1,3,4,6,7,8-hexahydro-1-trimethylsilyl-2H-pyrimido<1,2-a>pyrimidin | 149758-20-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,3,4,6,7,8-hexahydro-1-trimethylsilyl-2H-pyrimido<1,2-a>pyrimidin
• 英文别名: (1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine(-H))SiMe3；(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine)(1-)SiMe3；1,3,4,6,7,8-hexahydro-1-trimethylsilyl-2H-pyrimido[1,2-a]pyrimidine；2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidin-1-yl(trimethyl)silane
• CAS: 149758-20-3
• 化学式: C₁₀H₂₁N₃Si
• 分子量: 211.382
• InChiKey: ZYDPHEVTKSZOCF-UHFFFAOYSA-N

物化性质

• 沸点：
  259.4±23.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.59
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  18.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  氯甲基二甲基氯硅烷 、 1,3,4,6,7,8-hexahydro-1-trimethylsilyl-2H-pyrimido<1,2-a>pyrimidin 以94%的产率得到Chloro-dimethyl-(3,4,7,8-tetrahydro-2H,6H-pyrimido<1,2-a>pyrimidin-1-ylmethyl-C¹N⁹)-silicium
  参考文献：
  名称：

  Beiträge zur chemie der halogensilan-addukte

  摘要：

  1,3,4,6,7,8-hexahydro-1-trimethylsilyl-2H-pyrimido[1,2-a]pyrimidin (TMSTBD) (BSiMe3) reacts with chloromethyl(methyl)chlorosilanes to give (BCH2SiMenCl3-n) (n = 2, 1, 0) (5-7) and with 1-chloroethyltrichlorosilane to give (BCHCH3SiCl3) (8). Their solid-state and solution structures have been determined by X-ray crystallography (5), IR, Si-29, C-13 and H-1 NMR spectroscopy. The presence of the strong base B causes interesting changes of coordination at Si of 5 and 6 when compared with 1 and 2 that contain a weaker base B. All compounds are pentacoordinated in the solid-state, and 7 and 8 also in solution. The latter do not differ from their counterpart 3 containing a weak base B. On the other hand, the pentacoordinated solid-state structure of 5 is more strongly distorted towards tetracoordination at Si and ionization of the SiCl bond than 1, as shown e.g. by the remarkably long SiCl bond (2.679 angstrom). Solution data are consistent with the same pattern for the dissolved compounds. An increasing extent of tetracoordination at Si and ionization of the SiC] bond is observed for 5 and 6 when compared with 1 and 2. A shift to tetracoordination and SiCl ionization has been observed for the first time for a dichlorosubstituted silane (6). The extent of penta- or tetracoordination at Si is temperature and solvent dependent. Increase of temperature causes a shift to pentacoordination and vice versa (entropy effect). The effect of different solvents on the extent of penta- or tetracoordination at Si (ionization of the SiCl bond) can be correlated with their acceptor numbers (AN).

  DOI：

  10.1016/0022-328x(93)80034-9
• 作为产物：
  描述：

  三甲基氯硅烷 、 1,5,7-三氮杂双环[4.4.0]癸-5-烯 在 正丁基锂 作用下， 以 苯 为溶剂， 反应 12.0h， 以71%的产率得到1,3,4,6,7,8-hexahydro-1-trimethylsilyl-2H-pyrimido<1,2-a>pyrimidin
  参考文献：
  名称：

  High- and Mid-Valent Tantalum and Mono(peralkylcyclopentadienyl)tantalum Complexes of the Bicyclic Guanidinate Hexahydropyrimidopyrimidinate

