anti-6,6-dimethylhepta-2,4-diynal tosylhydrazone | 1243147-56-9

• 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: anti-6,6-dimethylhepta-2,4-diynal tosylhydrazone
• 英文别名: 6,6-dimethylhepta-2,4-diynal tosylhydrazone；N-[(E)-6,6-dimethylhepta-2,4-diynylideneamino]-4-methylbenzenesulfonamide
• CAS: 1243147-56-9
• 化学式: C₁₆H₁₈N₂O₂S
• 分子量: 302.397
• InChiKey: GDWIRVVOPBNMAR-GHRIWEEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  66.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  anti-6,6-dimethylhepta-2,4-diynal tosylhydrazone 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 0.5h， 生成 1-Diazo-6,6-dimethyl-hepta-2,4-diin
  参考文献：
  名称：

  二炔基碳烯衍生物：三重态叔丁基戊二炔（t -Bu-C≡C-C̈-C≡C-H）和二甲基戊二炔（Me-C≡C-C̈-C≡C-Me）的生成和表征

  摘要：

  由相应的重氮化合物前体以光化学方式制备了三重碳烯叔丁基戊二炔（t- BuC 5 H，1a）和二甲基戊二炔（MeC 5 Me，1b），并在低温基质（N 2或Ar）中于10 K下进行了光谱研究。这些物质的红外光谱，电子吸收光谱和电子顺磁共振光谱显示出与先前记录的戊二炔（HC 5 H）和甲基戊二炔（MeC 5 H）的光谱相似之处。EPR光谱产生零场分裂参数，这对于具有轴对称性的三重态卡宾是典型的（t-BuC 5 H，1a：| D / hc | = 0.61厘米-1，| E / hc | 〜0 cm -1；MeC 5 Me，1b：| D / hc | = 0.62 cm -1，| E / hc | 〜0 cm -1）。电子光谱的特征是在近紫外区和可见光区（350-430 nm）内具有弱的吸收（T 1 ←T 0），具有扩展的电子振动过程。几个-C 5的电子跃迁-对卡宾进行比较，发现过渡波长明显依赖于碳链的烷基取代水平。在O

  DOI：

  10.1021/jo101096n
• 作为产物：
  描述：

  6,6-dimethyl-hepta-2,4-diynal 、 对甲苯磺酰肼 以 乙醚 、 二氯甲烷 为溶剂， 以0.171 g的产率得到syn-6,6-dimethylhepta-2,4-diynal tosylhydrazone
  参考文献：
  名称：

  Synthesis of Simple Diynals, Diynones, Their Hydrazones, and Diazo Compounds: Precursors to a Family of Dialkynyl Carbenes (R¹—C≡C—C̈—C≡C—R²)

  摘要：

  A variety of substituted pentadiynols, -diynals, and -diynones have been prepared en route to precursors to dialkynyl carbenes (R-1-C C-C-C C-R-2). In light of the marginal stability associated with these simple systems, several strategies were required to assemble the carbon backbones. The requisite five-carbon skeletons were prepared using 4 + 1, 3 2, 2 + 2 + 1, and 2 + 1 + 1 + 1 coupling methodologies. The Dess Martin periodinane serves as an excellent method for the oxidation of pentadiynols to diynals and diynones, although many of the oxidized products are sufficiently reactive that they were not isolated; rather, they were generated in situ and intercepted with nucleophiles such as tosylhydrazide or trisylhydrazide. The hydrazone derivatives are generally reliable precursors to diazo compounds and carbenes, although cyclization of the hydrazone to afford a pyrazole can be a complicating factor in certain instances.

  DOI：

  10.1021/jo101125y

文献信息

• Synthesis of Simple Diynals, Diynones, Their Hydrazones, and Diazo Compounds: Precursors to a Family of Dialkynyl Carbenes (R¹—C≡C—C̈—C≡C—R²)
  作者：Nathan P. Bowling、Nicola J. Burrmann、Robert J. Halter、Jonathan A. Hodges、Robert J. McMahon

  DOI：10.1021/jo101125y

  日期：2010.10.1

  A variety of substituted pentadiynols, -diynals, and -diynones have been prepared en route to precursors to dialkynyl carbenes (R-1-C C-C-C C-R-2). In light of the marginal stability associated with these simple systems, several strategies were required to assemble the carbon backbones. The requisite five-carbon skeletons were prepared using 4 + 1, 3 2, 2 + 2 + 1, and 2 + 1 + 1 + 1 coupling methodologies. The Dess Martin periodinane serves as an excellent method for the oxidation of pentadiynols to diynals and diynones, although many of the oxidized products are sufficiently reactive that they were not isolated; rather, they were generated in situ and intercepted with nucleophiles such as tosylhydrazide or trisylhydrazide. The hydrazone derivatives are generally reliable precursors to diazo compounds and carbenes, although cyclization of the hydrazone to afford a pyrazole can be a complicating factor in certain instances.
• Dialkynyl Carbene Derivatives: Generation and Characterization of Triplet <i>tert</i>-Butylpentadiynylidene (<i>t</i>-Bu−C≡C−C̈−C≡C−H) and Dimethylpentadiynylidene (Me−C≡C−C̈−C≡C−Me)
  作者：Phillip S. Thomas、Nathan P. Bowling、Nicola J. Burrmann、Robert J. McMahon

  DOI：10.1021/jo101096n

  日期：2010.10.1

  spectroscopically in cryogenic matrices (N2 or Ar) at 10 K. The infrared, electronic absorption, and electron paramagnetic resonance spectra of these species exhibit numerous similarities to the spectra of pentadiynylidene (HC5H) and methylpentadiynylidene (MeC5H) recorded previously. EPR spectra yield zero-field splitting parameters that are typical for triplet carbenes with axial symmetry (t-BuC5H, 1a:

  由相应的重氮化合物前体以光化学方式制备了三重碳烯叔丁基戊二炔（t- BuC 5 H，1a）和二甲基戊二炔（MeC 5 Me，1b），并在低温基质（N 2或Ar）中于10 K下进行了光谱研究。这些物质的红外光谱，电子吸收光谱和电子顺磁共振光谱显示出与先前记录的戊二炔（HC 5 H）和甲基戊二炔（MeC 5 H）的光谱相似之处。EPR光谱产生零场分裂参数，这对于具有轴对称性的三重态卡宾是典型的（t-BuC 5 H，1a：| D / hc | = 0.61厘米-1，| E / hc | 〜0 cm -1；MeC 5 Me，1b：| D / hc | = 0.62 cm -1，| E / hc | 〜0 cm -1）。电子光谱的特征是在近紫外区和可见光区（350-430 nm）内具有弱的吸收（T 1 ←T 0），具有扩展的电子振动过程。几个-C 5的电子跃迁-对卡宾进行比较，发现过渡波长明显依赖于碳链的烷基取代水平。在O