1,3-bis(1,3,5-trimethylphenyl)-5,5-dimethyl-4-keto-tetrahydro-pyrimidinium chloride | 1370557-21-3

• 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: 1,3-bis(1,3,5-trimethylphenyl)-5,5-dimethyl-4-keto-tetrahydro-pyrimidinium chloride
• 英文别名: 1,3-dimesityl-5,5-dimethyl-4-oxo-3,4,5,6-tetrahydropyrimidin-1-ium chloride
• CAS: 1370557-21-3
• 化学式: C₂₄H₃₁N₂O*Cl
• 分子量: 398.976
• InChiKey: ZFDZCSNQUFIBGD-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  2.29
• 重原子数：
  28.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  23.32
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1,3-bis(1,3,5-trimethylphenyl)-5,5-dimethyl-4-keto-tetrahydro-pyrimidinium chloride 在 sodium hexamethyldisilazane 作用下， 以 苯 为溶剂， 反应 1.5h， 生成 1,3-dimesityl-5,5-dimethyl-6-oxo-3,4,5,6-tetrahydropyrimidin-1-ium-2-carbodithioate
  参考文献：
  名称：

  Tuning the Electronic Properties of Carbenes: A Systematic Comparison of Neighboring Amino versus Amido Groups

  摘要：

  A related series of six-membered carbenes featuring adjoining amino and/or amido groups (i.e, a diaminocarbene, a monoamido-aminocarbene (3), and a a diamidocarbene (6)) were systematically compared using crystallographic, spectroscopic, electro-chemical, and density functional theory methods. The solid-state structure of 3 was found to exhibit inequivalent nitrogen carbon bond lengths (C-carbene-N-amide= 1.395(4) angstrom vs C-carbene-N-amine = 1.323(4) angstrom). Moreover, the C-carbene-N-amide distance was longer than that measured in the solid-state structure of 6 (1.371(3) angstrom), while the C-carbene-N-amine distance was similar to that measured in the solid-state structure of a cyclic alkyl-aminocarbene (1.315(3) angstrom). Iridium complexes of the aforementioned carbenes were also evaluated, and the collected data revealed that the introduction of carbonyl groups to the carbene-containing scaffold had a nearly linear, additive effect on the E-1/2 potential of the carbene-ligated iridium I/II redox couple (+165 mV per carbonyl added) as well as the Tolman electronic parameter value of the corresponding carbene-Ir(CO)(2)Cl complex (ca. 7 cm(-1) per carbonyl added). Beyond attenuated ligand donicity, the introduction of carbonyl groups was found to broaden the chemical reactivity: unlike prototypical N-heterocyclic carbenes, including diaminocarbenes, the monoamido-aminocarbene was found to couple to isonitriles to form the respective ketenimines.

  DOI：

  10.1021/om3001586
• 作为产物：
  描述：

  N,N'-dimesitylformamidine 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 16.5h， 生成 1,3-bis(1,3,5-trimethylphenyl)-5,5-dimethyl-4-keto-tetrahydro-pyrimidinium chloride
  参考文献：
  名称：

  Tuning the Electronic Properties of Carbenes: A Systematic Comparison of Neighboring Amino versus Amido Groups

  摘要：

  A related series of six-membered carbenes featuring adjoining amino and/or amido groups (i.e, a diaminocarbene, a monoamido-aminocarbene (3), and a a diamidocarbene (6)) were systematically compared using crystallographic, spectroscopic, electro-chemical, and density functional theory methods. The solid-state structure of 3 was found to exhibit inequivalent nitrogen carbon bond lengths (C-carbene-N-amide= 1.395(4) angstrom vs C-carbene-N-amine = 1.323(4) angstrom). Moreover, the C-carbene-N-amide distance was longer than that measured in the solid-state structure of 6 (1.371(3) angstrom), while the C-carbene-N-amine distance was similar to that measured in the solid-state structure of a cyclic alkyl-aminocarbene (1.315(3) angstrom). Iridium complexes of the aforementioned carbenes were also evaluated, and the collected data revealed that the introduction of carbonyl groups to the carbene-containing scaffold had a nearly linear, additive effect on the E-1/2 potential of the carbene-ligated iridium I/II redox couple (+165 mV per carbonyl added) as well as the Tolman electronic parameter value of the corresponding carbene-Ir(CO)(2)Cl complex (ca. 7 cm(-1) per carbonyl added). Beyond attenuated ligand donicity, the introduction of carbonyl groups was found to broaden the chemical reactivity: unlike prototypical N-heterocyclic carbenes, including diaminocarbenes, the monoamido-aminocarbene was found to couple to isonitriles to form the respective ketenimines.

