cyclopropane-1,1-diyldimethanediyl bis(4-methylbenzenesulfonate) | 22308-08-3

• 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: cyclopropane-1,1-diyldimethanediyl bis(4-methylbenzenesulfonate)
• 英文别名: 1,1-Bis(tosyloxymethyl)cyclopropane；[1-[(4-methylphenyl)sulfonyloxymethyl]cyclopropyl]methyl 4-methylbenzenesulfonate
• CAS: 22308-08-3
• 化学式: C₁₉H₂₂O₆S₂
• 分子量: 410.512
• InChiKey: FWGDXXUTFPAPHX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• 海关编码：
  2904100000

反应信息

• 作为反应物：
  描述：

  cyclopropane-1,1-diyldimethanediyl bis(4-methylbenzenesulfonate) 以 melt 为溶剂， 反应 0.25h， 以62%的产率得到2-methylene-1,4-butanediol bis(4-methylbenzenesulfonate)
  参考文献：
  名称：

  Thermolytic rearrangements of 1,1-cyclopropanedimethanol disulfonates: cyclopropylcarbinyl cations revisited

  摘要：

  1,1-Cyclopropanedimethanol dimethanesulfonate (1a) and the corresponding ditosylate lb underwent thermal rearrangement at 110-140-degrees-C after melting. Short reaction time resulted in the formation of mixtures containing 1-(sulfonyloxy)cyclobutanemethanol sulfonates 5a,b (major), starting material, and 2-methylene-1,4-butanediol disulfonates 6a,b. Longer reaction times afforded complete conversion to disulfonates 6a,b, isolated in 49 and 62 % yield, respectively. These reactions are postulated to proceed via initial carbocation formation, presumably interconverting bicylobutonium and cyclopropylcarbinyl cations, which exist as ion pairs in the melt. Crossover experiments with dimesylate la and ditosylate lb offer support for the presence of ion pairs in the melt: internal return competed with external trapping of the intermediate cations. Reaction of la and 2-methylene-1,4-butanediol ditosylate (6b) gave a mixture in which 2-methylene-1,4-butanediol 1-mesylate 4-tosylate (8) predominated over the isomeric 4-mesylate 1-tosylate 7 by a 5:1 ratio. Crossover experiments with 6a and 6b indicated that partial allylic substitution was occurring for the open-chain products under the thermolysis conditions. Reaction of la with excess tetrabutylammonium tosylate at 114-15-degrees-C afforded mixed 1-(sulfonyloxy)cyclobutanemethanol sulfonates and 2-methylene-1,4-butanediol disulfonates formed competitively by internal return and tosylate interception. Acetolysis of la at 42-43-degrees-C afforded predominately products of internal return early on the reaction profile. Longer reaction times afforded predominately monoacetates while reactions run at 108-10-degrees-C afforded substantial amounts of diacetates. Acetolysis of 1-acetoxycyclobutanemethanol mesylate (12a) resulted in the substitution of the mesyloxy group with substantial rearrangement.

  DOI：

  10.1021/jo00063a039
• 作为产物：
  描述：

  1,1-环丙基二羧酸 在 吡啶 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 84.0h， 生成 cyclopropane-1,1-diyldimethanediyl bis(4-methylbenzenesulfonate)
  参考文献：
  名称：

  硫醇-二硫化物交换的结构-反应性关系

  摘要：

  平衡常数由 36 个二硫醇和三硫醇与衍生自 2-巯基乙醇或二硫苏糖醇的二硫化物之间的硫醇-二硫化物交换确定。反应在甲醇-d/水性缓冲液 (pH 7) 或甲醇中进行，在 25°C 下，使用 NMR 光谱跟踪反应。这些数据用于根据还原电位对二硫醇进行排序并推断其结构氧化时由它们形成的二硫化物。二硫醇的还原能力与氧化时形成的含二硫化物环的大小之间存在普遍的相关性：形成六元环的二硫醇还原性最强（K = 103-105 M 相对于氧化的 2-巯基乙醇）；五元和七元环的还原性降低约 1 个数量级。类似于 1 的化合物，2-乙二硫醇在相对稀释的溶液 (- 1 mM) 中形成环状双（二硫化物）二聚体，但在较高浓度下聚合。其他类别的二硫醇在氧化时形成聚合物。

  DOI：

  10.1021/ja00256a040

文献信息

• [EN] PYRAZOLOPYRIMIDINE INHIBITORS OF IRAK4 ACTIVITY<br/>[FR] INHIBITEURS DE L'ACTIVITÉ D'IRAK4 À BASE DE PYRAZOLOPYRIMIDINE
  申请人：MERCK SHARP & DOHME

  公开号：WO2016144846A1

  公开（公告）日：2016-09-15

  The present invention relates to pyrazolopyrimidine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.

  本发明涉及式(I)的IRAK4的吡唑吡咯啉抑制剂，并提供包含这种抑制剂的组合物，以及用于治疗IRAK4介导或相关疾病或病症的方法。
• [EN] THIENOPYRAZINE INHIBITORS OF IRAK4 ACTIVITY<br/>[FR] THÉNOPYRAZINES UTILISÉES COMME INHIBITEURS DE L'ACTIVITÉ DE L'IRAK4
  申请人：MERCK SHARP & DOHME

  公开号：WO2016144849A1

  公开（公告）日：2016-09-15

  The present invention relates to thienopyrazine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.

  本发明涉及式(I)的噻吩并吡嗪作为IRAK4的抑制剂，并提供包含此类抑制剂的组合物，以及用于治疗IRAK4介导的或相关的条件或疾病的方法。
• Synthesis of heterospiranes by cyclization of dinucleophiles with 1,1-bis(tosyloxymethyl)cyclopropane and -cyclobutane
  作者：Sven Rotzoll、Helmut Reinke、Peter Langer

  DOI：10.1016/j.tetlet.2007.11.123

  日期：2008.1

  A variety of heterocyclic spiranes were prepared by cyclization of dinucleophiles with 1,1-bis(tosyloxymethyl)cyclopropane and -cyclobutane.

  通过用 1,1-双(甲苯磺酰氧基甲基)环丙烷和-环丁烷环化双亲核试剂制备了多种杂环螺。
• [EN] PYRROLOTRIAZINE INHIBITORS OF IRAK4 ACTIVITY<br/>[FR] INHIBITEURS DE PYRROLOTRIAZINE DE L'ACTIVITÉ D'IRAK4
  申请人：MERCK SHARP & DOHME

  公开号：WO2016144848A1

  公开（公告）日：2016-09-15

  The present invention relates to pyrrolotriazine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.

  本发明涉及式(I)的IRAK4的吡咯三嗪抑制剂，并提供包含这些抑制剂的组合物，以及用于治疗IRAK4介导的或相关的疾病或病症的方法。
• [EN] PYRROLOPYRIDAZINE INHIBITORS OF IRAK4 ACTIVITY<br/>[FR] INHIBITEURS À BASE DE PYRROLOPYRIDAZINE D'ACTIVITÉ D'IRAK4
  申请人：MERCK SHARP & DOHME

  公开号：WO2016144847A1

  公开（公告）日：2016-09-15

  The present invention relates to pyrrolopyridazine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.

  本发明涉及式(I)的IRAK4的吡咯吡啶嘧啶抑制剂，并提供包含这种抑制剂的组合物，以及用于治疗IRAK4介导的或相关的疾病或症状的方法。