1,2-bis(tert-butoxycarbonyl)-1-(3,4,5-tridodecylsulfanylphenyl)hydrazine | 1374877-04-9

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1,2-bis(tert-butoxycarbonyl)-1-(3,4,5-tridodecylsulfanylphenyl)hydrazine
• CAS: 1374877-04-9
• 化学式: C₅₂H₉₆N₂O₄S₃
• 分子量: 909.543
• InChiKey: MLRABLBZSZYLMO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.91
• 重原子数：
  61.0
• 可旋转键数：
  37.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  67.87
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  1,2-bis(tert-butoxycarbonyl)-1-(3,4,5-tridodecylsulfanylphenyl)hydrazine 在 吡啶 、 三氟甲磺酸 、 溶剂黄146 作用下， 以 乙醇 、 二氯甲烷 、 2,2,2-三氟乙醇 为溶剂， 反应 0.03h， 生成 3,4,5-tridodecylsulfanylbenzaldehyde α-chloroformyl-3',4',5'-tridodecylsulfanylphenylhydrazone
  参考文献：
  名称：

  Induction of Columnar Discotic Behavior in Verdazyl Radicals with Alkylsulfanyl Substituents

  摘要：

  Substitution of the 1,3,5-triphenyl-6-oxoverdazyl radical with n-alkylsulfanyl groups lead to derivatives 1[n], which exhibit a columnar rectangular phase (Col(r) ) below 60 degrees C. Compounds 1[n] have a broad absorption band in the visible region with maxima at 540 and 610nm and redox potentials E0/+1 (1/2) = +0.99V and E0/-1 (1/2) = -0.45V vs. SCE. Time-of-flight (TOF) investigation of 1[8] revealed hole mobility of (h) = 1.52 x 10(-3) cm(2) V-1 s(-1) in the columnar phase with an activation energy E-a = 0.06 +/- 0.01eV. Magnetization studies of 1[8] demonstrated nearly ideal paramagnetic behavior in both solid and fluid phases above 200K and weak antiferromagnetic interactions at low temperatures. Verdazyl derivatives 1[n] were prepared in a sequence of reactions starting from 1-bromo-3,4,5-trifluorobenzene by alkylsulfanylation, followed by hydrazinylation, and finally 6-oxoverdazyl ring assembly using the Milcent method.

  DOI：

  10.1080/10426507.2012.736896
• 作为产物：
  描述：

  sodium dodecanethiolate 在 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 生成 1,2-bis(tert-butoxycarbonyl)-1-(3,4,5-tridodecylsulfanylphenyl)hydrazine
  参考文献：
  名称：

  Induction of Columnar Discotic Behavior in Verdazyl Radicals with Alkylsulfanyl Substituents

  摘要：

  Substitution of the 1,3,5-triphenyl-6-oxoverdazyl radical with n-alkylsulfanyl groups lead to derivatives 1[n], which exhibit a columnar rectangular phase (Col(r) ) below 60 degrees C. Compounds 1[n] have a broad absorption band in the visible region with maxima at 540 and 610nm and redox potentials E0/+1 (1/2) = +0.99V and E0/-1 (1/2) = -0.45V vs. SCE. Time-of-flight (TOF) investigation of 1[8] revealed hole mobility of (h) = 1.52 x 10(-3) cm(2) V-1 s(-1) in the columnar phase with an activation energy E-a = 0.06 +/- 0.01eV. Magnetization studies of 1[8] demonstrated nearly ideal paramagnetic behavior in both solid and fluid phases above 200K and weak antiferromagnetic interactions at low temperatures. Verdazyl derivatives 1[n] were prepared in a sequence of reactions starting from 1-bromo-3,4,5-trifluorobenzene by alkylsulfanylation, followed by hydrazinylation, and finally 6-oxoverdazyl ring assembly using the Milcent method.

  DOI：

  10.1080/10426507.2012.736896

文献信息

• Synthesis of oleophilic electron-rich phenylhydrazines
  作者：Aleksandra Jankowiak、Piotr Kaszyński

  DOI：10.3762/bjoc.8.29

  日期：——

  Phenylhydrazines 1 substituted with two or three long-chain alkyl, alkoxy or alkylsulfanyl groups were successfully prepared by acid-induced removal of the Boc group in hydrazides 2. The reaction is carried out with 5 equivalents of TfOH in CF₃CH₂OH/CH₂Cl₂ at −40 °C for 1.5 min. Under these conditions, the deprotected hydrazine 1 is fully protonated, which increases its stability in the reaction medium. The hydrazines were isolated in 60–86% yields and purities >90%. The hydrazides 2 were obtained in 43–71% yields from aryl bromides 5, which were lithiated with t-BuLi and subsequently reacted with di-tert-butyl azodicarboxylate (DTBAD).

  苯基肼1通过酸诱导去除肼酰胺2中的Boc基团，成功地取代了两个或三个长链烷基、烷氧基或烷基硫基团。反应在CF₃CH₂OH/CH₂Cl_{2>中以5当量的TfOH在-40°C下进行1.5分钟。在这些条件下，去保护的肼1被完全质子化，增加了其在反应介质中的稳定性。肼类产物以60-86%的产率和纯度>90%的纯度分离。肼酰胺2以43-71%的产率从芳基溴化物5中获得，该溴化物通过与t-BuLi锂化，然后与双tert-丁基叠氮二羧酸酯（DTBAD）反应得到。}