  摘要：

  Ta(hpp)Cl-4, Ta(hpp)(2)Cl-3, and (eta-C5Me4R)Ta(hpp)Cl-3 (R = Me, Et; hpp = anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, hppH) are readily formed in good to excellent yields by addition of (hpp)SiMe3 to TaCl5, Ta(hpp)Cl-4, or (eta-C5Me4R)TaCl4, respectively, in dichloromethane. Ta(hpp)Cl-4 in solution exhibits three CH2 multiplets in the proton NMR spectrum, consistent with a mirror plane that bisects the hpp ligand. The six-coordinate, yellow Ta(hpp)Cl-4 possesses a distorted octahedral solid-state structure with chelating hpp and Ta-N distances of 2.038(1) and 2.059(1) angstrom. Ta(hpp)(2)Cl-3 is fluxional in solution by proton NMR spectroscopy, with three CH2 multiplets at room temperature that split into additional multiplets at -50 degrees C, consistent with the six multiplets expected from the solid-state structure. In the solid state, bright yellow Ta(hpp)(2)Cl-3 has an approximately pentagonal bipyramidal structure with both hpp chelates coordinated in the pentagonal plane. Ta-N distances are 2.114(3) and 2.110(3) angstrom for one hpp ligand and 2.112(3) and 2.117(3) angstrom for the other. The proton and carbon-13 solution NMR spectra of (eta-C5Me4R)Ta(hpp)Cl-3 are consistent with a static solution structure at room temperature, with the two coordinated nitrogens in different chemical environments as shown by six different methylene resonances. The solid-state structure of bright pinkish-red (eta-C5Me5)Ta(hpp)Cl-3 is a four-legged piano stool with axial ligation, with one hpp nitrogen coordinated in the square plane and one nitrogen in the axial position opposite the cyclopentadienyl centroid. Addition of (hpp)SiMe3 to the organoditantalum(III) complex (eta-C5Me4R)(2)Ta-2(mu-Cl)(4) or Na/Hg reduction of (eta-C5Me4R)Ta(hpp)Cl-3 in benzene yields the first mid-valent tantalum hpp adduct, paramagnetic red (eta-C5Me4R)Ta(hpp)Cl-2. This Ta(IV) four-legged piano stool structure in the solid state has an hpp chelate with Ta-N distances of 2.118(3) and 2.091(3) angstrom. Intraligand bond distances and angles for the hpp ligands, proton and carbon-13 NMR solution spectra, EPR spectra, and UV-vis spectra for the new Ta(V) and Ta(IV) hpp complexes are discussed.

  DOI：

  10.1021/om400364m

文献信息

• Exploration of the Suitability of Bicyclic Guanidinates as Ligands in Catalytic Chemistry Mediated by Titanium
  作者：Martyn P. Coles、Peter B. Hitchcock

  DOI：10.1021/om0341092

  日期：2003.12.1

  The synthesis, structure, and reactivity of titanium complexes supported by the bicyclic guanidinate ligand derived from 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH) are described. In situ reaction between a THF solution of the lithium salt, (hppLi)n, and titanium chloride starting materials afforded the series of compounds Ti(hpp)nCl4-n(THF)x [n = 1, x = 1 (1); n = 2, x = 0 (3); n = 3

  描述了由1,3,4,6,7,8-六氢-2 H-嘧啶[1,2- a ]嘧啶（hppH）衍生的双环胍盐配体负载的钛配合物的合成，结构和反应活性。锂盐（hppLi）n的THF溶液与氯化钛原料之间的原位反应提供了一系列化合物Ti（hpp）n Cl 4 - n（THF）x [ n = 1，x = 1（1）; n = 2，x = 0（3）；n = 3，x = 0（4）]。由甲硅烷化的配体前体hppSiMe 3与TiCl 4在CH 2 Cl 2中反应合成了二聚体，无碱的复合物[Ti（hpp）Cl 2（μ-Cl）] 2（2）。的初步烯烃聚合的研究1 - 3使用MAO作为活化剂表示低活动。AlMe 3的3至2当量之间的反应导致形成新型三金属Ti（III）物种Ti AlMe 2（hpp）2 } Cl（μ-Cl）AlMe 3（5），突出了配体的非无害行为。通过中性配体前体，hppH和Ti（CH 2 Ph）4之
• Titanium complexes incorporating bicyclic guanidinate ligands. Structure of a novel titanium–aluminium complex
  作者：Martyn P. Coles、Peter B. Hitchcock

  DOI：10.1039/b102034j

  日期：——

  Synthetic routes to titanium complexes incorporating the bicyclic guanidinate, 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate, [hpp]−, are described; the first example of a chelating coordination mode for the [hpp]− anion and the trimetallic complex [Me2Al(hpp)2TiCl2·AlMe3] containing [hpp]− ligands that chelate to titanium and, in addition, bridge to an AlMe2 unit via nitrogen are reported.

