}(ClO4)4·12H2O (6) [mpba = 1,3-phenylenebis(oxamate), Mempba = 4-methyl-1,3-phenylenebis(oxamate), Me5dien = N,N,N′,N′′,N′′-pentamethyldiethylenetriamine, and dipn = dipropylenetriamine] have been synthesized through the “complex-as-ligand/complex-as-metal” strategy. Single-crystal X-ray diffraction analyses of 1, 3, and 5 show cationic MII2M′II6 entities (M, M′ = Cu and Ni) with an overall double-star architecture, which is made up of two oxamato-bridged MIIM′II3 star units connected through three meta-phenylenediamidate bridges between the two central metal atoms leading to a binuclear metallacryptand core of the meso-helicate-type. Dc magnetic susceptibility data for 1–6 in the temperature range 2–300 K have been analyzed through a “dimer-of-tetramers” model [H = −J(S1A·S3A + S1A·S4A + S1A·S5A + S2B·S6B + S2B·S7B + S2B·S8B) −J′S1A·S2B, with S1A = S2B = SM and S3A = S4A = S5A = S6B = S7B = S8B = SM′]. The moderate to strong antiferromagnetic coupling between the MII and M′II ions through the oxamate bridge in 1–6 (−JCu–Cu = 52.0–57.0 cm−1, −JNi–Cu = 39.1–44.7 cm−1, and −JNi–Ni = 26.3–26.6 cm−1) leads to a non-compensation of the ground spin state for the tetranuclear MIIM′II3 star units [SA = SB = 3SM′−SM = 1 (1 and 2), 1/2 (3 and 4), and 2 (5 and 6)]. Within the binuclear MII2meso-helicate cores of 1–4, a moderate to weak antiferromagnetic coupling between the MII ions (−J′Cu–Cu = 28.0–48.0 cm−1 and −J′Ni–Ni = 0.16–0.97 cm−1) is mediated by the triple m-phenylenediamidate bridge to give a ground spin singlet (S = SA−SB = 0) state for the octanuclear MII2CuII6 molecule. Instead, a weak ferromagnetic coupling between the NiII ions (J′Ni–Ni = 2.07–3.06 cm−1) operates in the binuclear NiII2meso-helicate core of 5 and 6 leading thus to a ground spin nonet (S = SA + SB = 4) state for the octanuclear NiII8 molecule. Dc magnetization data for 5 reveal a small but non-negligible axial magnetic anisotropy (D = −0.23 cm−1) of the S = 4 NiII8 ground state with an estimated value of the energy barrier for magnetization reversal of 3.7 cm−1 (U = −DS2). Ac magnetic susceptibility data for 5 show an unusual slow magnetic relaxation behaviour at low temperatures which is typical of “cluster glasses”. The temperature dependence of the relaxation time for 5 has been interpreted on the basis of the Vogel–Fulcher law for weakly interacting clusters, with values of 2.5 K, 1.4 × 10−6 s, and 4.0 cm−1 for the intermolecular interaction parameter (T0), the pre-exponential factor (τ0), and the effective energy barrier (Ueff), respectively.

