(五氟苯基)重氮甲烷 | 7651-11-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (五氟苯基)重氮甲烷
• 英文名称: pentafluorophenyl diazomethane
• 英文别名: 1-(Pentafluorphenyl)diazomethane；1-(diazomethyl)-2,3,4,5,6-pentafluorobenzene
• CAS: 7651-11-8
• 化学式: C₇HF₅N₂
• 分子量: 208.09
• InChiKey: PFNFRCKGOKJUBH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (五氟苯基)重氮甲烷 在 lithium hexamethyldisilazane 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 0.5h， 生成 N-[[di(propan-2-yl)amino]-[(2,3,4,5,6-pentafluorophenyl)methylidyne]-lambda5-phosphanyl]-N-propan-2-ylpropan-2-amine
  参考文献：
  名称：

  （膦基）（芳基）卡宾：芳基取代基对其稳定模式的影响

  摘要：

  广泛的（膦基）（芳基）卡宾，1b-d、10a,b 和 14a,b，是通过其重氮前体的光解制备的。通过实验和理论研究了芳环的空间和电子性质对这些卡宾的结构和稳定性的影响。在研究的不同稳定模式中，那些具有受体和旁观者芳基取代基的稳定模式产生稳定的或至少持久的卡宾，可以通过经典光谱方法完全表征。与此形成鲜明对比的是，以供体芳环为特征的新取代模式会产生非常短暂的卡宾。

  DOI：

  10.1021/ja0281986
• 作为产物：
  描述：

  五氟苯甲醛 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 48.07h， 生成 (五氟苯基)重氮甲烷
  参考文献：
  名称：

  醛与全氟苯基重氮甲烷通过碲化钇反应，由Rh 2（OAc）4催化形成反式烯烃

  摘要：

  Rh 2（OAc）4可通过全氟苯基重氮甲烷与活化的芳基醛通过硫代叶立德中间体的反应催化含全氟苯基的反式环氧化物的形成。相反，在相同的反应条件下，通过碲化碲中间体以优异的产率获得了反式烯烃。

  DOI：

  10.1016/j.tetlet.2006.06.065

文献信息

• New Azoniaboratacyclopropanes from (F3C)2BNMe2 and Diazomethane Derivatives – Structure ofcyclo-(F3C)2B–CPh2–NMe2 and HOB(CF3)2–CHC6F5–NHMe2
  作者：David J. Brauer、Hans Bürger、Silke Buchheim-Spiegel、Gottfried Pawelke

  DOI：10.1002/(sici)1099-0682(19990202)1999:2<255::aid-ejic255>3.0.co;2-f

  日期：1999.2.2

  cyclo-(F3C)2B–CR1R2–NMe2 [R1 = R2 = C6H5 (2a); R1/R2 = C12H8 (2b); R1 = H, R2 = C6H5 (2c), 4-FC6H4 (2d), 3-FC6H4 (2e), 2-FC6H4 (2f), C6F5 (2g), iPr (2h), tBu (2i); R1 = Me, R2 = C(=O)OMe (2j), C(=O)OEt (2k)] have been obtained from (F3C)2BNMe2 (1) and diazomethanes R1R2CN2. In contrast to compound 2a, the B–N bonds of 2b–2k hydrolyze to form the zwitterionic species Me2NH–CR1R2–B(CF3)2OH (3b–3k). The

  1,1-二甲基-2,2-双(三氟甲基)氮硼酸环丙烷，环-(F3C)2B–CR1R2–NMe2 [R1 = R2 = C6H5 (2a); R1/R2 = C12H8 (2b)；R1 = H、R2 = C6H5 (2c)、4-FC6H4 (2d)、3-FC6H4 (2e)、2-FC6H4 (2f)、C6F5 (2g)、iPr (2h)、tBu (2i)；R1 = Me, R2 = C(=O)OMe (2j), C(=O)OEt (2k)] 已从 (F3C)2BNMe2 (1) 和重氮甲烷 R1R2CN2 中获得。与化合物 2a 不同，2b-2k 的 B-N 键水解形成两性离子物质 Me2NH-CR1R2-B(CF3)2OH (3b-3k)。重氮乙酸酯 HC(N2)C(=O)OMe 和 HC(N2)C(=O)OtBu 与 1 反应形成三元环，三元环迅速水解形成 Me2NH-CR1R2-B(CF3)2OH
• The First Example of Catalytic Aziridination Mediated by Arsonium Ylides: Preparation of<i>trans-</i>Pentafluorophenyl-Containing Aziridines
  作者：Shizheng Zhu、Shifa Zhu、Yuanxi Liao

  DOI：10.1055/s-2005-868498

  日期：——

  formation of aziridines from tosyl imines and aromatic diazo compounds in a one-pot reaction. It is the first example of catalytic aziridination mediated by arsonium ylides. It gave aziridines in excellent diastereoselectivity with pentafluorophenyl diazomethane as the substrate. This catalytic reaction is complementary with the reaction mediated by sulfur ylides.

  三苯基胂催化甲苯磺酰亚胺和芳族重氮化合物在一锅反应中形成氮丙啶。这是由砷叶立德介导的催化氮丙啶化的第一个例子。它以五氟苯基重氮甲烷为底物以优异的非对映选择性得到氮丙啶。这种催化反应与硫叶立德介导的反应互补。
• Insertion Reactions of Diazomethanes and Electrophilic Boranes
  作者：Rebecca C. Neu、Douglas W. Stephan

  DOI：10.1021/om2011613

  日期：2012.1.9

  The electrophilic pentafluoroarylboranes B-(C6F5)(3), PhB(C6F5)(2), and ClB(C6F5)(2) react with (trimethylsilyl) diazomethane, diphenyldiazomethane, or (pentafluorophenyl)diazomethane, affording insertion into the one or two B-C bonds in a facile and high-yielding route to the boranes (Me3SiCH(C6F5))B(C6F5)(2), (Me3SiCH-(C6F5))(2)B(C6F5), (Me3SiCH(C6F5))(Me3SiCH(Ph))B-(C6F5), (C6F5)ClB(CPh2(C6F5)), and (C6F5)(2)B(CH(C6F5)(2)).
• Meese, Claus O., Liebigs Annalen der Chemie, 1985, # 8, p. 1711 - 1714
  作者：Meese, Claus O.

  DOI：——

  日期：——
• 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.