1,4-二氧杂螺[4.4]壬烷-7-甲腈 | 159329-38-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1,4-二氧杂螺[4.4]壬烷-7-甲腈
• 英文名称: 1,4-dioxaspiro[4.4]nonane-7-carbonitrile
• 英文别名: 1,4-dioxaspiro[4.4]nonane-8-carbonitrile
• CAS: 159329-38-1
• 化学式: C₈H₁₁NO₂
• 分子量: 153.181
• InChiKey: AIGSEZMXORSNKO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  42.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,4-二氧杂螺[4.4]壬烷-7-甲腈 在 copper(l) iodide 、 水 、 草酸 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 甲苯 、 苯 为溶剂， 反应 15.5h， 生成 trans-5,6-diphenylbicyclo<3.1.0>hexan-2-one
  参考文献：
  名称：

  General Theoretical Treatments of Solid-State Photochemical Rearrangements and a Variety of Contrasting Crystal versus Solution Photochemistry

  摘要：

  In continuing our investigations of control of excited state reactivity by inclusion in crystal lattices, we have encountered a variety of new examples of differing reactivity resulting from lattice restraints. Different theoretical treatments were tested and several proved applicable. Not only could the course of reactions imposed by the crystal lattice be predicted but also the ability to react versus lack of reactivity. For cyclohexenones with C-2 and C-5 substitution, either of two aryl groups at C-4 are available for migration; which one migrates depends on the lattice. One C-2 substituted and seven C-5 substituted cyclohexenones were investigated. Additionally some cyclopentenone photochemistry was investigated. Throughout, programming was developed to generate a ''mini crystal lattice'' having the appropriate space group symmetry and X-ray coordinates and with a central molecule surrounded by reactant molecules. Replacement of the central molecule with a transition state molecule provided a new ''mini-lattice''. Generally, the first diradical intermediate was used to simulate the reaction transition state. The mini-lattice was then subject to study. Overlap of the central, partially reacted species with the surrounding molecules provided one criterion. Molecular motion of the reactant excited state in forming the partially reacted species provided a test of least motion as a second criterion. A third test utilizing MM3 geometry optimization of the reacting species imbedded in the rigid mini-lattice, provided a measure of the increase in intra- and intermolecular energy of this molecule. A final approach determined the points of nearest molecule-lattice approach and mapped these in the form of a ''lock and key''; this has the advantage of indicating which interactions result in inhibition or lack thereof of a particular reaction route. Predicting ability to react proved important since reactivity falls into three categories: (I) no reaction in the lattice, (2) differing reactivity compared to solution, (3) the same behavior in solution. Perturbing an intermediate geometry toward that of the reactant and then determining the deformation energy provided a reactivity measure.

  DOI：

  10.1021/ja00124a008
• 作为产物：
  描述：

  3-氧代环戊烷甲腈 在 对甲苯磺酸 、 sodium sulfate 作用下， 以 乙二醇二甲醚 为溶剂， 反应 5.0h， 以60%的产率得到1,4-二氧杂螺[4.4]壬烷-7-甲腈
  参考文献：
  名称：

  [EN] D3 RECEPTOR AGONIST COMPOUNDS; METHODS OF PREPARATION; INTERMEDIATES THEREOF; AND METHODS OF USE THEREOF
  [FR] COMPOSÉS AGONISTES DU RÉCEPTEUR D3; PROCÉDÉS DE PRÉPARATION; INTERMÉDIAIRES DE CEUX-CI; ET LEURS PROCÉDÉS D'UTILISATION

  摘要：

  本文披露了包括多巴胺D3受体激动剂在内的新颖化合物、其组合物、使用方法以及合成这些化合物的方法。进一步披露了D3R选择性激动剂化合物，具体包括具有手性的双位点配体。

  公开号：

  WO2020210785A1

文献信息

• Facile synthesis of 2-azaspiro[3.4]octane
  作者：Subbiah Ramesh、Ramadas Balakumar、John R. Rizzo、Tony Y. Zhang

