1,3-diisopropyl-3,4,5,6-tetrahydropyrimid-2-ylidene | 223265-44-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: 1,3-diisopropyl-3,4,5,6-tetrahydropyrimid-2-ylidene
• 英文别名: 1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidine；1,3-diisopropyltetrahydropyrimid-2-ylidene；1,3-Di(propan-2-yl)-2,4,5,6-tetrahydropyrimidin-1-ium-2-ide
• CAS: 223265-44-9
• 化学式: C₁₀H₂₀N₂
• 分子量: 168.282
• InChiKey: ICMXFZASBXDZMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  6.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,3-diisopropyl-3,4,5,6-tetrahydropyrimid-2-ylidene 以 四氢呋喃 、 氘代苯 、 甲苯 为溶剂， 反应 6.0h， 生成 cis-Rh(1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidine)(PPh₃)₂F
  参考文献：
  名称：

  Ring-Expanded N-Heterocyclic Carbene Complexes of Rhodium with Bifluoride, Fluoride, and Fluoroaryl Ligands

  摘要：

  Thermolysis of Rh(PPh3)(4)H in the presence of the six-membered N-heterocyclic carbene 1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidine (6-Pr-i) gave the monocarbene complex Rh(6-Pr-i)(PPh3)(2)H as a 1:2 mixture of the cis- and trans-phosphine isomers la and 1b. This same isomeric mixture was formed as the ultimate product from treating Rh(PPh3)(3)(CO)H with 6-Pr-i at room temperature, although pathways involving both CO and PPh3 loss were observed at initial times. Treatment of 1a/1b with Et3N center dot 3HF generated the bifluoride complex cis-Rh(6-Pr-i)(PPh3)(2)(FHF) (2a), which upon stirring with anhydrous Me4NF was converted to the rhodium fluoride complex cis-Rh(6-Pr-i)(PPh3)(2)F (3a). Thermolysis of 1a/1b with C6F6 resulted in C-F bond activation to afford a mixture of 3a and the pentafluorophenyl complex trans-Rh(6-Pr-i)(PPh3)(2)(C6F5) (5b). Complexes 1b, 2a, 3a, and 5b were structurally characterized.

  DOI：

  10.1021/om300984v
• 作为产物：
  描述：

  3,4,5,6-tetrahydro-1,3-bis(1-methylethyl)pyrimidinium tetrafluoroborate 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 以40%的产率得到1,3-diisopropyl-3,4,5,6-tetrahydropyrimid-2-ylidene
  参考文献：
  名称：

  Complexation of stable carbenes with alkali metals

  摘要：

  稳定的二氨基羰基（包括咪唑-2-亚基）会与锂、钠和钾发生络合反应；报告了 1,3-二异丙基-3,4,5,6-四氢嘧啶-2-亚基 1 与 KN(SiMe3)2 的络合物晶体结构。

  DOI：

  10.1039/a808951e

文献信息

• Structural investigations of metalcarbonyl complexes with acyclic diamino carbenes
  作者：Guido D. Frey、Eberhardt Herdtweck、Wolfgang A. Herrmann

  DOI：10.1016/j.jorganchem.2006.01.033

  日期：2006.5

  and cyclic aminocarbene substituted carbonyl complexes of group 6 metals. The reaction of bis(diisopropyl)aminocarbene with photolytically produced (ether)M(CO)5 leads to unstable η1-carbene complexes, which convert to η2-carbene complexes; crystallographic data are presented for the tungsten complex, where one amino group of the carbene coordinates to the metal. The Mo and W η2-complexes can be converted

