dimethylhydrazone of the trimethylsilyl ester of benzoic acid | 112746-60-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dimethylhydrazone of the trimethylsilyl ester of benzoic acid
• 英文别名: O-trimethylsilyl-N-(dimethylamino)benzohydrazide；O-trimethylsilyl-N-(dimethylamino)benzimidate；dimethylhydrazone-1-trimethylsiloxyphenone；Me3SiOC(Ph)NNMe2；trimethylsilyl N,N-dimethylbenzenecarbohydrazonate
• CAS: 112746-60-8
• 化学式: C₁₂H₂₀N₂OSi
• 分子量: 236.389
• InChiKey: CQUOQEMJDZTQOS-UHFFFAOYSA-N

物化性质

• 沸点：
  110-112 °C(Press: 2 Torr)
• 密度：
  0.93±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.76
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  24.83
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  dimethylhydrazone of the trimethylsilyl ester of benzoic acid 在 silicon tetrafluoride 作用下， 以 氯仿 为溶剂， 以60.9%的产率得到difluorobis[N-(dimethylamino)phenylacetimidato-N,O]silicon
  参考文献：
  名称：

  Donor-stabilized silyl cations

  摘要：

  Silicon complexes with a new chelating donor group, the isopropylideneimino-acylimidato(N,O) moiety [OC(R)=NN=CMe2], have been prepared (9-12, 15), and their properties are compared with previously described silicon chelates (1, 2, and 16, respectively). The new ligand acts as a more powerful donor than the NNMe2 ligand, based on three criteria: (a) the new complexes form directly as pentacoordinate siliconium salts 9-12, i.e., the expected neutral hexacoordinate precursors ionize spontaneously; (b) comparison of crystallographic bond lengths with those of the NNMe2 complexes shows consistently shorter N-Si coordination bonds and longer Si-halogen bonds in equally substituted new relative to the previously studied complexes; (c) while in the previous series 1, the dihalo complexes 20-22, 25, resisted ionization at any temperature or solvent, the dibromo-isopropylideneimino complexes 19a and 19b ionize reversibly upon decrease of temperature in chloroform solution. Steric congestion forces the trans-dihalo configuration on the dichloro and bibromo complexes 18, 19. The ionization-resistant complexes 17, 18 and the partly ionized 19 form stable ionic siliconium salts when their counterions are replaced by I-, BPh4-, or by reaction with strong Lewis acids, AlCl3 and AlBr3. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(03)00550-3
• 作为产物：
  描述：

  三甲基氯硅烷 、 1-benzoyl-2,2-dimethylhydrazine 在 三乙胺 作用下， 以 苯 为溶剂， 以90%的产率得到dimethylhydrazone of the trimethylsilyl ester of benzoic acid
  参考文献：
  名称：

  Trimethylsilyl derivatives of 2,2-dimethylhydrazides of aromatic acids

  摘要：

  DOI：

  10.1007/bf00957450

文献信息

• Role of N-donor groups on the stability of hydrazide based hypercoordinate silicon(IV) complexes: Theoretical and experimental perceptions
  作者：Pothini Suman、Sannapaneni Janardan、Mohsin Y. Lone、Prakash Jha、Kari Vijayakrishna、Akella Sivaramakrishna

  DOI：10.1016/j.poly.2015.08.011

  日期：2015.10

  in solution. The hypercoordinate silicon dichelates undergo unique intermolecular chelate exchange reactions: (i) complete ligand transfer from the dichelates to PhSiCl 3 by a ligand priority order and (ii) bidentate ligand interchange between the dichelates and a trimethylsilyl-hydrazide precursor. Thermolysis of some selected hypercoordinated silicon(IV) complexes containing a silicon–carbon σ-bond

  摘要举例说明了五苯基卤化硅二螯合物[YSiL 2] + X-中的配体是三苯基膦亚氨基供体基团，其中L是双齿配体–OC（R）NN PPh 3）–（R = t -Bu-Ph或Ph ），Y ＝ Me，Ph，CH 2 Cl，CHCl 2，Cl或Br，X ＝ Cl或Br。所有新的配合物均通过NMR光谱和元素分析进行​​了表征。与PhCH 2基团相比，较远的取代基叔丁基或苯基具有更多的五配位特征，即使络合物具有更多的电离作用。DFT计算表明，由于带更多正电荷，中心硅原子需要更大的电子密度。结果，观察到较短的Si–O，Si–N和Si–Cl键。理论和实验分析均表明，膦酰氨基配体比先前研究的二甲基氨基和异丙叉亚氨基配体是更强的供体，导致所有络合物均为溶液中的五配位卤化硅盐。超配位硅二螯合物经历独特的分子间螯合物交换反应：（i）通过配体优先级顺序将配体从二螯合物完全转移至PhSiCl 3以及（ii）在二螯合物
• Stereodynamics of neutral six-coordinate silicon chelates: evidence for two non-dissociative rate processes
  作者：Inna Kalikhman、Daniel Kost、Morton Raban

  DOI：10.1039/c39950001253

  日期：——

  A DNMR spectroscopic study of the Stereodynamics of novel neutral six-coordinate silicon chelates reveals two distinct ligand site exchange processes, both of which are intramolecular non-dissociative.

