ethyl 2-cycloheptylidenepropanoate | 198492-94-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 2-cycloheptylidenepropanoate
• CAS: 198492-94-3
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: XQHBSQKTIYSWSD-UHFFFAOYSA-N

物化性质

• 沸点：
  270.5±9.0 °C(Predicted)
• 密度：
  0.968±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl 2-cycloheptylidenepropanoate 在 吡啶 、 nickel(II) iodide 、 bis(1,5-cyclooctadiene)nickel (0) 、 lithium aluminium tetrahydride 、 4-chloro-2-(4,5-dihydro-1H-imidazol-2-yl)pyridine 、 1,3-二环己基苯并咪唑氯化物 、 四丁基溴化铵 、 magnesium chloride 、 sodium t-butanolate 、 锌 作用下， 以 2-甲基-2-丁醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基乙酰胺 、 甲苯 为溶剂， 反应 54.0h， 生成
  参考文献：
  名称：

  用于四元中心引入的酰胺衍生物的Mizoroki-Heck环化

  摘要：

  我们报告了酰胺衍生物的非脱羰基Mizoroki-Heck反应。该转化依赖于镍催化的使用，并使用空间受阻的三和四取代的烯烃进行，以得到含有季中心的产物。可以高收率获得所得的多环或螺环产物。而且，该方法的非对映选择性变体使得能够接近带有邻近的，高度取代的sp 3立体中心的加合物。这些结果表明，酰胺衍生物可以用作组装复杂支架的基础。

  DOI：

  10.1002/anie.201703174
• 作为产物：
  描述：

  2-溴丙酸乙酯 在 sodium hydride 作用下， 以 乙二醇二甲醚 为溶剂， 反应 11.25h， 生成 ethyl 2-cycloheptylidenepropanoate
  参考文献：
  名称：

  Synthesis and Biological Evaluation of Cycloalkylidene Carboxylic Acids as Novel Effectors of Ras/Raf Interaction

  摘要：

  The protooncogenes Ras and Raf play important roles in signal transduction pathways regulated by mitogen-activated protein kinases. Mutations of Ras that arrest the protein in its active state are frequently implicated in tumor formation. We used Ras and Raf proteins in the yeast two-hybrid system to search for natural or synthesized substances capable of modulating Ras/ Raf interaction by specifically binding to one of the interacting partners. We found that cycloalkylidene carboxylic acids enhanced Ras/Raf interaction by acting on the cysteine-rich domain of Raf. Several analogues of the active substance 2-cyclohexylidene propanoic acid were synthesized and the importance of the semicyclic double bond in the stabilization of Ras/Raf interaction was demonstrated. Variation of the size and the substituents of the cyclic system as well as the length of the carboxylic acid resulted in enhanced Ras/Raf interaction.

  DOI：

  10.1021/jm011101q

文献信息

• Design, Synthesis and Structure-Odor Correlation of Novel Spiro[4.5]-decan-2-ones
  作者：Philip Kraft、Riccardo Cadalbert

  DOI：10.1055/s-2002-34847

  日期：——

  Dehydration and Rupe rearrangement of 2-(3,3-dimethylcyclohexyl)hex-3-yne-2,5-diol (9) furnished as a 3% byproduct the intense vetiver-like smelling 4,7,7-trimethyl-1-methylene­spiro[4.5]decan-2-one (11). Motivated by the commercial importance of vetiver oil and the lack of synthetic substitutes as well as the lack of insight into the structural requirements for vetiver odorants, an efficient synthetic route to vetiver-like smelling compounds was developed. It consists of Wittig-Horner-Emmons reaction of diverse cycloalkanones with triethyl 2-phosphonopropionate, subsequent Grignard reaction with in situ conversion to the trienolate, and classical Nazarov cyclization of the resulting dienones. This route not only leads to 11 in 61% yield in the final Nazarov cyclization, but also to 16 analogs, which provide insight into both, the Nazarov reaction and the structure-odor relationship of vetiver odorants. Other vetiver-like smelling compounds discovered include (1RS,4SR,5SR)-1,4,7,7-tetramethylspiro[4.5]decan-2-one (16), 4-methyl-1-methylenespiro[4.6]undecan-2-one (30) and 4-methyl-1-methylenespiro[4.7]dodecan-2-one (31).

