Methyl 4-fluoro-1-cubanecarboxylate | 141046-54-0

• 物质功能分类: 化学试剂 - 有机试剂 - 酯类
• 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: Methyl 4-fluoro-1-cubanecarboxylate
• 英文别名: Methyl 4-fluorocubane-1-carboxylate；methyl 4-fluorocubanecarboxylate；methyl (1s,2R,3r,8S)-4-fluorocubane-1-carboxylate
• CAS: 141046-54-0
• 化学式: C₁₀H₉FO₂
• 分子量: 180.179
• InChiKey: SITDWAAQDWEIQW-UHFFFAOYSA-N

物化性质

• 沸点：
  209.6±40.0 °C(Predicted)
• 密度：
  1.59±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 4-fluoro-1-cubanecarboxylate 在 lead(IV) acetate 、 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 4.25h， 生成 1-Fluoro-4-phenylcubane
  参考文献：
  名称：

  Synthesis and 19F and 13C NMR Studies of a Series of 4-Substituted Fluorocubanes: Resonance Dependence of 19F Chemical Shifts in a Saturated System

  摘要：

  The substituent chemical shifts and the carbon-fluorine coupling constants of a range of 4-substituted cubyl fluorides in solvents of varying polarity are presented. Least squares regressional analysis of the data indicates that the fluorine probe, while being somewhat less sensitive to field effects as a result of the low polarizability of the cubane C-F bond, nevertheless responds in the ''reverse'' manner in agreement with precedents established in other alicyclic systems. The dependence of (1)J(CF) upon electronegativity has been interpreted as evidence for the occurrence of sigma-induction over four bonds, the longest reported to date. Significantly, resonance parameters are found to be very important in describing the effect of substituents on both the fluorine chemical shifts and the magnitude of the one-bond and four-bond C-13-F-19 coupling constants. This represents one of the rare occasions that resonance effects have been observed in a fully saturated system in the ground state. A possible mechanism by which these resonance effects may be transmitted is presented.

  DOI：

  10.1021/jo00121a059
• 作为产物：
  描述：

  methyl 4-iodocubane-1-carboxylate 在 二氟代氙 作用下， 以 正己烷 为溶剂， 反应 5.0h， 以59%的产率得到Methyl 4-fluoro-1-cubanecarboxylate
  参考文献：
  名称：

  古巴笼 - 用于评估取代基对四元环的影响的敏感探针，第二部分

  摘要：

  4-甲氧基立方烷-1-羧酸甲酯 (1), 1-乙酰氨基-4-氟立方烷 (2), 4-乙酰氧基立方烷-1-羧酸甲酯 (3), 1,4-二氟立方烷 (4), 1, 的晶体结构4-二氯立方烷 (5) 和 N,N-二异丙基立方烷-1,4-二甲酰胺 (6) 已通过 X 射线衍射分析进行了研究。氟和氯取代基会导致连键缩短，如 4-haloccubane-1-carboxylates 中所见。笼键与酯取代基相邻，在该基团的 π 受体影响方面具有有利的取向，变得比 CH-CH 键长。此外，已经通过实验研究了该基团相对于立方烷骨架内的键的取向对键长的影响。还发现甲氧基的影响取决于取向。与甲基基团反面的笼键缩短，而与该基团呈gauche 方向的笼键加长。正如在卤素取代衍生物的情况下所见，由于该基团的 σ 受体性质，带有乙酰氧基取代基的键被缩短。在 6-31G* 水平下对化合物 1、2、4 和 5 进行的从头算计算证实了实验结果。

  DOI：

  10.1002/(sici)1099-0690(199905)1999:5<1253::aid-ejoc1253>3.0.co;2-m

文献信息

• Homolytic reactions of cubanes. Generation and characterization of cubyl and cubylcarbinyl radicals
  作者：Ernest W. Della、Nicholas J. Head、Philip Mallon、John C. Walton

  DOI：10.1021/ja00053a008

  日期：1992.12

  A series of 4-substituted cubyl radicals was generated by bromine atom abstraction from 1-bromo-4-substituted cubanes. EPR observations showed that the cubyl radicals abstracted secondary hydrogen atoms from the ethyl groups of triethylsilane and decayed mainly by second-order combination reactions. tert-Butoxyl radicals abstracted hydrogen atoms from cubane at least 26 times more rapidly than from

  通过从 1-bromo-4-取代的立方烷中提取溴原子，产生了一系列 4-取代的立方自由基。EPR 观察表明，cubyl 自由基从三乙基硅烷的乙基中提取二级氢原子，主要通过二级组合反应衰变。在-90 o C 时，叔丁氧基从立方烷中提取氢原子的速度至少比环丙烷快26 倍。立方烷上的吸电子取代基大大降低了这一速度。叔丁氧基自由基选择性地从甲基立方烷中提取笼氢而不是伯甲基氢
• Synthesis of bridgehead fluorides by fluorodeiodination
  作者：Ernest W. Della、Nicholas J. Head

  DOI：10.1021/jo00036a018

  日期：1992.5

  Fluorodeiodination is found to be an attractive procedure for the synthesis of bridgehead fluorides. Thus, treatment of the corresponding iodide with xenon difluoride in dichloromethane at ambient temperature generally leads to high yields of the fluoride. Evidence suggests the intermediacy of the bridgehead cation in this reaction, and accordingly the substrates which are unfavorably disposed to fluorodeiodination are the bicyclo[n.1.1]alkyl iodides. In this context the isolation of a small quantity of methyl 4-fluorobicyclo[2.1.1]hexane-1-carboxylate (46, R = COOMe) is significant because it represents the first occasion on which the elusive 1-bicyclo[2.1.1]hexyl cation has been trapped. We have also demonstrated that synthesis of the iodides themselves can be accomplished efficiently both by Barton halodecarboxylation and by treatment of the carboxylic acid with lead tetraacetate and iodine.
• Irngartinger, Hermann; Strack, Stefan; Gredel, Frank, Liebigs Annalen, 1996, # 3, p. 311 - 315
  作者：Irngartinger, Hermann、Strack, Stefan、Gredel, Frank

  DOI：——

  日期：——