2,3,4,5,6-pentafluorobenzaldehyde p-tosylhydrazone | 16096-88-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,4,5,6-pentafluorobenzaldehyde p-tosylhydrazone
• 英文别名: pentafluorobenzaldehyde tosylhydrazone；Pentafluorobenzaldehyde tosylhydrazone；4-methyl-N-[(2,3,4,5,6-pentafluorophenyl)methylideneamino]benzenesulfonamide
• CAS: 16096-88-1
• 化学式: C₁₄H₉F₅N₂O₂S
• 分子量: 364.296
• InChiKey: WHELWHBOHCBPRE-UHFFFAOYSA-N

物化性质

• 熔点：
  160-161 °C
• 沸点：
  419.5±55.0 °C(Predicted)
• 密度：
  1.49±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  66.9
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2,3,4,5,6-pentafluorobenzaldehyde p-tosylhydrazone 在 sodium hydride 作用下， 生成 (五氟苯基)重氮甲烷
  参考文献：
  名称：

  Meese, Claus O., Liebigs Annalen der Chemie, 1985, # 8, p. 1711 - 1714

  摘要：

  DOI：
• 作为产物：
  描述：

  五氟苯甲醛 、 对甲苯磺酰肼 以 甲醇 为溶剂， 反应 3.0h， 以82%的产率得到2,3,4,5,6-pentafluorobenzaldehyde p-tosylhydrazone
  参考文献：
  名称：

  通过 Co(II) 基金属自由基催化，用原位供体取代的重氮试剂进行烯烃的不对称自由基环丙烷化

  摘要：

  在碱存在下由磺酰腙原位生成的供体取代的重氮试剂可以作为 Co(II) 基金属自由基催化 (MRC) 的合适自由基前体。 D2-对称手性卟啉的钴(II)络合物[Co(3,5-DitBu-Xu(2'-Naph)Phyrin)]是一种有效的金属自由基催化剂，能够活化不同的N-芳基磺酰腙进行不对称自由基环丙烷化广泛的烯烃，以高产率提供相应的环丙烷，并有效控制非对映选择性和对映选择性。这种基于 Co(II) 的金属自由基体系代表了第一个可以有效利用供体型重氮试剂进行不对称烯烃环丙烷化的催化方案。

  DOI：

  10.1021/jacs.6b11336

文献信息

• Transition-Metal-Catalyzed Formation of <i>trans </i>Alkenes via Coupling of Aldehydes
  作者：Shifa Zhu、Yuanxi Liao、Shizheng Zhu

  DOI：10.1021/ol036197s

  日期：2004.2.1

  [reaction: see text] Rh(2)(OAc)(4) catalyzed the formation of exclusively trans fluorinated alkenes from aldehydes and pentafluorobenzaldehyde tosylhydrazone salts, which were readily prepared from pentafluorobenzaldehyde using the Bamford-Stevens reaction. A series of pentafluorophenyl-containing alkenes were synthesized from aldehydes in moderate to good yields under mild reaction conditions in a

  [反应：见正文] Rh（2）（OAc）（4）催化了醛和五氟苯甲醛甲苯磺酰salts盐的完全反式氟化烯烃的形成，它们很容易使用Bamford-Stevens反应由五氟苯甲醛制备。在温和的反应条件下，通过一锅反应，由醛以中等至良好的收率合成了一系列含五氟苯基的烯烃。这是首次报道将两种不同的醛偶合以仅形成反式烯烃。
• Serendipitous discovery of novel imidazolopyrazole scaffold as selective androgen receptor modulators
  作者：Xuqing Zhang、Xiaojie Li、George F. Allan、Tifanie Sbriscia、Olivia Linton、Scott G. Lundeen、Zhihua Sui

  DOI：10.1016/j.bmcl.2006.10.035

  日期：2007.1

  A novel imidazolopyrazole derivative has been fortuitously discovered as potent selective androgen receptor modulator with in vivo efficacy. (c) 2006 Elsevier Ltd. All rights reserved.
• Meese, Claus O., Liebigs Annalen der Chemie, 1985, # 8, p. 1711 - 1714
  作者：Meese, Claus O.

