2,2,6,6-tetramethylhepta-4-yn-3-one | 62688-81-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2,6,6-tetramethylhepta-4-yn-3-one
• 英文别名: 2,2,6-tetramethylhept-4-yn-3-one；2,2,6,6-tetramethylhept-4-yn-3-one
• CAS: 62688-81-7
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: NVOZRXXONBZHLU-UHFFFAOYSA-N

物化性质

• 沸点：
  39-40 °C
• 密度：
  0.872±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  2,2,6,6-tetramethylhepta-4-yn-3-one 在 sodium methylate 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 8.3h， 生成 4,6-ditert-butyl-1H-pyridin-2-one
  参考文献：
  名称：

  Effects of Hindrance in N-Pyridyl Imidazolylidenes Coordinated to Iridium on Structure and Catalysis

  摘要：

  The unhindered N-pyrid-2-yl imidazolidene NHC ligand has been shown to chelate to a Cp*Ir fragment (1). With the goal of weakening the coordination of the pyridyl substituent and enabling its role as pendant base or hemilabile ligand, a tert-butyl group at C-6 next to the pyridyl N was installed. Attempted coordination of the newly synthesized carbene ligand avoided N-coordination entirely, but led to unexpected C-metalation at C-3 by the Cp*Ir center. Successful formation of a weakly N-coordinated analogue was achieved by synthesizing a ligand with a second tert-butyl group at C-4. The complexes were studied using X-ray crystallography and NMR spectroscopy. The X-ray crystal structure of di-tert-butyl analogue 6 showed that in the solid the complex existed as a chloride-bridged dimer, with the pyridyl nitrogen uncoordinated. In solution, N-15 chemical shift information revealed that 6 existed with the pyridyl substituent N-coordinated, presumably as a monomer, but that addition of an amine ligand readily opened the chelate. Finally, 6 was used as a catalyst for intramolecular hydroamination of primary and secondary alkenylamines. Comparing (heteroaryl)NHC species, each with a tert-butyl group next to the nitrogen, which enables hydroamination, the rate differences are very modest but increase in the order imidazolyl < pyridyl < pyrimidyl, which may be an effect of basicity but because of the similarity in rates is better ascribed to counterbalancing of more than one factor, including hemilability. The (4,6-di-tert-butyl)pyridyl species 6 was shown to be much more effective compared to parent compound 1 without the tert-butyl groups, in which the chelating group was more tightly bound.

  DOI：

  10.1021/om400758b
• 作为产物：
  描述：

  (3,3-dimethylbut-1-yn-1-yl)magnesium bromide 在 Jones's reagent 作用下， 以 四氢呋喃 为溶剂， 生成 2,2,6,6-tetramethylhepta-4-yn-3-one
  参考文献：
  名称：

  炔酮的光化学 [3 + 2] 环加成反应。两种相似乙烯基卡宾中间体的不同命运和环丙烯醇的反应

  摘要：

  Par 辐射 de la tetramethyl-2,2,6,6 庚炔-4one-3 avec le tetramethylethylene dans C 6 H 6 , 形成 d'un cyclopropene-2ol-1 dont la thermolyse 导管 a une cetone allenique avec perte de C 3 H 6 . Par traitement avec NaOH形成d'une heptene-5one-3。Mecanisme: mise en jeu de carbenes

  DOI：

  10.1021/ja00320a023

文献信息

• Alleno-Acetylenic Cage (AAC) Receptors: Chiroptical Switching and Enantioselective Complexation of<i>trans</i>-1,2-Dimethylcyclohexane in a Diaxial Conformation
  作者：Cornelius Gropp、Nils Trapp、François Diederich

  DOI：10.1002/anie.201607681

  日期：2016.11.7

  (AACs) are highly conformation sensitive, the longest wavelength Cotton effect at 304 nm switches from Δϵ=+191 m−1 cm−1 for open (P)4‐AAC⊂acetonitrile to Δϵ=−691 m−1 cm−1 (ΔΔϵ=882 m−1 cm−1) for closed (P)4‐AAC⊂cyclohexane. Complete chiral resolution of (±)‐trans‐1,2‐dimethylcyclohexane was found in the X‐ray structures, with (P)4‐AAC exclusively bound to the (R,R)‐ and (M)4‐AAC to the (S,S)‐guest. Guest

