2-(3,3-dimethylbut-1-yn-1-yl)benzaldehyde | 183312-34-7

• 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: 2-(3,3-dimethylbut-1-yn-1-yl)benzaldehyde
• 英文别名: 2-(3,3-dimethyl-1-butynyl)benzaldehyde；2-(3,3-dimethylbut-1-ynyl)benzaldehyde
• CAS: 183312-34-7
• 化学式: C₁₃H₁₄O
• 分子量: 186.254
• InChiKey: XRLALNZBNYDJKM-UHFFFAOYSA-N

物化性质

• 沸点：
  296.8±23.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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-(3,3-dimethylbut-1-yn-1-yl)benzaldehyde 在 potassium iodide 、 palladium(II) iodide 作用下， 以 二氯甲烷 、 原甲酸三甲酯 为溶剂， 反应 18.0h， 生成 methyl 3-tert-butyl-1-methoxy-1H-isochromene-4-carboxylate
  参考文献：
  名称：

  通过 Pd 催化氧化羰基化（2-炔基）亚苄基胺衍生物多功能合成异喹啉和异色烯

  摘要：

  异喹啉-4-羧酸酯 3 和异色烯-4-羧酸酯 4 可以通过容易获得的（2-炔基亚苄基）胺衍生物的直接 PdI2 催化氧化杂环化/烷氧基羰基化方便地制备。特别地，(2-炔基苯亚甲基)(叔丁基)胺2通过N-环化选择性地提供异喹啉衍生物3，而N-(2-炔基苯亚甲基)-N'-苯肼5通过O-环化导致异色烯4的形成由水侵蚀基材的亚氨基而引起。在 80–100 °C 和 20–80 atm（25 °C）的 CO/空气 4:1 混合物的醇溶剂中，在 PdI2（2–10 mol-%）存在下进行反应结合 KI（KI/PdI2 摩尔比 = 10）。在亚胺2的情况下，使用脱水剂，例如原甲酸三烷基酯，

  DOI：

  10.1002/ejoc.201100739
• 作为产物：
  描述：

  2-碘苄醇 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 四丁基氟化铵 、 三乙胺 作用下， 以 1,4-二氧六环 为溶剂， 反应 150.5h， 生成 2-(3,3-dimethylbut-1-yn-1-yl)benzaldehyde
  参考文献：
  名称：

  Cyclization reactions of 2-alkynylbenzyl alcohol and 2-alkynylbenzylamine derivatives promoted by tetrabutylammonium fluoride

  摘要：

  The regioselectivity of the cyclization reaction of 2-ethynylbenzyl alcohol and 2-ethynylbenzylamine derivatives promoted by TBAF was investigated. Six-membered ring derivatives were obtained from the compounds, which have a butyl group on the triple bond. Whereas five-membered ring products were afforded from the substrates having hydrogen or aromatic substituents. on the acetylene moiety. It was also concluded that both the tetrabutylammonium cation and fluoride anion were essential for the cyclization. Thus, the actual mechanism and catalytic cycle were also suggested. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00991-7

文献信息

• Catch–Release System for Dosing and Recycling Silver(I) Catalyst with Status of Catalytic Activity Reported by Fluorescence
  作者：Indrajit Paul、Nikita Mittal、Soumen De、Michael Bolte、Michael Schmittel

  DOI：10.1021/jacs.9b01182

  日期：2019.4.3

  Addition of zinc(II) releases silver(I) from [Ag(1)]+ and generates the catalytically active and fluorescent complex [Ag(2)]+. In this networked state II ("release") both catalytic activity and emission at 472 nm are maximum. Removal of the original trigger regenerates networked state I. ON/OFF control and recycling of catalyst was demonstrated over three in situ cycles.

  由纳米开关 1 和附有蒽的冠醚 2 组成的银（I）捕获释放系统是由化学触发和离子转移驱动的。银 (I) 易位的任何状态都是通过 472 和 554 nm 的比率发射特征自行报告的。在自分类网络状态 I 中，银 (I) 离子在纳米开关 [Ag(1)]+（“捕获”）内被紧密屏蔽，因此它们的催化活性为零，而在 554 nm 处的发射最大。添加锌 (II) 从 [Ag(1)]+ 释放银 (I) 并生成具有催化活性和荧光的复合物 [Ag(2)]+。在这种网络状态 II（“释放”）中，472 nm 处的催化活性和发射都是最大的。移除原始触发器会重新生成网络状态 I。
• Bioinspired Intramolecular Diels-Alder Reaction: A Rapid Access to the Highly-Strained Cyclopropane-Fused Polycyclic Skeleton
  作者：Shifa Zhu、Zhengjiang Guo、Zhipeng Huang、Huanfeng Jiang

