N-methyl-1,3,5-triaza-7-phosphaadamantane trifluoromethanesulfonate | 877864-66-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: N-methyl-1,3,5-triaza-7-phosphaadamantane trifluoromethanesulfonate
• 英文别名: [N-methyl-1,3,5-triaza-7-phospfaadamantane][OSO2CF3]；(N-methyl-1,3,5-triaza-7-phosphaadamantane)(OTf)；[1-methyl-1,3,5-triaza-7-phosphaadamantane](OTf)；(1,3,5-triaza-7-phosphaadamantane-(Me))OTf；[mPTA][OSO2CF3]；(mPTA)(OTf)
• CAS: 877864-66-9
• 化学式: CF₃O₃S*C₇H₁₅N₃P
• 分子量: 321.26
• InChiKey: MBSOPHRCIYYJQD-NJJJQDLFSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.36
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  63.68
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  [RuClCp(PTA)₂] 、 N-methyl-1,3,5-triaza-7-phosphaadamantane trifluoromethanesulfonate 在 氟硼酸钠 作用下， 以 甲醇 为溶剂， 以57%的产率得到[RuCp(1,3,5-triaza-7-phosphaadamantane)₂(N-methyl-1,3,5-triaza-7-phosphaadamantane)](OTf)*(Cl)
  参考文献：
  名称：

  含有PPh3，mTPPMS，PTA和mPTA的钌配合物的易合成和水溶性（mTPPMS =间-三苯膦单磺酸盐，PTA = 1,3,5-三氮杂-7-磷金刚烷，mPTA = N-甲基-1,3,5 -triaza-7-phosphaadamantane）

  摘要：

  摘要具有[RuCpX（L1）（L2）] n +（L1，L2 = PPh3，mTPPMS（间苯三酚单磺酸单磺酸盐），PTA（1,3,5-triaza-7-phosphaadamantane））的新型水溶性{CpRu}配合物，合成了mPTA（N-甲基-1,3,5-三氮杂-7-磷金刚烷），并通过元素分析，红外光谱和核磁共振谱进行了表征。络合物[RuClCp（PPh3）（mPTA）]（OTf）（3·OTf），[RuCpI（PPh3）（mPTA）]·2I·EtOH（5·I·EtOH）·和[RuCpBr（PTA）2]·3.5还通过单晶X射线衍射表征了H 2 O（6·3.5H 2 O）。配合物的NMR光谱与其组成一致，也表明它们的固态结构保持在溶液中。这些结果综合了含有水溶性膦烷的{CpRu}配合物的制备路线，结构组成和溶解度的详尽概述。

  DOI：

  10.1016/j.ica.2016.06.019

文献信息

• DNA Interactions Mediated by Cyclopentadienidoruthenium(II) Complexes Containing Water‐Soluble Phosphanes
  作者：Antonio Romerosa、Mustapha Saoud、Tatiana Campos‐Malpartida、Chaker Lidrissi、Manuel Serrano‐Ruiz、Maurizio Peruzzini、Jose Antonio Garrido、Federico García‐Maroto

  DOI：10.1002/ejic.200601177

  日期：2007.6

  ruthenium(II) complexes Na2[RuCpX(mTPPMS)2] [X = Cl (1), I (2)] and Nax[RuCp(mTPPMS)(PR13)(PR23)](OTf)y [PR13 = PR23 = PPh3 (3), PTA (4), x = y = 0; PR13 = mTPPMS, PR23 = PTA (5), x = 1, y = 0; PR13 = mTPPMS, PR23 = mPTA (6), x = y = 0; PR13 = PR23 = mTPPMS (7), x = 2, y = 0; PR13 = PPh3, PR23 = PTA (8), x = y = 0; PR13 = mPTA, PR23 = PPh3 (9), x = 0, y = 1; mTPPMS = Ph2P(3-OSO2C6H4)–; PTA = 1,3,5-tr

  水溶性钌 (II) 络合物 Na2[RuCpX(mTPPMS)2] [X = Cl (1), I (2)] 和 Nax[RuCp(mTPPMS)(PR13)(PR23)](OTf)y [PR13 = PR23 = PPh3 (3), PTA (4), x = y = 0; PR13 = mTPPMS，PR23 = PTA (5)，x = 1，y = 0；PR13 = mTPPMS，PR23 = mPTA (6)，x = y = 0；PR13 = PR23 = mTPPMS (7), x = 2, y = 0; PR13 = PPh3，PR23 = PTA (8)，x = y = 0；PR13 = mPTA，PR23 = PPh3 (9)，x = 0，y = 1；mTPPMS = Ph2P(3-OSO2C6H4)–；PTA = 1,3,5-triaza-7-phOSphaadamantane；mPTA
• The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems
  作者：Antal Udvardy、Attila Csaba Bényei、Ágnes Kathó

