1,1-diferrocenyl-2-propyn-1-ol | 172660-59-2

• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: 1,1-diferrocenyl-2-propyn-1-ol
• 英文别名: 1,1-diferrocenylprop-2-in-1-ol；1,1-diferrocenylprop-2-yn-1-ol；1,1-diferrocenylpropynol
• CAS: 172660-59-2
• 化学式: C₂₃H₂₀Fe₂O
• 分子量: 424.105
• InChiKey: FNILCDRSBCGTAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.26
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  pentacarbonyl(tetrahydrofuran)chromium(0) 、 1,1-diferrocenyl-2-propyn-1-ol 在 n-butyllithium 、 phosgene 作用下， 以 四氢呋喃 为溶剂， 以39%的产率得到pentacarbonyl(3,3-bis[ferrocenyl]-1,2-propadienylidene)chromium
  参考文献：
  名称：

  铬，钼和钨的二茂铁基取代的亚烯基络合物：合成，结构和反应性

  摘要：

  摘要双（二茂铁基）取代的亚烯基络合物，[（CO）5 MCC CFc 2]（1a – c，Fc =（C 5 H 4）Fe（C 5 H 5），M = Cr（a），Mo（b ），W（c））是通过Fc 2 CO与Me 3 Si–C CH，KF / MeOH，正丁基锂和[（CO）5 M（THF）]的顺序反应获得的。为了合成相关的单（二茂铁基）亚烯基铬络合物[（CO）5 Cr CCC（Fc）R]（R = Ph，NMe 2），开发了三种不同的途径：（a）去质子化的炔丙醇HC的反应CC（Fc）（Ph）OH与[（CO）5 Cr（THF）]，然后用Cl 2 CO脱氧，（b）路易斯酸诱导从烯基（烷氧基）卡宾络合物[[CO）5 Cr C中除去醇（OR）CH C（NMe 2）Fc]，以及（c）用[Fc]取代[（CO）5 Cr CCC（OMe）NMe 2]中的OMe。当首先用Li [Fc]处理单（二茂铁基）亚烯基络合物[（CO）5

  DOI：

  10.1016/j.ica.2008.02.024
• 作为产物：
  描述：

  diferrocenylmethanone 、 1,1-diferrocenyl-3-(trimethylsilyl)prop-2-yn-1-ol 、 水 在 KOH 作用下， 以 甲醇 为溶剂， 以98%的产率得到1,1-diferrocenyl-2-propyn-1-ol
  参考文献：
  名称：

  Stable and Crystalline Allylium and Allenylium Salts with Ferrocenyl Substituents

  摘要：

  Allylic and allenylic carbenium ions, which have been reported in the literature to be labile or not isolable at all, have no inherent instability. Progressive substitution with ferrocenyl groups affords allylic cations, whose stability toward photochemical decay and nucleophilic collapse increases with increasing number of ferrocenyl substituents, if the allylic moiety is at least 2-fold-substituted with ferrocenes in the 1,3-positions. The unmatched cation-stabilizing capacity of metallocenes is illustrated in cyclopentadienyl( 1,3-diferrocenyl-1-yliumpentalenyl)iron tetrafluoroborate, a compound which survives exposure to sunlight in aqueous solution for days. In addition to full characterization for these allylium salts by the usual analytical and spectroscopic methods, X-ray analysis of cyclopentadienyl(1,3-diferrocenyl- 1-yliumpentalenyl)iron tetrafluoroborate showed (a) deviations of the regular conformation of the ferrocenyl substituents in the 1,3-positions that are similar to those observed in other simple metallocenyl-stabilized carbenium ions, indicative of electronic stabilization by intramolecular charge delocalization, (b) these two ferrocenyl substituents are structurally distorted in an unequal manner and seem to contribute unequally in this charge delocalization, but the observed dissymmetric structure is most likely the result of crystal forces, and (c) the annelated ferrocene of this formal pentalene system is undistorted, ruling out (together with results from solution NMR measurements) any significant conjugation; therefore, this cation should be envisaged as an allylium system and not as an antiaromatic cyclopentadienyl cation. In the case of allenylium <-> propargylium ions, attachment of two ferrocenes results in labile or intermediate propargylium ions, which can be trapped with triethylamine to afford ammonium allenes, formally Lewis base complexed allenylium salts, with an interesting bent allene unit as is evidenced by single-crystal structure analysis. Introduction of a third ferrocene into the allenylium <-> propargylium system affords 1,3,3-triferrocenylallen-1-ylium tetrafluoroborate, the first stable and fully characterized allenylium compound, with only minor resonance contributions from the propargylium structure, proven most clearly by the observation of an extremely intense and acceptor-shifted cumulenic stretching vibration of 2151 cm(-1) in the IR spectrum.

