5,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)-2,4-dihydropyrimidin-3-ium-2-id-6-one | 1370557-22-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯啉
• 英文名称: 5,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)-2,4-dihydropyrimidin-3-ium-2-id-6-one
• CAS: 1370557-22-4
• 化学式: C₂₄H₃₀N₂O
• 分子量: 362.515
• InChiKey: NXDYXHODYZTKCG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  23.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)-2,4-dihydropyrimidin-3-ium-2-id-6-one 在 phosphorus 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以74.8%的产率得到5,5-Dimethyl-1,3-bis(2,4,6-trimethylphenyl)-2-[2,3,4-tris[[5,5-dimethyl-4-oxo-1,3-bis(2,4,6-trimethylphenyl)-1,3-diazinan-2-ylidene]phosphanyl]tetraphosphetan-1-yl]phosphanylidene-1,3-diazinan-4-one
  参考文献：
  名称：

  通过[2 + 2]环磷加成反应的二磷通过碳激活白磷来促进中性P8团簇的分离

  摘要：

  并列在一起：用羰基修饰的卡宾容易活化白磷，得到卡宾稳定的P 4和P 8簇。力学证据表明，P 8团簇（见X射线衍射的结构：C灰色，P橙色，N蓝色，O红色）是由瞬态二膦物质的[2 + 2]环加成形成的。

  DOI：

  10.1002/anie.201301137
• 作为产物：
  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 0.5h， 生成 5,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)-2,4-dihydropyrimidin-3-ium-2-id-6-one
  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

• ³¹P NMR Chemical Shifts of Carbene-Phosphinidene Adducts as an Indicator of the π-Accepting Properties of Carbenes
  作者：Olivier Back、Martin Henry-Ellinger、Caleb D. Martin、David Martin、Guy Bertrand

  DOI：10.1002/anie.201209109

  日期：2013.3.4

  Beyond the Tolman electronic parameter: The 31P NMR chemical shifts of easily synthesized carbene–phenylphosphinidene adducts allow the determination of the relative π‐acceptor properties of carbenes. In combination with the Tolman electronic parameter value, the relative pure σ‐donation of carbenes can also be evaluated.

  超越托尔曼电子参数：易于合成的卡宾 - 苯基膦亚基加合物的31 P NMR 化学位移允许确定卡宾的相对 π 受体特性。结合托尔曼电子参数值，还可以评估卡宾的相对纯 σ 供体。
• 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。
• Carbene-derived α-acyl formamidinium cations: organic molecules with readily tunable multiple redox processes
  作者：Cassie L. Deardorff、R. Eric Sikma、Christopher P. Rhodes、Todd W. Hudnall

  DOI：10.1039/c5cc06322a

  日期：——

  Singlet carbenes can impart stability, but can also be used to tailor the electrochemical properties of redox-active organic molecules.

  单重自由基碳烯可以提供稳定性，同时也可以用来调节可氧化还原有机分子的电化学性质。