2,2-dimethyl-5-methhoxyindan-1-ol | 165072-42-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 2,2-dimethyl-5-methhoxyindan-1-ol
• 英文别名: 2,2-dimethyl-5-methoxyindan-1-ol；5-Methoxy-2,2-dimethyl-1-indanol；5-methoxy-2,2-dimethyl-2,3-dihydro-1H-indene-1-ol；5-methoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-ol；5-Methoxy-2,2-dimethyl-1,3-dihydroinden-1-ol
• CAS: 165072-42-4
• 化学式: C₁₂H₁₆O₂
• mdl: MFCD11219534
• 分子量: 192.258
• InChiKey: LTZDOFUSNTZXAB-UHFFFAOYSA-N

物化性质

• 沸点：
  310.1±37.0 °C(Predicted)
• 密度：
  1.080±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-5-methhoxyindan-1-ol 在 citrate buffer 、 potassium 12-tungstocobalt(III)ate 作用下， 生成 5-methoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-one
  参考文献：
  名称：

  立体电子效应对烷基芳族自由基阳离子的侧链断裂的作用。5-甲氧基-2,2-二甲基茚满-1-醇自由基阳离子的反应性

  摘要：

  对2,2-二甲基-5-甲氧基茚满-1-醇（1）自由基阳离子在酸性水溶液（pH≤4）中的反应进行了动力学和产物研究。1 +作为唯一的反应经历CH质子去质子化，k = 4.6×10 4  s -1。动力学数据已与1-（4-甲氧基苯基）乙醇（2）和1-（4-甲氧基苯基）-2,2-二甲基-1-丙醇（3），表明当C–H键被迫形成几乎与π系统对齐的构象时，去质子率增加。1 +和3 +的DFT计算结果也支持了可裂键与π系统重叠是发生键断裂的重要条件的结论。

  DOI：

  10.1016/s0040-4020(02)00468-4
• 作为产物：
  描述：

  1-Chloro-5-methoxy-2,2-dimethyl-indan 在 丙酮 作用下， 生成 2,2-dimethyl-5-methhoxyindan-1-ol
  参考文献：
  名称：

  取代基对2,2-二甲基茚满-1-基氯的溶剂分解的影响

  摘要：

  根据LArSR等式分析了取代基对2，2-二甲基茚满-1-基氯的溶剂分解的影响，得到ϱ ＝ -5.81，r ＝ 1.14。讨论了α-叔丁基苄基阳离子体系的共面性。

  DOI：

  10.1016/s0040-4039(00)74121-9

文献信息

• Enantioselective Synthesis of Indanes with a Quaternary Stereocenter via Diastereoselective C(sp³)–H Functionalization
  作者：Jun Chen、Zhan Shi、Ping Lu

  DOI：10.1021/acs.orglett.1c02513

  日期：2021.10.1

  A practical synthesis of enantioenriched indane derivatives with quaternary stereocenters was developed via sequential enantioselective reduction and C–H functionalization. Good to excellent enantioselectivity could be achieved by either the CuH-catalyzed asymmetric reduction or the Corey–Bakshi–Shibata (CBS) reduction of indanone derivatives. The subsequent diastereospecific and regioselective rhodium-catalyzed

  通过顺序对映选择性还原和 C-H 功能化开发了具有四元立体中心的对映体富集茚满衍生物的实用合成。通过CuH催化的不对称还原或茚满酮衍生物的Corey-Bakshi-Shibata（CBS）还原可以实现良好的对映选择性。随后的非对映特异性和区域选择性铑催化的甲基 C-H 键甲硅烷基化导致具有四元中心的茚满衍生物。该策略进一步应用于（nor）伊卢达烷和葡萄烷倍半萜类化合物的合成。
• Silylative Kinetic Resolution of Racemic 2,2‐Dialkyl 5‐ and 6‐Membered Cyclic Benzylic Alcohol Derivatives Catalyzed by Chiral Guanidine, ( <i>R</i> )‐ <i>N</i> ‐Methylbenzoguanidine
  作者：Shuhei Yoshimatsu、Kenya Nakata

  DOI：10.1002/adsc.201900761

  日期：2019.10.22

  Efficient silylative kinetic resolution of racemic 2,2‐dialkyl 5‐ and 6‐membered cyclic benzylic alcohols was achieved using diphenylmethylchlorosilane (Ph2MeSiCl) or phenyldimethylchlorosilane (PhMe2SiCl) as a silyl source catalyzed by chiral guanidine. The reaction could be applied to a broad range of 2,2‐dialkyl 1‐indanols with good s‐values, irrespective of the electronic nature of the substituent

  使用二苯基甲基氯硅烷（Ph 2 MeSiCl）或苯基二甲基氯硅烷（PhMe 2 SiCl）作为手性胍催化的甲硅烷基来源，可实现高效消旋的2,2-二烷基5-和6-元环状苄醇的甲硅烷基动力学拆分。不论底物芳环上取代基的电子性质和C2位上取代基的类型如何，该反应均可用于具有良好s值的各种2,2-二烷基1-茚满醇。另外，反应中可以采用几种2，2-二甲基6元环和杂环醇。
• 芳香环苄基邻位双烷基的合成方法
  申请人：乐威医药（江苏）股份有限公司

  公开号：CN114262250A

  公开（公告）日：2022-04-01

  本发明公开了一种芳香环苄基邻位双烷基的合成方法。其中，芳香环苄基邻位双烷基具有式I所示的结构：其中，式I中，R为甲基、乙基、丙基或丁基，R’为卤素、烷基或烷氧基，X为‑CH2‑、‑ ‑、‑O ‑或‑ ‑；合成方法包括以下步骤：S1，在碱性条件下通过双烷基化反应得到且双烷基化反应中采用先加碱再加的加料顺序；S2，采用硼氢化钠、硼氢化锂、氢化铝锂或BH3将S1中制得的还原为以及S3，通过三乙基硅烷和三氟化硼乙醚或三氟乙酸与S2中制得的反应，制备得到芳香环苄基邻位双烷基。在本发明的条件下可以高产率得到终产品，底物适用性宽，对设备要求不高，适合放量生产。
• 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.
• The role of oxygen acidity on the side-chain fragmentation of ring methoxylated benzocycloalkenol radical cations
  作者：Monica Bellanova、Massimo Bietti、Michela Salamone

  DOI：10.1016/s0040-4039(03)01620-4

  日期：2003.8

  The reactivity of 2,2-dimethyl-5-methoxyindan-1-ol (1) and 2,2-dimethyl-6-methoxytetral-2-ol (2) radical cations has been studied both in acidic and basic solution. At pH less than or equal to 4 both 1(.+) and 2(.+) undergo C-alpha-H deprotonation as the exclusive reaction with k = 4.6 x 10(4) and 3.2 x 10(4) s(-1), respectively. In basic solution 1(.+) and 2(.+) behave as oxygen acids undergoing -OH-induced alpha-OH deprotonation in a diffusion controlled process (k(-OH) approximate to 10(10) M-1 s(-1)). An intermediate alkoxyl radical is formed which undergoes a 1,2-hydrogen atom shift in competition with C-C beta-scission (with 1(.+)) or as the exclusive pathway (with 2(.+)). A behavior which is interpreted in terms of the greater ease of ring-opening of a five membered ring as compared to a six-membered one. (C) 2003 Elsevier Ltd. All rights reserved.