Sodium 1,2-(dicarbomethoxy)cyclopentadienide | 68348-90-3

• 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: Sodium 1,2-(dicarbomethoxy)cyclopentadienide
• 英文别名: sodium 1,2-bis(methoxycarbonyl)cyclopentadiene；1,2-Bismethoxycarbonylcyclopentadienid；Na[C5H3(COOMe)2-1,2]；sodium;dimethyl cyclopenta-1,3-diene-1,2-dicarboxylate
• CAS: 68348-90-3
• 化学式: C₉H₉O₄*Na
• 分子量: 204.158
• InChiKey: YQZBBXOVDMOZQF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.02
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  99mTc-pertechnetate 、 Sodium 1,2-(dicarbomethoxy)cyclopentadienide 生成 (CpCOOH)(99m)Tc(CO)3
  参考文献：
  名称：

  Cyclopentadienyl Chemistry in Water: Synthesis and Properties of Bifunctionalized [(η⁵-C₅H₃{COOR}₂)M(CO)₃] (M = Re and^99mTc) Complexes

  摘要：

  Complexes of the [(eta(5)-C5H4COOR)M(CO)(3)] type (M = (99)mTc, Re; R = targeting function) are basic bioorganometallic structures with the potential of combining molecular imaging ((99)mTc) with therapy (cold Re or (186)/Re-188). So far, the single carboxylate group on the cyclopentadienyl ring (C-p(-)) limited targeting to one function. The concept of C-p(-) as a scaffold for attaching biological molecules could be extended substantially with two or more functionalities bound to the C-p(-) ligand. Accordingly, the rarely studied bis-substituted cyclopentadienyl ligands [C5H3(1,2-COOMe)(2)](-) and [C5H3(1,3-COOMe)(2)](-) were synthesized and their coordination to the fac-{M(CO)(3)}(+) moiety was studied in water. Both ligands are deprotonated at physiological pH and do not undergo Diels-Alder reactions. In water, they react directly with [Re(OH2)(3)(CO)(3)](+) to form [(eta(5)-C5H3{1,2-COOMe}(2))Re(CO)(3)] and [(eta(5)-C5H3{1,3-COOMe}(2))Re(CO)(3)]. Controlled hydrolysis at neutral to alkaline pH gives the monoesters and fully hydrolyzed [(eta(5)-C5H3{1,2-COOH}(2))Re(CO)(3)] and [(eta(5)-C5H3{1,3-COOH}(2))Re(CO)(3)]. Thermal treatment leads to decarboxylation and formation of [(eta(5)-C5H4COOH)Re(CO)(3)]. The corresponding 99mTc homologues are directly accessible under slightly acidic conditions from [(99)mTcO(4)](-) in high yields. In the presented strategy, the C-p(-) ring acts as a scaffold for attaching multiple targeting agents or pharmacophores at the same time.

  DOI：

  10.1021/om501029e
• 作为产物：
  描述：

  Tl[C₅H₃(1,2-COOMe)₂] 、 sodium bromide 以 甲醇 、 水 为溶剂， 反应 2.0h， 以91%的产率得到Sodium 1,2-(dicarbomethoxy)cyclopentadienide
  参考文献：
  名称：

  Cyclopentadienyl Chemistry in Water: Synthesis and Properties of Bifunctionalized [(η⁵-C₅H₃{COOR}₂)M(CO)₃] (M = Re and^99mTc) Complexes

  摘要：

  Complexes of the [(eta(5)-C5H4COOR)M(CO)(3)] type (M = (99)mTc, Re; R = targeting function) are basic bioorganometallic structures with the potential of combining molecular imaging ((99)mTc) with therapy (cold Re or (186)/Re-188). So far, the single carboxylate group on the cyclopentadienyl ring (C-p(-)) limited targeting to one function. The concept of C-p(-) as a scaffold for attaching biological molecules could be extended substantially with two or more functionalities bound to the C-p(-) ligand. Accordingly, the rarely studied bis-substituted cyclopentadienyl ligands [C5H3(1,2-COOMe)(2)](-) and [C5H3(1,3-COOMe)(2)](-) were synthesized and their coordination to the fac-{M(CO)(3)}(+) moiety was studied in water. Both ligands are deprotonated at physiological pH and do not undergo Diels-Alder reactions. In water, they react directly with [Re(OH2)(3)(CO)(3)](+) to form [(eta(5)-C5H3{1,2-COOMe}(2))Re(CO)(3)] and [(eta(5)-C5H3{1,3-COOMe}(2))Re(CO)(3)]. Controlled hydrolysis at neutral to alkaline pH gives the monoesters and fully hydrolyzed [(eta(5)-C5H3{1,2-COOH}(2))Re(CO)(3)] and [(eta(5)-C5H3{1,3-COOH}(2))Re(CO)(3)]. Thermal treatment leads to decarboxylation and formation of [(eta(5)-C5H4COOH)Re(CO)(3)]. The corresponding 99mTc homologues are directly accessible under slightly acidic conditions from [(99)mTcO(4)](-) in high yields. In the presented strategy, the C-p(-) ring acts as a scaffold for attaching multiple targeting agents or pharmacophores at the same time.