  DOI：

  10.1021/om00012a025

文献信息

• Tetraferrocenyl-[3]-cumulene
  作者：Benno Bildstein、Manuela Schweiger、Holger Kopacka、Klaus Wurst

  DOI：10.1016/s0022-328x(97)00266-0

  日期：1998.2

  is synthesized from tetraferrocenyl-methoxy-hydroxy-butyne by reduction with stannous chloride. Other reducing agents, including iron carbonyls, samarium(II) iodide, low-valent titanium, and trimethylchlorosilane/zinc, failed or gave inferior results. With the McMurry reagent the reduction goes further and tetraferrocenylbutadiene is obtained. The title compound is an electron-rich cumulene, as shown

  通过用氯化亚锡还原由四茂铁基-甲氧基-羟基-丁炔合成四茂铁基-[3]-异丙苯（四茂铁基丁三烯）。其他还原剂，包括羰基铁，碘化sa（II），低价钛和三甲基氯硅烷/锌，均未通过或给出了较差的结果。使用McMurry试剂，还原反应进一步进行，获得了四铁茂铁基丁二烯。如循环伏安法所示，标题化合物是富电子的异丙苯。由于中心异丙苯功能性的空间屏蔽，未观察到已建立的丁三烯反应性（复合物形成或二聚作用），但简单的基于二茂铁的氧化还原或电荷转移化学反应是可能的。
• Reaction of the RuTp(PR3)Cl fragment with alkynols: Formation of carbene, vinylidene, allenylidene, and carbyne complexes
  作者：Sonja Pavlik、Kurt Mereiter、Michael Puchberger、Karl Kirchner

  DOI：10.1016/j.jorganchem.2005.04.035

  日期：2005.12

  The reaction of RuTp(COD)Cl (1) with PR3 (PR3 = (PPh2Pr)-Pr-i, (PPr3)-Pr-i, PPh3) and propargylic alcohols HC equivalent to CCPh2,OH, HC equivalent to CCFc(2)OH (Fc = ferrocenyl), and HC equivalent to CC(Ph)MeOH has been studied. In the case of PR3 = (PPh2Pr)-Pr-i, (PPr3)-Pr-i and HC equivalent to CCPh2OH. the 3-hydroxyvinylidene complexes RuTp((PPh2Pr)-Pr-i)(=C=CHC(Ph)(2)OH)Cl (2a) and RuTp((PPr3)-Pr-i)(=C=CHC(Ph-2)OH)Cl (2b) were isolated. With PR3 = PPh2iPr and HC equivalent to CCFc(2)OH as well as with PR3 = PPh3 and HC equivalent to CCPh,OH dehydration takes place affording the allenylidene complexes RuTp((PPh2Pr)-Pr-i)(=C=C=CFC2)Cl (3b) and RuTp(PPh3)(=C=C=CPh2)Cl (3c). Similarly, with (PPh2Pr)-Pr-i and HC equivalent to CC(Ph)MeOH rapid elimination of water results in the formation of the vinylvinylidene complex RuTp((PPh2Pr)-Pr-i)(=C=CHC(Ph)=CH2)Cl (4). In contrast to the reactions of the RuTp(PR3)Cl fragment with propargylic alcohols, with HC equivalent to C(CH2)(n)OH (it = 2, 3, 4, 5) six-, and seven-membered cyclic oxycarbene complexes RuTp(PR3)(=C4H6O)Cl (5), RuTp(PR3)(=C5H8O)Cl (6), and RuTp(PR3)(=C6H10O)Cl (7) are obtained. On the other hand, with 1-ethynylcyclohexanol the vinylvinylidene complex RuTp((PPh2Pr)-Pr-i)(=C=CHC(6)Hq)Cl (8) is formed. The reaction of the allenylidene complexes 3a-c with acid has been investigated. Addition of CF3COOH to a solution of 3a-c resulted in the reversible formation of the novel RuTp vinylcarbyne complexes [RuTp((PPh2Pr)-Pr-i)(equivalent to C-CH=CPh2)Cl](+) (9a), [RuTp((PPh2Pr)-Pr-i)(equivalent to C-CH=CFc(2))Cl](+) (9b), and [RuTp(PPh3)(equivalent to CCH-CPh2)Cl](+) (9c). The structures of 3a, 3b, and 5b have been determined by X-ray crystallography. (c) 2005 Elsevier B.V. All rights reserved.