  描述了合成包含双环氨基脲的钛复合物的合成路线，1,3,4,6,7,8-六氢-2H-嘧啶[1,2-a]嘧啶脲，[hpp]⁻。首次报道了[hpp]⁻阴离子的螯合协调模式，以及包含[hpp]⁻配体的三金属复合物[Me2Al(hpp)2TiCl2·AlMe3]，该配体不仅与钛螯合，还通过氮与AlMe2单元桥接。
• Structural Consequences of the Prohibition of Hydrogen Bonding in Copper−Guanidine Systems
  作者：Sarah H. Oakley、Martyn P. Coles、Peter B. Hitchcock

  DOI：10.1021/ic0495970

  日期：2004.8.1

  The synthesis and structure of copper(I) complexes supported by N-substituted bicyclic guanidines is described. The N-methyl-substituted bicyclic guanidine 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine (hppMe) reacted with copper(I) chloride to afford the ion-pair [Cu(hppMe)(2)][CuCl(2)] (1), a rare example of a compound containing an unsupported Cu...Cu interaction. The analogous reaction

  描述了由N-取代的双环胍负载的铜（I）配合物的合成和结构。N-甲基取代的双环胍1,3,4,6,7,8-六氢-1-甲基-2H-嘧啶并[1,2-a]嘧啶（hppMe）与氯化铜（I）反应得到离子对[Cu（hppMe）（2）] [CuCl（2）]（1），该化合物为罕见的包含不受支持的Cu ... Cu相互作用的化合物。然而，与CuI的类似反应提供了mu，mu-di-halo-bridge-bridged二聚体[CuI（hppMe）]（2）（2）。在氮处包含三甲基甲硅烷基取代基可提供足够的空间阻碍环境，以支持CuCl（hppSiMe（3））（3）中两个配位的铜中心。化合物1-3已得到充分表征，包括单晶X射线衍射研究。
• Tantalum chloride species incorporating anionic and cationic guanidine components
  作者：Delia B. Soria、Joanna Grundy、Martyn P. Coles、Peter B. Hitchcock

  DOI：10.1016/s0277-5387(03)00364-4

  日期：2003.8

  Attempted preparation of tantalum complexes incorporating the anionic guanidinate ligand derived from 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine (hppH) are reported. Reaction of (hpp)SiMe3 and TaCl5 in a 1:1 ratio gave the bis-guanidinate compound rather than the expected mono-ligand species. Reaction of 2 equiv of (hpp)SiMe3 or in situ generated [hpp]Li with TaCl5 afforded a solid which analysed correctly for the compound (hpp)(2)TaCl3. X-ray structural analysis of the crystallised product identified the coordination isomer [Ta(hPP)(4)][TaCl6], with a distorted dodecahedral cation and a regular octahedral anion. During the course of this study, two closely related hydrolysis products, [(hppH(2))](2)[TaCl6}Cl}] and [(hppH(2))](3)[TaCl6}(2)Cl}].MeCN were isolated and structurally characterised, each containing [hppH(2)](+) cations and [Cl](-) and [TaCl6](-) anions in extended arrays, linked by intermolecular hydrogen bonds. (C) 2003 Elsevier Ltd. All rights reserved.
• Soria, Delia B.; Grundy, Joanna; Coles, Martyn P., Journal of Organometallic Chemistry, 2005, vol. 690, p. 2278 - 2284
  作者：Soria, Delia B.、Grundy, Joanna、Coles, Martyn P.、Hitchcock, Peter B.

  DOI：——

  日期：——