3,3,7,7-tetramethyl-1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine | 899838-78-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 3,3,7,7-tetramethyl-1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine
• 英文别名: 3,3,7,7-tetramethyl-2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2-a]pyrimidine；3,3,9,9-tetramethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene；HTMhpp；3,3,7,7-tetramethyl-4,6,8,9-tetrahydro-2H-pyrimido[1,2-a]pyrimidine
• CAS: 899838-78-9
• 化学式: C₁₁H₂₁N₃
• 分子量: 195.308
• InChiKey: HMWZPUGIBJYLLO-UHFFFAOYSA-N

物化性质

• 熔点：
  25 °C (sublm)
• 沸点：
  253.9±23.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  27.6
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,3,7,7-tetramethyl-1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine 在 盐酸 作用下， 以 邻二氯苯 为溶剂， 反应 1.0h， 以100%的产率得到3,3,9,9-tetramethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene hydrochloride
  参考文献：
  名称：

  Syntheses of very soluble alkylated bicyclic guanidinate ligands and structural characterization of a dipalladium paddlewheel

  摘要：

  Fool-proof syntheses of two highly soluble tetraalkylated bicyclic guanidinates which are characterized by the NC(N)N core are reported along with the structures of the corresponding hydrochlorides. The compound with alkyl = methyl was used to prepare a paddlewheel species with a Pd-2(4+) core devoid of a strong metal-metal bond but potentially useful as precursor to a rare single bonded Pd-2(6+) species. The Pd1...Pd2 separation is only 2.5488(12) angstrom and the local coordination for each of the d(8) Pd(II) atoms is square planar. Published by Elsevier Ltd.

  DOI：

  10.1016/j.poly.2012.06.002
• 作为产物：
  描述：

  N,N-bis(2,2-dimethyl-3-iminohydroxypropyl)amine hydrochloride 在 二硫化碳 、 对甲苯磺酸 、 sodium hydroxide 作用下， 以 乙醇 、 对二甲苯 、 水 为溶剂， 100.0 ℃ 、7.58 MPa 条件下， 反应 76.0h， 生成 3,3,7,7-tetramethyl-1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine
  参考文献：
  名称：

  Syntheses of very soluble alkylated bicyclic guanidinate ligands and structural characterization of a dipalladium paddlewheel

  摘要：

  Fool-proof syntheses of two highly soluble tetraalkylated bicyclic guanidinates which are characterized by the NC(N)N core are reported along with the structures of the corresponding hydrochlorides. The compound with alkyl = methyl was used to prepare a paddlewheel species with a Pd-2(4+) core devoid of a strong metal-metal bond but potentially useful as precursor to a rare single bonded Pd-2(6+) species. The Pd1...Pd2 separation is only 2.5488(12) angstrom and the local coordination for each of the d(8) Pd(II) atoms is square planar. Published by Elsevier Ltd.

  DOI：

  10.1016/j.poly.2012.06.002

文献信息

• Increasing the solubility of strong reducing agents containing Mo24+ units and alkyl-substituted guanidinate ligands
  作者：F. Albert Cotton、Carlos A. Murillo、Xiaoping Wang、Chad C. Wilkinson

  DOI：10.1039/b707201e

  日期：——

  Six very soluble paddlewheel compounds containing Mo2n+ units, n = 4, 5, 6, and two alkyl-substituted bicyclic guanidinate ligands have been synthesized. The quadruply bonded complexes with n = 4, Mo2(TMhpp)4 and Mo2(TEhpp)4, (TMhpp = the anion of 3,3,9,9-tetramethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene and TEhpp = the anion of 3,3,9,9-tetraethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene) are easily oxidized. The electrode potentials in THF are −1.08 and −1.17 V vs. Ag/AgCl, respectively, for the Mo25+/4+ couple. These potentials are in accord with the low ionization potentials for the quadruply bonded compounds. Because of the high solubility of the Mo24+ compounds in most common organic solvents they are attractive candidates for use as strong reducing agents in homogeneous systems.

  合成了六种溶解度很高的桨轮化合物，其中含有 Mo2n+ 单元（n = 4、5、6）和两个烷基取代的双环胍配体。 n = 4、Mo2(TMhpp)4 和 Mo2(TEhpp)4 的四键配合物，（TMhpp = 3,3,9,9-四甲基-1,5,7-三氮杂双环[4.4.0]dec 的阴离子-4-ene和TEhpp = 3,3,9,9-四乙基-1,5,7-三氮杂双环[4.4.0]dec-4-ene的阴离子）很容易被氧化。对于 Mo25+/4+ 电对，THF 中的电极电位相对于 Ag/AgCl 分别为 -1.08 和 -1.17 V。这些电势与四键化合物的低电离电势一致。由于 Mo24+ 化合物在大多数常见有机溶剂中具有高溶解度，因此它们是在均相体系中用作强还原剂的有吸引力的候选者。
• Exploring the Intricacies of Weak Interactions in Metal–Metal Bonds Using an Unsymmetrical Carbonyl Precursor and a Triple-Bonded W₂⁶⁺ Paddlewheel
  作者：Gina M. Chiarella、Chao Feng、Carlos A. Murillo、Qinliang Zhao

