6-Methoxy-2,2-dimethyl-1-indanyl pivalate | 165072-46-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 6-Methoxy-2,2-dimethyl-1-indanyl pivalate
• 英文别名: 6-methoxy2,2-dimethyl-2,3-dihydro-1H-inden-1-ylpivalate；6-methoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl 2,2-dimethylpropanoate；(6-Methoxy-2,2-dimethyl-1,3-dihydroinden-1-yl) 2,2-dimethylpropanoate
• CAS: 165072-46-8
• 化学式: C₁₇H₂₄O₃
• 分子量: 276.376
• InChiKey: HKEKDOMODNZDCJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-Methoxy-2,2-dimethyl-1-indanyl pivalate 在 甲醇 作用下， 以13%的产率得到6-Methoxy-2,2-dimethyl-1-indanyl methyl ether
  参考文献：
  名称：

  The Photochemistry of Conformationally Rigid Benzylic Esters: 2,2-Dimethyl-1-indanyl Acetates and Pivalates

  摘要：

  The photochemistry, in methanol, of substituted 2,2-dimethyl-1-indanyl acetates 9a-c and pivalates 10a-c has been studied. In agreement with previous studies on benzylic esters, the results show that the substituents change the yield of products derived from the ion pair. The mechanistic conclusion reached is that the substituents change the oxidation potential of the indanyl radicals and thus the rate constant of electron transfer for converting the radical pair to the ion pair. The results also reveal two other substituent effects. First, substituents can increase the overall efficiency of the photoreaction by enhancing homolytic cleavage, The second effect is conformational. In compounds where the bond that is cleaving is conformationally mobile, such as the C-O bond in benzylic esters, substituents on the ring can change the population of the reactive conformer and thus the overall efficiency of the reaction. For the indanyl acetate esters, the difference in excited-state reaction rate between the m- and p-methoxy substituted ester is 15:1. For the m- and p-methoxy substituted benzyl acetates, this difference in reaction rate is 48:1. The larger difference in reaction rate for the conformationally mobile benzylic esters is attributed to a higher population of the unreactive conformer for the p-methoxy substituted ester.

  DOI：

  10.1021/jo00118a024
• 作为产物：
  描述：

  2-溴-5-甲氧基苯甲酸 在 2,6-二甲基吡啶 、 甲醇 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 四(三苯基膦)钯 、 氯化亚砜 、 三甲基乙酸钾 、 potassium carbonate 、 三乙胺 、 N,N-二甲基甲酰胺 、 lithium chloride 作用下， 以 四氢呋喃 、 2-甲基四氢呋喃 、 5,5-dimethyl-1,3-cyclohexadiene 、 二氯甲烷 、 甲苯 为溶剂， 反应 79.0h， 生成 6-Methoxy-2,2-dimethyl-1-indanyl pivalate
  参考文献：
  名称：

  分子内钯（0）催化的C（sp3）合成1-茚满醇和1-茚满胺？高度化：构象效应的影响

  摘要：

  尽管存在不利的空间相互作用，但通过分子内钯（0）催化的C（sp 3）H芳基化反应合成了一系列含有叔C1原子的有价值的1-茚满醇和1-茚满胺。正如索普-英戈尔德效应所预期的那样，发现反应的效率与C2处的取代度有关。此外，C1上的杂原子取代基的性质对C1和C2上的非对映选择性有显着影响；实际上，获得了1-茚满醇和1-茚满胺，它们具有相反的相对构型。对相应的反应中间体进行X射线和DFT优化结构的分析，为深入了解这些取代基引起的微妙构象效应提供了有用的见识。

  DOI：

  10.1002/chem.201402907

文献信息

• METHOD FOR PRODUCING 1-INDANOLES AND 1-INDANAMINES
  申请人：BAYER CROPSCIENCE AKTIENGESELLSCHAFT

  公开号：US20160340370A1

  公开（公告）日：2016-11-24

  A description is given of a process for preparing 1-indanols and 1-indanamines by palladium-catalyzed arylation and of the use thereof as intermediates for the synthesis of fine chemicals and of active agrochemical ingredients.

  通过钯催化芳基化的方法制备1-吲哚醇和1-吲哚胺的过程描述，并将其用作合成精细化学品和活性农药成分的中间体。
• VERFAHREN ZUR HERSTELLUNG VON 1-INDANOLEN UND 1-INDANAMINEN
  申请人：Bayer CropScience Aktiengesellschaft

  公开号：EP3099671B1

  公开（公告）日：2017-12-27
• US9796737B2
  申请人：——

  公开号：US9796737B2

  公开（公告）日：2017-10-24
• Synthesis of 1-Indanols and 1-Indanamines by Intramolecular Palladium(0)-Catalyzed C(sp³)H Arylation: Impact of Conformational Effects
  作者：Simon Janody、Rodolphe Jazzar、Arnaud Comte、Philipp M. Holstein、Jean-Pierre Vors、Mark J. Ford、Olivier Baudoin

  DOI：10.1002/chem.201402907

  日期：2014.8.25

  A range of valuable 1‐indanols and 1‐indanamines containing a tertiary C1 atom were synthesized by intramolecular palladium(0)‐catalyzed C(sp3)H arylation, despite unfavorable steric interactions. The efficiency of the reaction was found to correlate with the degree of substitution at C2, as expected from the Thorpe–Ingold effect. Additionally, the nature of the heteroatomic substituent at C1 had

  尽管存在不利的空间相互作用，但通过分子内钯（0）催化的C（sp 3）H芳基化反应合成了一系列含有叔C1原子的有价值的1-茚满醇和1-茚满胺。正如索普-英戈尔德效应所预期的那样，发现反应的效率与C2处的取代度有关。此外，C1上的杂原子取代基的性质对C1和C2上的非对映选择性有显着影响；实际上，获得了1-茚满醇和1-茚满胺，它们具有相反的相对构型。对相应的反应中间体进行X射线和DFT优化结构的分析，为深入了解这些取代基引起的微妙构象效应提供了有用的见识。
• The Photochemistry of Conformationally Rigid Benzylic Esters: 2,2-Dimethyl-1-indanyl Acetates and Pivalates
  作者：J. A. Pincock、P. J. Wedge

  DOI：10.1021/jo00118a024

  日期：1995.6

  The photochemistry, in methanol, of substituted 2,2-dimethyl-1-indanyl acetates 9a-c and pivalates 10a-c has been studied. In agreement with previous studies on benzylic esters, the results show that the substituents change the yield of products derived from the ion pair. The mechanistic conclusion reached is that the substituents change the oxidation potential of the indanyl radicals and thus the rate constant of electron transfer for converting the radical pair to the ion pair. The results also reveal two other substituent effects. First, substituents can increase the overall efficiency of the photoreaction by enhancing homolytic cleavage, The second effect is conformational. In compounds where the bond that is cleaving is conformationally mobile, such as the C-O bond in benzylic esters, substituents on the ring can change the population of the reactive conformer and thus the overall efficiency of the reaction. For the indanyl acetate esters, the difference in excited-state reaction rate between the m- and p-methoxy substituted ester is 15:1. For the m- and p-methoxy substituted benzyl acetates, this difference in reaction rate is 48:1. The larger difference in reaction rate for the conformationally mobile benzylic esters is attributed to a higher population of the unreactive conformer for the p-methoxy substituted ester.