(+/-)-2-(4'-iodobutyl)cycloheptanone | 101493-08-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-2-(4'-iodobutyl)cycloheptanone
• 英文别名: 2-(4-Iodobutyl)cycloheptan-1-one
• CAS: 101493-08-7
• 化学式: C₁₁H₁₉IO
• 分子量: 294.176
• InChiKey: VTVPSFGVONRIHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-2-(4'-iodobutyl)cycloheptanone 在 一水合肼 、 六甲基二硅氮烷 、 lithium hexamethyldisilazane 、 硫酸肼 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 生成 bicyclo<4.4.1>undecan-11-one
  参考文献：
  名称：

  Structure−Property Relationships in Trimethylenemethane-Type Biradicals. 2. Synthesis and EPR Spectral Characterization of Dinitroxide Biradicals

  摘要：

  Several trimethylenemethane-type (TMM-type) dinitroxide biradicals have been prepared that differ in tert-butylaminoxylphenyl ring torsion angles by virtue of different steric demands of their "spin-protecting groups". In addition, the synthesis of a TMM-type dinitroxide having a planar pi-system is reported. The synthetic route employed for the planar TMM-type biradical is general and should therefore expand, the utility of TMM-type biradicals that are susceptible to bond torsions that attenuate exchange coupling. The compounds presented are designed to be effective to map out J-coupling/conformation space in TMM-type biradicals. EPR spectroscopic parameters (hfcc and D-values) were compared to determine if their values reflected differences in conformation in the series of biradicals. Interestingly, neither N- nor H-hfcc varied within our series of biradicals/monoradicals in a regular fashion, indicating that there is no apparent relationship between N- or H-hfcc and conformation (as judged by molecular mechanics calculations). However, D-values, estimated from relative intensities of Delta m(s) = 1 and Delta m(s) = 2 transitions, are consistent with a varied degree of delocalization in the dinitroxides: smaller D-values for biradicals having smaller aryl torsions (and greater delocalization), and larger D-values for dinitroxides having greater aryl torsions (and less delocalization). All the biradicals studied, except 5(..), exhibited linear Curie plots. The linear Curie plots are consistent with both triplet ground-states and singlet-triplet degeneracies. Interestingly, dinitroxide 6(..) exhibited a linear Curie plot, despite the lack of a pi-coupling fragment. Biradical 5(..), however, is a ground-state singlet; species with the triplet lying about 140 cal/mol above the singlet.

  DOI：

  10.1021/jo990061j
• 作为产物：
  描述：

  2-(4'-chloro-n-butyl)cycloheptanone 在 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 12.0h， 生成 (+/-)-2-(4'-iodobutyl)cycloheptanone
  参考文献：
  名称：

  Structure−Property Relationships in Trimethylenemethane-Type Biradicals. 2. Synthesis and EPR Spectral Characterization of Dinitroxide Biradicals

  摘要：

  Several trimethylenemethane-type (TMM-type) dinitroxide biradicals have been prepared that differ in tert-butylaminoxylphenyl ring torsion angles by virtue of different steric demands of their "spin-protecting groups". In addition, the synthesis of a TMM-type dinitroxide having a planar pi-system is reported. The synthetic route employed for the planar TMM-type biradical is general and should therefore expand, the utility of TMM-type biradicals that are susceptible to bond torsions that attenuate exchange coupling. The compounds presented are designed to be effective to map out J-coupling/conformation space in TMM-type biradicals. EPR spectroscopic parameters (hfcc and D-values) were compared to determine if their values reflected differences in conformation in the series of biradicals. Interestingly, neither N- nor H-hfcc varied within our series of biradicals/monoradicals in a regular fashion, indicating that there is no apparent relationship between N- or H-hfcc and conformation (as judged by molecular mechanics calculations). However, D-values, estimated from relative intensities of Delta m(s) = 1 and Delta m(s) = 2 transitions, are consistent with a varied degree of delocalization in the dinitroxides: smaller D-values for biradicals having smaller aryl torsions (and greater delocalization), and larger D-values for dinitroxides having greater aryl torsions (and less delocalization). All the biradicals studied, except 5(..), exhibited linear Curie plots. The linear Curie plots are consistent with both triplet ground-states and singlet-triplet degeneracies. Interestingly, dinitroxide 6(..) exhibited a linear Curie plot, despite the lack of a pi-coupling fragment. Biradical 5(..), however, is a ground-state singlet; species with the triplet lying about 140 cal/mol above the singlet.

  DOI：

  10.1021/jo990061j

文献信息

• Rearrangements of Bicyclic Nitrones to Lactams:  Comparison of Photochemical and Modified Barton Conditions
  作者：Yibin Zeng、Brenton T. Smith、John Hershberger、Jeffrey Aubé

  DOI：10.1021/jo035004b

  日期：2003.10.1

  The rearrangement of nitrones to lactams can be carried out by photochemical activation or by treatment with Tf(2)O followed by KOH-promoted rearrangement (a modification of conditions originally introduced by Barton). Substrates in which the nitrone is part of a fused bicyclic ring system have traditionally proven problematic for this kind of reaction. In this study, a series of mono-, bi-, and tricyclic

  将硝酮重排成内酰胺可以通过光化学活化或通过用Tf（2）O处理，然后进行KOH促进的重排（对Barton最初引入的条件的修改）来进行。传统上证明，其中硝酮是稠合双环系统一部分的底物对于这种反应是有问题的。在这项研究中，准备了一系列单环，双环和三环稠合的硝酮，以研究产物对硝酮环大小和系链长度的依赖性。结果表明，苯中硝酮的光化学重排可提供相当不错的内酰胺收率（30-68％），而两步非光化学过程可提供相同目标的平均收率稍高（30-95％）。
• Lanthanides in organic synthesis. 3. A general procedure for five- and six-membered ring annulation
  作者：Gary A. Molander、Jeffrey B. Etter

  DOI：10.1021/jo00360a025

  日期：1986.5
• MOLANDER G. A.; ETTER J. B., J. ORG. CHEM., 51,(1986) N 10, 1778-1786
  作者：MOLANDER G. A.、 ETTER J. B.

  DOI：——

  日期：——