3,6-dibromo-9-tetradecyl-9H-carbazole | 1034311-85-7

• 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: 3,6-dibromo-9-tetradecyl-9H-carbazole
• CAS: 1034311-85-7
• 化学式: C₂₆H₃₅Br₂N
• 分子量: 521.379
• InChiKey: PVUMJPSIZXKYSD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.02
• 重原子数：
  29.0
• 可旋转键数：
  13.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  4.93
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  3,6-dibromo-9-tetradecyl-9H-carbazole 、 在 tris-(dibenzylideneacetone)dipalladium(0) 、 三叔丁基膦 、 potassium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 24.0h， 以71%的产率得到
  参考文献：
  名称：

  Self-Assembly of Nanometer-Sized Boroxine Cages from Diboronic Acids

  摘要：

  By use of the reversible trimerization of boronic acids, the series of boroxine cages 3-mer, 6-mer, and 12-mer were constructed from rationally designed diboronic acids whose bond angles between two C-B bonds are 60 degrees, 84 degrees, and 117 degrees, respectively. Boroxine cages 6-mer and 12-mer have 1.5 and 2.5 nm sized cavities, respectively.

  DOI：

  10.1021/jacs.5b02716
• 作为产物：
  描述：

  3,6-二溴咔唑 、 溴代十四烷 在 四丁基碘化铵 、 sodium hydroxide 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以90%的产率得到3,6-dibromo-9-tetradecyl-9H-carbazole
  参考文献：
  名称：

  Self-Assembly of Nanometer-Sized Boroxine Cages from Diboronic Acids

  摘要：

  By use of the reversible trimerization of boronic acids, the series of boroxine cages 3-mer, 6-mer, and 12-mer were constructed from rationally designed diboronic acids whose bond angles between two C-B bonds are 60 degrees, 84 degrees, and 117 degrees, respectively. Boroxine cages 6-mer and 12-mer have 1.5 and 2.5 nm sized cavities, respectively.

  DOI：

  10.1021/jacs.5b02716

文献信息

• Synthetic, Mechanistic, and Computational Investigations of Nitrile-Alkyne Cross-Metathesis
  作者：Andrea M. Geyer、Eric S. Wiedner、J. Brannon Gary、Robyn L. Gdula、Nicola C. Kuhlmann、Marc J. A. Johnson、Barry D. Dunietz、Jeff W. Kampf

  DOI：10.1021/ja800020w

  日期：2008.7.1

  The terminal nitride complexes NW(OC(CF3)(2)Me)(3)(DME) (1-DME), [Li(DME)(2)][NW(OC(CF3)(2)Me)(4)] (2), and [NW(OCMe2CF3)(3)](3) (3) were prepared in good yield by salt elimination from [NWCl3](4). X-ray structures revealed that 1-DME and 2 are monomeric in the solid state. All three complexes catalyze the cross-metathesis of 3-hexyne with assorted nitriles to form propionitrile and the corresponding alkyne. Propylidyne and substituted benzylidyne complexes RCW(OC(CF3)(2)Me)(3) were isolated in good yield upon reaction of 1-DME with 3-hexyne or 1-aryl-1-butyne. The corresponding reactions failed for 3. Instead, EtCW(OC(CF3)Me-2)(3) (6) was prepared via the reaction of W-2(OC(CF3)Me-2)(6) with 3-hexyne at 95 degrees C. Benzylidyne complexes of the form ArCW(OC(CF3)Me-2)(3) (Ar = aryl) then were prepared by treatment of 6 with the appropriate symmetrical alkyne ArCCAr. Three coupled cycles for the interconversion of 1-DME with the corresponding propylidyne and benzylidyne complexes via [2 + 2] cycloaddition-cycloreversion were examined for reversibility. Stoichiometric reactions revealed that both nitrile-alkyne cross-metathesis (NACM) cycles as well as the alkyne cross-metathesis (ACM) cycle operated reversibly in this system. With catalyst 3, depending on the aryl group used, at least one step in one of the NACM cycles was irreversible. In general, catalyst 1-DME afforded more rapid reaction than did 3 under comparable conditions. However, 3 displayed a slightly improved tolerance of polar functional groups than did 1-DME. For both 11-DME and 3, ACM is more rapid than NACM under typical conditions. Alkyne polymerization (AP) is a competing reaction with both 1-DME and 3. It can be suppressed but not entirely eliminated via manipulation of the catalyst concentration. As AP selectively removes 3-hexyne from the system, tandem NACM-ACM-AP can be used to prepare symmetrically substituted alkynes with good selectivity, including an arylene-ethynylene macrocycle. Alternatively, unsymmetrical alkynes of the form EtCCR (R variable) can be prepared with good selectivity via the reaction of RCN with excess 3-hexyne under conditions that suppress AP. DFT calculations support a [2 + 2) cycloaddition-cycloreversion mechanism analogous to that of alkyne metathesis. The barrier to azametalacyciobutadiene ring formation/breakup is greater than that for the corresponding metalacyclobutadiene. Two distinct high-energy azametalacyclobutadiene intermediates were found. These adopted a distorted square pyramidal geometry with significant bond localization.