  DOI：

  10.1021/om501029e

文献信息

• Effect of the Substitution on the Protonation of Allyl Cyclopentadienyl Molybdenum(II) Compounds
  作者：Jan Honzíček、Pavel Kratochvíl、Jaromír Vinklárek、Aleš Eisner、Zdeňka Padělková

  DOI：10.1021/om2010244

  日期：2012.3.26

  Synthesis, characterization, and reactivity of new allyl cyclopentadienyl molybdenum(II) compounds [(η3-C3H4R1)(η5-C5H3(R2)2)Mo(CO)2] (R1 = H, COOMe; R2 = COOMe, CONHtBu) are reported. Although these compounds are structural analogues of [(η3-C3H5)(η5-Cp)Mo(CO)2], their reactivity is very different. While protonation of [(η3-C3H5)(η5-Cp)Mo(CO)2] gives a cationic cyclopentadienyl complex, the presented

  合成，表征，和新的环戊二烯基烯丙基钼的反应（II）的化合物[（η 3 -C 3 H ^ 4 - [R 1）（η 5 -C 5 H ^ 3（R 2）2）的Mo（CO）2 ]（R 1 = H，COOMe； R 2 = COOMe，CONH t Bu）。虽然这些化合物是[（η的结构类似物3 -C 3 H ^ 5）（η 5 -Cp）的Mo（CO）2 ]，它们的反应性非常不同的。尽管质子化[（η 3 -C 3ħ 5）（η 5 -Cp）的Mo（CO）2 ]给出的阳离子性的环戊二烯基配合物，所呈现的化合物给予阳离子烯丙基配合物[（η 3 -C 3 H ^ 4 R）的Mo（CO）2（NCMe）3 ] [ BF 4 ]（R = H，COOMe）或稳定的阳离子烯丙基环戊二烯基络合物。理论计算表明，这种行为是环戊二烯基配体中的官能团对质子化具有高度亲和力的结果。
• Cyclopentadienyl 1,2- and 1,3-Disubstituted Cobalt Sandwich Compounds {η⁵-[MeOC(O)]₂C₅H₃} Co(η⁴-C₄Ph₄): Precursors for Sterically Hindered Bidentate Chiral and Achiral Ligands
  作者：Nem Singh、Anil J. Elias

  DOI：10.1021/om300027c

  日期：2012.3.12

  acids 3 and 4 by refluxing with aqueous KOH in ethanol. The diacyl chloride of 4 was generated in situ by the reaction of 4 with oxalyl chloride and this, on further reaction with ferrocene under Friedel–Crafts conditions, yielded the novel bis-metallocenyl acenequinone 5, having both the iron and cobalt sandwich units in the same compound. The dicarboxylic acid 3 on reaction with oxalyl chloride followed

  发现环戊二烯基钠Na C 5 H 4 [C（O）OMe]}与氯甲酸甲酯ClC（O）OMe以2：1的摩尔比反应生成1,2,1的钠盐混合物-和1，3-二苯甲氧基环戊二烯基。该混合物中，在甲苯与氯化钴（PPH回流3）3和二苯基乙炔，导致环戊二烯的形成1,3-和1,2-二酯衍生的钴化合物三明治η 5 - [MeOC（O）] 2 C ^ 5 ħ 3 }的Co（η 4 -C 4博士4）（1，2）在85％的产率。1,3-和1,2-二酯1和通过将KOH水溶液在乙醇中回流，将2转化为二羧酸3和4。4与草酰氯的反应原位生成4的二酰氯，然后在Friedel-Crafts条件下与二茂铁进一步反应，生成新型的双金属茂烯并苯醌5，在该结构中同时具有铁和钴夹心单元相同的化合物。与草酰氯反应的二羧酸3，然后与（S）-2-氨基-3-甲基-1-丁醇，三乙胺和甲磺酰氯反应，将其转化为新的1，3-双（恶唑啉）环戊二烯基衍生的双齿手性复杂的[η
• Stable Enols of Carboxylic Esters. The Poly(methoxycarbonyl)cyclopentadiene Systems
  作者：Yi Xiong Lei、Giovanni Cerioni、Zvi Rappoport

