1-(2-pyridyl)-3,3-diethoxyprop-1-yne | 49836-19-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 1-(2-pyridyl)-3,3-diethoxyprop-1-yne
• 英文别名: 2-(3,3-diethoxy-prop-1-ynyl)-pyridine；2-(3,3-Diethoxyprop-1-ynyl)pyridine
• CAS: 49836-19-3
• 化学式: C₁₂H₁₅NO₂
• 分子量: 205.257
• InChiKey: AHRBWTKWZGIFSZ-UHFFFAOYSA-N

物化性质

• 沸点：
  292.0±35.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  31.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(2-pyridyl)-3,3-diethoxyprop-1-yne 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 (Et₄N)₂[MoOS₈] 、 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 48.0h， 生成
  参考文献：
  名称：

  The Role of –OEt Substituents in Molybdenum-Assisted Pentathiepine Formation—Access to Diversely Functionalized Azines

  摘要：

  1,2,3,4,5-pentathiepines (PTEs) are naturally occurring polysulfides of increasing scientific interest based on their identified pharmacological activities. Artificial PTEs with N-heterocyclic backbones are efficiently synthesized via mediation by a molybdenum–oxo-bistetrasulfido complex. A common feature of all precursor alkynes successfully used to date in this reaction is the presence of a –CH(OEt)2 group since the previously postulated mechanism requires the presence of one OEt– as the leaving group, and the second must become a transient ethoxonium moiety. This raised the question of whether there really is a need for two, maybe only one, or possibly even zero ethoxy substituents. This research problem was systematically addressed by respective variations in the precursor-alkyne derivatives and by employing one related allene species. It was found that the total absence of ethoxy substituents prevents the formation of PTEs entirely, while the presence of a single ethoxy group results in the possibility to distinctly functionalize the position on the resulting N-heterocyclic pyrrole five ring in the target compound. This position was previously exclusively occupied by an –OEt for all products of the molybdenum-mediated reaction. The allene was applied with similar success as precursor as with the related alkyne. The now-employable significant change in precursor composition gives access to a whole new PTE subfamily, allowing further modulation of (physico)-chemical properties such as solubility, and provides additional insight into the mechanism of PTE formation; it comprises a merely partial validation of the previous hypothesis. The new alkyne precursors and pentathiepines were characterized by a variety of instrumental analyses (NMR, mass spec, UV–vis) and in six cases (one alkyne precursor, one unexpected side product, and four PTEs) by single-crystal X-ray diffraction. Syntheses, isolation procedures, analytical data, and the impact of the findings on the previously proposed mechanism are described in detail herein.

  DOI：

  10.3390/molecules29163806
• 作为产物：
  描述：

  2-溴吡啶 、 丙醛二乙基乙缩醛 在 copper(l) iodide 、 palladium diacetate 、 三乙胺 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以43 %的产率得到1-(2-pyridyl)-3,3-diethoxyprop-1-yne
  参考文献：
  名称：

  七种中氮茚衍生的五硫杂平的合成：对 C-9 位硝基取代的强电子结构响应

  摘要：

  合成了七种新的 1,2,3,4,5-五硫杂平[6,7-a]中氮茚嗪，其中五硫杂平部分带有从 C–H 衍生为 F-、Cl-、Br-、I 的中氮茚骨架-、NO2-和CH3-取代分别位于相对于吡啶部分上的氮杂基团的间位。它们的制备通过两个常见步骤进行：（i）（4-取代）2-溴-或2-氯吡啶与丙炔基3,3-二乙缩醛之间的Sonogashira偶联，以及（ii）由钼氧代介导的闭环反应-双四硫复合物和元素硫。后者同时促进 1,2,3,4,5-五硫吡啶链/环和中氮茚环的形成。以2-溴-5-氨基吡啶为起始原料，通过Sandmeyer反应制备氟代衍生物。使用芬克尔斯坦反应的金属辅助变体从 5-溴-2-炔基吡啶获得碘衍生物。讨论了探索不同反应条件的要求以及最终产物的不同收率。通过一组光谱/分析表征研究了不同取代对吡啶部分、其电子结构和各自化学性质的影响。有趣的是，在所有情况下，与其他六种研究的衍生物相比，硝基

  DOI：

  10.3390/molecules29010216

文献信息

• Preparation of Ethyl Arylpropiolates from Aryl Iodides by Palladium-Catalyzed Cross-Coupling Reaction
  作者：Takao Sakamoto、Futoshi Shiga、Akito Yasuhara、Daishi Uchiyama、Yoshinori Kondo、Hiroshi Yamanaka

  DOI：10.1055/s-1992-26214

  日期：——

  The palladium-catalyzed cross-coupling reaction of aryl iodides with 3,3,3-triethoxy-1-propyne gave 1-aryl-3,3,3-triethoxy-1-propynes which were converted to the corresponding ethyl arylpropiolates. The arylpropiolates were also synthesized from the cross-coupling reactions of aryl iodides with 2-ethoxycarbonyl-1-ethynylzinc chloride or ethyl (tributylstannyl)propiolate, but the reactions were not generally applicable.

  钯催化的芳基碘与3,3,3-三乙氧基-1-丙炔的交叉偶联反应生成1-芳基-3,3,3-三乙氧基-1-丙炔，这些产物被转化为相应的乙基芳基丙二酸酯。芳基丙二酸酯也可以通过芳基碘与2-乙氧羰基-1-乙炔基锌氯或乙基（三丁基锡基）丙二酸酯的交叉偶联反应合成，但这些反应并不普遍适用。
• Sonogashira reaction of aryl halides with propiolaldehyde diethyl acetal catalyzed by a tetraphosphine/palladium complex
  作者：Mhamed Lemhadri、Henri Doucet、Maurice Santelli

  DOI：10.1016/j.tet.2005.06.062

  日期：2005.10

  All-cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C3H5)]2 efficiently catalyzes the Sonogashira reaction of propiolaldehyde diethyl acetal with a variety of aryl bromides and chlorides. A minor electronic effect of the substituents of the aryl bromide was observed. Similar reaction rates were observed in the presence of activated aryl bromides such as 4-trifluoromethylbromobenzene and deactivated

  清一色顺-1,2,3,4-四（二苯基膦基）环戊烷/ [的PdCl（C 3 H ^ 5）] 2有效地催化丙醛二乙基乙缩醛与各种芳基溴化物和氯化物的Sonogashira反应。观察到芳基溴的取代基的电子效应较小。在活化的芳基溴化物（例如4-三氟甲基溴苯）和失活的芳基溴化物（例如溴苯甲醚）的存在下，观察到相似的反应速率。该反应的营业额最高可达到95,000。甚至芳基氯化物和杂芳基溴化物或氯化物也已被该催化剂成功地炔基化。此外，芳基卤化物上的各种取代基如氟，三氟甲基，乙酰基，苯甲酰基，甲酰基，硝基，二甲基氨基或腈是可容许的。
• SHVARTSBERG M. S.; MOROZ A. A.; KOZHEVNIKOVA A. N., IZV. AN CCCP. CEP. XIM., 1978, HO 4, 875-879
  作者：SHVARTSBERG M. S.、 MOROZ A. A.、 KOZHEVNIKOVA A. N.

  DOI：——

  日期：——