  DOI：10.1002/chem.201304839

  日期：2014.2.24

  bioinsipred gold‐catalyzed tandem Diels–Alder/Diels–Alder reaction of an enynal and a 1,3‐diene, forming the highly‐strained benzotricyclo[3.2.1.02,7]octane skeleton, was reported. In contrast, a Diels–Alder/Friedel–Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels–Alder reaction of a pyrylium intermediate with a

  据报道，生物吸附的金催化的烯类和1,3-二烯的串联Diels-Alder / Diels-Alder反应形成了高应变的苯并三环[3.2.1.0 2,7 ]辛烷骨架。相反，当使用银盐作为催化剂时，发生了狄尔斯-阿尔德/弗里德尔-克拉夫特串联反应。尽管两个反应都经历了类似的吡啶鎓中间体与1,3-二烯的Diels-Alder反应，但它们具有不同的反应机理。前者进行了逐步的Diels-Alder反应，而后者则进行了协调一致的反应。
• Synthesis of Pyrrolo[1,2-<i>b</i>]isoquinolines via Gold(I)-Catalyzed Cyclization/Enyne Cycloisomerization/1,2-Migration Cascade
  作者：Liangliang Song、Guilong Tian、Luc Van Meervelt、Erik V. Van der Eycken

  DOI：10.1021/acs.orglett.0c02310

  日期：2020.8.21

  of the migrating group is comprehensively investigated. The study of the mechanism indicates that the pathway involving a gold carbenoid species is the main pathway and that the 1,2-migration of alkyl and aryl groups to the gold carbenoid occurs in an intramolecular fashion. This cascade reaction is also employed as the key step for the synthesis of a decumbenine B analogue.

  开发了金（I）催化的N-炔基2-乙酰胺的级联转化，用于快速有效地合成吲哚并立定支架。通过顺序的亲核环化/烯炔环异构化/ 1,2-迁移过程，各种吡咯并[1,2- b]异喹啉在温和条件下以区域特异性和会聚的方式获得。在此过程中可以耐受各种烷基和芳基迁移基团。全面研究了迁移组的电子效应。对机理的研究表明，涉及金类胡萝卜素的途径是主要途径，并且烷基和芳基的1，2-迁移以分子内方式发生。该级联反应也被用作合成癸二烯B类似物的关键步骤。
• Synthesis of Novel Enyne-Allenes, Their Thermal C²-C⁶ Cyclization, and the Importance of a Benzofulvene Biradical in the DNA Strand Cleavage¹
  作者：Michael Schmittel、Michael Maywald、Marc Strittmatter

  DOI：10.1055/s-1997-726

  日期：1997.2

  Novel enyne-allenes without acceptor substituents have been prepared from propargyl acetates by Pd-catalyzed addition of arylzinc chloride or by cuprate addition. Their thermal reaction afforded exclusively the C2-C6 and no Myers-Saite cyclization products. In one case, intermolecular hydrogen abstraction and DNA strand cleavage were observed.

  没有受体取代基的新型烯炔-丙二烯已经从乙酸炔丙酯通过 Pd 催化的芳基氯化锌加成或铜酸盐加成制备。它们的热反应仅提供 C2-C6，没有 Myers-Saite 环化产物。在一种情况下，观察到了分子间夺氢和 DNA 链断裂。
• Gold Catalysis: β-Ketonaphthalenes<i>via</i>Molecular Gymnastics of 1,6-Diyne-4-en-3-ols
  作者：Tobias Lauterbach、Sebastian Arndt、Matthias Rudolph、Frank Rominger、A. Stephen K. Hashmi

  DOI：10.1002/adsc.201300396

  日期：2013.6.17

  1,6‐Diyne‐4‐en‐3‐ols with one terminal alkyne were applied as test substrates for a possible dual catalyzed cyclization. Instead of a dual catalysis cycle, naphthyl ketone derivatives were obtained as single products. The regioselectivity of the obtained products is unprecedented. Instead of the expected naphthyl ketones bearing the keto group in the α‐position, the keto group is positioned in the

  将带有一个末端炔烃的1,6-二炔-4-烯-3-醇用作测试底物，以进行可能的双重催化环化反应。代替双重催化循环，获得了萘基酮衍生物作为单一产物。所得产物的区域选择性是空前的。通过将起始材料进行复杂的重排，可以使酮基位于萘基骨架的ß位，而不是在α位上带有酮基的预期的萘基酮。