  对新型中性六配位硅螯合物立体动力学的 DNMR 光谱研究揭示了两种不同的配体位点交换过程，这两种过程都是分子内非解离的。
• Tautomeric Equilibrium between Penta- and Hexacoordinate Silicon Chelates. A Chloride Bridge between Two Pentacoordinate Silicons
  作者：Inna Kalikhman、Olga Girshberg、Lutz Lameyer、Dietmar Stalke、Daniel Kost

  DOI：10.1021/ja004118r

  日期：2001.5.1

  an unexpected equilibrium mixture, 10a right arrow over left arrow 11a, between a neutral hexacoordinate silicon chelate with a covalent chloro ligand (10a) and an ionic pentacoordinate silicon complex (11a). The equilibrium reaction consists formally of a migration of the covalent chloro ligand from silicon to an adjacent ammonium nitrogen, as a chloride anion, and thus constitutes a novel type of

  O-三甲基甲硅烷基-1,1-二甲基-2-三氟乙酰肼 (1a) 与氯甲基（甲基）二氯硅烷的反应提供了出乎意料的平衡混合物，10a 右箭头超过左箭头 11a，在中性六配位硅螯合物与共价氯配体之间(10a) 和离子五配位硅络合物 (11a)。平衡反应形式上包括共价氯配体从硅迁移到相邻的铵氮，作为氯阴离子，因此构成了一种新型的互变异构反应。晶体学和核磁共振数据为反应提供了证据。讨论了温度、溶剂、取代基和反离子对互变异构平衡的影响：当混合物温度升高时，平衡比 10a/11a 增加。在甲苯中形成混合物，非电离溶剂，使平衡完全向中性 10a 移动。当初始酰肼具有苯基 (11c) 或氢 (11b) 基团作为取代基而不是 CF3 时，平衡向离子侧移动。使用三氟甲磺酸三甲基甲硅烷基酯用三氟甲磺酸酯代替氯化物反离子，将 10a/11a 混合物转移到离子侧。对 10/11 的逐步形成进行了低温 NMR 监测，并提供了对反应机理的深入了解。在尝试生长
• Revisiting Methyl-Halide Elimination Reactions in Hydrazide Based Hypercoordinate Silicon(IV) Complexes
  作者：Sannapaneni Janardan、Pothini Suman、Akella Sivaramakrishna、Kari Vijayakrishna

  DOI：10.1080/15533174.2014.988239

  日期：2016.2.1

  of hypercoordinate silicon(IV) complexes are synthesized by the reactions of O-silylated N,N-dimethylhydrazides with YSiCl3 (Y = cyclohexyl and i-Bu). All the complexes are characterized by 1H, 13C, and 29Si-NMR spectroscopy. The influence of steric and electronic behavior of remote substituents and the groups attached to silicon on the methyl halide elimination reactions of these complexes are discussed

  通过O-甲硅烷基化的N，N-二甲基酰肼与YSiCl 3（Y =环己基和i -Bu）反应合成了一组超配位的硅（IV）配合物。所有配合物的特征在于1 H，13 C和29 Si-NMR光谱。讨论了远程取代基和与硅连接的基团的空间和电子行为对这些配合物的甲基卤化物消除反应的影响。甲基卤化物消除的速率强烈依赖于亲核试剂强度（即，I - >溴- >氯- ）和远程取代基R（R =我<吨-Bu
• Neutral Hexacoordinate Silicon Complexes. Synthesis, Structure, and Stereodynamics: Evidence for Two Nondissociative Ligand-Exchange Mechanisms
  作者：Daniel Kost、Inna Kalikhman、Morton Raban

  DOI：10.1021/ja00151a015

  日期：1995.11

  Novel hexacoordinate silicon compounds 1-4 with two identical bidentate ligands, respectively, are readily prepared in high yields from the reaction of XSiCl(3) (X = H, Me, Ph, Cl) with the O-trimethylsilyl derivatives of N,N-dimethyl carbohydrazides 6. The NMR spectra of all compounds indicate that a single diastereomer is present in solution, of the possible six, within NMR detection limits. The published X-ray crystallographic structure of one of the complexes, as well as an analysis of the H-1, C-13 and Si-29 NMR spectra and their temperature dependence, conforms to an octahedral geometry with the oxygen ligands and the pair of monodentate ligands cis to each other, respectively, and the nitrogens in a trans position. All of the complexes show temperature dependence of their NMR spectra, characteristic of fluxional behavior. Two rate processes (topomerizations) take place on the NMR time scale in compounds 1-3, at activation free energies ranging, respectively, between 10.6 and 16.4 kcal/mol, and 15.0 and 18.5 kcal/mol. A single process is observed for the C-2v symmetric 4 complexes. A remarkable solvent dependence of barriers is observed, suggesting that ligand site exchange is associated with dissociation or weakening of Si-ligand bonds. The simultaneous exchange of N-methyl groups and benzyl methylene protons in 3d is evidence that no Si-N bond cleavage and chelate ring opening take place during topomerization. The persistence of Si-29-F-19 one-bond coupling, observed in the Si-29 NMR spectrum at temperatures well above the fast exchange limit temperature, proves that no ionic dissociation of the Si-halogen bond takes place. It is concluded that topomerization occurs in a nondissociative, intramolecular Ligand site exchange process. A likely mechanism that accounts for all of these observations is a 1,2-shift of adjacent ligands, X and Cl, or the two oxygen ligands, via a ''bicapped tetrahedron'' intermediate or transition state.