  DOI：10.1016/j.jorganchem.2012.07.042

  日期：2012.10

  New air-stable, water-soluble Ru(II)–phosphane complexes were synthesized in high purity by the reaction of cis-[RuCl2(dmso)4] with 2 equivalents of 1,3,5-triaza-7-phosphaadamantane (pta) and its N-methyl and N-benzyl derivatives (pta-Me and pta-Bn, respectively). All new complexes were characterized by elementary analysis and spectroscopic methods (NMR, ESI-MS) and the molecular structures of cis

  通过顺式-[RuCl 2（dmso）4 ]与2当量的1,3,5-triaza-7-phosphaadamantane（ pta）及其N-甲基和N-苄基衍生物（分别为pta-Me和pta-Bn）。所有新的配合物均通过元素分析和光谱法（NMR，ESI-MS）以及顺-顺-反-[RuCl 2（dmso）2（pta）2 ]，顺-顺-反-[RuCl ]的分子结构进行了表征。2个（dmso）2（pta-H）2 ] Cl 2（在酸性溶液中获得）和顺式-顺式-反式-[RuCl 2（dmso）2（pta-Me）2 ]（CF 3 SO 3）2是通过单晶X射线衍射测定。 在温和的条件下，顺式-[RuCl 2（dmso）4 ]以100％的选择性积极催化烯丙基醇转化为相应的酮，而在同一反应中，新的Ru（II）-pta络合物显示出中等的活性和选择性。
• Synthesis, Characterization, and DNA Binding of New Water-Soluble Cyclopentadienyl Ruthenium(II) Complexes Incorporating Phosphines
  作者：Antonio Romerosa、Tatiana Campos-Malpartida、Chaker Lidrissi、Mustapha Saoud、Manuel Serrano-Ruiz、Maurizio Peruzzini、Jose Antonio Garrido-Cárdenas、Federico García-Maroto

  DOI：10.1021/ic051053q

  日期：2006.2.1

  techniques. X-ray crystal structures of [RuClCp(PPh3)(PTA)] (2), [RuCpI(PPh3)(PTA)] (3), and [RuCpI(mPTA)(PPh3)](OSO2CF3) (9) have been determined. The binding properties toward DNA of the new hydrosoluble complexes have been studied using the mobility shift assay. The ruthenium chloride complexes interact with DNA depending on the hydrosoluble phosphine bonded to the metal, while the corresponding compounds

  新的水溶性钌（II）手性配合物[RuCpX（L）（L'）]（n +）（X = Cl，I. L = PPh3; L'= PTA，mPTA; L = L'= PTA，mPTA ）（PTA = 1,3,5-triaza-7-phOSphaadamantane; mPTA = N-methyl-1,3,5-triaza-7-phOSphaadamantane）已通过NMR和IR光谱及元素分析进行​​了表征。还制备了盐mPTA（OSO2CF3），并通过光谱技术对其进行了全面表征。[RuClCp（PPh3）（PTA）]（2），[RuCpI（PPh3）（PTA）]（3）和[RuCpI（mPTA）（PPh3）]（OSO2CF3）（9）的X射线晶体结构决定。已经使用迁移率变动分析研究了新的水溶性复合物对DNA的结合特性。氯化钌络合物根据与金属结合的水溶性膦与DNA相互作用，而相应的化合物与碘化物[RuCpI（PTA）2]（1），
• Rationalization of the inhibition activity of structurally related organometallic compounds against the drug target cathepsin B by DFT
  作者：Angela Casini、Fabio Edafe、Mikael Erlandsson、Luca Gonsalvi、Antonella Ciancetta、Nazzareno Re、Andrea Ienco、Luigi Messori、Maurizio Peruzzini、Paul J. Dyson

  DOI：10.1039/c003218b

  日期：——

  A series of organometallic compounds of general formula [(arene)M(PTA)nXm]Y (arene = η6-C10H14, η-C5Me5); M = Ru(II), Os(II), Rh(III) and Ir(III); X = Cl, mPTA; Y = OTf, PF6) have been screened for their cytotoxicity and ability to inhibit cathepsin B in vitro, in comparison to the antimetastatic compound NAMI-A. The Ru and Os analogues and NAMI-A showed similar enzyme inhibition properties (with IC50 values in the low μM range), whereas the Rh(III) and Ir(III) compounds were inactive. In order to build up a rational for the observed differences, DFT calculations of the metal complexes adducts with N-acetyl-L-cysteine-N′-methylamide, a mimic for the Cys residue in the cathepsin B active site, were performed to provide insights into binding thermodynamics in solution. Initial structure–activity relationships have been defined with the calculated binding energies of the M–S bonds correlating well with the observed inhibition properties of the compounds.

