13C-diphenyldiazomethane | 5134-76-9

• 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: 13C-diphenyldiazomethane
• 英文别名: 1,1a(2)-(Diazomethylene-13C)bis[benzene]；[diazo(phenyl)(113C)methyl]benzene
• CAS: 5134-76-9
• 化学式: C₁₃H₁₀N₂
• 分子量: 195.225
• InChiKey: ITLHXEGAYQFOHJ-KCKQSJSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  15.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  36.4
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  13C-diphenyldiazomethane 以 gaseous matrix 为溶剂， 生成
  参考文献：
  名称：

  Matrix Isolation of Diphenylsulfene and Diphenyl-α-sultine

  摘要：

  Diphenylsulfene (5) and diphenyl-alpha-sultine 6 were generated in cryogenic matrices by three independent routes: (i) the thermal reaction of diphenylcarbene (8) and SO2, (ii) the photochemically induced hetero Wolff rearrangement of sulfonylcarbene 11, and (iii) oxygen transfer from ozone to diphenylsulfine 16. Isotopic labeling with C-13 and O-18 allows for the assignment of several characteristic IR vibrations of 5. Irradiation with lambda > 375 nm results in the rearrangement of 5 to 6, which is the first alpha-sultine that has been characterized spectroscopically. The final Product on UV irradiation of 6 is benzophenone (9) and sulfur monoxide.

  DOI：

  10.1021/ja962949k
• 作为产物：
  描述：

  在 sodium hydride 作用下， 以 二氯甲烷 为溶剂， 生成 13C-diphenyldiazomethane
  参考文献：
  名称：

  联苯激活B-F键：硼和碳之间可逆的1,2-氟迁移

  摘要：

  在低温基质中进行的实验表明，三重态二苯卡宾通过两步反应插入到BF 3的非常牢固的BF键中。第一步是在二苯卡宾的单线态和BF 3之间形成牢固结合的路易斯酸碱配合物。该步骤涉及将卡宾的自旋态从三重态转化为单重态。第二步需要可见光光化学活化，以在卡宾中心正式插入到BF 3的形成过程中诱导1,2-F从硼迁移到相邻的碳原子。1,2-F迁移在短波长紫外线照射下是可逆的，因此导致回到路易斯酸碱加合物。

  DOI：

  10.1002/anie.201610179

文献信息

• Synthesis, Structure, and Reactivity of a Gold Carbenoid Complex That Lacks Heteroatom Stabilization
  作者：Robert J. Harris、Ross A. Widenhoefer

  DOI：10.1002/anie.201404882

  日期：2014.8.25

  neutral gold cycloheptatrienyl complex [(P)Au(η1‐C7H7)] (P=P(tBu)2(o‐biphenyl)) with triphenylcarbenium tetrafluoroborate at −80 °C led to the isolation of the cationic gold cycloheptatrienylidene complex [(P)Au(η1‐C7H6)]+ BF4− in 52 % yield, which was characterized in solution and by single‐crystal X‐ray diffraction. This cycloheptatrienylidene complex represents the first example of a gold carbenoid

  从中立金环庚三烯基配合物[（氢化物提取P）的Au（η 1 -C 7 ħ 7）]（P = P（吨丁基）2（ø -联苯）），与三苯基碳鎓四氟硼酸盐在-80℃下导致了隔离的阳离子金cycloheptatrienylidene配合物[（P）的Au（η 1 -C 7 ħ 6）] + BF 4 -以溶液和单晶X射线衍射表征为52％的收率。该环庚三烯亚基络合物代表了金类胡萝卜素络合物的第一个例子，该化合物缺乏电子不足的C1碳原子的共轭杂原子稳定性。该配合物的环庚三烯亚基配体是反应性的。它可以被温和的氢化物供体还原，并在存在吡啶N-氧化物的情况下转化为对苯二酚。
• The Highly Reactive Benzhydryl Cation Isolated and Stabilized in Water Ice
  作者：Paolo Costa、Miguel Fernandez-Oliva、Elsa Sanchez-Garcia、Wolfram Sander

  DOI：10.1021/ja507894x

  日期：2014.11.5

  Diphenylcarbene (DPC) shows a triplet ground-state lying approximately 3 kcal/mol below the lowest singlet state. Under the conditions of matrix isolation at 25 K, DPC reacts with single water molecules embedded in solid argon and switches its ground state from triplet to singlet by forming a strong hydrogen bond. The complex between DPC and water is only metastable, and even at 3 K the carbene center slowly inserts into the OH bond of water to form benzhydryl alcohol via quantum chemical tunneling. Surprisingly, if DPC is generated in amorphous water ice at 3 K, it is protonated instantaneously to give the benzhydryl cation. Under these conditions, the benzhydryl cation is stable, and warming to temperatures above 50 K is required to produce benzhydryl alcohol. Thus, for the first time, a highly electrophilic and extremely reactive secondary carbenium ion can be isolated in a neutral, nucleophilic environment avoiding superacidic conditions.
• Olah, George A.; Alemayehu, Mesfin; Wu, An-Hsiang, Journal of the American Chemical Society, 1992, vol. 114, # 21, p. 8042 - 8045
  作者：Olah, George A.、Alemayehu, Mesfin、Wu, An-Hsiang、Farooq, Omar、Prakash, G.K. Surya

  DOI：——

  日期：——