  脱水和鲁佩重排反应生成的2-(3,3-二甲基环己基)己-3-炔-2,5-二醇(9)以3%的副产物获得了具有强烈的香根草气味的4,7,7-三甲基-1-亚甲基­螺[4.5]十烷-2-酮(11)。鉴于香根草油的商业重要性、缺乏合成替代品以及对香根草气味成分结构要求的不足之处，开发了一条有效的合成香根草气味化合物的路线。该路线包括将多种环烷酮与三乙基2-膦丙酸酯进行威蒂格-霍纳-埃蒙斯反应，随后进行格林纳德反应并原位转化为三烯醇盐，最终进行经典的纳扎罗夫环化反应。该合成路线不仅在最后的纳扎罗夫环化中以61%的产率得到化合物11，还得到16种类似物，为纳扎罗夫反应及香根草气味成分的结构-气味关系提供了见解。其他发现的具有香根草气味的化合物包括(1RS,4SR,5SR)-1,4,7,7-四甲基螺[4.5]十烷-2-酮(16)、4-甲基-1-亚甲基螺[4.6]十一烷-2-酮(30)以及4-甲基-1-亚甲基螺[4.7]十二烷-2-酮(31)。
• anti-Selective aminofluorination of alkenes with amidines mediated by hypervalent iodine(<scp>iii</scp>) reagents
  作者：Hui Chen、Atsushi Kaga、Shunsuke Chiba

  DOI：10.1039/c5ob01854d

  日期：——

  anti-Aminofluorination of alkenes with amidines was enabled by hypervalent iodine(iii) reagents, affording 4-fluoroalkyl-2-imidazolines. Further reductive ring-opening of the 2-imidazoline moiety could deliver highly functionalized 3-fluoropropane-1,2-diamine derivatives.

  烯烃与胺基甲烷胺反氟化作用，由高价碘（III）试剂实现，形成4-氟烷基-2-咪唑啉。进一步还原开环2-咪唑啉基团可制备高度官能化的3-氟丙烷-1,2-二胺衍生物。
• Regio- and Stereoselectivity of Water Elimination as a Function of Ring Size
  作者：Björn Greve、Peter Imming

  DOI：10.1021/jo970989g

  日期：1997.11.1

  The elimination of water from tertiary alcohols was studied for carbocycles of ring size 5-16. The resulting olefins 3-5 were discriminated by NMR spectroscopy. The relative amount of their formation reflects the steric idiosyncrasies of the respective ring systems. The behavior of the medium-sized rings yielded experimental proof to the I-strain concept.

  对于环号为5-16的碳环化合物，研究了从叔醇中消除水的方法。所得烯烃3-5通过NMR光谱鉴别。它们形成的相对量反映了各个环系统的空间特质。中型环的行为为I应变概念提供了实验证明。
• Greve, Bjoern; Imming, Peter; Laufer, Stefan, Angewandte Chemie, 1996, vol. 108, # 11, p. 1312 - 1314
  作者：Greve, Bjoern、Imming, Peter、Laufer, Stefan

  DOI：——

  日期：——
• Bicyclic β-Hydroxytetrahydrofurans as Precursors of Medium Ring Keto-Lactones
  作者：Helena M. C. Ferraz、Luiz S. Longo

  DOI：10.1021/jo0626109

  日期：2007.4.1

  The reaction of a series of cis-fused bicyclic beta-hydroxytetrahydrofurans with ruthenium tetraoxide, generated in situ from ruthenium trichloride and sodium periodate, afforded 9- and 10-membered keto-lactones in moderate to good yields, in a clean and straightforward fashion. The starting beta-hydroxyethers were obtained from the corresponding 3-alkenols by two alternative procedures, depending on their pattern of substitution: (a) epoxidation by dimethyldioxirane, followed by base-catalyzed cyclization of the resulting epoxyalcohol, and (b) thallium trinitrate-mediated cyclization of the 3-alkenols, a method already described by our group.