  一系列具有一般公式 [(arene)M(PTA)nXm]Y 的有机金属化合物（arene = η6-C10H14, η-C5Me5；M = Ru(II), Os(II), Rh(III) 和 Ir(III)；X = Cl, mPTA；Y = OTf, PF6）已被筛选以评估其细胞毒性和在体外抑制胱蛋白酶 B 的能力，并与抗转移化合物 NAMI-A 进行了比较。Ruthenium 和 osmium 的类似物及 NAMI-A 显示出相似的酶抑制特性（IC50 值在低 μM 范围内），而铑(III) 和铱(III) 化合物则表现为无活性。为了探讨观察到的差异，进行了金属配合物与 N-乙酰-L-半胱氨酸-N′-甲酰胺的 DFT 计算，该物质模拟了胱蛋白酶 B 活性位点中的半胱氨酸残基，以提供关于溶液中结合热力学的见解。初步的结构-活性关系已被定义，计算得到的 M–S 键结合能与化合物的观察到的抑制特性良好相关。
• Photo-aquation of cis-[RuCl₂(mPTA)₄](CF₃SO₃)₄in water (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane)
  作者：Rugiada Girotti、Antonio Romerosa、Sonia Mañas、Manuel Serrano-Ruiz、Robin Perutz

  DOI：10.1039/c0dt00885k

  日期：——

  On irradiating the complex cis-[RuCl2(mPTA)4](CF3SO3)4 (2) with near UV light at room temperature, (OC-6-13)-[RuCl2(mPTA)3(H2O)](CF3SO3)3 (3) was obtained. Complex 3 is the product of the substitution in 2 of one mPTA by a H2O molecule and the rearrangement from cis to trans of the two chlorides. The selective photo-reaction of 2 is produced with radiation of 300 < λ < 400 nm or with λ = 367 nm in 50 min (Φ367 nm (D2O) = 0.18 ± 0.01). The reaction is not reversible with visible light. The transformation of 2 into 3 is not dependent on the pH but only on the radiation used. Reaction of 3 with NaCl leads to (OC-6-21)-[RuCl3(mPTA)3](CF3SO3)2 (4) which could be directly obtained by irradiation of 2 with λ = 367 nm in water and 5 eq. of NaCl (Φ367 nm (D2O) = 0.17 ± 0.01). Complex 4 turns slowly to 2 in water with 1 eq. of mPTA under light of λ > 416 nm. Complete conversion of 4 into 2 was achieved after more than one day. All complexes were characterized by elemental analysis, IR and NMR spectroscopy, and 2, 3 and 4 by single crystal X-ray determination. An easy synthesis for the ligand mPTA(CF3SO3) is also reported.

  在室温下用近紫外光照射复合物 cis-[RuCl2(mPTA)4](CF3SO3)4 (2)，获得了 (OC-6-13)-[RuCl2(mPTA)3(H2O)](CF3SO3)3 (3)。复杂的3是2中一个mPTA被水分子替代以及两个氯离子从顺式重排为反式的产物。2的选择性光反应是在300 < λ < 400 nm或 λ = 367 nm下进行的，持续50分钟（Φ367 nm (D2O) = 0.18 ± 0.01）。该反应在可见光下不具可逆性。2转化为3不依赖于pH值，而只依赖于所用的辐射。3与NaCl的反应得到 (OC-6-21)-[RuCl3(mPTA)3](CF3SO3)2 (4)，该化合物可通过用 λ = 367 nm照射2与5等摩尔的NaCl在水中直接获得（Φ367 nm (D2O) = 0.17 ± 0.01）。在 λ > 416 nm 的光照射下，复合物4在水中缓慢转化为2，反应需要1等摩尔的mPTA。4完全转化为2的过程超过一天。所有复杂物均通过元素分析、红外光谱和核磁共振光谱进行表征，而2、3和4则通过单晶X射线衍射进行鉴定。此外，还报告了一种合成配体mPTA(CF3SO3)的简易方法。