N'-((2R,5S,E)-2-isopropyl-5-methylcyclohexylidene)-4-methylbenzenesulfonohydrazide | 144786-60-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: N'-((2R,5S,E)-2-isopropyl-5-methylcyclohexylidene)-4-methylbenzenesulfonohydrazide
• 英文别名: trans-menthonetosylhydrazone；menthonetosylhydrazone；4-methyl-N-[(E)-[(2S,5R)-5-methyl-2-propan-2-ylcyclohexylidene]amino]benzenesulfonamide
• CAS: 144786-60-7
• 化学式: C₁₇H₂₆N₂O₂S
• 分子量: 322.472
• InChiKey: BXRWSQVTYFNXCJ-BRDLOHTJSA-N

物化性质

• 沸点：
  444.6±38.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 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：

  N'-((2R,5S,E)-2-isopropyl-5-methylcyclohexylidene)-4-methylbenzenesulfonohydrazide 在 palladium on activated charcoal lithium aluminium tetrahydride 、 正丁基锂 、 四甲基乙二胺 、 氨 、 氢气 、 lithium 、 sodium hydride 、 氯化铵 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 为溶剂， 反应 3.84h， 生成 (7S,10R)-trans-calamenene
  参考文献：
  名称：

  Aromatic annulation on the p-menthane monoterpenes: enantiospecific synthesis of the trans and cis isomers of calamenene and 8-hydroxycalamenene

  摘要：

  A new enantiospecific route to sesquiterpenes of the calamenene family is described. The synthetic pathway starts from easily available 3-oxygenated-p-menthane monoterpenes and affords the title compounds by a homologation-benzannulation sequence. The trans and cis isomers of the natural compounds calamenene and 8-hydroxycalamenene were obtained in enantiopure form starting from (-)-menthone and (+)-isomenthone, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.05.037
• 作为产物：
  描述：

  (-)-薄荷酮 、 对甲苯磺酰肼 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 N'-((2R,5S,E)-2-isopropyl-5-methylcyclohexylidene)-4-methylbenzenesulfonohydrazide
  参考文献：
  名称：

  Aromatic annulation on the p-menthane monoterpenes: enantiospecific synthesis of the trans and cis isomers of calamenene and 8-hydroxycalamenene

  摘要：

  A new enantiospecific route to sesquiterpenes of the calamenene family is described. The synthetic pathway starts from easily available 3-oxygenated-p-menthane monoterpenes and affords the title compounds by a homologation-benzannulation sequence. The trans and cis isomers of the natural compounds calamenene and 8-hydroxycalamenene were obtained in enantiopure form starting from (-)-menthone and (+)-isomenthone, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.05.037

文献信息

• Stereoselective Csp³-Csp²Bond-Forming Reactions by Transition-Metal-Free Reductive Coupling of Cyclic Tosylhydrazones with Boronic Acids
  作者：Manuel Plaza、M. Carmen Pérez-Aguilar、Carlos Valdés

  DOI：10.1002/chem.201600837

  日期：2016.4.25

  The reactions between alkenylboronic acids and tosylhydrazones derived from substituted cyclohexanones lead to the construction of disubstituted cyclohexanes with total regio‐ and stereoselectivity. In these transition‐metal‐free processes, a Csp3−Csp2 and Csp3−H bond are formed on the same carbon atom. The stereoselective reaction is general for 2‐, 3‐, and 4‐substituted cyclohexanone tosylhydrazones

  烯基硼酸与衍生自取代环己酮的甲苯磺酰nes之间的反应导致构建具有总区域和立体选择性的双取代环己烷。在这些无过渡金属的过程中，Csp 3 -Csp 2和Csp 3 -H键在同一碳原子上形成。立体选择性反应通常适用于2、3和4取代的环己酮甲苯磺酰nes以及2取代的环戊酮。但是，没有观察到无环衍生物的立体选择性。DFT计算模型表明，反应的立体选择性是通过硼酸通过最赤道的轨迹在其最稳定的椅子构象上对重氮环己烷的反应来确定的。
• Garner, Charles M.; Mossman, Brett C.; Prince, Mark E., Tetrahedron Letters, 1993, vol. 34, # 27, p. 4273 - 4276
  作者：Garner, Charles M.、Mossman, Brett C.、Prince, Mark E.

  DOI：——

  日期：——
• Structure analyses of menthone- and isomenthone-tosylhydrazones, C17H26N2O2S
  作者：D. F. Mullica、C. M. Garner、M. E. Prince、B. C. Mossman、E. L. Sappenfield

  DOI：10.1007/bf01161333

  日期：1992.10

  The crystal and molecular structures of two configurational isomers of the title compound have been determined by three-dimensional, single-crystal X-ray diffractometry. Both (2S,5R)- and (2R,5R)-4-methylbenzenesulfonic acid-[5-methyl-2-(1-methylethyl)cyclohexylidene] hydrazide (hereafter referred to as menthone- and isomenthone-tosylhydrazone, or I and II, respectively) crystallize in the orthorhombic space group P2(1)2(1)2(1) (No. 19, D2(4)) with four formula units per cell and a = 5.209(1), b = 17.501(1), c = 20.154(1)angstrom and a = 5.281(1), b = 17.300(1), 20.422(1)angstrom, respectively. The phase problems were solved by direct methods and the respective final full-matrix least-squares refinements of 1767 and 3010 unique reflections converged to R = 0.046 and 0.052. In both structures. the toluenesulfonamide group occupies a position anti to the more substituted side of the cyclohexyl ring, the C(16)-C(11)-N(2) angles are significantly wider than 120', and each sulfonamide nitrogen (1) atom appears to exhibit a distorted trigonal pyramidal geometry. The structures differ in the positioning of the isopropyl and methyl substituents on the cyclohexane ring, with the trans isomer I having both groups equatorial, while the cis isomer II exhibits an axial isopropyl group. The molecules in the crystal lattice are held together by van der Waals forces. X-ray powder diffraction, conoscopic, infrared, and H-1 and C-13 NMR analyses have been performed.