6,6-dimethyl-1-phenylhepta-1,4-diyn-3-ol | 162467-52-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 6,6-dimethyl-1-phenylhepta-1,4-diyn-3-ol
• 英文别名: 1-(1,1-Dimethylethyl)-5-phenyl-1,4-pentadiyn-3-ol
• CAS: 162467-52-9
• 化学式: C₁₅H₁₆O
• 分子量: 212.291
• InChiKey: CSGWKPQLEYDPDV-UHFFFAOYSA-N

物化性质

• 沸点：
  341.9±32.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  6,6-dimethyl-1-phenylhepta-1,4-diyn-3-ol 在 manganese(IV) oxide 、 sodium tetrahydroborate 、 sodium ethanolate 、 sulfur 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 2-(1,1-dimethylethyl)-6-phenyl-4-methylthiapyrylium hexafluorophosphate
  参考文献：
  名称：

  A Comparison of Linear Optical Properties and Redox Properties in Chalcogenopyrylium Dyes Bearing Ortho-Substituted Aryl Substituents and tert-Butyl Substituents

  摘要：

  A series of thiapyrylium pentamethine dyes (4 and 12-15) bearing 2,2'-di-tert-butyl-6,6'-diphenyl, 2,2'-di-tert-butyl-6,6'-bis(2,6-dimethylphenyl), 2,2'-di-tert-butyl-6,6'-bis(2-methylphenyl), 2,2',6,6'-tetrakis(2,6-dimethylphenyl), and 2,2',6,6'-tetrakis(2-methylphenyl) substituents, respectively, were prepared and their linear optical properties and electrochemical redox properties were measured and compared to thiapyrylium pentamethine dyes 3 and 5. The tert-butyl and 2,6-dimethylphenyl substituents give nearly identical chromophores with respect to values of lambda(max), molar extinction coefficients (epsilon), bandwidths at half-height (v(1/2)), and lack of absorption in the visible spectrum. The 2-methylphenyl substituent imparts linear optical properties that are intermediate between those of the tert-butyl and phenyl substituents. The 2,6-dimethylphenyl and 2-methylphenyl substituents impart greater oxidative stability based on anodic shifts in oxidation potential.

  DOI：

  10.1021/jo026645u
• 作为产物：
  描述：

  苯乙炔 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 生成 6,6-dimethyl-1-phenylhepta-1,4-diyn-3-ol
  参考文献：
  名称：

  Gold-Catalyzed [4 + 1]-Annulation Reactions between 1,4-Diyn-3-ols and Isoxazoles To Construct a Pyrrole Core

  摘要：

  This work reports gold-catalyzed [4 + 1]-annulation reactions between 1,4-diyn-3-ols and isoxazoles or benzisoxazoles to yield pyrrole derivatives. The reaction chemoselectivity is controlled by an initial attack of an isoxazole at a less hindered alkyne to form gold carbenes, further inducing a 1,2-migration of a second alkyne group. A broad substrate scope of 1,4-diyn-3-ols, isoxazoles and even benzisoxazoles highlighted the reaction utility.

  DOI：

  10.1021/acs.orglett.8b01398

文献信息

• Synthesis of Highly Substituted 3-Formylfurans by a Gold(I)-Catalyzed Oxidation/1,2-Alkynyl Migration/Cyclization Cascade
  作者：Tao Wang、Shuai Shi、Max M. Hansmann、Eva Rettenmeier、Matthias Rudolph、A. Stephen K. Hashmi

  DOI：10.1002/anie.201310146

  日期：2014.4.1

  3‐Formylfuran derivatives are core structures of a variety of bioactive natural products. However, procedures for their preparation are still rare and generally inefficient in terms of atom economy: These methods require multiple steps or harsh reaction conditions and show selectivity problems. An efficient gold(I)‐catalyzed cascade reaction that leads to 3‐formylfurans from easily accessible starting

  3-甲酰呋喃衍生物是多种生物活性天然产物的核心结构。但是，制备它们的程序仍然很少见，并且就原子经济性而言通常是低效的：这些方法需要多个步骤或苛刻的反应条件，并显示出选择性问题。现在描述一种有效的金（I）催化的级联反应，该反应可从易于获取的起始原料生成3-甲酰呋喃。在N存在下，从相应的对称和不对称的1,4-二炔-3-醇中获得了多种3-甲酰基呋喃氧化效果好至极佳。同位素标记实验以及DFT计算都支持一种机制，在这种机制下，在最初的氧转移后，1,2-炔基迁移比氢化物转移更有利；随后进行环化以提供所需的官能化的呋喃核。
• Copper-Catalyzed Cascade Aminoalkynylation–Oxidation of Propargylic Alcohols: Stereospecific Synthesis of (<i>Z</i>)-2-Amino Conjugated Enynals/Enynones
  作者：Jiaqiong Sun、Guangfan Zheng、Yongmei Fu、Lihong Wang、Yan Li、Qian Zhang