  在这里，我们报告第6组金属的无环和环状氨基卡宾取代的羰基配合物的合成。双（二异丙基）aminocarbene与光解产生（醚）M（CO）的反应5所导致不稳定的η 1种-carbene复合物，其转换为η 2个-carbene络合物; 给出了钨配合物的晶体学数据，其中卡宾的一个氨基与金属配位。的Mo和Wη 2-可以在消除丙烯的情况下将复合物转化为亚胺复合物；具有化学，光谱和晶体学数据的特征。进行了新的双（二烷基）氨基卡宾和相应的亚甲基盐的DFT计算，并与后者的相应晶体学数据进行了比较。在（乙醚）Cr（CO）5与游离的六元环卡宾的反应过程中的副反应中，形成了三核的阴离子金属羰基羰基Nido络合物（C 14 H 10 Cr 3 O 12）2-，可以通过光谱学和晶体学数据来表征。
• Active catalysts for the Suzuki coupling: Palladium complexes of tetrahydropyrimid-2-ylidenes
  作者：Sabine K. Schneider、Wolfgang A. Herrmann、Eberhardt Herdtweck

  DOI：10.1016/j.molcata.2005.08.046

  日期：2006.2

  An alternative way to synthesize a mixed N-heterocyclic carbenes (NHC) phosphine palladium(II) complex is described in this work. A free carbene, generated by deprotonation of a tetrahydro-pyrimidinium salt, was reacted with Pd(PPh3)(2)Cl-2 to yield the desired mixed NHC phosphine palladium(II) complex.In this work, we have combined the superior activity of mixed NHC phosphine palladium complexes in Suzuki-coupling reactions with the additional advantage of a stronger or-donating ligand. The combination of these two effects results in an increased catalytic activity in Suzuki reactions than found for corresponding mixed imidazole-ylidene phosphine complexes.Using this new class of catalysts, TONs of approximately 1 Mio. after a reaction time of 14 h can be achieved. Desactivated bromoarenes could also be coupled efficiently, using quite a low amount of catalyst (0.005 mol%). Even aryl chlorides can be coupled: TONs of approximately 6000 can be reached after only 14 It without any detectable catalyst deterioration using only 0.01 mol% of catalyst. (c) 2005 Elsevier B.V. All rights reserved.
• Ring-Expanded N-Heterocyclic Carbene Complexes of Rhodium with Bifluoride, Fluoride, and Fluoroaryl Ligands
  作者：Candela Segarra、Elena Mas-Marzá、John P. Lowe、Mary F. Mahon、Rebecca C. Poulten、Michael K. Whittlesey

  DOI：10.1021/om300984v

  日期：2012.12.24

  Thermolysis of Rh(PPh3)(4)H in the presence of the six-membered N-heterocyclic carbene 1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidine (6-Pr-i) gave the monocarbene complex Rh(6-Pr-i)(PPh3)(2)H as a 1:2 mixture of the cis- and trans-phosphine isomers la and 1b. This same isomeric mixture was formed as the ultimate product from treating Rh(PPh3)(3)(CO)H with 6-Pr-i at room temperature, although pathways involving both CO and PPh3 loss were observed at initial times. Treatment of 1a/1b with Et3N center dot 3HF generated the bifluoride complex cis-Rh(6-Pr-i)(PPh3)(2)(FHF) (2a), which upon stirring with anhydrous Me4NF was converted to the rhodium fluoride complex cis-Rh(6-Pr-i)(PPh3)(2)F (3a). Thermolysis of 1a/1b with C6F6 resulted in C-F bond activation to afford a mixture of 3a and the pentafluorophenyl complex trans-Rh(6-Pr-i)(PPh3)(2)(C6F5) (5b). Complexes 1b, 2a, 3a, and 5b were structurally characterized.
• Complexation of stable carbenes with alkali metals
  作者：Roger W. Alder、Michael E. Blake、Christel Bortolotti、Simone Bufali、Craig P. Butts、Emma Linehan、Josep M. Oliva、A. Guy Orpen、Michael J. Quayle

  DOI：10.1039/a808951e

  日期：——

  Stable diaminocarbenes, including imidazol-2-ylidenes, undergo complexation with lithium, sodium and potassium species; the crystal structure of a complex of 1,3-diisopropyl-3,4,5,6-tetrahydropyrimid-2-ylidene 1 with KN(SiMe3)2 is reported.

  稳定的二氨基羰基（包括咪唑-2-亚基）会与锂、钠和钾发生络合反应；报告了 1,3-二异丙基-3,4,5,6-四氢嘧啶-2-亚基 1 与 KN(SiMe3)2 的络合物晶体结构。