  四个带有OH末端的对映纯1,3-二乙炔基（DEA）被连接在间苯二酚[4]芳烃空洞的边缘上。该系统在由圆形H键阵列封闭的笼形和开放式之间进行构象转换，叔醇基向外延伸。笼型在非极性溶剂中占主导地位，在小极性溶剂中呈开放构象。在溶液和X射线共晶结构中都确认了这两种状态。异炔乙炔笼（AAC）的ECD光谱对构象高度敏感，最长波长在304 nm处的棉花效应从开放的（P）4 -AAC乙腈的Δϵ = + 191  m -1  cm -1切换到Δϵ = −691  m -1 厘米-1（ΔΔ ε = 882 米-1 厘米-1），用于封闭（P）4 -AAC⊂cyclohexane。在X射线结构中发现了（±）-反-1,2-二甲基环己烷的完全手性拆分，其中（P）4- AAC仅与（R，R）-和（M）4- AAC结合（S，S）-访客。客体夹杂物以较高能量的双轴构象发生。
• 一种以炔酮制备1,3-二酮类化合物的方法
  申请人：温州大学

  公开号：CN109776293B

  公开（公告）日：2022-04-05

  一种以炔酮制备1,3‑二酮类化合物的制备方法，包含以下步骤：S1：将所述α‑炔基酮化合物、水、金盐和银盐置于反应溶剂中得到前体混合物，所述α‑炔基酮化合物、水、金盐和银盐的摩尔比为：1:1～50:0.001～0.10：0.002～0.15；S2：将步骤S1中得到的前体混合物置于0～50℃的反应温度下反应得到所述1,3‑二酮类化合物，反应时间为5分钟～48小时。该方法反应条件简单，无需酸或碱性添加剂，产率高，可大规模运用于现代化生产中。
• PI3 KINASE INHIBITORS AND USES THEREOF
  申请人：NIU DEQIANG

  公开号：US20110230476A1

  公开（公告）日：2011-09-22

  The present invention provides compounds, compositions thereof, and methods of using the same.

  本发明提供了化合物、其组合物以及使用相同的方法。
• Enantiopure, Monodisperse Alleno-acetylenic Cyclooligomers: Effect of Symmetry and Conformational Flexibility on the Chiroptical Properties of Carbon-Rich Compounds
  作者：Pablo Rivera-Fuentes、Belén Nieto-Ortega、W. Bernd Schweizer、Juan T. López Navarrete、Juan Casado、François Diederich

  DOI：10.1002/chem.201100131

  日期：2011.3.28

  A series of enantiopure, monodisperse alleno‐acetylenic cyclooligomers were synthesized. The single‐crystal X‐ray structures of the cyclic trimer and hexamer were resolved, providing insights into the symmetry of these molecules. Electronic circular dichroism (ECD), optical rotatory dispersion (ORD), Raman spectroscopy, and vibrational circular dichroism (VCD) data were analyzed with the aid of theoretical

  合成了一系列对映纯，单分散的烯基炔属环寡聚体。解析了环状三聚体和六聚体的单晶X射线结构，从而洞悉了这些分子的对称性。借助理论计算对电子圆二色性（ECD），旋光色散（ORD），拉曼光谱和振动圆二色性（VCD）数据进行了分析。这种多维方法最终提供了通用指南，可用于设计具有强烈手性的富碳化合物。
• The Synthesis of Highly Substituted Isoxazoles by Electrophilic Cyclization:  An Efficient Synthesis of Valdecoxib
  作者：Jesse P. Waldo、Richard C. Larock

  DOI：10.1021/jo701942e

  日期：2007.12.1

  A large number of functionally substituted 2-alkyn-1-one O-methyl oximes have been cyclized under mild reaction conditions in the presence of ICl to give the corresponding 4-iodoisoxazoles in moderate to excellent yields. The resulting 4-iodoisoxazoles undergo various palladium-catalyzed reactions to yield 3,4,5-trisubstituted isoxazoles, including valdecoxib.

  大量官能取代的 2-alkyn-1-one O-甲基肟在温和的反应条件下在 ICl 存在下环化，以中等至极好的收率得到相应的 4-碘异恶唑。所得的 4-碘异恶唑经过各种钯催化反应生成 3,4,5-三取代的异恶唑，包括伐地考昔。