  DOI：10.1021/acs.orglett.8b02272

  日期：2018.9.21

  Copper-catalyzed cascade aminoalkynylation–oxidation of propargylic alcohols has been realized, sterospecifically providing an array of (Z)-2-amino conjugated enynals/enynones in good yields under mild conditions. This transformation involves a rare 1,3-alkynyl migration of propargylic alcohols and simultaneously forms C–C, C–N, and C═O bonds. Furthermore, (Z)-2-amino conjugated enynals were applied

  铜催化的炔丙醇的级联氨基炔化反应已经实现，在温和条件下立体定向提供了良好收率的（Z）-2-氨基共轭烯醇/烯酮阵列。这种转化涉及稀有的炔丙基醇的1,3-炔基迁移，并同时形成C–C，C–N和C = O键。此外，（Z）-2-氨基共轭烯被应用于有效地合成3,5-二取代-1 H-吡咯-2-甲醛和共轭烯醇衍生物。
• Method for preparation of an intermediate dye product
  申请人：——

  公开号：US20020022723A1

  公开（公告）日：2002-02-21

  The present invention provides a novel method for the synthesis of an intermediate dye product having the following formula: 1 wherein L is S, Te, or Se; R 1 and R 2 are either the same or different aryl or alkyl compounds; R 3 is hydrogen or a short chain alkyl group; and Z is an anion. The process to formulate this intermediate compound entails reacting an R 1 -acetylene compound with an R 2 -acetylene compound (compounds A) into an enol ether compound with the R 1 and/or R 2 constituents (compound D) And from compound D, it forms into an intermediate dye compound having an L-based cyclic ring with the R 1 and/or R 2 constituents (compound F). With compound F the desired dye can be made with a greater overall yield for mass production.

  本发明提供了一种合成中间染料产物的新方法，其具有以下结构式：其中L为S、Te或Se；R1和R2为相同或不同的芳香族或烷基化合物；R3为氢或短链烷基基团；Z为阴离子。制备这种中间化合物的过程包括将R1-乙炔化合物与R2-乙炔化合物（化合物A）反应成为具有R1和/或R2组分的烯醚化合物（化合物D），然后从化合物D形成具有基于L的环状环的中间染料化合物，其中含有R1和/或R2组分（化合物F）。通过化合物F，可实现所需染料的更高总产量，用于大规模生产。
• Synthesis of Fully Substituted 3-Formyl-4-iodofurans<i>via</i>a Gold(I)-Catalyzed Oxidation/1,2-Alkynyl Migration/Cyclization/Iodination Cascade
  作者：Tao Wang、Shuai Shi、Matthias Rudolph、A. Stephen K. Hashmi

  DOI：10.1002/adsc.201400356

  日期：2014.7.7

  A highly efficient gold(I)‐catalyzed cascade reaction for the synthesis of fully substituted 3‐formyl‐4‐iodofurans has been developed. Mechanistic investigations indicate a reaction pathway that involves a direct iodination reaction of the organogold intermediate via functionalization of the AuC(sp2) bond, instead of a direct iodination of the 3‐formylfurans.

  已开发出一种高效的金（I）催化级联反应，用于合成完全取代的3-甲酰基-4-碘代呋喃。机械调查表明，涉及organogold中间的直接碘化反应的反应途径通过在Au的官能 C（SP 2）键，而不是3- formylfurans的直接碘化。
• Recyclable gold(I)-catalyzed oxidative cyclization of 1,4-diyn-3-ols leading to highly substituted 3-formylfurans
  作者：Xiaoqiang Xiao、Siqi Liu、Mingzhong Cai

  DOI：10.1016/j.jorganchem.2022.122527

  日期：2022.12

  An efficient heterogeneous gold(I)-catalyzed cascade oxidation/1,2-alkynyl migration/cyclization reaction of 1,4-diyn-3-ols has been developed. The reaction proceeds effectively in toluene at room temperature by using 3 mol% of MCM-41-anchored sterically demanding NHC-gold(I) complex [MCM-41-IPrAuOTf] as catalyst and 3,5-dichloropyridine N-oxide as oxidant and offers a general and practical route for

  开发了一种高效的非均相金 (I) 催化级联氧化/1,2-炔基迁移/1,4-diyn-3-ols 的环化反应。以 3 mol% 的 MCM-41 锚定的空间要求高的 NHC-gold(I) 配合物 [MCM-41-IPrAuOTf] 作为催化剂，3,5-二氯吡啶N-氧化物作为氧化剂，反应在室温下在甲苯中有效进行。为从容易获得的起始材料合成多种 3-甲酰基呋喃提供了一种通用且实用的途径，其产率从良好到极好。这种异质化的金 (I) 催化剂可以通过简单的离心过程轻松回收，并且可以重复使用六次以上，而不会显着降低其催化效率。