  DOI：——

  日期：——
• Asymmetric Radical Cyclopropanation of Alkenes with In Situ-Generated Donor-Substituted Diazo Reagents via Co(II)-Based Metalloradical Catalysis
  作者：Yong Wang、Xin Wen、Xin Cui、Lukasz Wojtas、X. Peter Zhang

  DOI：10.1021/jacs.6b11336

  日期：2017.1.25

  Donor-substituted diazo reagents, generated in situ from sulfonyl hydrazones in the presence of base, can serve as suitable radical precursors for Co(II)-based metalloradical catalysis (MRC). The cobalt(II) complex of D2-symmetric chiral porphyrin [Co(3,5-DitBu-Xu(2'-Naph)Phyrin)] is an efficient metalloradical catalyst that is capable of activating different N-arylsulfonyl hydrazones for asymmetric radical

  在碱存在下由磺酰腙原位生成的供体取代的重氮试剂可以作为 Co(II) 基金属自由基催化 (MRC) 的合适自由基前体。 D2-对称手性卟啉的钴(II)络合物[Co(3,5-DitBu-Xu(2'-Naph)Phyrin)]是一种有效的金属自由基催化剂，能够活化不同的N-芳基磺酰腙进行不对称自由基环丙烷化广泛的烯烃，以高产率提供相应的环丙烷，并有效控制非对映选择性和对映选择性。这种基于 Co(II) 的金属自由基体系代表了第一个可以有效利用供体型重氮试剂进行不对称烯烃环丙烷化的催化方案。
• Laser Flash Photolysis Study of Phenylcarbene and Pentafluorophenylcarbene
  作者：Atnaf Admasu、Anna Dóra Gudmundsdóttir、Matthew S. Platz

  DOI：10.1021/jp963332s

  日期：1997.5.1

  Laser flash photolysis (LFP) (XeCl, 308 nm, 17 ns) of phenyldiazomethane and pentafluorophenyldiazomethane releases phenylcarbene (PC) and pentafluorophenylcarbene (PFPC), respectively. In acetonitrile solvent the carbenes react rapidly to form nitrile ylides which have convenient absorption maxima for optical detection (lambda(max)=350 nm). Phenylcarbene and pentafluorophenylcarbene each react with acetonitrile with an absolute rate constant of 2.4x10(6) M-1 s(-1) in CF2ClCFCl2 (Freon-113) at ambient temperature. The lifetimes of spin-equilibrated PC and PFPC are 190 and 500 ns in Freon-113, respectively. and the lifetime of each carbene is deduced to be 22 ns in neat acetonitrile. LFP of phenyl and pentafluorophenyldiazomethane in the presence of pyridine leads to the expected pyridine ylide. The observed absolute rate constants of reaction of spin equilibrated PC and PFPC with pyridine are 1.9 x 10(7) and 5.1 x 10(7) M-1 s(-1), respectively, in Freon-113 at ambient temperature. From this data, one can deduce singlet-triplet splittings (Delta G(ST), 298 K) of 2.3 and 3.1 kcal/mol for PC and PFPC, respectively, which is the difference in energy between the triplet minimum and the point of intersection of the singlet and triplet carbene plus pyridine surfaces. LFP of phenyldiazomethane and pentafluorophenyldiazomethane in acetonitrile containing carbene scavengers (e.g., alcohols, alkenes, and silanes) gives reduced yields of nitrile ylides. Analysis of the yield of ylide as a function of quencher by the Stern-Volmer method gives k(Q) tau values of carbene quenching. Low-temperature (77 K) photolysis of pentafluorophenyldiazomethane generates the persistent EPR spectrum of triplet pentafluorophenylcarbene which is the ground state of this carbene. However, photolysis of pentafluorophenyldiazomethane at ambient temperature generates stable reaction products derived from capture of singlet pentafluorophenylcarbene. Thus the properties of pentafluorophenylcarbene are remarkably similar to those of phenylcarbene. Each carbene has a triplet ground state but reacts in solution at ambient temperature through a low-lying excited singlet state. The lack of a fluorine substituent effect on the behavior of phenylcarbene is compared to that in singlet phenylnitrene.