  式为 Na2[Cu2(mpba)3][Cu(Me5dien)]6}(ClO4)6·12H2O (1), Na2[Cu2(Mempba)3][Cu(Me5dien)] 的同金属和异金属八核配合物6}(ClO4)6·12H2O (2), Na2[Ni2(mpba)3][Cu(Me5dien)]6}(ClO4)6·12H2O (3), Na2[Ni2(Mempba)3][Cu (Me5dien)]6}(ClO4)6·9H2O (4)、[Ni2(mpba)3][Ni(dipn)(H2O)]6}(ClO4)4·12.5H2O (5) 和 [Ni2 (Mempba)3][Ni(dipn)(H2O)]6}(ClO4)4·12H2O (6) [mpba = 1,3-亚苯基双(草酸酯), Mempba = 4-甲基-1,3-亚苯基双(草酸酯) ），Me5dien = N,N,N',N'',N''-五甲基二亚乙基三胺，dipn = 二亚丙基三胺]通过“配合物作为配体/配合物作为金属”策略合成。 1、3和5的单晶X射线衍射分析显示阳离子MII2M'II6实体（M，M'= Cu和Ni）具有整体双星结构，由两个oxamato桥联的MIIM'组成II3 星形单元通过两个中心金属原子之间的三个间苯二酰胺桥连接，形成内消旋型双核金属隐配体核心。通过“四聚体二聚体”模型分析了 2-300 K 温度范围内 1-6 的直流磁化率数据 [H = −J(S1A·S3A + S1A·S4A + S1A·S5A + S2B·S6B) + S2B·S7B + S2B·S8B) −J′S1A·S2B，其中 S1A = S2B = SM 且 S3A = S4A = S5A = S6B = S7B = S8B = SM′]。 MII 和 M'II 离子之间通过 1-6 的草酸盐桥产生中度至强的反铁磁耦合（−JCu–Cu = 52.0–57.0 cm−1，−JNi–Cu = 39.1–44.7 cm−1，−JNi –Ni = 26.3–26.6 cm−1) 导致四核 MIIM′II3 星单元的基自旋态不补偿 [SA = SB = 3SM′−SM = 1 (1 和 2), 1/2 ( 3和4)和2(5和6)]。在 1-4 的双核 MII2 介观螺旋核内，MII 离子之间存在中度至弱的反铁磁耦合（−J′Cu–Cu = 28.0–48.0 cm−1 和 −J′Ni–Ni = 0.16–0.97 cm−1 ）由三重间苯二胺桥介导，为八核 MII2CuII6 分子提供地自旋单线态 (S = SA−SB = 0) 状态。相反，NiII 离子之间的弱铁磁耦合 (J′Ni–Ni = 2.07–3.06 cm−1) 在 5 和 6 的双核 NiII2 介观螺旋核心中运行，从而导致地自旋诺奈特 (S = SA + SB = 4）八核NiIII8分子的状态。 5 的直流磁化数据揭示了 S = 4 NiIII8 基态的小但不可忽略的轴向磁各向异性 (D = -0.23 cm−1)，磁化反转的能量势垒估计值为 3.7 cm−1 (U =−DS2)。 5 的交流磁化率数据显示出低温下不寻常的慢磁弛豫行为，这是“簇玻璃”的典型特征。 5 的弛豫时间的温度依赖性已根据弱相互作用团簇的 Vogel-Fulcher 定律进行了解释，分子间相互作用参数值为 2.5 K、1.4 × 10−6 s 和 4.0 cm−1 ( T0)、指前因子 (τ0) 和有效能垒 (Ueff)。
• Synthesis and nootropic activity of oxamoylamino acids
  作者：G. P. Petyunin、A. S. Zaks、V. N. Petyunina、Zh. V. Dmitrievskaya、T. A. Kapitonenko

  DOI：10.1007/bf00773611

  日期：1988.11
• FR1567434
  申请人：——

  公开号：——

  公开（公告）日：——
• N,N'-(phenylene)dioxamic acids and their esters as antiallergy agents
  作者：John B. Wright、Charles M. Hall、Herbert G. Johnson

  DOI：10.1021/jm00207a016

  日期：1978.9

  A series of dialkyl N,N'-(m-phenylene)dioxamates was synthesized by treatment of the requisite m-phenylenediamines with an alkyloxalyl chloride in the presence of triethylamine. Hydrolysis with sodium hydroxide solution gave the corresponding N,N'-(m-phenylene)dioxamic acids. Several N,N'-(p-phenylene)dioxamic acids were synthesized also in the same manner starting with the requisite p-phenylenediamines. These compounds were tested in the rat passive cutaneous anaphylaxis (PCA) assay. When tested iv, activity was found in the N,N'-(m-phenylene) dioxamic acids up to 2500 times that shown by disodium cromoglycate [50% inhibition at 0.001 mg/kg for N,N'-(2-chloro-5-cyano-m-phenylene)dioxamic acid (compound 61)]. Oral activity was seen in this series of compounds with duration of activity up to 120 min. Oral activity was detected in diethyl N,N'-(2-chloro-5-cyano-m-phenylene)dioxamate (compound 38) at levels of drug as low as 0.1 mg/kg.
• PETYUNIN G. P.; DMITRIEVSKAYA ZH. V.; DROGOVOZ S. M.; ANTKIV T. V., XIM.-FARMATS. ZH., 20,(1986) N 7, 827-830
  作者：PETYUNIN G. P.、 DMITRIEVSKAYA ZH. V.、 DROGOVOZ S. M.、 ANTKIV T. V.

  DOI：——

  日期：——