1,3-diethyl-2,4,5,6-tetrahydropyrimidin-1-ium-2-ide | 794591-34-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,3-diethyl-2,4,5,6-tetrahydropyrimidin-1-ium-2-ide
• CAS: 794591-34-7
• 化学式: C₈H₁₆N₂
• 分子量: 140.228
• InChiKey: GEKPCAOGYCVUEM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  hydridotetakis(triphenylphosphine)rhodium(I) 、 1,3-diethyl-2,4,5,6-tetrahydropyrimidin-1-ium-2-ide 以 苯 为溶剂， 反应 16.5h， 以80%的产率得到
  参考文献：
  名称：

  Rh–FHF and Rh–F Complexes Containing Small N-Alkyl Substituted Six-Membered Ring N-Heterocyclic Carbenes

  摘要：

  Heating the six-membered ring N-heterocyclic carbenes 6-Me and 6-Et with Rh(PPh3)(4)H afforded the rhodium monocarbene hydride complexes Rh(6-NHC)-(PPh3)(2)H as a mixture of cis- and trans-P,P isomers (4a/b, NHC = 6-Me; ratio = 1:20; 5a/b, NHC = 6-Et; ratio = 1:9). Reaction of 4a/b with Et3N center dot 3HF gave only the trans-P,P isomer of the bifluoride complex Rh(6-Me)(PPh3)(2)(FHF) (6b), whereas 5a/b reacted to form Rh(6-Et)(PPh3)(2)(FHF) as a mixture of cis- and trans-phosphine isomers (7a/b). Variable temperature H-1 and F-19 NMR spectroscopy showed that 6b and the previously reported 6-Pr-i carbene analogue cis-Rh(6-Pr-i)(PPh3)(2)(FHF) (2a; Organometallics 2012, 41, 8584) were fluxional in solution. F-19 Magnetization transfer experiments revealed F exchange in both compounds and afforded similar Delta H-double dagger values (2a, 51 +/- 5 kJ mol(-1); 6b, 60 +/- 6 kJ mol(-1)) but somewhat different values of Delta S-double dagger (2a, -70 +/- 17 J mol(-1) K-1; 6b, -27 +/- 18 J mol(-1) K-1). The fluoride complexes cis-Rh(6-Me)(PPh3)(2)F (8a), cis-/trans-Rh(6-Et)(PPh3)(2)F (9a/b), and the previously reported 6-Pr-i analogue 3a could be formed upon C-F activation of CF3CF=CF2 by 4a/b, 5a/b, and Rh(6-Pr-i)(PPh3)(2)H (1a/b), respectively. Complex 3a reacted slowly with H-2 to partially reform 1a/b but rapidly with CO to give Rh(6-Pr-i)(PPh3)(CO)F (10) and Rh(PPh3)(2)(CO)F, and also quickly with Me3SiCF3 to form cis-Rh(6-Pr-i)(PPh3)(2)(CF3) (11a). Complexes 4b, 5b, 6b, 7b, and 11a were structurally characterized.

  DOI：

  10.1021/om500122e