  DOI：10.1021/jo000046a

  日期：2000.6.1

  C(5)H(6)(-)(n)()(CO(2)Me)(n)(), n = 5 (Cp-5), n = 4 (Cp-4), n = 3 (1, 2,4-; Cp-3) and n = 2 (1,2-; 1,2-Cp-2-I) were investigated. The X-ray diffractions of Cp-5 (known), Cp-4, and Cp-3 showed an enol of ester structure in the solid state. The enolic hydrogen forms a symmetrical hydrogen bond to a neighboring ester carbonyl, so that the vicinal "enolic" CO(2)Me groups in the 1, 2-C(=CO(2)Me)-C(CO(2)Me)(4) moiety

  聚（甲氧羰基）环戊二烯C（5）H（6）（-）（n）（）（CO（2）Me）（n）（）的结构，n = 5（CP-5），n = 4 （CP-4），n ＝ 3（1、2，4-； CP-3）和n ＝ 2（1,2-； 1,2-CP-2-I）。CP-5（已知），CP-4和CP-3的X射线衍射显示固态的酯结构的烯醇。烯醇氢与相邻的酯羰基形成对称氢键，因此在1，2-C（= CO（2）Me）-C（CO（2）Me ）（4）部分相同。三种烯醇的相关X射线参数相似。CP-3-CP-5的CP-MAS光谱通常类似于CDCl（3）中的（13）C NMR光谱，除了一些差异大多<1 ppm。CDCl（3）中CP-3-CP-5的（1）H，（13）C和（17）O NMR光谱与氢键烯醇的光谱一致。最具特征的是分别在19.7-20.1和221-225 ppm处的OH基团的（1）H和（17）O信号。将质子加到1，2-双（甲氧基羰基）环戊
• Toward the Synthesis of Indenyl Molybdenum Compound [(η³-Ind)(η⁵-Cp)Mo(CO)₂]: Modified Compounds and Structure of a Previously Unrecognized Intermediate
  作者：Jan Honzíček、Jaromír Vinklárek、Milan Erben、Jakub Lodinský、Libor Dostál、Zdeňka Padělková

  DOI：10.1021/om400305z

  日期：2013.6.24

  The mechanism of synthesis of [(eta(3)-Ind')(eta(5)-Cp)Mo(CO)(2)] was studied on methyl-substituted derivatives (Ind' = 2-MeC9H6; 4,7-Me2C9H5). It was observed that the initial step involving reaction with HCl gives dimeric chloride species [(eta(5)-Ind')Mo(CO)(2)(mu-Cl)}(2)]. This outcome differs from the structure suggested in the literature. Furthermore, it was demonstrated by various examples that compounds of the formula [(eta(5)-Ind')Mo(CO)(2)(mu-Cl)}(2)] are convenient starting materials giving [(eta(3)-Ind')(eta(5)-Cp')Mo(CO)(2)] through the reaction with appropriate cyclopentadienides. The variability of this method was demonstrated on several examples including weakly donating Cp ligands bearing strong electron-withdrawing functional groups [C5H4COOMe, (1,2-MeOCO)(2)C5H3, and 1,2-((BuNHCO)-Bu-t)(2)C5H3] as well as Cp ligands bearing a pendant amine arm (C5H4CH2CH2NMe2). Similar eta(3)-indenyl complexes are formed when using other univalent six-electron ligands such as carbaborane (9-Me2S-7,8-nido-C2B9H10) or scorpionate (Tp, Tp*). The attempts to synthesize [(eta(3)-Ind)(eta(5)-Cp)Mo(CO)(2)] from [(eta(3)-C3H5)(eta(5)-Cp)Mo(CO)(2)] have failed because the initial reaction with HCl does not give the expected [(eta(5)-Cp)Mo(CO)(2)(mu-Cl)}(2)] but trivial [(eta(5)-Cp)Mo(CO)(3)Cl].
• Electrostatic catalysis by ionic aggregates. 7. Interactions of dipolar indicator molecules with ionic clusters
  作者：Y. Pocker、James C. Ciula

  DOI：10.1021/ja00195a028

  日期：1989.6