  DOI：10.1021/acs.inorgchem.6b01728

  日期：2016.9.19

  characterized by a central C(N)3 unit joining two fused six-membered rings with CH2CMe2CH2 units spanning two of the nitrogen atoms, allowed isolation of W2(μ-CO)2(μ-TMhpp)2(η2-TMhpp)2, 1, a precursor of W2(TMhpp)4Cl2 ( J. Am. Chem. Soc. 2013, 135, 17889; TMhpp = [(CH2CMe2CH2)2(C(N)3)]). Subsequent heating of 1 followed by reaction with TlPF6 generates [W2(TMhpp)4](PF6)2, 2. Compound 1 has an edge-sharing

  W（CO）6与四甲基化的双环胍盐配体的逐步反应，其特征在于中心的C（N）3单元将两个稠合的六元环与跨越两个氮原子的CH 2 CMe 2 CH 2单元相连，从而实现了W的分离2（μ-CO）2（μ-TMhpp）2（η 2 -TMhpp）2，1，的前体w ^ 2（TMhpp）4氯2（J.化学会志。 2013，135，17889; TMhpp = [（CH 2 CMe 2 CH2）2（C（N）3）]）。的后续加热1接着通过与TlPF 6生成[W 2（TMhpp）4 ]（PF 6）2，2。化合物1具有W 2（μ-CO）2 4+核具有半桥羰基的边缘共享生物体六面体（ESBO）排列，而化合物2具有W 2 6+的桨轮结构核心被四个四甲基取代的双环胍盐配体所覆盖。该化合物还具有沿着金属-金属键的六氟磷酸根阴离子，这些阴离子位于亚甲基基团内，这是通过弱C-H···F相互作用网络来防止的，氟原子紧密接近双金属单
• A Strong Metal-to-Metal Interaction in an Edge-Sharing Bioctahedral Compound that Leads to a Very Short Tungsten–Tungsten Double Bond
  作者：Gina M. Chiarella、F. Albert Cotton、Carlos A. Murillo、Qinliang Zhao

  DOI：10.1021/ic402992n

  日期：2014.2.17

  An ionic edge-sharing bioctahedral (ESBO) species has been prepared having a tetramethylated bicyclic guanidinate with two fused six-membered rings characterized by a fairly flat N-C(N)-N skeleton and abbreviated as TMhpp. The anion has two W-IV atoms bridged by two oxo groups; the metal atoms are also spanned by two bridging guanidinate ligands, and each has two monodentate chlorine atoms. The complex formulated as (H(2)TMhpp)(2)[W(mu-O)(mu-TMhpp)Cl-2](2) has the shortest W-W distance (2.3318(8) angstrom) of any species with a sigma(2)pi(2) electronic configuration. The anion and cations are connected by hydrogen bonds. To unambiguously ascertain the existence of the double-bonded W-2(mu-O)(2) entity, density functional theory calculations and natural bond orbital analyses were done on an analogous but hypothetical species with a W-2(mu-OH)(2) core having trivalent tungsten atoms and a possible sigma(2)pi(2)delta(2) electronic configuration. The calculations decidedly support the presence of tungsten-oxo instead of tungsten-hydroxo groups and thus the existence of the double-bonded W-2(mu-O)(2) core. The strong bonding interaction between metal atoms is a clear indication that under certain circumstances the two octahedra in ESBO species do not behave as the sum of two mononuclear compounds.
• Soluble paramagnetic Ru26+ paddlewheels with alkyl-substituted bicyclic guanidinates
  作者：Gina M. Chiarella、Carlos A. Murillo、Mark D. Young

  DOI：10.1016/j.poly.2015.07.031

  日期：2016.1

  Syntheses are reported for two diruthenium compounds having the formula Ru-2(TRhpp)(4)Cl-2, where R = Me (1) and Et (2) and TRhpp is the anion of a tetraalkyl-substituted bicyclic guanidinate. The Ru-2(6+) core of 1 is enclosed by four tetramethyl-substituted bicyclic guanidinates and two chlorine atoms positioned along the Ru-Ru axis. Each compound possesses two unpaired electrons at ambient temperature consistent with a formal bond order of three and a sigma(2)pi(4)delta(2)pi*(2) (Q(8)pi*(2)) electronic configuration. The compounds are EPR-silent as determined by examination of frozen dichloromethane solutions at 77 K using an X-band spectrometer. There is a short Ru-Ru distance of 2.2896(15) angstrom. Published by Elsevier Ltd.
• Solubilizing the Most Easily Ionized Molecules and Generating Powerful Reducing Agents
  作者：Gina M. Chiarella、F. Albert Cotton、Jason C. Durivage、Dennis L. Lichtenberger、Carlos A. Murillo

  DOI：10.1021/ja408291k

  日期：2013.11.27

  Two very soluble compounds having W-2(bicyclic guanidinate)(4) paddlewheel structures show record low ionization energies (onsets at 3.4 to 3.5 eV) and very negative oxidation potentials in THF (-1.84 to -1.90 V vs Ag/AgCl). DFT computations show the correlation from the gas-phase ionization energies to the solution redox potentials and chemical behavior. These compounds are thermally stable and easy to synthesize in high yields and good purity. They are very reactive and potentially useful stoichiometric reducing agents in nonpolar, nonprotonated solvents.