  DOI：10.1039/c9ob00306a

  日期：——

  Our annulation strategy utilized for the synthesis of 2-azaspiro[3.4]octane is explained. Three successful routes for the synthesis were developed. One of the approaches involved annulation of the cyclopentane ring and the remaining two approaches involved annulation of the four membered ring. All three approaches employ readily available starting materials with conventional chemical transformations

  说明了我们用于合成2-azaspiro [3.4]辛烷的环空策略。开发了三种成功的合成途径。一种方法涉及环戊烷环的环空，其余两种方法涉及四元环的环空。所有这三种方法均采用具有常规化学转化和最小限度的色谱纯化的容易获得的起始原料，以提供标题化合物。还讨论了这三种方法的优缺点。
• Samarium diiodide-mediated pinacolization of diketones—II. Synthesis of polycyclic frameworks containing a cyclobutane-1,2-diol and a cyclopentane-1,2-diol
  作者：Olaf Nowitzki、Ira Münnich、Holger Stucke、H.M.R. Hoffmann

  DOI：10.1016/0040-4020(96)00688-6

  日期：1996.9

  The title reaction has been applied to the synthesis of a variety of polycyclic networks. Scope and limitations of the procedure are evaluated.

  标题反应已应用于多种多环网络的合成。评估程序的范围和局限性。
• Synthesis of Bridgehead Substituted Bicyclo[2.2.1]Heptanes. Radical Cyclization of an Oxime Ether and an α,β-Unsaturated Ester
  作者：EW Della、AM Knill

  DOI：10.1071/ch9941833

  日期：——

  The synthesis of bicyclo[2.2.1]heptanes with useful functionality at each bridgehead is achieved by radical cyclization of appropriately substituted 4-methylene- and 4-benzyloxyimino- cyclohexylmethyl radicals. The latter process, for example, leads to a bridgehead amine. Optimum yields are achieved when the reactions are conducted at 110� with slow addition of tributyltin hydride; under these conditions, the uncyclized isomer is either not detected, or formed in very small quantity. Production of a mixture of five- and six-membered cycloalkanones from similar treatment of the analogous 4-oxocyclohexylmethyl radicals reveals that the reaction is medicated by the corresponding 1-norbornyloxy radical.

  通过对适当取代的 4-亚甲基和 4-苄氧基亚氨基环己基甲基进行自由基环化，可以合成在每个桥头都具有有用官能团的双环[2.2.1]庚烷。例如，后一过程会产生桥头胺。当反应在 110� 温度下进行并缓慢加入氢化三丁基锡时，可获得最佳产率；在这些条件下，未环化的异构体要么检测不到，要么形成的数量极少。通过对类似的 4-oxocyclohexylmethyl 自由基进行类似处理，生成五元和六元环烷酮混合物，结果表明该反应受相应的 1-正硼氧基自由基的影响。
• D3 RECEPTOR AGONIST COMPOUNDS; METHODS OF PREPARATION; INTERMEDIATES THEREOF; AND METHODS OF USE THEREOF
  申请人：The United States of America, as Represented by The Department of Health and Human Services

  公开号：EP3953350A1

  公开（公告）日：2022-02-16
• [EN] D3 RECEPTOR AGONIST COMPOUNDS; METHODS OF PREPARATION; INTERMEDIATES THEREOF; AND METHODS OF USE THEREOF<br/>[FR] COMPOSÉS AGONISTES DU RÉCEPTEUR D3; PROCÉDÉS DE PRÉPARATION; INTERMÉDIAIRES DE CEUX-CI; ET LEURS PROCÉDÉS D'UTILISATION
  申请人：US HEALTH

  公开号：WO2020210785A1

  公开（公告）日：2020-10-15

  Disclosed herein are novel compounds including dopamine D3 receptor agonists, compositions thereof, methods of use thereof, and processes of synthesizing the same. Further disclosed are D3R selective agonist compounds, specifically bitopic ligands comprising chirality.

  本文披露了包括多巴胺D3受体激动剂在内的新颖化合物、其组合物、使用方法以及合成这些化合物的方法。进一步披露了D3R选择性激动剂化合物，具体包括具有手性的双位点配体。