4-ethynyl-4-hydroxycyclohexanone | 70097-77-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-ethynyl-4-hydroxycyclohexanone
• 英文别名: 4-Ethynyl-4-hydroxycyclohexan-1-one
• CAS: 70097-77-7
• 化学式: C₈H₁₀O₂
• 分子量: 138.166
• InChiKey: FTQXRFNSCAKNOI-UHFFFAOYSA-N

物化性质

• 沸点：
  84-87 °C(Press: 1 Torr)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-ethynyl-4-hydroxycyclohexanone 在 4-二甲氨基吡啶 、 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 硫酸 、 三乙胺 、 sodium nitrite 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 1.58h， 生成 1-((2-azidophenyl)ethynyl)-4-oxocyclohexyl acetate
  参考文献：
  名称：

  Au催化2-炔基芳基叠氮化物衍生物形成功能化喹啉

  摘要：

  开发了一种新方法，可按照金催化的1,3-乙酰氧基转移/环化/ 1,2-基团转移序列将2-炔基芳基叠氮化物衍生物转化为官能化的多取代喹啉。该转化在温和的反应条件下进行，是有效的，并且可以耐受多种官能团。

  DOI：

  10.1021/ol4019634
• 作为产物：
  描述：

  1,4-环己二酮 在 正丁基锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 为溶剂， 反应 0.5h， 生成 4-ethynyl-4-hydroxycyclohexanone
  参考文献：
  名称：

  Au催化2-炔基芳基叠氮化物衍生物形成功能化喹啉

  摘要：

  开发了一种新方法，可按照金催化的1,3-乙酰氧基转移/环化/ 1,2-基团转移序列将2-炔基芳基叠氮化物衍生物转化为官能化的多取代喹啉。该转化在温和的反应条件下进行，是有效的，并且可以耐受多种官能团。

  DOI：

  10.1021/ol4019634

文献信息

• Ruthenium-Catalyzed Cross-Coupling of Tertiary Propargyl Alcohols with ω-Alkynenitriles: A Regio- and Stereoselective Surrogate for an Aldol Condensation
  作者：Barry M. Trost、Nuno Maulide、Michael T. Rudd

  DOI：10.1021/ja8077686

  日期：2009.1.21

  A novel catalytic alkyne cross-coupling reaction is reported which connects tertiary propargyl alcohols with omega-alkynylnitriles with perfect atom economy. This remarkable process generates highly functionalized, stereodefined dienones that are formal aldol products in a single step. Moreover, the specificity of the cyano substituent for this reaction demonstrates the unique and somewhat underappreciated

  报道了一种新型催化炔交叉偶联反应，该反应将叔炔醇与具有完美原子经济性的 omega-炔腈连接起来。这一非凡的过程可在一个步骤中生成高度官能化的立体二烯酮，它们是正式的羟醛产物。此外，该反应的氰基取代基的特异性证明了该官能团的独特且有些被低估的性质。
• Baeyer-Villiger Oxidation and Oxidative Cascade Reactions with Aqueous Hydrogen Peroxide Catalyzed by Lipophilic Li[B(C6F5)4] and Ca[B(C6F5)4]2
  作者：Muhammet Uyanik、Daisuke Nakashima、Kazuaki Ishihara

  DOI：10.1002/anie.201204286

  日期：2012.9.3

  Efficient and selective: Two lipophilic catalysts were used for Baeyer–Villiger (BV) oxidations to give lactones in high yields (see scheme). Cascade reactions involving this BV oxidation were used to selectively obtain either unsaturated carboxylic acids or hydroxylactones in high yields from β‐silyl cyclohexanones.

  高效和选择性：两种亲脂性催化剂用于Baeyer-Villiger（BV）氧化，以高收率得到内酯（请参阅方案）。涉及这种BV氧化的级联反应用于从β-甲硅烷基环己酮中高收率选择性地获得不饱和羧酸或羟基内酯。
• METHOD FOR MANUFACTURING ESTER
  申请人：Ishihara Kazuaki

  公开号：US20130217898A1

  公开（公告）日：2013-08-22

  The present invention relates to a method for manufacturing an ester from a ketone or an aldehyde, which is a reactive substrate, by a Baeyer-Villiger oxidation reaction using hydrogen peroxide, and in this method, as a catalyst, M(BAr 4 ) n , which is a metal borate, is used (M represents an alkali metal or an alkaline earth metal; Ar represents an aryl; and n is the same number as the valence of M). For example, when cyclohexanone was used as the reactive substrate, and Sr[B(3,5-CF 3 C 6 H 3 ) 4 ] 2 was used as the catalyst, ε-caprolactone was obtained at an isolated yield of 82%.

  本发明涉及一种从酮或醛（作为反应底物）制造酯的方法，该方法通过使用过氧化氢进行巴耶-维利格氧化反应，在该方法中，作为催化剂使用了M(BAr4)n，该催化剂是一种金属硼酸盐（M代表碱金属或碱土金属；Ar代表芳基；n与M的化合价相同）。例如，当环己酮作为反应底物，Sr[B(3,5-CF3C6H3)4]2作为催化剂时，得到了ε-己内酯，其分离收率为82%。
• Functionally Selective Dopamine D₂/D₃ Receptor Agonists Comprising an Enyne Moiety
  作者：Christine Hiller、Ralf C. Kling、Frank W. Heinemann、Karsten Meyer、Harald Hübner、Peter Gmeiner

  DOI：10.1021/jm400520c

  日期：2013.6.27

  Dopaminergics of types 1 and 2 incorporating a conjugated enyne as an atypical catechol-simulating moiety were synthesized in enantiomerically pure form and investigated for their metabolic stability. Radioligand binding studies indicated high affinity to D-2-like receptors. The test compounds were evaluated for their ability to differentially activate distinct signaling pathways. Measurement of D-2L- and D-2S-mediated [S-35]GTP gamma S incorporation in the presence of coexpressed G alpha(o) and G alpha(i) subunits showed significantly biased receptor activation for several test compounds. Thus, the 2-azaindolylcarboxamide (S)-2a exhibited substantial functional selectivity for D-2S-promoted G(o) activation over G(i) coupling. The most significant bias was determined for the triazolylalkoxy-substituted benzamide (S)-2c that displayed higher potency for G(o) activation than for G, coupling at the D-2L subtype. Functional selectivity for beta-arrestin recruitment over G(i) activation was observed for the biphenylcarboxamide (R)-1 and the 2-benzothiophenylcarboxamide (S)-2d, whereas the 2-substituted azaindole (S)-2a preferred beta-arrestin recruitment compared to G(o) coupling.
• An Unusual Ruthenium-Catalyzed Dimerization of Propargyl Alcohols
  作者：Barry M. Trost、Michael T. Rudd

  DOI：10.1021/ja0111636

  日期：2001.9.1