  DOI：

  10.1021/om3001586

文献信息

• Reductive Synthesis of Aminal Radicals for Carbon–Carbon Bond Formation
  作者：David A. Schiedler、Yi Lu、Christopher M. Beaudry

  DOI：10.1021/ol500024q

  日期：2014.2.21

  Aminal radicals were generated by reduction of the corresponding amidine or amidinium ion. The intermediate radicals participate in C–C bond-forming reactions to produce fully substituted aminal stereocenters. No toxic additives or reagents are required. More than 30 substrate combinations are reported, and chemical yields are as high as 99%.

  通过还原相应的idine或am离子可生成氨基自由基。中间基团参与C–C键形成反应，以产生完全取代的氨基立体中心。不需要有毒的添加剂或试剂。据报道有30多种底物组合，化学收率高达99％。
• The development of carbon–carbon bond forming reactions of aminal radicals
  作者：David A. Schiedler、Jessica K. Vellucci、Yi Lu、Christopher M. Beaudry

  DOI：10.1016/j.tet.2014.12.067

  日期：2015.3

  Aminal radicals were generated and used in synthetic reactions for the first time. Aminal radicals are formed from aminals by radical translocation using AIBN and a stoichiometric hydrogen atom donor, or by SmI2 reduction of N-acyl amidines or amidinium ions in the presence of a proton source. Aminal radicals were found to participate in inter- and intramolecular C–C bond forming reactions with electron

  首次产生了氨基自由基，并将其用于合成反应中。通过使用AIBN和化学计量的氢原子供体的自由基易位，或通过在质子源存在下SmI 2还原N-酰基am或am离子，由氨基缩醛形成氨基自由基。发现氨基自由基参与与电子不足的烯烃的分子间和分子内CC键形成反应。化学收率高达99％。
• Stable Singlet Carbenes as Organic Superbases
  作者：François Vermersch、Sima Yazdani、Glen P. Junor、Douglas B. Grotjahn、Rodolphe Jazzar、Guy Bertrand

  DOI：10.1002/anie.202111588

  日期：2021.12.20

  Pyrazol-4-ylidenes, a type of mesoionic carbenes, also named cyclic-bentallenes (CBA), can be more basic than Verkade proazaphosphatrane and even Schwesinger phosphazene P4(tBu). With these results it is demonstrated that carbenes should not be overlooked as neutral purely organic superbases.

  Pyrazol-4-ylidenes 是一种中离子卡宾，也称为环 Bentallenes (CBA)，比 Verkade proazaphosphatrane 甚至 Schwesinger phosphazene P 4 ( t Bu) 的碱性更强。这些结果表明，作为中性纯有机超强碱不应忽视卡宾。
• Determining the π-Acceptor Properties of N-Heterocyclic Carbenes by Measuring the⁷⁷Se NMR Chemical Shifts of Their Selenium Adducts
  作者：Annika Liske、Kathrin Verlinden、Hannes Buhl、Klaus Schaper、Christian Ganter

  DOI：10.1021/om400858y

  日期：2013.10.14

  assessment of the π-acceptor strength of N-heterocyclic carbenes is presented. The 77Se chemical shifts of the easily available selenium carbene adducts 1·Se–7·Se correlate with the π-acceptor character of the respective carbenes. The observed δ(77Se) values cover a range of almost 800 ppm, with increasing π-acidity leading to a downfield shift of the signal.

  提出了一种新的评估N-杂环卡宾的π-受体强度的方法。易于获得的硒卡宾加合物1 ·Se- 7 ·Se的77 Se化学位移与各个碳烯的π受体特征相关。观察到的δ（77 Se）值几乎覆盖了800 ppm的范围，随着π酸度的增加，导致信号的场下偏移。