2,6-Diisopropyl-4-phenylpyrylium tetrafluoroborate | 87828-74-8

• 英文名称: 2,6-Diisopropyl-4-phenylpyrylium tetrafluoroborate
• 英文别名: 4-phenyl-2,6-diisopropylpyrylium tetrafluoroborate
• CAS: 87828-74-8
• 化学式: BF₄*C₁₇H₂₁O
• 分子量: 328.158
• InChiKey: CDKCDQALPPBTRV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  2,6-Diisopropyl-4-phenylpyrylium tetrafluoroborate 在 氘代3-氨基-5-吗啉-4-甲基-恶唑-2-啉酮 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以30%的产率得到2,6-Diisopropyl-4-phenylphosphinine
  参考文献：
  名称：

  磷苯作为铑催化的羰基化反应的单齿pi受体配体。

  摘要：

  在这项研究中提出了新的一类用于末端和内部烯烃加氢甲酰化的膦/铑催化剂。通过使膦或三（三甲基甲硅烷基）膦与相应的吡啶鎓盐缩合来制备一系列的磷苯1-14。已经制备了反式-[（磷苯）2RhCl（CO）]配合物21-25，并通过X射线晶体结构分析进行了光谱学和研究。辛-1-烯的加氢甲酰化已用于确定最佳的催化剂预形成和反应条件。已经进行了使用15种单磷苯的加氢甲酰化研究。催化性能主要受空间影响，其中磷苯8 /铑体系是最具活性的催化剂。已确定辛基-1-烯的加氢甲酰化反应的最高达45370 h（-1）的周转频率。在进一步的研究中，研究了对更高取代度的烯烃的加氢甲酰化活性，并将其与标准工业三苯基膦/铑催化剂进行了比较。磷苯与三苯基膦催化剂之间的反应性差异随着去往取代度更高的烯烃的增加而增加。甚至四取代的烯烃也与磷苯催化剂反应，而三苯膦体系无法生成任何产物。已经进行了原位压力NMR实验以鉴定催化剂的静止状态

  DOI：

  10.1002/1521-3765(20010716)7:14<3106::aid-chem3106>3.0.co;2-y
• 作为产物：
  描述：

  异丁酰氯 、 2-苯基-1-丙烯 在 三氯化铝 作用下， 反应 24.0h， 以15%的产率得到2,6-Diisopropyl-4-phenylpyrylium tetrafluoroborate
  参考文献：
  名称：

  Rotational equilibria in 1,2,6-trisubstituted pyridinium cations and reactions of 2-Isopropylpyrylium cations

  摘要：

  Abstract2‐Isopropyl‐6‐phenyl‐ and 2,6‐diisopropyl‐pyridiniums with bulky 1‐substituents show temperature‐variable NMR spectra which are interpreted in terms of restricted rotation. 2‐Isopropyl‐4,6‐diphenylpyrylium can be deprotonated at the isopropyl group to give an anhydro base which forms new pyryliums with electrophiles.

  DOI：

  10.1002/omr.1270211002

文献信息

• Kinetics and mechanisms of nucleophilic displacements with heterocycles as leaving groups. Part 12. Regio- and stereo-chemistry of nucleophilic displacement and solvolysis reactions of N-(α-methylallyl)-and N-(α-phenylethyl)-pyridiniums
  作者：Alan R. Katritzky、Yu Xiang Ou、Giuseppe Musumarra

  DOI：10.1039/p29830001449

  日期：——

  N-(α-Methylallyl)pyridiniums rearrange to the N-(γ-methylallyl) analogues in a process analogous to ion return. In the tricyclic series the process (9)→(4) occurs spontaneously. In the monocyclic series (1) can be isolated and thermally rearranged into (2); this rearrangement is intramolecular. N-(α-Phenylethyl)pyridiniums solvolyse in HOAc–NEt3 with predominant inversion of configuration (90%). In

  N-（α-甲基烯丙基）吡啶以类似于离子返回的过程重排为N-（γ-甲基烯丙基）类似物。在三环系列中，过程（9）→（4）自发发生。在单环系列中，可以将（1）分离并热重排为（2）；这种重排是分子内的。在HOAc-NEt 3中的N-（α-苯乙基）吡啶溶剂化物主要反转构型（90％）。在2,4,6-三苯基系列中，这是自发发生的。分离的1-（α-苯乙基）-2-异丙基-4,6-二苯基吡啶鎓在氯苯中具有一级动力学并且具有外消旋作用。
• Conversions of N-vinylpyridinium cations into tricyclic cage compounds
  作者：Alan R. Katritzky、Olga Rubio

  DOI：10.1021/jo00177a013

  日期：1984.2
• Orientation of Pyrylium Guests in Cucurbituril Hosts
  作者：Arumugam Thangavel、Chariklia Sotiriou-Leventis、Richard Dawes、Nicholas Leventis

  DOI：10.1021/jo202434z

  日期：2012.3.2

  According to recent reports, supramolecular complexes of the pyrylium cation with cucurbit[x]urils (CB[x], x = 7, 8) show promising photoluminescence suitable for electroluminescent devices. In turn, photoluminescence seems to be related to the stereochemistry of the complexes; however, that has been controversial. Here, we report that in H2O, 2,6-disubsituted-4-phenyl pyryliums (Pylm) form dimers quantitatively (equilibrium constants >10(4) M-1), but they enter as such only in the larger CB[8]. In terms of orientation, H-1 NMR shows that Me-Pylm, Ph-Pylm, and t-Bu-Pylm insert their 4-phenyl groups in either the CB[7] or CB[8] cavity. The orientation of iPr-Pylm in the iPr-Pylm@CB[7] complex is similar. Experimental conclusions are supported by DFT calculations using the M062X functional and the 6-31G(d) basis set. In the case of (iPr-Pylm)(2)@CB[8], H-1 NMR of both the guest and the host indicates that both guests might enter CB[8] from the same side with their iPr groups in the cavity, but DFT calculations leave room for ambiguity. In addition to the size and hydrophobicity of the 2,6-substituents of the guests, as well as the size and flexibility of the hosts, theory reveals the importance of explicit solvation (H2O) and finite temperature effects (particularly for H-1 NMR shielding calculations) in the determination of the stereochemistry of those complexes.